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8022268
EL-NAGGAR, LETICIA JIMENEZ
PART I: IRIDOID GLYCOSIDES FROM MENTZELIA DECAPTETALA.

PART II: IRIDOIDS. - A REVIEW
The Ohio State University PH.D. 1980
University
Microfilms
International 300 N. Zeeb Road, Ann Arbor, MI 48106 18 Bedford Row, London WC1R 4EI, England
PART I .IRIDOID GLYCOSIDES FROM MENTZELIA DECAPETALA.
PART II. IRIDOIDS.- A REVIEW.
Presented in Partial Fulfillment of the Requirements for
the Degree Doctor of Philosophy in the Graduate
School of The Ohio State University
By
Leticia Jimenez El-Naggar, B.S., M.S.
* * * * * *
The Ohio State University
1980
Reading Committee: Approved By
Prof. J.L. Beal
Prof. R .W . Doskotch
Prof. L.W. Robertson
Prof. D.D. Miller
College of Pharmacy
I dedicate this dissertation to
My Parents s Ernesto & Reyes Maria
My Husband : Sha'aban
My Son : Pouad
as a gift of my love.
ii
ACKNOWLEDGMENTS
With my deepest gratitude to my adviser, Professor Jack L. Beal
for his invaluable teachings, continuous encouragement and care. It has
been an honor to work under his supervision.
Many times the author consulted with Professor Raymond W. Doskotch
who always graciously offered his suggestions and criticisms. His help
was greatly appreciated.
Special thanks are due to Professor Larry W. Robertson and my fellow
graduate students and friends for making of this period a real learning
experience.
My sincere gratitude to all my Family for their continuous moral
support and love.
I acknowledge the help provided by Dr. Jack Fowble and Librarians
Mrs Virginia Hall, Mr Nicholas Felt, and Miss Mary Amorose during the
preparation of this dissertation.
This work will not have been possible without the love and patience
of my husband Dr. Sha'aban F. El-Naggar to whom I present my eternal love
and gratitude.
lii
VITA
February 1st., 1 9 5 1 ..................... B o m - Mexico, D.F., Mexico
July, 1973 .............................. B.S., in Pharmacy

Universidad Nacional
Autonoma de Mexico
Mexico.
March, 1975.............................. M.S., in Pharmacy

(Synthesis of Drugs)
Autonoma de Mexico
Mexico.
August, 1972-1973........................ Research Associate

Physiology Department
Instituto Politecnico
Nacional, Mexico.
1973~1975 .............................. Instructor, Cell Biology

Autonoma de Mexico
Mexico.
1975-1980................................ Research Associate

Pharmacognosy and Natural
Products Chemistry, College
of Pharmacy, The Ohio State
University
Columbus, Ohio.
FIELDS OF STUDY
Major Fields Pharmacognosy and Natural Products Chemistry.
iv
PUBLICATIONS
B.S. dissertations Contribucion al Estudio de los Lipidos de Schistocerca

paranensis, Universidad Nacional Autonoma de Mexico, Adviser: Professor
Jorge Reyes L., (1973)*
M.S. dissertation: Determinacion de las Estructuras de la Budleina A y

de la Budleina B, Universidad Nacional Autonoma de Mexico, Adviser:
Professor Eugene A. Bratoeff., (1975)*
A. Romo de Vivar, C. Guerrero, E. Diaz, E.A. Bratoeff, and L. Jimenez.

The Germacranolides of Viguiera buddleiaeformis. Structures of Budlein-A
and -B., Phytochemistry, 15, 525 (19?6).
L. El-Naggar, J.L. Beal, L.M. Parks, K.N. Salman, P. Patil, and A.E.
Schwarting., A Note in the Isolation and Identification of Two
Pharmacologically Active Constituents of Euphorbia pilulifera.,
J. Natural Products (Lloydla), M , 73 (1978;.
L. J. El-Naggar, and J.L. Beal., Iridoids.- a Review., J. Natural

Products (Lloydia), accepted for publication, (1980).
L.J. El-Naggar, J.L. Beal and R.W. Doskotch., Iridoid Glycosides from
Mentzelia decapetala., International Research Congress on Natural
Products as Medicinal Agents. Strasbourg, France (1980).
v
TABLE OF CONTENTS
Page
ACKNOWLEDGMENTS ................................................. iii
VITA ......................................................... iv
LIST OF ILLUSTRATIONS ....................................... xii
LIST OF TABLES ................................................ xvi
GENERAL INTRODUCTION ............................................. 1
PART I. IRIDOID GLYCOSIDES FROM MENTZELTA DECAPETALA .......... 2
INTRODUCTION ................................................ 4
OBJECTIVES OF RESEARCH .......................................... 6
ISOLATION OF IRIDOID GLYCOSIDES FROM MENTZELTADECAPETALA ____ 7

12
Iridoids of Mentzelia decape tala .................. .
7-Chlorodeutziol ..................................... 12
Mentzeloside .........................
Loasaside ................................. 22
Sweroside ............................................. 29
Decapetaloside ................................... 30
Strictoside ................................
Glucoside X ..................................
Decaloside ............................................ 38
Glucoside V (10-0-3-glucosyl-decaloside).............. 39
Glucoside VII ...................................... ^5
Scopoletin ........ .............................. .
Isolation of a Hypotensive Principle fromM . decapetala... ^8

vi
TABLE OF CONTENTS (continued) p&ge
Pharmacological Assays and Results ............... 50
EXPERIMENTAL .................................................... 52
Equipment and Services .................................... 52
Parity of Reagents and Solvents ........................... 53
Source of Plant Material ................ 5^
Extraction and Initial Partition Procedures ............... 55
Chromatographic Studies of the n-butanol and water solubles.. 55
Column Chromatography of the n-butanol Solubles on
Sephadex LH-20 and Isolation of Rutin ..................... 58
Identification of Rutin ................................... 58
Column Chromatography of the non-phenolic part of
the n-butanol solubles fraction .......................... 59
Purification of 7-Chlorodeutziol ........................ 59
Physical and Spectral data of 7-Chlorodeutziol ...... 60
Acid Hydrolysis of 7-Chlorodeutziol and
Identification of Glucose ................... 61
Acetylation of 7-Chlorodeutziol and Jones*
Oxidation on the Acetate ............................ 61
Emulsin Hydrolysis of 7-Chlorodeutziol ........ 63
Acetylation of 7-Chlorodeutziol Aglycone ........... 64
Hydrogenation of 7-Chlorodeutziol .................. 64
Acetylation of 3 »4-Dihydro- 7-Chlorodeutziol ....... 65
Emulsin Hydrolysis of 3»^_Dihydro“ 7-Chlorodeutziol ... 66
Cyclization of ?-Chlorodeutziol, Synthesis of
Mentzeloside .......... 67
vii
TABLE CP CONTENTS (continued)
Page
Synthesis of 7-Chlorodeutziol fromMentzeloside .... 6?
Extraction of 7-Chlorodeutziol with a Non-
Halogenated Solvent System ......................... 68
Stability of 7-Chlorodeutziol ................. 68
Isolation of Mentzeloside ............................... 69
Physical and Spectral Data for Mentzeloside ......... 69
Acetylation of Mentzeloside ............ 70
Purification of Loasaside ................................ 70
Physical and Spectral Data for Loasaside ........... . 71
Acid Hydrolysis of Loasaside and Identification
of Glucose ......................................... 71
Acetylation of Loasaside ............................ 72
Hydrogenation of Loasaside ...................... 72
Acetylation of 7i8-Bihydro-loasaside ............ 73
Deoxygenation of Mentzeloside and Formation of
Loasaside and of Isoloasaside ........................ 7^
Synthesis of 7,8-Dihydro-loasaside through
Hydrogenation and Hydrogenolysis of Decaloside....... 75
Hydrogenation of Decaloside ................ 75
Hydrogenolysis of Dihydro-decaloside .......... 76
Isolation of Sweroside and Decapetaloside .............. 76
Spectral data for Sweroside ........ 77
Acid Hydrolysis of Sweroside ....................... 77
Acetylation of Sweroside ........... 77
viii
TABLE OF CONTENTS (continued)
Plage
Hydrogenation of Sweroside Tetraacetate ........... 78
Spectral Data for Decapetaloside .................. 79
Acid Hydrolysis of Decapetaloside ................. 79
Acetylation of Decapetaloside ..................... 79
Isolation of Strictoside ......... 80
Spectral Data for Strictoside ..................... 81
Acid Hydrolysis of Strictoside .................... 81
Acetylation of Strictoside ........................ 81
Emulsin Hydrolysis of Strictoside ...... 82
Acetylation of Strictoside Aglycone ............... 83
Purification of Glucoside X ............................ 84
Acid Hydrolysis of Glucoside X ......... 84
Column Chromatography of the Water Solubles Fraction .... 84
Column Chromatography of the Water Solubles-Iridoid
Fraction ................. 85
Purification of Decaloside ................ 85
Physical and Spectral Data for Decaloside ...... 85
Acetylation of Decaloside ......................... 86
Purification of Glucoside-V ............................ 86
Spectral Data for Glucoside-V .................... 87
Acid Hydrloysis of Glucoside-V .................... 87
Acetylation of Glucoside-V ........................ 88
Hydrogenation of Glucoside-V ............... 88
Emulsin Hydrolysis of Tetrahydro-glucoside-V ..... 89
Acetylation of Aglycone ^4 90
ix
TABLE OF CONTENTS (continued)
Page
Acetylation of Tetrahydro-glucoside-V ............. 90
Acid Methanolysis of Tetrahydro-glucoside-V ....... 91
Acetylation of 1-O-Methyl-glucoside-V ........ 92
Permethylation of Tetrahydro-glucoside-V ....... 92
Hydrolysis of the Permethylated Product ...... 93
Isolation of Glycoside-VII ........ 93
Spectral Data for Glycoside-VII ................... 9k
Acetylation of Glycoside-VII ...... 9k
Acid Hydrolysis of Glycoside-VII ..... 95
Isolation and Identification of Scopoletin ............. 96

Separation of the Tertiary and Quaternary Alkaloidal
Fractions .............................................. 97
Column Chromatography of the Tertiary Alkaloids ....... 98
Column Chromatography of the Quaternary Alkaloids ..... 98
Pharmacological Studies on the Extracts and Isolated
Compounds ................ 99
Hypotensive Activity ................ 99
Antibiotic Assay ................................ 100
Antifungal Activity ......... 100
Antifeeding Test .................................. 101
BIBLIOGRAPHY ................................................ 103
SPECTRA APPENDIX ............................................ 105
PART II. IRIDOIDS.- A REVIEW .............................. I67
INTRODUCTION ................................................ 168

x
TABLE CF CONTENTS (continued)
Page
IRIDOID COMPOUNDS ........................................... 172
Iridoid Glycosides: eight carbon basic skeleton ........ 172
Iridoid Glycosides : nine carbon basic skeleton ...... 173
Iridoid Glycosides: ten carbon basic skeleton ......... 202
Secoiridoid Glycosides : simple ....................... 231
Secoiridoid Glycosides: terpene conjugated ........ 238
Secoiridoid Glycosides: phenolic conjugated ........... 239
Bisglycosidic Iridoids and Secoiridoids ............... 244
Non-glycosidic Iridoids: miscellaneous ................ 251
Nonglycosidic Iridoids: plumiera type ................. 257
Nonglycosidic Iridoids: valeriana type ................ 260
Calculated molecular weight of Iridoids .............. 265
Names and Synonymns of Iridoids Cited in the Review 269
BIBLIOGRAPHY ................................................ 273
xi
LIST OF ILLUSTRATIONS
Figure Page
1. Compounds previously reported from M. decapetala ......... 5
2. Fractionation scheme for isolation of iridoids from
Mentzelia decape tala tops................................ 8
3. Compounds isolated from M. decape tala tops................ H
4. Chemical transformations for 7-chlorodeutziol ............ 18
5. Proposed fragmentation pattern for loasaside.......... 23
6. Deoxygenation mechanism for mentzeloside.................. 26
7. Chemical correlations of loasaside........................ 28
8. Proposed fragmentation scheme for decapetaloside 31
9. Proposed fragmentation scheme for strictoside............. 35
10. Chemical transformations of glucoside-V................... ^
11. Fractionation scheme for isolation of alkaloids from
Mentzelia decapetala tops................................ **9
12. IR Spectrum of Rutin (KBr)................................ 106
13. UV Spectrum of Rutin ......... 107
14. *H-NMR Spectrum of Rutin (CDÔD)............. *08
15. IR Spectrum of 7-Chlorodeutziol (KBr).................... 109
16. ^H-NMR Spectrum of 7-Chlorodeutziol (d o )................ HO
17. ^ C - N M R Spectrum of 7-Chlorodeutziol (OgO)............... HI
18. ^H-NMR Spectrum of 7-Chlorodeutzlol Hexaacetate (CDCl^).. H2
19. 13C-NMR Spectrum of 7-Chlorodeutzlol Hexaacetate H3
20. Mass Spectrum of 7-Chlorodeutziol Hexaacetate............ H**
21. ^H-NMR Spectrum of 7-Chlorodeutziol Aglycone ............ H5

xii
LIST OF ILLUSTRATIONS (continued)
Figure B&S®
22. ^ C - N M R Spectrum of 7-Chlorodeutziol Aglycone........... 116
23. 1H-NMR Spectrum of 7-Chlorodeutziol Aglycone Triacetate. 117
24. Mass Spectrum of 7-Chlorodeutziol Aglycone Triacetate... 118
25. Si-NMR Spectrum of 3,4-Dihydro- 7-Chlorodeutziol. 119
26. *H-NMR Spectrum of 3,4-Dihydro- 7-ChlorodeutziolH e x a a c e t a t e 120
27. Mass Spectrum of 3,4-Dihydro-7-Chlorodeutziol Aglycone.. 121
28. *H-NMR Spectrum of Mentzeloside (DgO)............. 122
29. "^C-NMR Spectrum of Mentzeloside (DgO)................... 123
30. *H-NMR Spectrum of Mentzeloside Pentaacetate.......... 124
31. ^ C - N M R Spectrum of Mentzeloside Pentaacetate............ 125
32. IR Spectrum of Loasaside................................ 126
33. Mass Spectrum of Loasaside............................... 127
34. ^H-NMR Spectrum of Loasaside(DÔ) ..... 128
35. *^C-NMR Spectrum of Loasaside (DgO) ................. 129
36. *H-NMR Spectrum of Loasaside Pentaacetate............. 130
37. ^ C - N M R Spectrum of Loasaside Pentaacetate............. 131
38. ^H-NMR Spectrum of 7»8-Dihydro Loasaside................ 132
39. ^H-NMR Spectrum of 7 18-Dihydro Loasaside Pentaacetate ... 133
40. 1H-MMR Spectrum of 6,7- Isoloasaside (D£0) ............... 134
41. *H-NMR Spectrum of Sweroside 135
42. ^ C - N M R Spectrum of Sweroside ....................
43. ^H-NMR Spectrum of Sweroside Tetraacetate ............... 137
44. ^^C-NMR Spectrum of Sweroside Tetraacetate ..... 138
45. Mass Spectrum of Sweroside Tetraacetate ................. 139

xiii
LIST CF ILLUSTRATIONS (continued)
Figure Page
46. *H-NMR Spectrum of 8,10-Dihydro Sweroside Tetraacetate... 1^0
47. *H-NMR Spectrum of Decapetaloside (DgO).................. ^1
48. Mass Spectrum of Decapetaloside ......................... 1^*2
49. *^C-NMR Spectrum of Decapetaloside ................
50. ^H-NMR Spectrum of Decapetaloside Pentaacetate .......... 1^
51. Mass Spectrum of Decapetaloside Pentaacetate ......... 1^5
52. *^C-NMR Spectrum of Decapetaloside Pentaacetate ........ 1^6
53* ^H-NMR Spectrum of Strictoside (DgO) ...............
54. Mass Spectrum of Strictoside .................. . I**'®
55* ^ C - N M R Spectrum of Strictoside (DgO) ...... . 1^9
56. ^H-NMR Spectrum of Strictoside Pentaacetate ............. 150
57. Mass Spectrum of Strictoside Pentaacetate .............. 151
58. ^C-NMR Spectrum of Strictoside Pentaacetate ........... 152
59. *H-NMR Spectrum of Strictoside Aglycone Diacetate .... 153
60. ^H-NMR Spectrum of Decaloside (DgO) .................... 154
61. H-NMR Spectrum of Decaloside Hexaacetate .............. 155
62. *^C-NMR Spectrum of Decaloside Hexaacetate ........... 156
63 . *H-NMR Spectrum of Glucoside-V (DgO) .................... 157
64. *^C-NMR Spectrum of Glucoside-V (DgO) ................... 158
65 . *H-NMR Spectrum of Glucoside-V-Nonaacetate ...... 159
66. ^ C - N M R Spectrum of Glucoside-V-Nonaacetate ......... 160
67. ^H-NMR Spectrum of Tetrahydro-glucoside-V-Aglycone-
Triacetate ............................................ 161
68. *H-NMR Spectrum of Glycoside-VII (D O) ................ 1^2

xiv
LIST CF ILLUSTRATIONS (continued)
Figure Page
69. ^ C - N M R Spectrum of Glycoside-VII (DÔ)......... 163
70. *H-NMR Spectrum of Glycoside-VH-Octaacetate ............ 164
71. ^ C - N M R Spectrum of Glycoside-VII-Ocatacetate ........... 165
72. *H-NMR Spectrum of Scopoletin (CDÔD) ................... 166
xv
LIST OF TABLES
Table Page
1. Results of the column chromatography of the iridoid

n-butanol solubles fraction on silica gel 60........ 9
2. Results on the charcoal column chromatography

of the water-solubles fraction............... 10
3. Results of the column chromatography of the iridoid-

water-solubles fraction on silica gel 60 ............ 10
13
4. ^C-nmr of iridoids from Mentzelia decapetala (DÔ)... 20
13
5. C-nmr of iridoid-acetates from Mentzelia
decape tala (CDCl^)......................... .......... 21
6 . Thin layer chromatography of the compounds isolated

fron the n-butanol and water solubles ............... 56
7. Paper chromatography of the compounds isolated from

the n-butanol and water solubles .................... 5?
8 . Gas chromatography of the compounds isolated from

the n-butanol and water solubles ....... 58
LIST OF PLATES
Plate Page
I. Mentzelia decapetala .................................... 3
xvi
GENERAL INTRODUCTION
This dissertation has been divided into two parts. Part I
consists on the experimental results obtained from the study of the
iridoid glycosides from Mentzelia decapetala (Loasaceae), and includes
isolation, structure elucidation and pharmacological activity of the
compounds obtained from our studies.
Part II is a literature survey of iridoid compounds reported
through January 1980. It includes the structural formula, as well as
the physical and spectral data of over 220 compounds reported in the
literature.
1
PART I. IRIDOID GLYCOSIDES FROM MENTZFLTA DECAPETALA.
2
3W
Plate I. Mentzelia decapetala.

INTRODUCTION
Mentzelia decapetala (Pursh) Urban and Gilg, family Loasaceae, is
a stout, erect, biennial plant from six to twenty four inches high
with rough pale grey steins, creamy white flowers, coarsely toothed
alternate leaves and encapsulated fruits which contain numerous seeds
(1). It grows in North-America, from Iowa to the Rocky Mountains and
Northwards to Southern Canada .
The family Loasaceae belongs to the order Violales (Parietales)
and to the class Dicotyledon, and comprises about 15 genera and 250
species (2).
Until I960 few chemical investigations had been done on this genus.
In i960, Earle et al (3 ) studied the seed oil content of Mentzelia
decapetala. In 1972, Danielson (4) isolated two iridoid glucosides
from extracts of the flowers and seed pods of M. decapetala. These
two compounds were named mentzeloside (jL) and decaloside (2). They
also detected the presence of at least eight other iridoid compounds
using a two dimensional paper chromatographic technique. Some of these
compounds were claimed to be free aglycones. No further investigation
was done on these compounds. Danielson also reported the presence of
the carbohydrates glucose, fructose and sucrose, as well as the presence
of the flavonol glycoside rutin (3 ) from the same plant.
In 197^, P. Kooiman (5 ) described a paper chromatographic
comparison of loganoside (4) with the extracts of leaves and seeds of
several members of the family Loasaceae, and claimed the presence of

k
loganic acid (j>) too.No further isolation or identification proceedures
were reported. Kooiman established the possibility of the wrong
classification of this family in the order Violales, and suggested a
reclassification of the family in the neighborhood of the Gentianales
or the Scrophulariales; his studies were supported by the unique
presence of iridoid glycosides in some members of the family Loasaceae
and their absence in the other families of this order.
Some taxonomic studies in the family Loasaceae have been reported,
dealing with the differentiation of members of the family based on their
soluble seed-protein content, and in some cases by means of cytological
and morphological examinations (6, 7).
The structures of some of the previously reported compounds from
M. decapetala are given in figure 1.
HO COOH
CH, I
OGIu OG Iu 3 OGIu
Mentzeloside (!_) Decaloside (2) Loganic acid (£)
OH
OH
HO
HO
CH Rutinosyl
C lu
HO
Loganoside (4)
Rutin (2)
Figure 1. Compounds previously reported from M. decapetala.

OBJECTIVES CF RESEARCH
In a preliminary screening for hypotensive activity of plant
extracts in this laboratory, it was found that the ethanolic extract of
Mentzelia decapetala, family Loasaceae, produced a significant lowering
of the mean arterial pressure of dogs and rabbits, when injected
intravenously to the anesthesized animal.
Several reports in the literature described the presence of iridoid
compounds in this genus (4, 5)» two of these compounds have been
characterized. Since some iridoid-type compounds have been found to
exhibit a hypotensive activity , e.g. oleuropein (8), elenolide (9)*
etc. One of our objectives was to separate and identify the iridoid
compounds of Mentzelia decapetala, as well as investigate their possible
pharmacological activity.
Moreover, because of the fact that M. decapetala gives a weak
positive test for alkaloids, and many alkaloids are known for their
hypotensive effect, the study of this alkaloidal fraction was undertaken.
6
ISOLATION OF IRIDOID GLYCOSIDES FROM MENTZELIA DECAPETALA.
The alcoholic extract residue obtained by percolation at room
temperature of the dried and ground tops of Mentzelia decapetalat was
tested for iridoid glucosides content, by the use of a paper
chromatographic technique and subsequent color development with vanillin-
hydrochloric acid spray reagent, as established by Danielson (10).
The first part of the purification procedure involved partitioning
of the residue between immiscible solvent pairs: the dried ethanolic
extract was partitioned between chloroform and water; the aqueous phase
was then extracted successively with ethyl acetate and n-butanol, while,
the chloroform phase was evaporated and the resulting residue was
partitioned between hexane and methanol containing 10% water, as shown
in figure 2. Paper chromatography indicated the presence of iridoids
mainly in the n-butanol and water-soluble fractions, as established by
their color reactions with the vanillin spray reagent (these colors
varied from bright red to pink and purple), the ethyl acetate solubles
presented only a slight coloration.
From the methanol solubles a compound with noniridoid structure
crystallized out, and it was identified as scopoletin (6), a coumarin.
The n-butanol solubles were purified through a Sephadex LH-20
column, to separate a phenolic yellow pigment (25%) which was identified
as rutin Q ) • The remaining 75% of the n-butanol extract was
chromatographed over silica gel G 60 containing 5% water. From the
eluted fractions seven iridoid glucosides were obtained after further
purification (table 1). ^

8
Powdered Mentzella decapetala
Tops (1.0 Kg)
% EtOH
percolation
2- Evaporation
EtOH extract residue Marc

(100 g)
CHClo/H_0 partitioning
(21X3)
I____________ r
HÔ-solubles CHGl^-solubles
(15 g)
Extracted with EtOAc Hexane/90^ MeOH partitioning

(31 x 3) (21 x 3)
1 I---- 1
HgO-solubles EtOAc- MeOH- Hexane-
solubles solubles solubles
(4.0 g) (7.5 g) (7.5 g)
Extraction with n-BuOH

l(31 x 3) Scopoletin
HÔ-solubles n-BuOH-solubles
(59 g) (16 g)
t I
I 1
I
decaloside 7-chlorodeutziol
mentzeloside
iridoid VII loasaside
strictoside
iridoid V sweroside
decapetaloside
decaloside
rutin
glucoside X
Figure 2. Fractionation scheme for isolation of irldolds
from Mentzella decapetala tops.

9
Table 1. Results of the column chromatography of the iridoid
n-butanol solubles fraction on silica gel 6 0 .
Fraction # Weight (g) Compound:
1- 68 1.1 (-)
69- 88 1.3 glucoside X
89-103 1.2 sweroside, decapetaloside
104-155 1.7 strictoside
156-218 1.4 loasaside
219-255 1.1 mentzeloside
256-291 3.9 7-chlorodeutziol
292-wash 3-2 decaloside, rutin
The purification of the water-soluhles fraction was carried out by
using a column of charcoal with selective elution of the sugars and
iridoids. The aqueous solution of this fraction was applied onto the
charcoal column and eluted successively with water and increasing
concentrations of ethanol in water. The eluted fractions were
concentrated under vacuum, and the residues were examined by spotting a
sample of the material on a filter paper and spraying with vanillin-
hydrochloric acid. After heating the paper a bright red color
indicated the presence of the iridoids. The results from this column
are presented in table 2.
Fractions 7-13 of the charcoal column were further chromatographed
over silica gel 60. From the eluted fractions, some of the iridoids
isolated from the n-butanol solubles were obtained, and two new iridoid
glucosides were separated after further purification (table 3).
The structural formulas for the above compounds are in figure 3*

io
Table 2 Results on the charcoal column chromatography
of the water-solubles fraction.
Fraction # Eluate Solvent Weight Iridoid's Test

(Vol. in liters) (tyjsEtOH) (g) (Vanillin Spray)
i 1.5 100: 0 5-5 (-)

2 1.0 100: 0 5.8
3 1.0 90: 10 5.1
4
5
1.0
1.0
87 s 13
85 s 15
3-7
1.3 f—J
6
7
8
1.0
1.0
1.0
80;. 20
75 s 25
0.5
0.3
w
(±)
75 s 25 0.5 (+)
9 1.0 70; 30 0.9
10 1.0 65 s 35 0.5
ll 1.0 60: 40 0.7
12 1.0 50; 50 0.6
13 3.0 0;100 0.9 (+)
Table 3. Results of the column chromatography of the iridoid

water-solubles fraction on silica gel 60.
Fraction # Weight (g) Compound:
1- 30 0.2 (-)
31- 45 0.1 glucoside X
46- 57 0.3 glucoside X, strictoside
58- 98 0.8 mentzeloside, and traces of

loasaside and strictoside.
99-119 1.9 mentzeloside, 7-chlorodeutziol ,

and traces of loasaside
120-123 0.2 7-chlorodeutziol
124-143 2.0 decaloside
144-15? 1.5 glycoside VII
158-194 3.0 glycoside VII and glucoside V

11
HQ CH CH
Cl I*
HO G lu Glu
?-Chlorodeutziol (?)
Loasaside (21)
CH
OH HOCH O G Iu
OGIu
Strictoside (41) Decapetaloside (^4)
Glu
Sweroside (31) Scopoletin (6)
HQ
+
(CH3 )3-N-CH2-CH2-OH
Choline (61)
O G Iu
Glucoside V (4?)
Figure 3. Compounds isolated Mentzella decapetala tops.

12
Iridoids of Mentzella decapetala.
Prom the above isolation procedures (tables 1 and 3)1 nine iridoids
were isolated and characterized. These compounds contain either an
iridoid or secoiridoid skeleton. Six of these compounds axe new natural
products, the remaining three axe known natural products. All axe
considered individually.
O*
HO
HO-
OH HO
Iridoid
7-Chlorodeutziol (7) was isolated as an optically active, white
crystalline material [_ mp. 126-8° d, [V]D -132° (water) ]]. It was
soluble in aqueous or alcoholic solvents and insoluble in less polar
organic solvents. It had the molecular formula C^HgÔ^Cl, supported
HO CH
C l t *
HO O G Iu
z
by elemental analysis, and gave a positive Beilstein test (11), as well
as a yellowish brown coloration with vanillin spray reagent. The ir*
spectrum of this compound showed absorption bands at 3^00 cm"* (hydroxyl)
and 1670 cm (enol ether). The ultraviolet spectrum displayed a

* Please refer to spectra appendix.
13
#
X 209 nm which was assigned for a it — >rr transition of an
max
isolated double bond.
Its glucosidic nature was determined by acid hydrolysis, which
yielded an unstable aglycone and a sugar identified by glc and tic as
glucose.
1 * 13 *
Examination of the H-nmr and C-nrar spectrum of 2 showed a
broadened singlet at6 6.10 ppm which was assigned to the enol ether proton
at C-3, this chemical shift is comparable with the value at6 6.13 Ppm
assigned for mentzeloside (12). Since this signal did not display
evidence of cis-olefinic coupling,the possibility of a C-4 substitution
was suggested. The presence of a three proton signal at 6 1.6? ppm
(singlet) could account for this substitution. Presence of a broad
singlet at 6 2.34 ppm (2H) was assigned for the bridgehead protons at
C-5 and C-9 of an iridoid skeleton, the acetal protons at C-l of the
aglycone and C-l' of the sugar unit appeared as doublets at 6 5*36 PPm
(J 1.6 Hz) and 4.75 (J 7*6 Hz) respectively.

13
The C-nmr indicated the presence of fifteen carbons, six of them
corresponding to a glucose moiety (13) at 6 (l')l00.3d, (2 ') 74.6d, (3 *)
77.6d, (4')71.6d, (5')77.3d, and (6’)62.8t ppm . The remaining nine
carbons constitute the iridoid skeleton. From these nine carbons, the
o
glucosidic linkage in C-l was assigned at 6 95*2 d ppm, two sp
hybridized carbons at 6 135 «3 d and 115*7 s which corresponded to C-3
and C-4 of the enol ether respectively. The lack of multiplicity at
C-4 in the undecoupled spectra confirmed its substitution, therefore the
methyl group that appears at 6 16.8q can be assigned unequivocally at
C-4, as in the case for mentzeloside. Two carbons carrying oxygen

14
appeared at 6 82.Id, and 6 78.1dj one carbon carrying chlorine appeared
at 6 70.9d, and finally two methine carbons appeared at 6 4 6 ,4d and
41.5d ppm.
The above data has lead us to the partial structure 8 ,
CH
OH-
4
OH-
O G Iu
8
Chemical transformations of 7-chlorodeutziol (figure 4) were
performed as follows: acetylation of 7-chlorodeutziol resulted in the
formation of an optically active hexaacetate £. Elemental analysis of
this compound established the molecular formula C g ^ H ^ O ^ C l ; the ir
spectrum did not show any free hydroxyl absorption, indicating complete
acetylation. This was confirmed by acetylation under stronger conditions
followed by Jones' oxidation of the acetylated compound which resulted
in no change of £.
Emulsin hydrolysis yielded the aglycone 10, and glucose, the latter
was identified by tic. comparison with an authentic sample.
The aglycone 10 was further acetylated under standard conditions
producing the triacetate 11. . Irradiation experiments on this triacetate
allowed us to establish the substitution sequence as well as the relative

1 *
stereochemistry in the molecule. The H-nmr of 11^ showed a broad
singlet at 6 6.10 (H at C-3), a broad singlet at 6 6.17 (H at C-l), a
multiplet at 6 5*42-5*26 which Integrates for two protons base of
acetates, and a multiplet at 6 4.06 for the proton base of chlorine,

15
the bridgehead protons at C-5 and C-9 appeared as a multiplet between
62.70-2.60 ppm. A three proton broad singlet at 61.70 was assigned to
the methyl at C-4, while the 3 acetates appeared at 62.13 (6H), and 2.09.
Upon irradiation of the signal at 6 2.60 ppm (H*s at C-5 & C-9)
two doublets appear for the protons base of the acetates (at 6 5 .^2-
5.26 ppm); the proton at 4.06 appeared as a clear double doublet, the
acetate signals were completely resolved, and the proton at C-l became
a sharp singlet at 6 6.17 ppm.
Furthermore, irradiation at the protons base of the acetates (6
5.42-5.20) produced a singlet for the signal at 6 4.06. This fact
clearly defined the position of the chlorine at C-7 since its location
at C-6 or C-8 would not have produced a singlet.
Finally irradiation at 6 4.06 ppm (H base of chlorine) resulted in
the formation of a broad singlet in the region of the protons base of
the acetates.
*
The mass spectral data for the triacetate was in accordance to the
proposed structures m/e were found at M+ - acetate at 286, with a 288
peak (M+2 ) in proportion 3 *1 * as well as an M+ - 2 acetates at 226
alongside with a 228 peak in proportion 3 : 1.

Hydrogentation of 7-chlorodeutziol in presence of 5% Pd/C
yielded the corresponding dihydroderivative 12 that was identified
by the absence of the signal at 1670 cm-* in the ir spectrum (enol-
ether signal), as well as the absence of a signal at 6 5*99 in the

1
H-nmr spectrum, and the shift of the three proton methyl signal from
6 I .63 ppm to 6 0.88 ppm with a change in multiplicity from a singlet
to a doublet (J 6 Hz). Acetylation of the dihydroderivative 12

1 Jt
afforded 12, , whose H-nmr spectrum indicated the presence of six
acetates, which excluded the possibility of hydrogenolysis during the
hydrogenation process.
Emulsin hydrolysis of 12 yielded a crystalline aglycone 14 ( mps
ll4°d), its MS*-accounted for a molecular ion at 222 (1.3 %)* as well as
m/e at 204 (M+- HgO), 206 (M+2, ratio 3:1); 186 (M+- 2H20), 188 ( M+2,
ratio 3*1); and 18? (M+ - Cl), 189 (M+2, ratio 3*1) •
13
An undecoupled C-nmr spectrum of compound 14 accounted for nine
carbons with the expected multiplicity.
Finally 7-chlorodeutziol was submitted to the action of potassium
carbonate in methanol to give mentzeloside (1), which was identical with
an authentic sample (mp, mixed mp , ir, Si-nmr). Therefore establishing
the structure and stereochemistry of 7-chlorodeutziol as in £.
Synthesis of 7-chloro deutziol from mentzeloside was achieved by
treatment of mentzeloside with hydrochloric acid in methanol.

This is not the first time that chlorine has been found as a
substituent in iridoid glucosidesj the iridoids linarioside (15, 14),
eustoside (16, 15), and valechlorine (17, 16) contain a chlorine atom
too. R= i*ovol»royl
1?
In all of these cases, the corresponding epoxy derivative:
antirrinoside 18 , eustomoside 19, and valtrate 20 , have "been isolated
from the same plant source. The possibility of the biosynthesis of
linarioside and valechlorine through the attack of a chloride anion on
the oxiran ring has been proposed. Analysis of the plant material in
the initial extraction stages had ruled out the possibility of the
compounds being artifacts produced during extraction and/or separation
procedures,
R= i s o v a l e r o y l
CH„OAc
RO<
'3 OGIu Glu

18 19 ^
In our case, the possibility that 7-chlorodeutziol could be an
artifact produced during extraction and/or separation process was ruled
out not only by examination of the original ethanolic plant extract,
but by carrying out the isolation proceedure in the absence of
halogenated solvents. Under this conditions 7-chlorodeutziol was
also isolated.
7-Chlorodeutziol was found to decompose upon standing at room
temperature (turning black in a period of 6-8 months), however, it is
stable upon exposure to acid alumina in ethanol, as well as upon
addition of calcium carbonate in methanol. Adsorption of the compound
onto neutral alumina (activity grade-l) and suspension in methanol
produced after several days a small quantity of mentzeloside.

HO AcQ CH
Ac <5 G lu (A c)
Glu
HO CH
HO Glu
7
HQ CH HQ CH
Chi Ch.
HO HO
O G Iu
Emulsi n
Ac 20 _pyr A C«0 - Py |
AcO CH CH
HQ CH
C lu
AcO AcO OAc
Figure 4. Chemical transformations for 7-Chlorodeutziol.

Mentzeloside (_1) is a known iridoid glucoside which has been
isolated from Mentzella decapetala (12), and from Deutzia scabra
( family Saxifragaceae) with the name of deutzioside (1?).
HO
Glu
1
The identity of mentzeloside, was established by direct
comparison of its physical constants (mp, CoGD , ir, ms, ^H-nmr)
with those of an authentic sample. Furthermore, the prepared acetate
derivative was found to be identical in its physical and spectral data
with the reported literature values (12).

13
The C-nmr of both the free compound and its acetate are presented
in tables 4 and 5 respectively.

Table 4. ^C-nmr of iridoids from Mentzella decapetala (Do0)
Carbon # 7-chlorodeutziol mentzeloside loasaside strictoside decapetaloside decaloside sweroside

7 1 21 41 2 21
1 95.2 96.7 97.7 95.4 97.1 97.7 98.1

3 135.3 135.6 135.7 133.4 133.9 139.0 153.8
4 115.7 113.4 114.5 116.1 115.8 116.4 105.3
5 46.4 42.5 48.4 35.7 44.7 47.5 27.0
6 82.1 78.4 81.2 27.6 27.4 80.9 24.9
7 70.9 56.4- 134.7 32.8 29.8 134.3 70.1

8 78.1 59.6 134.9 74.7 38.4 135.7 131.9
9 41.5 41.0 46.9 50.6 42.8 43.4 42.2
10 16.8 15.8 16.4 15.4 65.8 61.3 169.8
11 - - - - 15.6 - 121.2
1' 100.3 99.8 99.3 99.1 97.1 99.1 98.8
2' 74.6 73.4 73-5 73.3 73-3 73.3 73.2

3' 77.6 76.9 77.0 76.7 76.7 76.7 76.8
V 71.6 70.2 70.4 70.2 70.1 70.1 70.1
5’ 77.3 76.4 76.5 76.3 76.2 76.3 76.1
6* 62.8 61.2 6I.5 61.3 61.2 61.8 61.3
N>
O
13 *
Table 5• C-nmr of iridoid-acetates from Mentzella decapetala (CDCL^)
Carbon # 7-chlorodeutziol mentzeloside loasaside strictoside decapetaloside decaloside sweroside

(Ac x 6) (Acx5) (Acx5) (Acx5) (Acx5) (Acx6) (Acx4)
1 91.1 97.8 94.8 93.0 94.3 96.8 96.6
3 135-3 136.5 136.8 134.5 134.0 141.5 151.3

4 108.8 111.0 111.3 112.4 112.0 110.9 105.5
5 45.3 41.9 47.9 35.1 45.5 46.9 27.5

6 80.3 80.1 82.1 26.4 26.9 82.3 24.7
7 64.2 55.4 135.0 30.4 28.2 135.6 68.2
8 80.3 55.3 131.6 76.5 37.2 132.2 131.2
9 40.3 38.0 42.9 49.1 38.6 40.8 42.1
10 15.6 I6.5 16.6 15.6 67.8 64.0 121.0
11 - - - - 15.6 - 165.0
1’ 95.6 96.0 96.1 95.8 95.9 96.8 96.0

2' 70.6 70.9 71.0 71.1 71.1 70.9 70.6
3’ 72.1 72.8 72.9 72.9 72.8 72.8 72.3

4' 68.2 68.4 68.6 68.8 68.7 68.4 68.2
5' 72.5 72.2 72.2 72.2 72.7 72.2 72.3

6' 61.7 61.9 62.1 62.0 62.1 61.9 61.8
* Addit lonal signals for the Acetate un:Its are pr*jsent.

ro
22
Loasaside (21) was isolated as an optically active, white crystalline
n o
material L mP ! turns pink at 193 » and then melts with decomposition at
216-220°, -150° (HgO) It was soluble in aqueous or alcoholic
solvents and insoluble in less polar organic solvents.
CH
G lu
Its mass spectrum* showed a molecular ion at m/e 330, which
corresponds to C^HggOg* and a strong (M-l62)+ ion at m/e 168 which
indicated loss of glucose. This type of fragmentation has been found
to be a prominent feature of the mass spectrum of the iridoid glucosides;
other prominent fragments for this molecule are proposed in figure 5 *
The iridoid nature of loasaside was

♦
indicated by the formation of
a black polymer upon acid hydrolysis alongside with a sugar identified
by glc and tic as glucose.

—1
The ir spectrum of loasaside showed absorption bands at y± 00 cm
(hydroxyl), and 1665 cm * (enol ether). A band at 20? nm in the uv

*
spectrum was attributed to a if — » tt transition of an enol ether
double bond in which the £ carbon does not bear a carbonyl substituent.
Examination of the H-nmr and the C-nmr spectrum further
supported the proposed structure. A broadened one-proton signal at 6
5-9^ ppm was designated as the a proton of an enol ether, the lack of
23
+•
CH
CH
-162
Glu
M+ s 330 (2.57° m/e : 168 (49%)
CH HO CH
-h 2o
o+
m/e : 95 (1?%) ^ s 122
Figure 5. Proposed fragmentation pattern for loasaside.

24
multiplicity indicated that C-4 was substituted. Presence of a three-
proton signal at 6 1.54 ppm (broad singlet) could account for the
substitution of C-4 with this methyl group. A slightly broadened two
proton singlet at 6 5*86 ppm was assigned to two olefinic protons. The
lack of any visible coupling between these olefinic protons can be
attributed to an system as A v/j — > 0 (18). This type of signal
has been reported for decaloside (2 ), and a great similarity was found
upon comparison of the spectral data of both compounds, with the
exception of the methyl signal at C-4 for losaside which is not present
in decaloside. The latter compound bears instead a hydroxy-methylene
moiety at C-4. A one proton doublet at 6 4.93 ppm (J 5*1 Hz) was
assigned to the acetal proton at C-l of the aglycone.
The ^ C - n m r revealed the presence of 15 carbons. Six of the carbons
corresponded to those of the glucose moiety £at 6(1 ')99»2 , (2 *)?3 *5 » (3 ')
77.0 , (4') 70.4, (5') 76.5* and (6 ') 61.5 "the remaining nine
carbons constitute the iridoid skeleton. The glucosidic linkage at C-l

2
was assigned at 6 97«7 » four carbons were sp hybridized at 6 135.7 ,
114.5i 134.9i and 134.7 and were assigned at C-3» C-4, C-7 and C-8
respectively. One carbon carrying oxygen appeared at 6 81.1, while the
bridgehead methine carbons were assigned at 648.4 and 646.9 ppm. The
methyl group at 616.4 ppm could be assigned at either C-4 or C-8 , as in
22, 22*
CH
CH,
22
25
The position of the methyl at C-4 is supported by the presence of
the C-3 proton as a broad singlet (long distance coupling), as well as
the similarity in chemical shift of the CH^- in losaside with those of
7-chlorodeutziol (7) and mentzeloside (1_) (1 .54, 1.67 and 1.61 ppm
respectivelly), as compared to those of linaride (23) (1.88 ppm), in
which the methyl group appears at C-8 .

6 7
The second olefinic function could be assigned at either A or A
(24, 25)« However, in A îridoids the olefinic proton on C-6 appears
between 6 6.1 and 6.3 ppm (19)» while the proton at C-7 appears between
6 5*6 and 6 5*7 PPm (19)* For A-iridoids, in which the C-8 position
does not carry a substituent, the only existing compound is decaloside
which presents a broad singlet signal at 6 5*83 (2H) ; this signal is
comparable with the one of losaside (6 5*86 ppm, 2H).
CH
HQ
HO
OGIu OGIu
22
Chemical transformations for loasaside are presented in figure ? .
When loasaside was reacted with acetic anhydride, a highly
unstable acetate was obtained. The ir, and ^H-nmr spectra did not
display any bands assignable to free hydroxyl functions, thereby
eliminating the possibility of a tertiary alcoholic function in the
starting material. Five acetates were accounted for, thus only one
of them must be present on the aglycone part , since the other four
constitute the glucose-tetraacetate moiety.

26
Up to this point the structure of loasaside can he pictured as in 26
with the stereochemistry at C-l, C-5, C-6 and C-9 remaining to be
determined.
CH
OGIu
26
Several attempts were made to correlate loasaside with mentzeloside,
via an epoxidation proceedure, without success. However, we were able
to correlate mentzeloside with losaside via a deoxygenation reaction
performed on mentzeloside in the presence of sodium iodide, zinc,
sodium acetate, and acetic acid. (20). The reaction is believed to occur
via the formation of an "lodohydrin intermediate” in situ, through a
sodium iodide-zinc complex, followed by debydrohalogenation in the
presence of zinc.(20)
OGIu
Zn-I 21
Zn
CH?
2 27
28
Figure 6 . Deoxygenation mechanism for mentzeloside.

27
Nucleophilic substitution on the epoxy function of mentzeloside
has shown preferentiallity for a C-7 attack of the nucleophile (4),
this would lead to an intermediate 2? which could undergo elimination
either an A 28, or at i 21 . In our case, the conditions for this
reaction produced very poor yields of the unsaturated products, however,
we were able to detect the presence of both loasaside(21), and the A -
product 28, try glc, tic, and finally both compounds were isolated and
their ^H-nmr spectra taken. The presence of the A u n s a t u r a t i o n
was demonstrated for 28 ‘by the presence of two signals in the *H-nmr
spectra at 6 6.08 ppm, and 6 5 *68ppm which can be assigned at the
protons on C-6 and C-7 respectively. This data is in agreement with
the reported values for this type of unsaturation (19)-
Furthermore, loasaside was correlated with decaloside (2) through
the following experiments: partial hydrogenation of decaloside in the
presence of H^, Rh/c, yielded the 7 »8 -dihydrodecaloside(29) which was
then subjected to hydrogenolysis in the presence of H,,, Pd/c, to yield
a material 22. that was identical (tic, *H-nmr), with the product of
hydrogenation of loasaside in the presence of » Pd/c which yielded the
7,8-dihydro-loasaside-
The hydrogenated product obtained from loasaside was further
acetylated in presence of acetic anhydride-pyridine to yield the penta-
acetate, which ruled out the possibility of hydrogenolysis of the
allylic alcohol.
Since both decaloside and mentzeloside have an established
stereochemistry at C-l, C-5» C-6 and C-7 we can conclude that loasaside
is compound 2 1 .
28
HO CH AcO CH
Glu Gl u ( A c )
CH AcO CH
G lu Glu (A c)
21
A c O -Pyr
HQ HQ CH
Ho- Pd/C
OG Iu OG Iu Glu
30
Figure 7• Chemical correlations of loasaside.

29
Sweroslde (21) is a known secoiridoid glucoside which has not "been
isolated before from Mentzella species. Its identity was concluded by
comparison of the physical and spectral data of its acetate (32) with
the reported literature values (21), and by direct comparison of both
the free compound and the acetate with authentic samples.
O G Iu
21
Furthermore, hydrogenation of the acetate was performed and the
obtained data were compared with the respective literature values given
for the dihydro-sweroside tetraacetate(33).

13 *
The C-nmr of both the free compound and the acetate were
obtained and this data is presented in tables 3 and 4.
G lu (Ac) O G Iu(A c)
22 22
30
Decapetaloslde (34) was obtained as an oily residue. Acid
hydrolysis gave decomposition products and glucose which was identified
by glc, and tic analysis. Emulsin hydrolysis produced an aglycone and
glucose, this indicated the presence of a g-glucosidic linkage.
CH.
HOCH O G Iu
1 ^
The analysis of the H-nmr of 34 , indicated the presence of a
proton at 6 5*90 ppm (broad singlet) which was assigned to the a proton
of an enol ether system, its chemical shift indicated no 3-carbonyl
substituent, and the lack of multiplicity of this proton indicates a
C-4 substituent. Furthermore, the presence of a signal at 6 1.3& ppm
which integrated for three protons could account for a methyl at C-4,
as it has been the case with mentzeloside, 7-chlorodeutziol , and
loasaside. The glucosidic proton at C-l appeared as a doublet centered
at 6 4.99 ppm (J 4.1 Hz). The C-nmr indicated the presence of
sixteen carbons, six of them belong to the glucose unit (table 4), and
2
the remaining ten carbons account for the aglycone part. Two sp
hybridized carbons at 6 133*9 and 115.8 ppm were assigned for C-3 and
C-4 respectivelly, The glycosidic carbon at C-l appeared at 6 97.1 ppm,
one carbon carrying oxygen was at 6 65.8 and it was assigned to a

3
hydroxy-methylene unit. An sp hybridized carbon at 6 15.6 ppm was
assigned to the methyl group, while three methine carbons appeared at 6
44.7, 42.8, and 3 8 ppm. Two methylene carbons are present at 6 29*8,
and 27.4 ppm.

*
The mass spectrum of decapetaloside, showed a molecular ion at
m/e y ±6 (1.4%), which is in agreement with a molecular formula of
^16^26°8’ a laas*c l°n Peak at M - 162 (M - glucose). A proposed
fragmentation scheme for this molecule appears in figure 8•
-» +
Cu •
-162
hoch2 ch 2o h 6 h
O G Iu
M+ : 346.(1.4%) m/e : 184 (100%)
+
<fH 3
fl c h 2o h ^
m/e : 121 (17#) m/e s 136 (17#) m/e * 135 (68%)
Figure 8. Proposed fragmentation scheme for decapetaloside.

32
Decapetaloside (34) has the same molecular weight as mentzeloside,
(the CHÔH "being equivalent to an epoxy-hydroxy group), and the initial
fragmentation pattern for both molecules is essentially the same, since
it involves the loss of a common sugar moiety; however, the loss of the
hydroxy-methylene group from the aglycone-fragment leads in decapetalo
side to a prominent peak at m/e 135 (68%), which appears in
mentzeloside as a small peak m/e 135 (H^)«
Upon acetylation of decapetaloside, a crystalline, optically
active pentaacetate was obtained, 35, E mp. 114-5°, [/G D -90° (CHCl^)!]
with a molecular formula supported by elemental analysis.
Its ir indicated complete acetylation since no free hydroxyl group was
detected. The mass spectrum indicated a molecular ion at m/e 556 (0.6%).
Since there are only five acetates only one of them must be in the
aglycone part, and the other four in the glucose moiety.
The presence of a ten carbon iridoid skeleton in which a methyl
group and a hydroxy-methylene group are present, indicates biogenetically
that C-4 and C-8 must bear a substituent. The methyl group could appear
at either C-4,^4, or C-8, 36 , with the hydroxy-methylene group occupying
the remaining position.
CH
HOCH. AcOCH2 O C M Ac). CH O G Iu

O G Iu
21 22 2i
33
The chemical shift for the methyl group, "both in the JC-nmr (6
15.6 ppm), and the *H-nmr (6 1 . J S ppm), is very similar to those of
mentzeloside (l_)(at 6C 15*8; 6^1.60 ppm ), 7-chlorodeutziol (at ^16.8;
1.67ppm), and loasaside(at 6^15 *4; 6^1.54 ppm), which suggested a methyl
group at C-4, while the signal for the methyl group at C-8, as in
montinioside (37) appeared at 6C 19*3» 6H 1.18 ppm.
Moreover, if the hydroxy-methylene group was at C-4, its allylie
acetate should appear at 6 4.69 as in the case for decaloside (2 ).
however, acetates for saturated hydroxy-methylenes have been reported
at 6 4.06[adoxoside (28)],and 6 4.05-4.20 [patrinoside (29)] which are
in agreement with the value for the acetate of decapetaloside which
appeared at 6 3*98-4.20.
COOCH
HO-
HOCH
OGIu OGIu HOCH
22. 28
29
The stereochemistry of the protons at C-5 and C-9 was assumed to
be cis, as is the case with all iridoid glucosides isolated so far. Up
to this point, the structure and stereochemistry of decapetaloside can
be established as in 24* with the stereochemistry at C-8 remaining to
be determined.
34
Strictoside (41) was obtained as an oily residue *.Acid hydrolysis
indicated the presence of glucose, which was identified by tic, and by
glc of its TMS-derivative. Emulsin hydrolysis produced an aglycone and
glucose, which indicated a 0-glucosidic linkage.
CH;
OH
OGIu
The analysis of the H-nmr , indicated the presence of a proton at
6 5*89 (broad singlet), which was assigned to the a proton of an enol
ether system; its chemical shift indicated no (3-carbonyl substituent,
and the lack of multiplicity of this proton indicated a C-4 substituent.
Furthermore, the presence of a signal at 6 1.38 ppm,which integrated for
three protons, could account for a methyl at C-4, as was the
case with the already discussed iridoids from Wentzelia , The glucosidic
proton at C-l appeared as a doublet centered at 6 5*14 ppm (J 3*5 Hz).

13 *
The C-nmr indicated the presence of fifteen carbons, six of them
belong to the glucose unit (table 4), and the remaining nine carbons
2
account for the aglycone part. Two sp hybridized carbons at 6 133.4d
and 6 116.Is ppm were assigned for C-3 and C-4 respectivelly. The
glycosidic carbon appeared as a doublet at 6 95*4, one carbon carrying
oxygen at 6 76.?d ppm. Four sp-^ hybridized carbons are present: two of
them carrying only one proton were assigned to the bridgehead carbons
*The name was derived from Wentzella strictlssima from which it was also
isolated.
35
at 6 35*?d (C-5) and 6 50*6 d (C-9) • two other carbons each of them
carrying two protons at 6 2?.6t, and 32.8t, were assigned to C-6 and
C-7 respectively. Finally the methyl group appears at 6 15*5 as a
quartet.
*
The mass spectrum of strictoside showed a molecular ion peak at
m/e 332 ( 0 . 3 %)» which is in agreement with a molecular formula of
C15H24°8> and fragments at M+ - 162 (43%) for the loss of glucose. A
proposed fragmentation scheme for this molecule appears in figure 9.
CH; +
■>
-162
OGIu
OH OH
,+
M : 332 (0.5%) m/e : 170 (43??)
m/e : 135 (10%) 2/e : 133 (19%)
OH
n/s. 95 (47%) m/e s 108 (24%) m/e s 124 (16??)
Figure $ . Proposed fragmentation scheme for strictoside.

36
Upon acetylation of strictoside, a crystalline, optically active
pentaacetate was obtained, 42, [[ mp 14-9-150°, [aUl) -118°, (CHCl^)J,
it had a molecular formula ^25^34^13 suPPorê<^ ^y elemental analysis.
The ir indicated complete acetylation since no free hydroxyl groups
were detected. The mass spectrum indicated a molecular ion at m/e 5^2
(0.72%), alongside with the loss of the glucose tetraacetate moiety
M+ 331.
Based on the above data a proposed structure for strictoside can
be pictured as in 43.
CH
OGIu
The presence of a hydroxy group on the aglycone was supported by

13
the C-nmr as well as the formation of a pentaacetate. This hydroxy1-
function can be assigned at either C-6, C-7, or C-8, since C-5 and C-9
carry one proton each.
In order to define the position of the hydroxy function several
experiments were done: comparison of strictoside with 7,8-dihydro-
losaside, indicated that both compounds are chromatographically and
spectroscopically different. This excludes the possibility of a 68-
hydroxy substitution, Emulsin hydrolysis of strictoside yielded an
aglycone 44, which upon acetylation produced the corresponding
diacetate 4£ . Examination of the H-nmr of the diacetate 4£ indicated

37
the presence of the C-l proton as a doublet centered at 6 6.18 ppm (J 4-
Hz), a broad singlet at 6 6.00 ppm assigned to the proton at C-3» a
multiplet centered at 6 5*00 ppm which was assigned to the proton base
of the acetate (either at C-6, C-7, or C-8), a complex signal at 6 2.60
ppm assigned for one of the bridgehead protons, and the other bridgehead
proton at 6 2.35 ppm. The two acetates appeared at 6 2.03, and 6 2.12,
the methyl group at 6 1.58 ppm and the methylene protons underneath the
region of the methyl and acetate groups.
The following sets of irradiation experiments were carried outs
irradiation at the doublet centered at 6 6.18 (C-l proton) affected the
signal at 6 2.35 which is then assigned as the C-9 proton| irradiation
at the broad singlet at 6 6.00 (C-3 proton) sharpened the singlet for
the methyl group at 6 1.58; irradiation of the proton base of the
acetate affected the signal at 6 2.35, which had been assigned as the
C-9 proton. Irradiation of the signal at 6 2.60 affected the signal at
6 2.35 which indicated its relationship, the signal at 6 2.60 was then
assigned to the allylie proton at C-5. Finally upon irradiation at 6
2.35 the doublet at 6 6.18 (proton at C-l) became a singlet, and the
signal of the proton base of the acetate suffered deformation, slight
change was also noticed in the proton at 6 2.60. With these
experiments, the location of the hydroxy group in the aglycone part
can be assigned at C-8, leaving then the structure of strictoside as in
CH
OH
OGIu
38
Preliminary Investigation of Glucoside X . Glucoside X was obtained
as an oily residue. Acid hydrolysis yielded glucose, which was
identified by glc analysis of its TMS derivative. The glucoside gave a
negative reaction with vanillin-hydrochloric acid spray reagent. Its
^H-nmr did not show any characteristic proton for an iridoid structure.
The possibility of an aromatic ring was suggested by the presence of an
intense signal at 6 ?.00 ppm. No further investigation was done on
this fraction.
Decaloside (2), is a known iridoid glucoside which has been isolated
from Mentzelia decapetala (18). The identity of decaloside,
was established by comparison of its physical and spectral data with
those reported in the literature (18). Furthermore, its acetate
HO
O G Iu
2
derivative was prepared and found to be identical in its physical and
spectral data with the reported literature values for decaloside
hexaacetate.
13
The C-nmr data of both the free compound and its acetate are
presented in tables 4 and 5 respectively. The 6,7-dihydro-decaloside
derivative was also prepared.

39
Glucoside V (10-0-g-glucosyl-decaloside) (47) , was obtained as a
highly hygroscopic white amorphous powder. It was soluble in aqueous
and alcoholic solvents and insoluble in less polar organic solvents.
The iridoid nature of glucoside V was indicated by the formation of a
black tarry residue upon acid hydrolysis. The sugar resulting from the
hydrolysis was identified ty glc of its IMS derivative as glucose.
HO CH« O G I u
O G Iu
47
1 *
The analysis of the H-nmr of 47 indicated a great similarity
with the ^H-nmr spectra of decaloside. A broadened one-proton signal
at 6 6.47 ppm was designated as the a proton of an enol ether system,
its chemical shift indicated no (3 carbonyl substituent, and the lack of
multiplicity of this proton indicated a C-4 substituent. No signal
comparable to a vinylic methyl at C-4 could be observed, as in the
cases of mentzeloside (_1), 7-chlorodeutziol (£), loasaside (21), and
decapetaloside (34), so, a hydroxy methylene group at C-4, as in the case

A
of decaloside (2)/was suspected, although poor resolution of the H-nmr
did not permit a specific assignement at this stage. A slightly
broadened two proton singlet at 6 5-91 ppm was assigned to two olefinic
protons, the lack of any visible coupling between these olefinic protons
can be attributed to an A^ system as Av/j ---> Q (18). This type of

40
signal has been found in decaloside (2) and in loasaside (21), thus
7
allowing us to assign the unsaturation to a 6 -double bond.
The high polarity of this compound suggested the presence of more
than one sugar moiety; additional evidence was provided by the strong
signals in the *H-nmr in the region of 63.10-4.50 which corresponded to
the protons base of alcoholic functions. Furthermore, the low Rf value
of this compound supported the presence of more than one sugar moiety.
13 *
Analysis of the C-nmr Indicated the presence of 21 carbons, 12
of them corresponding to two glucose units at 6 (1') 101.7, (1") 99.4,
(2 ’) 73-7, (2 ") 73-3, (3') 76.8 , (3 ”) 76.5, (4') 7 0 .2 , (4”) 7 0 .2 , (5 ')
76.3, (5") 76.3, (6 ') 61.3, (6") 6I .3 ppm, and the remaining nine
carbons constitute the iridoid skeleton . The glucosidic linkage at C-l
was assigned at 6 98.4, a second glucosidic linkage at C-10 was assigned
at 6 69.9, four carbons were sp2 hybridized at 6 141.2, 135-9, 133.9,
and 113.4ppm and were assigned to C-3, C-7, C-8 and C-4 respectively.
One carbon carrying oxygen appeared at 680.8 ppm, while the bridgehead
methine carbons were assigned at 6 47.5, and 44.5 ppm.
Up to this point the structure of glucoside V can be assigned as
in 48, in which the basic skeleton of decaloside can be recognized.

The assignement of a second glucosyl moiety could be located at either
-O
-G lu
O G Iu -
48
41
C-l, producing a glucosyl decaloside as in the case of genipin-gentobio-
side (49) in which two sugar units are together , or at C-10 or C-6 as
is the case in 5-Or3-gluc°syl antirrinoside (50) and melittoside (51)
in which the two sugar moieties are on different carbons.
COOCH3
OGIu O G Iu
HOT H m _
2. O G fu-G lu CH^ OGIu HOCHj q g Iu
6 - 1'
49 ^0 51
Acetylation of glucoside V resulted in the formation of an acetate

1 *
which presented nine acetate moieties. The ir and H-nmr spectra did
not display any bands assignable to free hydroxyl functions, thereby
eliminating the possibility of a tertiary alcoholic function in the
starting material. The analysis of the *H-nmr spectra of the acetate
(52, figure 10) indicated again similarities with that one of decaloside
hexaacetate. A broadband one proton signal at 6 6 .3I ppm was assigned
to the C-3 proton. Two vicinally coupled olefinic protons appeared at
6 6.05 and 5*89 ppm, the magnitude of the coupling constant (j 6Hz) was
suggestive of a cis olefinic coupling in a five membered ring.
A multiplet at 6 5-63 was attributed to an allylie acetate methine at
C-6 . This multiplet is also present in the ^H-nmr spectra of decaloside
which indicates that the position at C-6 does not bear a glucosyl moiety
since acetylation at this position is achieved. The bridgehead protons
at C-5 and C-9 appeared as complex signals at 6 2.79 and 3*0? PPm »
respectively. The absence of the two one proton quartets at 6 4.69

42
and 4.33 ppm,which were assigned to the coupled methylene protons of an
acetylated primary alcohol at C-4 in decaloside, indicated that this
position must be substituted in glucoside V, and the possibility of the
second glucose moiety at C-10 is strongly suggested.
Hydrogenation of glucoside V was carried out using rhodium on
charcoal as a catalyst, in order to reduce the chances of hydrogenolysis.
The tetrahydro derivative (53) was obtained. Under the same conditions
of hydrogenation, decaloside produced only the dihydro-derivative
suggesting that the presence of a substituent at C-10 allows the

3
hydrogenation of the A - double bond.
The tetrahydro-derivative (52) upon acetylation, produced a nona-
acetate which was indicative that no hydrogenolysis has taken place.
Compound 52 was hydrolyzed by emulsin producing the aglycone 54.
This hydrolysis indicated the 3 glucosidic nature of the glucoside.
Upon acetylation, aglycon 54 produced the triacetate 5 5 .
Acid methanolysis (22) of 52 yielded in addition to glucose, the
monomethyl acetal 56, which still retained one molecule of glucose. This
eliminated the possibility of the two glucose units being together .
Acetylation of this methyl acetal 56, yielded the corresponding
pentaacetate 57.
Finally exhaustive methylation followed by hydrolysis (23) did
not show any evidence of the presence of trimethyl glucose, and only
tetramethyl glucose was present. This data was obtained by glc analysis
of the hydrolyzed product (24). This experiment further demonstrated
that the two glucose units were located in different positions in the
molecule and not as a dlsacharide unit.

43
Based on the comparison of the spectral data of Both decaloside
and glucoside V, as well as the spectral data of their acetates, plus
the similarities in the optical rotatory powers of the derivatives of
both compounds it is proposed that glucoside V is: 10-0-P-glucosyl-
decaloside and its structure is as stated in 47.
This structure is in agreement with the chemical reactions which
were performed on glucoside V and a summary of these reactions is
presented in figure 10.
HO
O G Iu
Q C H 2 O G I u ( A c )4 CH2 O G I u ( A c )4
57 ® C H 3 CH2 O G I u 52 OG , u <AcU
AcjO-Pyr
4 7 OG Iu
H2 ~ /C AcO
CH2 OG Iu CH2OAc
CH2 O G I u
53 OGIu
A c , 0-P y r
C H 2 O G I u ( C H 3 )4 AcO CH2 O G Io (A c U HO
O G Iu (CH 3 )4 O G Iu ( O A c )4 54 OH
figure 10. Chemical trsmsf orjn&tions of glucoside V«

45
Glycoside VII (j58)» was obtained as a white amorphous powder from
methanol. It was soluble in aqueous and alcoholic solutions and insolu
ble in less polar organic solvents. The iridoid nature of glycoside VII
was indicated by the formation of a black tarry residue upon mild acid
hydrolysis. The presence of two sugars was indicated by paper
chromatography of the hydrolyzed product. One of the sugars corresponded
in color and Rf value with those of an authentic sample of glucose. The
second sugar presented a gray-black coloration when sprayed with
p-anisidine hydrochloride spray reagent, and it had a higher Rf than
that one of glucose.
HO CH ~0 -deoxysugar
O GIu
38
1 *
The analysis of the H-nmr of ^8, indicated a great similarity
with those of decaloside (2) and glucoside V (4£). A broadened one
proton signal at 6 6.32 ppm was designated as the a proton of an enol
ether system, its chemical shift indicated no 8 carbonyl substituent
and the lack of multiplicity of this proton indicates a C-4
substituent. No signal for a methyl at C-4 was present, therefore a
hydroxy methylene unit was again suspected, as in decaloside and
glucoside V. A slightly broadened two proton singlet at 6 5*94 ppm
was assigned to two olefinic protons, the lack of coupling of these

46
n
protons and its chemical shift strongly suggested a A - double "bond for
glucoside VII.
13 *
Analysis of the ^C-nmr indicated the presence of 21 carbons, six
of them corresponded to a glucose moiety at 6 (1') 102.0, (2') 73*2,
(3')?6.8, (4')70.1, (5')76.2, and (6’) 61.2, and nine carbons constituted
the iridoid skeleton . The glucosidic linkage at C-l was assigned at 6
98.3 ppm, a second glycosidic linkage at C-10 was assigned at 6 64.2,

2
four carbons were sp hybridized at 6 14-1.2, 135*8 , 133*9 »and 113*3 PPm
and were assigned to C-3» C-7, C-8 and C-4- respectively. One carbon
carrying oxygen was assigned at 680.7* while the bridgehead methine
carbons were assigned at 64-7.5* and 44-.4- ppm. The six remaining carbons
corresponded to another sugar moiety at 699*2, 75*5*71*0, 73 *2 ,69.8 and
34.8. Up to this point the structure of glucoside VII can be assigned as
in jj9, in which the basic skeleton of decaloside can be recognized and
a second sugar moiety is present at either C-l or C-10.
HO
- Sugar 2
-G lu
52
When glucoside VII was acetylated, an octaacetate 60 was obtained.
1 *
The ir and H-nmr spectra did not display any bands assignable to a
free hydroxyl function thus eliminating the possibility of tertiary
alcohols. The analysis of the ^H-nmr of the acetate 60 indicated, as in
decaloside and glucoside V, the presence of a broadband one proton signal

4?
at 66.30 which corresponded to the proton at C-3. Two vicinally coupled
olefinic protons appeared at 6 6.09 and 6 5*93 PPm i which were assigned
to the protons at C-7 and C-8. A multiplet at 6 5*60 ppm was attributed
to an allylic acetate methine at C-6. This multiplet is also present
in both decaloside (2), and glucoside V (42.) and indicated that the
position at C-6 does not bear a glucosyl moiety since acetylation at
this position is achieved. The bridgehead protons at C-5 and C-9
appeared as complex signals at 6 2.78 and 6 3*07 ppm respectively.
The absence of the two one proton quartets at 6 4.69 and 6 4.33 PPm*
which were assigned to the coupled methylene protons of an acetylated
primary alcohol at C-4 in decaloside, indicated that this position in
glucoside VII must be substituted.
The presence of eight acetates may be accounted for by 4 of them
in the glucose moiety and 1 in the iridoid skeleton (at C-6).leaving 3
acetates for the other sugar moiety. The possibility of a deoxy-sugar
was confirmed by a positive Keller-Killiani test (25) performed on a
hydrolyzate of glycoside VII. Since the sugar moiety must bear a six
carbon unit, and no methyl signal is apparent from the ^H-nmr spectra
the presence of a 2, 3» or 4 deoxy sugar is suggested. Only one report
of a glycoside bearing a 2-deoxyhexose was found (26) for a cardenolide
in Erysimum perofskianum.
Hydrogenation of glycoside VII In the presence of rhodium on
charcoal produced the tetrahydro derivative, which was submitted to
emulsin hydrolysis. No aglycone product could be separated from the
reaction mixture.
48
The decalosyl residue for this glycoside was determined by
cleavage of the octaacetate in the presence of boron trifluoride-
ethereate in acetic anhydride• From this reaction two products were
detected by tic. : decaloside hexaacetate, and the corresponding deoxy-
sugar acetate. The first one was identified by tic and co-tlc with a
sample of decaloside hexaacetate. Further investigation on the deoxy-
sugar moiety is still in progress.
Scopoletin (6}, is a known coumarin which had not been previously
isolated from Mentzelia decapetala. It crystallized from the methanol
solubles extract (figure 2), and was identified by comparison of its
physical and spectral data with the reported literature values (27)-
Isolation of a Hypotensive Principle from Mentzelia dgcapgtala.
The alcoholic extract residue of the dried and ground tops of
M. decapetala, was found to produce a decrease in the mean arterial
pressure of anesthesized dogs and rabbits. Separation of the tertiary
and quaternary alkaloidal fractions was performed as established in
figure 11. Pharmacological assays indicated that the hypotensive
activity was present in both tertiary and quaternary alkaloidal fractions.
Further purification of the tertiary alkaloidal fraction through
column chromatography lead to the isolation of a non-alkaloidal
component, scopoletin, a coumarin which was characterized through its

Powdered Mentzella decapetala
(Tops, 6 . 0 Kg)
1- 95% BtOH, percolation.
2- Evaporation
EtOH extract residue Marc

(l.OKg)
1% Citric acid solution (5 l)

|Filtration_______
Filtrate Precipitate
I
Extracted with EtOAc
(5 1 x 4)
I-------
EtOAc-solubles 2% Citric âcid-solubles
(28 g)
Extracted with CHC10

(6 1 x 2 ) 3
I-------- 1
CHCl^-solubles 2% Citric acid solubles
(1*6 g) I
Neutralize with NH,-OH, pH 8
I 4
Neutral aqueous solution
Extracted with CHCi„

r *-----1 3
CHCl^(Tertiary alkaloids) Aqueous solution
(3.0 g)
1- Acetic acid
2 - 2 % Ammonium
Reineckate
Reinecke salts Aqueous phase
Amberlite IRA-Cl'
Quaternary chlorides
(1^ g)
Figure 11. Fractionation scheme for isolation of alkaloids

from Mentzella decapetala tops.
50
physical and spectroscopic properties. Scopoletin (6) also crystallised
from the methanol solubles fraction as shown in figure 2. No further
data was obtained from this alkaloidal fraction due to the extremely
low yield of the alkaloidal contents.

The quaternary alkaloidal fraction was also purified through column
chromatography. Initial thin layer chromatographic examination of this
fraction indicated the presence of choline, which was identified by its
Rf value, and its violet color upon spraying with Dragendorff-spray
reagent, and by comparison with an authentic sample. Choline was eluted
in fractions 187-213 of the column chromatography. It has reported
that choline produces a decrease on the mean arterial pressure, which
was confirmed by a pharmacological assay of both the isolated choline
and an authentic sample.
It is worth noting that the presence of iridoid compounds may
lead to a false positive test for alkaloids. Since it is a well known
fact that iridoids react with ammonium hydroxide (28) substituting the
heterocyclic oxygen with nitrogen, producing then the corresponding
nitrogen containing artifacts.In our studies, all attempts to isolate
alkaloids were unsuccessful even though fractions did give a precipitate
with Valser's reagent.
Pharmacological Assays and Results.
Samples of the crude ethanolic extract, the tertiary and quaternary
alkaloidal fractions, and the individual components isolated from
Mentzella decapetala, were subjected to preliminary biological evaluation.
The crude ethanolic extract, the tertiary and quaternary alkaloidal
fractions and choline produced a decrease in the mean arterial pressure

51
of anesthetized dogs and rabbits,* meanwhile, the single iridoid
components were devoid of any hypotensive activity. These analysis were
carried out by Dr John Banning of the Department of Phramacology, College
of Pharmacy, The Ohio State University.
Antimicrobial tests for the crude ethanolic extract, rutin, and
scopoletin gave negative results. These analysis were carried out by
Mrs. Tsai-Wu at the Department of Pharmacognosy and Natural Products
Chemistry, College of Pharmacy, The Ohio State University.
Antifungal tests for the iridoids: 7-chlorodeutziol , mentzeloside,
loasaside, decapetaloside and glucoside V also gave negative results.
These analysis were performed by Miss Linda Basham from the Ohio
Agricultural Research and Development Center in Wooster, Ohio.
An Insect feeding activity assay of an ethanolic extract of
Mentzella decapetala indicated no feeding inhibition at a dose of
25 mg/ml. This test was performed tsy Mr. T. ODell and Ms. L. Girard
of the U.S. Forest Service.
The results and testing proceedures used are reported in the
experimental part.
EXPERIMENTAL
Equipment and Services.
Melting points were uncorrected and were determined using a Thomas-
Hoover Unimelt Apparatus, and recorded in degrees Centigrade. The
infrared spectra were determined using a Beckman model 4230 Infrared
Spectrometer, in either chloroform solution with 0.1 mm path length
cells, or in KBr pellet, where absorption bands were recorded in cm-*.
Ultraviolet spectra were determined in methanol in a Beckman model 5260
Ultraviolet and Visible Spectrometer, where absorptions were measured
in nm. *H-nmr spectra were determined in the stated deuterated solvent
using either TMS as internal standard or DSS as external standard . The
60 MHz spectra were taken on a Varian A-60A instrument, while the 90 MHz
spectra were taken on a Bruker-HX 90 instrument equipped with Fourier
Transform, where chemical shifts are measured in ppm on the 6 scale, .

13
and coupling constants are measured in Hz. The C-nmr spectra were
taken on a Bruker-yp 80 instrument equipped with Fourier Transform at
20.1 MHz, where chemical shifts are measured in ppm of the 6 scale, and
coupling constants in Hz. Dioxane was used as external standars. These
spectra were provided by Dr. Jack L. Fowble, of the College of Pharmacy,
The Ohio State University. Mass spectra were measured with an AEI MS-9
Mass Spectrometer, provided by Mr. A. Weisenberger, Chemistry Department
The Ohio State University, or determined on a Hewlett-Packard 5985 GC-
Ms (DIP) apparatus, by Br* Jinn Wu of the College of Medicine, The Ohio
State University. Finally some of the spectra were determined on a

52
53
Du Pont Model 21-491 "by Dr- Jack L. Fowble* of the College of Pharmacy,
The Ohio State University. The Gas chromatograms were taken on a
Hewlett-Packard Gas Chromatograph Apparatus model 5710A, equipped with
a flame ionization detector, under the stated conditions. The Optical
Rotations were measured on a Perkin-Elmer 241 Polarimeter at the sodium
D-line.
Purity of Reagents and Solvents.
All reagents were analytical grade. Percolation was performed with
95% ethyl alcohol, U.S.P.. All solvents were redistilled. Silica gel
G and silicic acid were from E. Merck (Darmstadt, Germany), or
Mallinkrodt (Chemical Company, St. Louis, Mo. U.S.A.), Silica Gel # 1-6
were obtained through a settling technique as follows: Six four liter
beakers are placed in series, silica gel (1 kg) is placed in the first
beaker and stirred with 4 liters of water. The suspended material is
allowed to settle for one minute, then the top one third volume is
poured into the second beaker. The volume of the first beaker is
completed with water and stirred and settle again. The pouring off
process is continued, when the second beaker is up to capacity, its
contents are stirred and the top one third volume is poured off into
the third beaker after a two-minute settling period. The stirrlng-
settling-decanting technique is continued through the sixth beaker
with the settling time of 4 minutes for the third beaker, 8 minutes for
the fourth, 16 minutes for the fifth and 22 minutes for the sixth,
until only clear* water is poured off from the sixth beaker. The
adsorbent of each beaker is collected , dried and activated at 110°C
for six hours, the numbers 1-6 corresponding to the beaker number.
&
Anisaldehyde Spray Reagent.- 5 nil of p-anisaldehyde in 90 ml of 95$
ethanol and 5 ml of conc. sulfuric acid.
p-Anisidine Hydrochloride Spray Reagent.- p-anisidine.HCl (lg) with
sodium bisulfite (0.1 g) dissolved in 10 ml of methanol and 120 ml of
n-butanol.
Source of Plant Material.
Mentzella decapetala (tops) was harvested from the Ohio State
University Medicinal Plant Garden during the flowering stage. The
plant material was dried in a forced draft oven at 40°C and powdered in
a Wiley mill.
55
Extraction and Initial Partition Procedures.
Powdered plant material (1 kg) was extracted with 95^ ethanol
(~37 liters) at room temperature. The percolate was concentrated
in vacuo using a rotary evaporator to give a semisolid residue (100 g).
This residue was partitioned between two liters each of chloroform and
water. The water soluble part was re-extracted with two 2-liter
portions of chloroform. The combined chloroformic extract was
evaporated to dryness under reduced pressure at 40°C to produce 15 g of
residue. The water soluble part was extracted three times with three
liter portions of ethyl acetate. The combined ethyl acetate extract
was evaporated to dryness to give b g of residue. The aqueous phase
after the ethyl acetate extraction was then extracted with three 3-liter
portions of n-butanol, which was previously saturated with water.
Concentration of the n-butanol extracts yielded 16 g of residue.
Finally,the resulting aqueous phase was also evaporated to dryness
yielding 59 g of residue.
The chloroformic residue (15 g) was further partitioned between
90%, aqueous methanol and hexane, two liters each. The methanolic phase
was re-extracted with two 2-liter portions of hexane. The combined
hexane extract was evaporated to dryness ( 7.5 g residue). The aqueous
methanol phase was also evaporated to give 7.5 g residue.
Chromatographic studies of the n-butanol and water solubles.
The different compounds isolated from the n-butanol and water solubles
were studied by using thin layer chromatography, paper chromatography
and gas liquid chromatography:

56
Thin layer chromatographic investigation was performed on silica
gel G (Merck) plates of 0.2 mm thickness using the following solvent
systems. Rf values of the different compounds are presented in table 6 .
Solvent System-I : chloroform-methanol-water 60s 15*4 (lower phase)
Solvent System-II : n-butanol saturated with water (upper phase)
Solvent System-Ill: chloroform-methanol 3*1
Spray reagent: anisaldehyde-sulfuric acid.
Table 6 • Thin layer chromatography of the compounds isolated from the

n-butanol and water solubles.
Compound Rf value in the corresponding Color reaction
solvent system
I II III
7-chlorodeutziol 0.08 0.51 0.61 brown

mentzeloside 0.13 0.53 ‘0.33 pink
loasaside 0.17 0.60 0.60 r e d -- brown
strictoside 0.24 0.64 0.56 red
sweroside 0.23 0.69 0.35 purple
decapetaloside 0.29 O .69 O .63 purple
decaloside 0.08 0.42 0.42 purple
glucoside-VII 0.03 0.16 0.33 red
glucoside-V 0.00 0.15 0.16 red
glucoside-X 0.33 0.79 0.36 purple
rutin 0.04 tail tail yellow
Paper chromatography was performed on Whatman paper 3 MM,
using assending technique, with the following solvent systems. Rf
values of the different compounds are presented in table 7 .
Solvent System IV : n-butanol-acetic acid-water 63:10:27
Solvent system V : n-butanol saturated with water.
Spray Reagent: Vanillin-hydrochloric acid in methanol.

Both tic, and paper chromatography analysis were used with the
above solvent systems throughout the purification procedures.

57
Table 7. Paper chromatography of the compounds isolated from the

Compound Rf value in the corresponding Color reaction

solvent system
IV V
7-chlorodeutziol 0.46 0.41 pink

mentzeloside 0.39 0.32 pink
loasaside 0.51 0.43 pink
strictoside 0.61 0.51 red-- orange
sweroside 0.50 O .38 light pink
decapetaloside 0.59 0.60 light pink
decaloside 0.29 0.21 purple
glucoside-VII 0.18 0.05 purple
glucoside-V 0.11 0.03 purple
Gas liquid chromatography was carried out using a gas chromatograph
apparatus with a hydrogen flame ionization detector, carrier gas He
(rate $1 ml/min, 20 psi), hydrogen (35 psi), sensitivity 128 x 10,
temperature: oven 250°G, detector 300°C» injector 300°C. A 3% OV-l?
column (circular type, 1 .5m) was activated by baking it during 48 hours
at 320°G detached from the detector (flow rate of helium 15 ml/min).
The different samples were trimethyl silylated using the following
technique (29) : a mixture of anhydrous pyridine (10 ml, Pierce Chemical
Co. ), hexamethyldisilizane (HMDS, 2 ml, Pierce Chemical Co), and tri
methyl chlorosilane (TMSS, 1 ml, Pierce Chemical Co.) was used for
trimethylsililation. A sample of glucoside (or glucoside mixture) 1 mg
was mixed with the reagent solution, 0.5 ml, and the reaction mixture
was warmed in a stoppered vial at 40°C for 15 min, and a 2-5 fil
aliquot injected into the gas chromatograph. Retention times for the
different compounds are presented in table 8 •

58
Table 8 • Gas chromatography of the compounds isolated from the
Compound Retention Time (min)
7-chlorodeutziol 10.0
mentzeloside 12.2
loasaside 7.8
strictoside 6.4
decapetaloside 8.0
decaloside 8.12, 13.0
sweroside 27.8
glucoside VII 8.4
glucoside V 4.8, 8.8
glucoside X 4.6
rutin 5-0
Column Chromatography of the n-Butanol Solubles on Sephadex LH-20 and
Isolation of Rutin.
The n-butanol solubles fraction was divided into three parts
(8.6 g each), each part was then applied to the top of a 100 g sephadex
IH-20 column (3 cm id x 65 cm length), using methanol as eluent.
Fractions of 300 drops (~ 7*5 ml) were collected. Fractions 1-20 (19*3
g) contained non-flavonoid material, fractions 21-30 contained flavonoid
material which cxystallized from methanol (o.4 g)., as well as from
methanol-water.
Identification of Rutin.-
The rutin sample had a up. of 215°C (melted with effervescence, but
became plastic at 195°C). It had an [ d J ^ D + 90 (c 0.1, CHÔH)
[compared with a commercial sample from Fluka, A.G. Bucks S.G. Lab,
[ a J ^ D +8° (c 0.1, CHÔH) J. The ir of both the isolated (figure ig ) ^
commercial sample showed bands at 3400, I65O, 1600, 1500, 1450, I36O, .
1200, 1090, and 900 cm"1 . The uv (figure 13 ) (CHÔH, c 1 mg %)
presents bands at Xmax* nm (log €)s 259 (4.4), 266 sh (4.1 ), 299 sh
59
(4.1 ), 359 ( ^ )? uv (MeOH-NaOMe) 272 ( 4 .5), 327 ( 4.2 ). ^10 ( 4.5 )
(MeOH-AlCl3 ) 275 ( ^-5), 303 ( ^.1 ), 433 ( ^.5); (MeOH-AlCl3-HCl) 272
(4.4 ), 300 ( 4.1), 363 sh ( 4.4), J+00 ( O.O); (MeOH-NaOAc) 380 (4.3),
271 (4.5)5 (Me0H-Na0Ac-H3B03 ) 38O (4.4), 262 (4 .5 ) .These data are in
agreement with reported literature values (30). *H-nmr (CD^D, 60 MHz)
(figure 14)presented signals at 6(ppm); 1.10 (d, CH^rhamnose), 3*30-
3.50 (m, protons base of OH for sugars), 5*10 (m, glycosidic protons),
6.26 (d, J 2 Hz, H6 or Hg ), 6.40 (d, J 2 Hz, Hg or Hg ), 6 .90 (d, J 10 Hz,
HgI), 7.10 (m, H^,), 7*19 (s, Hgt). Tic.: Rf 0.6 (Polyamide, Solvent
system Methanol-acetic acid water 9:0.5:0.5). All of these data were
identical with those of an authentic sample of rutin.
Column Chromatography of the Non-phenolic Part of the n-Butanol Solubles
Fraction.
The non-phenolic material obtained from the sephadex LH-20 column
(19-3 g) was adsorbed on 25 g of silica gel # 1 and applied on the top
of a silica gel 60 column ( 1 kg, Merck, particle size 60-100 mesh,
deactivated with 5% water; 6.5 cm id x 60 cm lenght), and using
solvent system I as eluent. Fractions of 5^ ini were collected, after
initial 800 ml of a hold-up volume. The fractions were combined
according to the tic analysis, using solvent system I, and to the
weight profile. The resulting fractions are presented in table 1.
Purification of 7-chlorodeutziol.
Fractions 256-278 (2.75 g) from the non-phenolics n-butanol
solubles column, were dissolved in methanol and adsorbed on 2 g of

60
silica gel # lf and applied on the top of a column of florisil (51 g»
60-100 mesh, J.T. Baker; 2 cm id x 42 cm l) using as eluent increasing
amounts of methanol in chloroform as follows: CHCly-MeOH 9sl(3»6 liters),
85:15 (0.5 liter), 80:20 (0.5 liter), 75:25 (0.5 liter), and 70:30 (0.5
liter). Fractions of 9 ®1 were collected with an automatic fraction
collector, and tic control of the individual fractions was done. The
first 3.6 liters did not contain any material, and were collected together
then fractions 30-80 contained a crystalline material (932 mg) which was
further recrystallized from methanol-chloroform 1 :9 , producing colorless
needles of 7-chlorodeutziol.
Physical and Spectral data of 7-chlorodeutziol.

_2
7-Chlorodeutziol gives colorless needles (yield •“ 5 x 10 %,
OO r\
related to dried tops) j mp. 126-8 C with decomposition ; [aj D -132
(c 1.0, H20) , [a]20D -132° (c 2.2, CHÔH); uv (CHÔH, c 0.42 mg/ml)
\max (nm) (log €) 209 (3*50) ; ir (KBr ) (figure 1 5 ) vmax: 3400, 1620,
1670, 1090, 890 cm-1 5 ^H-nmr (90 MHz, D20, figure 16) 6 (ppm): I .67
(s, 3H, CH^ at C-4), 2.34 ( hr. s. , 2H, H's at C-5 and C-9), 3*47 (hr.
s., sugar protons), 3*9? (m, H's at C-6 and C-8 ), 4.75 (d, J 7.6 Hz, H
at C-l'), 5.36 (d, J 1.6 Hz, H at C-l), 6.10 (s, H at C-3). ^C-nmr
( see tahle 4, figure 17 ) . 7-Chlorodeutziol . gave a positive
Beilstein's test: green coloration upon heating on a copper wire loop.
Its mass spectrum could not he obtained because the compound is not
volatile enough.
Analysis calculated for C ^ H ^ O ^ C l . ^ O : C, kS% ; H, 6 .2 5 % 5 Cl, Q.75% .
Found: C, 44.73#J H, 6.24^; Cl, 8 .88#.

61
Acid Hydrolysis of* 7-Chlorodeutziol and Identification of Glucose.
7-Chlorodeutziol (2) (5 mg) was dissolved in one ml of
0.5N sulfuric acid and the reaction mixture was "boiled at 95° C during
90 min. After this time, calcium hydroxide (20 mg) was added, the
reaction mixture was filtered and the filtrate evaporated to dryness.
To this residue 0.5 ml of the trimethyl-silyl reagent (as in GLC of
n-butanol solubles) was added. The solution was mixed thoughly and
then warmed in a stoppered vial at 40°C for 15 min. A 2.5 (J-l aliquot
was then injected to the GC.
The gas chromatograph apparatus was used under the following
conditions: solid support: 3% OV-17 (prepared as for the initial GC
investigations), carrier gas: helium (51 ml/min, 20 psi), (35 psi),
air (26 psi); temperature, for oven 180°C, for detector 250°C, for "
injector 200°C; attenuation 64 x 10.
The hydrolysis product of 7-chlorodeutziol presented two peaks
with retention times 5*8 min and 7*8 min, which were identical to the
peaks of P-D glucose (5*8 min), and a-D glucose (7.8 min), as
established by direct comparison with an authentic sample.
Agetylation of 7-Chlorodeutzlol and Jones' Oxidation on the Acetate.
A quantity of 110 mg of 7-chlorodeutziol was dissolved in 2 ml of
pyridine and 2 ml of acetic anhydride was added. The mixture was
allowed to stand overnight at room temperature and then refluxed for 2
hours on a steam bath. The mixture was then poured into a flask
that contained a mixture of ice-water, a crystalline material was
obtained. The material was recovered by filtration and recrystallized

62
form methanol producing 105 mg of colorless crystalline needles of 7-
chlorodeutziol hexaacetate (£).
Acetylation under more drastic conditions was carried out as
follows: a quantity of 50 ®g o f 7-chlorodeutziol was dissolved in

1 ml of pyridine to which 1 ml of acetic anhydride was added. The
reaction was carried out on a steam bath for 12 hours. The mixture was
evaporated to dryness and the residue dissolved in 3 ml of acetic
anhydride to which four drops of BF^-ethereate were added, after 3
minutes of reaction ice was added and the mixture was extracted with
chloroform, recrystallization from methanol produced a compound
identical with £.
Jones oxidation was performed on compound £: (£) (6 mg) was
dissolved in 3 ml of acetone, while stirring the solution at 20°C, one
ml of Jones reagent was added (prepared by dissolving 670 mg of chromic
trioxide in 0.6 ml of sulfuric acid and then addition of water to
complete a 5 ml volume). The reaction mixture was stirred for several
minutes, no color change was apparent, then the excess of reagent was
quenched by addition of methanol. The reaction mixture was concentrated
under vacuo, and reextracted with a mixture of chloroform-water. The
starting material £ was found by tic, *H-nmr to be present in the
chloroform fraction.
Physical and Spectral Data for 7-Chlorodeutziol Hexaacetate £ ,
Compound £ has a mp. of 124-5°C , [af]20D -125° (c 2.6, CHCl^);
Rf o.24 (benzene-ethyl acetate 3 t l ) i ir (CHCl^) no OH absorption, and
vmax at 1760 (acetate); ^H-nmr (90 Mhz, CDCl^, figure 18 ) signals at 6
(ppm): 1.92-2.12 (s, 18H, 6 acetates), I .65 (s, 3H» CH^ at C-4), 2.62-
2.71 (br. s., 2H, H ’s at C-5, and G-9), 3-7? (m, H's of sugar ),4.30-
4.00 (m, H's at C-6 and sugar ), 5.20-4.80 (protons base of acetate),
5.31 (br. s., H at C-l), 6.03 (s, H at C-3) s ^ C - n m r (see table 5»
figure 19 ); ms (figure 20 ) 634 (0.4^), among others.
Analysis calculated for C g ^ H ^ O ^ C l : C, 51*10 ; H, 5*52% . Found
C, 50.91%! H, 5*59%.
Emulsin Hydrolysis of 7-Chlorodeutziol.
7-Chlorodeutziol (100 mg) was dissolved in 2 ml of distilled
water and 30 mg of emulsin (Nutritional Biochemical Corp.) was added.
After eight days at room temperature the reaction mixture was
evaporated to dryness and extracted with a hot mixture of chloroform-
methanol 1:1. Evaporation of the solvent gave a residue (89 mg) which
presented on tic a major spot (Rf 0.39» solvent system I). This .
material did not crystallize and decomposed upon standing. It was
purified using column chromatography ( silica gel #4, 6 g, solvent system
I), fractions of 150 drops (3 ml) were collected. Tic analysis showed
presence of the aglycone 10, in tubes 4-9 (34 mg, Rf an above). The
sugar part was compared hy tic with an authentic sample of glucose.
^H-nmr analysis of aglycone 10 (90 Mhz, CDÔD, figure 21)» indicated
besides the absence of the signal for the sugar moiety , the following
signals 6 (ppm): I .65 (s, 3H, CHât C-4), 2.37-2.22 (m, 2H, H's at C-5
and C-9)» 3*80 (broad singlet, 3H» H's at C-6, C-7» and C-8), 5*04 (d,
J 3*6 Hz, H at C-l), and 6.00 (s, 1H, H at C-3) ; ^ C - n m r (Acetone-d^,
figure 22 ) signals at 6 (ppm) (1) 90.6, (3) 134.4, (4) 110.4, (5 ) 46.7
64
(6) 80.7, (7) 70.6, (8) 76.5* (9) 40.6, and (10) 14.6.
Acetylatlon of 7-ChIorodeutzlol Aglycone (10).
The hydrolysis product 10 (34 mg) was dissolved in 1 ml of pyridine
and 1 ml of acetic anhydride was added to the mixture which was let
stand at room temperature for 22 hours, at which time tic analysis
indicated that no starting material remained. The reaction mixture was
poured into iced-water and then extracted with chloroform. The
chloroform extract was concentrated under vacuo, and purified through
successive column chromatography (with silica gel # 5» and silica gel 60
P F ^ with chloroform as eluent. The pure acetate 11_ had an Rf of 0.16
in CHClî and O .63 in benzene-ethyl acetate 3*1» "both in silica gel
plates. The ir of 11^ (CHCl^) indicated a vmax at 1750 cm \ and no free
OH "band. The ^H-nmr (CDCl^, figure 23) had the following signals at 6
(ppm): 1.70 (s, 3H, CH^ at C-4), 2.09 (s, 3H, Ac), 2.13 (s, 6H, 2Ac),
2.70-2.60 (m, 2H, H's at C-5 and C-9), 4.06 (m, H at C-7), 5-42-5.26 (m,
2H, H's at C-6, C-8), 6.10 (hr.s., H at C-3), 6.17 (hr.s., H at C-l).
*^C-nmr (CDCl^) had signasls at 6 (ppm) (l) 88.1, (3 ) 136.4, (4) 108.0,
(5) 44.6, (6) 80.8, ( ? ) 64.1, (8) 80.2, (9) 40.4, (10) 15.0 (3 carhonyl
carbons) 169.4, (3 methyl-acetate carbons) 21.0 . The ms (figure 24) had
a molecular ion at M-AcOH, 286 (4.2$), with an M + 2 peak at 288 (1.4%).
Hydrogenation of 7-Chlorodeutzlol.
Activated palladium on charcoal (25 mg, 10%), was suspended in 10
ml of spectra grade methanol. The suspension was subjected to a
hydrogen atmosphere until saturation of the catalyst (3 hours). After

65
saturation, a quantity of 121 mg of £ dissolved in 0.5 ml of water and
0.5 ml of methanol was injected into the reaction mixture and hydrogena
tion proceeded until no more hydrogen was consumed (5 hours). The
reaction mixture was then filtered though a scintered glass filter
funnel and the precipitate washed with methanol and water. The filtrates
were collected and evaporated to dryness (140 mg). The hydrogenated
compound 12 crystallized from methanol-chloroform (Is9) as aggregates of
microneedles, mp. 128-131°C (with decomposition); Rf 0.05 in solvent

2p n
system-I with silica gel plates; [of] D -88 (c 1.0, HgO); ir (KBr) the
signal at 16?0 cm 1 was not present, otherwise spectra was as for 7»

J
H-nmr (CDÔD, 90 MHz, figure 25) gave the following signals at 6 (ppm):
0.88 (d, J 6 Hz, 3H, CH^ at C-4), 1.30-2.24 (complex absorption due to
protons at C-5, C-9 and C-4), 4.22-3-22 (protons base of hydroxyl groups)
4.55 (d, J 7.3 Hz, H at C-l’), 5.26 (s, H at C-l).
Acetylation of 3,4-Dihydro-7-Chlorodeutziol (12).
Compound 12 (10 mg) was dissolved in 0.5 ml of pyridine to which
1 ml of acetic anhydride was added. The reaction mixture was placed in
a steam bath for 4 hours at which time tic indicated the absence of
starting material. Addition of ice to the reaction mixture produced
crystalline microneedles of 1^, which were recrystallized from water
(6.9 mg). Compound 1^ had a mp. of 191-3°C; Rf 0.22 (benzene-ethyl
acetate 3*1); ir (CHCl^) indicated the absence of free OH and a vmax at
1755 cm"1 (acetate; 1H-nmr (CDCly 90 MHz, figure 26) had the following
signals at 6 (ppm) 5 0.92 (d, J 5 .7 , CH^ at C-4), 2.02-2.13 (6 singlets,
18H, 6 Ac), 3.12-3.63 (protons at C-7 and C-3, complex signal), 4.00-
66
4.42 (complex signal for sugar protons), 5*24-4.77 (protons base of
acetates), 5.55 (d, J 6.0 Hz, H at C-l'), 5*67 (d, J 6.4 Hz, H at C-l).
A Beilstein's test was positive indicating that chlorine was still
present.
Emulsin Hydrolysis of 3.4-Qih.ydro-7-Chlorodeutziol (IP*).
Compound 12 (100 mg) was dissolved in 1 ml of water to which 10 mg
of emulsin was added. The reaction flask was placed on a water bath at
32°C and after 103 hours no starting material was present as indicated
by tic control. The reaction mixture was then evaporated to dryness and
then extracted with 40 ml of a hot mixture of chloroform-ethanol (1:1).
The extractive was filtered and concentrated under vacuo. The reaction
mixture was further extracted with hot methanol and filtered, the
filtered extracts were combined, dried and dissolved in ethyl acetate,
from which a precipitate was obtained. This precipitate was soluble in
water, and by tic analysis was identified as glucose (Rf 0.03 in solvent
system i). The remaining ethyl acetate extract (58 mg) was purified
through a column of silica gel # 4 (7g» 1.5 cm id x 6 cm l) using
solvent system I as eluent. Fractions of 1 ml were collected.
Fractions 20-27 (27 mg) upon addition of water and methanol and after
evaporation left a crystalline residue 14. It had the following physical
data:Rf. 0.39 ( solvent system I); mp. 114°C with decomposition; uv
(CHÔH) end absorption after 204 nm; *H-nmr (pyridine-d^, 90 MHz) had
signals at 6 (ppm): 0.90 (d, J 6.4 Hz, CH^ at C-4), 1.80 (m, H at C-4),
2.38-2.56 (dd, H at C-5), 2.89-3*07 (dd, H at C-9), 3*52-3*69 (dd,H at
C-3)» 3*89-4*13 (dd, H at C-3), 4.47-4.92 (complex signal, 3H, H's at

67
C-6, C-7 and C-8 ), 5*91 (br.s., H at C-l); ^ C - n m r (pyridlne-d^) had
signals at 6 (ppm): (1) 91.8d, (3) 6 3 .7t, (4) 3 0 .8d, (6 ) 82.3d, (7)
75»ld, (8 ) 79.7d, (9) ^7*?d, and (10) 15.8q_. The mass spectrum (figure
2 7 ) presented a molecular ion peak at m/e 222 (2%), alongside with
other peaks.
Cyclization of 7-Chlorodeutziol.- Synthesis of Mentzeloside.
Compound 7 (50 rag) was placed in a 50 ml round bottom flask and a
solution of 210 mg of anhydrous potassium carbonate in 20 ml of methanol
was added. The reaction mixture was stirred for 17 hours at 25°C at
which time tic indicated the absence of starting material. The mixture
was the concentrated under vacuo and suspended in solvent system I,and
applied to the top of a silica gel # k column (5 g» 1 cm id x 5 cm l),
using the same solvent system. Fractions of 50 drops (1 ml) were
collected. Fractions 61-80 contained 23 mg of material, which after
recrystallization from methanol yielded 11 mg of mentzeloside, which
was identified by its mp, mixed mp, ir, and ^H-nmr in comparison with a
reference sample.
Synthesis of 7-Chlorodeutziol from Mentzeloside.
Mentzeloside (7 mg) was dissolved in 5 ml of methanol to which 1 ml
of a 0.02N solution of hydrochloric acid was added. The mixture was
stirred for four days at room temperature. Partial transformation of
mentzeloside into 7-chlorodeutziol occurred, as indicated by tic, co-
tic of the reagent and product.

68
Extraction of 7-Chlorodeutziol with a Non-Halogenated Solvent System. p
An ethanollc extract (11.2 g) of M. decapetala, tops, was
partitioned between 50 ml each of ethyl ether and water. The water
solubles were further extracted with four 50-ml portions of ethyl ether.
The ethereal fractions were combined and then concentrated under vacuo
to yield 3*5 g of ether solubles. The aqueous fraction after extraction
with ether, was partitioned with three 50-ml portions of ethyl acetate.
The ethyl acetate extracts were then combined and concentrated under
vacuo to produce 0.2 g of extract. The resulting aqueous solution was
then extracted with five 50-ml portions of n-butanol saturated with
water. The n-butanol extracts were combined and dried to produce 1.23 g
of extract. The remaining aqueous solution was then concentrated to
yield 2.5 g of aqueous residue.
The n-butanol solubles (1.2 g) were applied on the top of a florisil
column (52g, 60-100 mesh, J.T. Baker, 25 cm id x 34 cm l), and eluted
with benzene-methanol (3si). Fractions of 15 ml were collected. Tic
and paper chromatography indicated the presence of 7-chlorodeutziol in
tubes 2-7.
Stability of 7-Chlorodeutzlol.
7-Chlorodeutziol is an unstable crystalline compound which
decomposes upon standing in the presence of air or light, producing
black material in a period of 6-8 months. Upon exposure to acid alumina
and reflux in ethanol no change was observed in a period of three hours.
Compound 7 was dissolved in methanol and calcium carbonate powder
was added. The sample was stirred at room temperature during 24 hours
69
with no apparent change in the compound as monitored "by tic.
When compound £ was adsorbed into neutral alumina (activity grade I,
in proportion 1:100), and suspended in methanol and stirred at room
temperature for 6 days, tic analysis indicated the presence of
mentzeloside plus some starting material.
Isolation of Mentzeloside (2)
Mentzeloside was present in fractions 219-255 of the n-butanol-non-
phenolics column. For its purification the following procedure was
followed: 850 mg of crude material was dissolved in methanol and
adsorbed on 2 g of florisil which was then applied on the top of a
florisil column (51 g» 60-100 mesh, 2 cm id x 42 cm l), and eluted with
increasing proportions of methanol in chloroform. Fractions of 900
drops (15 ml) were collected in an automatic fraction collector.
Mentzeloside was obtained as a crystalline material from fractions 130-
140. The physical and spectral data of the crystalline material was
compared with those of an authentic sample of mentzeloside.
Physical and Spectral Data for Mentzeloside.
Mentzeloside is a white crystalline material that exhibits the
following properties: mp. 260° (dec), [ a J ^ D -100° (c 1.0, HÔ); ClAt.
mp. 266°C, [of|23D -100.88 (c 1.02, ly)) (4)3; its ^ - n m r (D20, 90 MHz,
figure 28 ) had the following signals at 6 (ppm): 1.60 (s, 3H, CH^ at
C-4), 2.70, 2.10 ( two triplets for H's at C-5 and C-9), 3.90-3.50 (m,
complex pattern of H*s carrying oxygen), 4.15 (d, J 7.6 Hz, H at C-l*),
4.85 (d, J 10 Hz, H at C-l), 6.24 (br.s., H at C-3); l3C-nmr (D20,

figure 2 9 1 table 4).
?o
Acetylation of Mentzeloside.
Mentzeloside (45 mg) was dissolved in 1.5 ml of pyridine to which
1.5 ml of acetic anhydride was added. The reaction mixture was refluxed
on a steam "bath for 4 hours, then a mixture of methanol and water was
added and the acetate crystallized out. The material was collected "by
filtration (50 mg). Mentzeloside acetate had a mp. 201°C (Lit 199°C),
the ir indicated no free hydroxyl, and the presence of acetate hands at
vmax 1760, and the enol ether at vmax 1620 cm Rf 0.5 (benzene-ethyl
acetate 3:1); *H-nmr (CDCl^, 90 Mhz, figure 3 0 ) presents signals at 6
(ppm): 1.46 (s, CH^ at C-4), 2.30 (m, 1H, H at C-5_. 2.50 (m, 1H, H at
C-9), 3.56 (complex pattern for protons at C-7, C-8 and C-5f)» 4.80-4.10
(proton base of acetates), 6.00 (br.s., 1H, H at C-3)* five acetates p
present at 2.07, 2.03, 1.99* 1.96 1.94; l3C-nmr (CDCly table 5. figure
31).
Purification of Loasaside.
Fractions 165-217 (1.4 g) of the n-butanol, non-phenolic column,
contained a compound which gave a pink color on tic upon spraying with
anisaldehyde-sulfuric acid. This color rapidly fades to a yellow-brown
color. Purification of this fraction was achieved by succesive column
chromatography. Fractions 165-217 (1.4 g) were adsorbed on 4 g of
florisil and poured at the top of a florisil column (51 g* 60-100 mesh,
2 xm id x 42 cm l) using chloroform-methanol (9si) as eluent, fractions
of 900 drops (15 ml) were collected per tube. Tubes 41-122 contained
the material (446 mg) which was further purified through a silica gel 60
column (45g, 5*6 cm id x 10 cm l) using solvent system I as eluent.
Loasaside which was collected from fractions 71-190 (311 mg) was
71
passed through a silica gel # 4 column (75 g, 1 cm id x 55 cm l) with
solvent system-I as eluent. Fractions of 15 ml were collected. Tubes
47-63 containedloasaside(21)as a crystalline material (150 mg), which
was recrystallized from methanol-chloroformCl:9>as tiny shiny needles.
Physical and Spectral Data for Loasaside.
L o a s aside has the following melting characteristics: it turns pink
at 193°C and melts with decomposition at 2l6-220°Ci -150° ( c 1.3.
H20); uv (CHÔH, c 0.26 g$) Xmax, nm (log €) 207 (3*55); 3 r (KBr) vmax
3400, 1665, 1620, 1350, 1380, 1150, 1100, 1045, 1010, 975. 965, 840,
•4
800 cm- (figure 3 2 ). The mass spectrum (figure 33) had a molecular ion
peak at 330 (0.6%) . The ^H-nmr (D2°» 90 MHz, f i g u r e ^ ) presented the
following signals at 6 (ppm) 1.5^ (br. s., 3H, CH^ at C-4), 2.42-2.38
(dd, 2H, H's at C-5 and C-9), 3*57 (protons base of hydroxyl groups,
sugar moiety), 4.93 (d» J 5*1 Hz, H at C-l), 5 *86 (br. s., 2H, H's at
C-7 and C-8 ), and 5*9^ (br. s., H at C-3). The l3C-nmr (D20) is given
in table 4, figure 35 .
Acid Hydrolysis of Loasaside and Identification of Glucose.
Loasaside (21) (2 mg) was dissolved in one ml of 0.5 N
sulfuric acid and the reaction mixture was heated at 95°C during 90 min.
The material began to turn black at 90°C. After 90 min a quantity of
20 mg of calcium hydroxide was added, the reaction mixture was then
filtered and the filtrate evaporated to dryness.Preparation of the
trimethyl, silyl derivative and gas chromatographic analysis was carried
out in the same conditions as for 7-chlorodeutziol. From this analysis

72
the sugar moiety was identified as glucose.
Acetylation of Loasaside.
Loasaside (36 mg) was dissolved in 0.5 ml of pyridine and 0 .5 ml of
acetic anhydride was added. After three hours on a steam hath the
reaction mixture was evaporated to dryness after addition of methanol
and toluene. Addition of ethanol to the dried residue produced a crude
crystalline material (58 mg). The crystalline material was purified by
chromatography on silica gel 60 (8g, i cm id x 8 cm l), using benzene-
ethyl acetate (9:1) as eluent. Fractions of 50 drops (1 ml) were
collected. Losaside acetate was obtained in fractions 6-9. Loasaside
acetate had a mp 153-6°C, and Rf 0.41 on silica gel with benzene-ethyl
acetate (3*1) as solvent. This acetate was highly unstable and turned
yellow upon exposure to the light. The ir (CHCl^) showed no signals
for free hydroxyl groups and vmax at 1750,1600, 1370, 1050 cm”*.
The *H-nmr (CDCl^, 90 MHz, figure36) presented signals at 6(ppm): 1.66
(br.s., CH^ at C-4), five acetates at 2.10, 2.06, 2.03, 2.01 (x2),
5.90-6.03 (dd, 3H, H's at C-7 and C-8 besides a broad singlet for H at
C-3)> 5-53 (complex signal assigned for the allylic acetate at C-6), 4.87-
5.44 (signals for the protons base of acetates and glucosidic protons).
The *^C-nmr (CDCl^) is presented in table 5> figure 37 .
Hydrogenation of Loasaside.
Palladium in charcoal (4.4 mg, 10^), was suspended in 1.5 ml of
methanol and saturated with hydrogen for a two hour period, then,a
solution of 10 mg of loasaside in 0.4 ml of methanol was added andthe

73
reaction was maintained under a hydrogen atmosphere for 90 min. The
suspension was then filtered through a scintered glass funnel and the
residue was washed with methanol. The filtrates were concentrated under
vacuo yielding 10.8 mg of 7,8 dihydro-1osaside. It had a Rf 0.23
(solvent system i) on silica gel and gave a blue coloration upon spraying
with anisaldehyde-sulfuric acid. The *H-nmr 90 MHz, figure38 )
indicated the absence of the signal at 5*86 which integrated for two
protons, other features of the spectra are signals at 6 (ppm) 6.04 (br.
s., 1H, H at C-3), 5*23 (d, J 2.5 Hz, H at C-l), 3*70-4.40 (protons base
of hydroxy-groups), 2.45 (br.s., 2H, H's at C-5 and C-9), 1.57 (s, 3H,
CH^ at C-4), 1,00-1,90 (broad base of saturated protons at C-7 and C-8 ).
Acetylation of 7,8-Dihydro-loasaslde.
7,8 Dihydro-loasaside(10 mg) was dissolved in 0.5 ml of pyridine
and 0.5 ml of acetic anhydride was added. The reaction mixture was
reacted on a steam bath for one hour, then left at room temperature for
12 hours. After evaporation of the excess reagents followed by addition
of methanol and toluene, an oily residue was obtained. Its H-nmr (CDCl^
figure 3 9 ) indicated the presence of five acetates at 6 (ppm)s 2 .02,
1*95 (x2), 1.94, and 1.90, alongside withsignals at 5*87 (br.s., H at
C-3), 5*14-4.63 (complex pattern of protons base of acetates, plus
glucosidic protons), 4.15 (m, for the non-allylie acetate proton at C-6),
3*59-3*70 (remaining protons of the sugar moiety), 2.44 (br.s., 2H, H's
74
Deoxygenation of Mentzeloside and Formation of Loasaside and of A -
Isoloasaside.
A 210 mg quantity of sodium iodide (Mallinckrodt) and 70 mg of
sodium acetate, were dissolved in 4.2 ml of glacial acetic acid
containing 0.3 ml of water. The mixture was ice-cooled and then 300 mg
of activated zinc powder was added . To this mixture, mentzeloside (105
mg) was added over a period of ten minutes. The reaction was kept in
an ice "bath with continuous stirring and under nitrogen for one hour.
It was then filtered, diluted with water and concentrated under high
vacuum. The resulting residue was dissolved in 4 ml of water and 1 ml
of glacial acetic acid was added. The reaction was maintained under
nitrogen, in an ice bath and with stirring for one hour. The resulting
reaction mixture was filtered through one gram of activated charcoal
(Norit A lypeO, which was washed with 40 ml of water, and then with 40
ml of methanol. The methanol filtrate was concentrated under vacuo
producing a residue (83 mg) which was chromatographed on a column of
silica gel 60 (10g, 1 cm id x 10 cm 1) using solvent system I as eluent.
Fractions of 200 drops (2 ml) were collected. Tubes 26-40 contained 5

6 1
mg of A -isoloasaside. Its H-nmr (D2°» 90 MHz, figure 4,0 ) indicated
the presence of two double doublets centered at 6 6.08 and 5*68 ppm
(H's at C-6 and C-7 respectively), and signals at 6 (ppm) 5*88 (br.s,,
H at C-3), 5.13 (d, J 3.8, H at C-l), 3*10-3.72 (protons base of
hydroxyl groups), 2.25 (m, 2H, H's at C-5 and C-9), and 1.43 (s, 3H,
CH^ at C-4). Tubes 41-42 (32 mg) contained loasaside and mentzeloside.
Additional chromatography of these fractions led to the isolation of
2.6 mg of pure loasaside which was identified ty its ^H-nmr, tic, co-tlc
75
and paper chromatography analysis. Furthermore, the presence of
loasaside from this reaction mixture was detected through glc analysis
of its TMS derivative.
Synthesis of 7,8-Dihydro-loasaside through Hydrogenation and
Hydrogenolysis of Decaloside.
• Rhodium on charcoal (25 mg, 5%, MCB)
was suspended in 1 ml of ethanol and saturated with a hydrogen
atmosphere for five hours. To the stirred suspension, 100 mg of
decaloside dissolved in 1 ml of ethanol containing two drops of water,
was added. The reaction was stirred at 21°C for 3*3 hours under a
hydrogen atmosphere, then the reaction mixture was filtered. The
filtrate was evaporated to dryness (99 mg) and adsorbed in 1 g of
silica gel # 1 and poured on the top of a silica gel 60 column (25 g,
1 cm id x 25 cm l ) . Chromatography was carried out with solvent system
III as eluent. Fractions of 330 drops (3.5 ml) were collected. The
residue from tubes 29-40 crystallized from ethyl acetate (55 mg) as a
hygroscopic material. The absence of the signal at 6 5-88 ppm in the
^H-nmr (DÔ) indicated saturation of the 6,7 bond.Furthermore, presence
of a series of multiplets in the region of 1.00-2.00 account for the

13
newly saturated protons. The -'C-nmr (Dg0 ) presented signals at 6 (ppm):
(1)97.0, (3)139.2, (4)115.2, (5)42.1, (6 )7 6 .7 , (7)31.5, (8)24.3, (9)
39.1, (10)61.5, (l')99.0, (2')73-2, (3')76.6, (4')70.1, (5’)76.1, (6')
61. 2 .
Hydrogenolysis of 7 , 8-Dlhydro-d.ecaloside. Palladium on charcoal
(17 mg, 10%), and 7 ,8-dihydro-decaloside (20 mg) were suspended in 2.5
ml of absolute ethanol, and the stirred solution was left under a
hydrogen atmosphere at 2l°C during five hours. The reaction was then
filtered and concentrated under vacuo. The residue (17 mg) was passed
through a silica gel ^ 25^ co^-umn (5g» 0.5 cm id x 12 cm l), using
solvent system I. Fractions of 50 drops (0.5 ml) were collected.
From tubes 70-100 a compound which exhibited a single spot upon tic
analysis was obtained (5 mg). It had Rf 0.23 with solvent system I on
silica gel . Its ^H-nmr (OÔ) was superimpossable with that of 7»8
dihydro-loasaside. After spraying with anisaldehyde-sulfuric acid the
same blue color and Rf value appears for both compounds.
Isolation of Sweroside and Decapetaloslde.
The residue of the combined fractions 89-103 (1 g) of the column
chromatography of the non-phenolics n-butanol solubles was adsorbed on
3g of silica gel # 1 and applied on the top of a florisil column (51 g,
100-200 mesh, 2 cm id x 4.2 cm l) and chromatographed with 0.5 liter of
chloroform and 2.5 liters of chloroform-methanol (9 *1) as eluent.
Fractions of 4-5 ml were collected. Upon tic analysis, fractions 18-32
(0.5 g) were found to contain two components which were separated
through thick layer chromatography with 2 silica gel G plates, 20 cm x
20 cm, 0.5 mm thickness, and n-butanol saturated with water as eluent.
A quantity of 90 mg of material was applied to each plate, and after
developing and drying the two fractions were eluted with methanol. The
first fraction corresponding to the zone with Rf 0 .65 yielded 85 mg of

77
decapetaloside, the second fraction Rf 0.55 yielded 95 mg of sweroside.
Spectral Data for Sweroside.
Sweroside was obtained as an oily residue. Its 1H-nmr (D20, figure
41) had the following signals at 6 (ppm): I .65 (m, H's at C-6 ), 2.67
(m, 2H, H's at C-5 and C-9)» 3*20-4.20 ( protons base of hQrdroxyl and
proton at C-7)» 5*18-5*32 (m, 3H» H at C-8 , and 2H at C-10), 5.40 (d,
J 1*9 Hz, H at C-l), 7*^7 (d, J 2.2 Hz, H at C-3). The l3C-nmr (DgO)
is given in table 4, figure 42.
Acid Hydrolysis of Sweroside.
Sweroside (4 mg) was dissolved in 1 ml of 0.5N sulfuric acid,
and the reaction mixture was heated for 90 min at 95°C. After this time
calcium hydroxide (20 mg) was added. The reaction mixture was filtered
and the filtrate evaporated to dryness. The residue was analyzed
through its TMS-derivative under the same conditions as described for
7-chlorodeutziol, and glucose was identified as the sugar residue.
Acetylation of Sweroside.
The residue obtained from the combined fractions 23-32 from the
florisil colum (50 mg) was dissolved in 0.5 ml of pyridine and 0.5 ml
of acetic anhydride was added. The reaction mixture was maintained on
a steam bath for two hours, then methanol and toluene were added
followed by evaporation under high vacuum. Upon addition of ethanol,
colorless rosettes were formed (26 mg) which corresponded to sweroside
tetraacetate. It gave the following data: mp. 165°C; Rf 0.29 (benzene-
etyl acetate 3*1)f Qx]25D -166° (c 4.3, CHCl^); uv (CHCl^, c 7*8 mg#)
has a Xmax , nm (log €) of 243 (3 .69); ir (CHCl^) vmax: I76O, 1720, 1620
78
990, and 903 cm"*; *H-nmr (CDCl^, figure 4 3 ) signals at 6 (ppm)s 1.97,
2.00, 2.03, 2.09 (4 acetates), 7*56 (d, J 2.5 Hz, H at C-3), 5*45-5*20
(complex pattern for H's at C-8 and C-10). The **^C-nmr (CDCl^) is
given in table 5 * figure 44 . The mass spectrum (figure 45 ) had a
molecular ion at 526 (0.11%) among other fragments. All of these data
are in agreement with the reported literature values for sweroside
tetraacetate (21), as well as with data obtained with direct comparison
with an authentic sample.
Hydrogenation of Sweroside Tetraacetate.
Palladium on charcoal (10 mg, 10%) was suspended in one ml of
methanol and the reaction mixture was saturated with hydrogen for three
hours. A sample of sweroside tetraacetate (10 mg) dissolved in 1 ml of
chloroform-methanol (1:1), was injected into the system. Hydrogenation
proceeded at 23°C for two hours, then the reaction was filtered, and
concentrated under vacuo. The resulting residue was crystallized from
chloroform-ethanol to yield microneedles of dihydrosweroside
tetraacetate (10 mg), which.had a'mp. 183-5 °C; [ o J ^ D -114.5° (c 4.0,
CHCl^); uv (CHCl^, c 3*2 mg %) X max, nm (log €) 244 (2.9)» (CHCl^)
vmax: 1?60, 1?10, 1620, 1610, 1230, 1070, 1040 cm-1; ^ - n m r (CDCly
figure 46) signals at 6 (ppm) 7.44 (d, J 2.5, H at C-3), 5*36 (d, J 1.5
Hz, H at C-i), 4.85-5*18 (proton base of acetate), 4.11-4.37 (®, 2H, H's
at C-7), 3*73 (m» sugar residue), 2.77 (m, 2H, H's at C-5 and C-9),
2.03, 1.97, 1*94, and 1.89 ( 4 Ac), 0.90 (deformed triplet of ethyl
side chain). [Lit. mp 180-1°C, [of]^D -108°, other values are in
agreement with those reported in the literature (21) J*

79
Spectral Data for Decapetaloside
Decapetaloside (85 mg) was obtained as an oily residue. Its 1H-nmr
(DgO , figure 4 ? )presented the following signals at 6 (ppm): 1 .00-1.90
(m, protons at C-6 , and C-7), I .36 (s, 3H, CH^ at C-4), 2.35 (m, 2H,
H's at C-5 and C-9), 3*20-3.70 (protons of sugar moiety plus protons at
C-10), 5*00 (d, J 4.1 Hz, H at C-l), 5 .9I (hr.s., 1H at C-3). S mass
spectrum (figure 48) presents a molecular ion peak at 346 (1.4?5), The
13
C-nmr (DgO) is given in table 4, figure 49.
Acid Hydrolysis of Decapetaloside.
Decapetaloside (26 mg) was dissolved in 1 ml of 0.5 N sulfuric acid
The reaction mixture was then heated at 95° C for 90 minutes, then calcium
hydroxide (20 mg) was added. The reaction mixture was filtered and the
filtrate evaporated to dryness. Glc analysis of the TMS derivative of
the residue was carried out as described for 7-chlorodeutziol. The
presence of glucose was determined from this analysis.
Acetylation of Decapetaloside.
The mother liquors (140 mg) obtained upon acetylation of 90 mg
of the residue obtained from fractions 18-32 from the above sweroside-
decapetaloside column, were chromatographed on silica gel 60 (15g» 1 cm
id x 15 cm 1) using hexane-ethyl acetate (3si) as eluent. Fractions of
100 drops were collected. From this column, fractions 51-75 yielded a
crystalline material (55 mg) identified as decapetaloside pentaacetate.
It had the following physical and spectral data: mp 114-5°C; Coff^D -90°
(c 3*7* CHCl^); lr (CHCl^) indicated the absence of free hydroxyl signal
and vmax at: 1760-1740 (acetate), 1370, 1230, 1040, 910, 990 cm *. The
80
^ - n m r (CDGl^, figure 50 ) had the following signals at 6 (ppm): 2.08,
2.05, 2.03, 2.01, 1.98 (5 acetates), 5*94 (br.s., H at C-3), 4.90-5*25
(complex pattern for protons base of acetate and glucosidic protons),
3 .67-4.25 (protons base of acetate at C-10, and remaining sugar protons)
2.48 (m, 2H, H ’s at C-5 and C-9), 1.48 (s, 3H, CH^ at C-4).
The mass spectrum (figure 51 ) had a molecular ion peak at 558 (0.6^),
The ^ C - n m r (CDCl^) is presented in table 5 figure 52 . Analysis
calculated for 0, 56.11%; H, 6 .5 2 % . Found: C, 5 6 .99î H,
6 .70^.
Isolation of Strictoside.
The residue from combined fractions 104-155 (1*75 g) from the non-
phenolic n-butanol solubles column, contained a substance that appeared
as a brilliant red spot upon tic development. This residue was filtered
through florisil (4 g, 1 cm id x 4 cm l) with benzene-methanol (3*1) as
eluent. A single fraction of 120 ml was collected. Upon evaporation ,
its residue (958 mg) was chromatographed on silica gel 60 1^254 (100 g,
2.5 cm id x 45 cm l), with solvent system I. Fractions of 30 nil were
collected. The residue from the combined fractions 13-22 (606 mg) was
further purified on a silica gel 60 column (lOOg, 2.5 cm id x 45
cm 1) with solvent system I. Fractions of 30 ml were collected. The
residue from fractions 46-50 (242 mg) yielded an homogeneous spot upon
tic analysis. While the compound did not crystallize. It was
characterized as strictoside.
81
Spectral Data for Strictoside.
Strictoside was isolated cis an oil. Its *H-nmr ^ S ure 53 )
had the following signals at 6 (ppm): 1.38-1.03 (methylene protons at
C-6 and C-?), 1.38 (s, 3«, at C-4), 1.95 (m, 1H, H at C-9), 2.50
(m, 1H, H at C-5)t 3-15-4.02 (protons of sugar moiety plus C-8 proton),
5.14 (d, J 3.5 Hz, H at C-l), 5*89 ("br.s., H at C-3). The mass spectrum
13
(figure 5^) has a molecular ion peak at 332 (0.5%); the C-nmr (DÔ)
is presented in table 4, figure 55 .
Acid Hydrolysis of Strictoside.
Strictoside (5 mg) was dissolved in 1 ml of 0.5N sulfuric acid
and the reaction mixture was heated at 95°C for 90 min., then calcium
hydroxide (20 mg) was added. The reaction mixture was filtered, and
the filtrate then evaporated. The TMS derivative was prepared from the
residue, and its glc analysis was carried out as described for 7-chloro
deutziol. From this analysis the sugar moiety was identified as
glucose.
Acetylation of Strictoside.
Strictoside (82 mg) was dissolved in 1.5 ml of pyridine and 1.5
ml of acetic anhydride was added. The reaction was maintained on a
steam bath for 27 hours, then methanol and toluene were added and the
reaction mixture was evaporated to dryness. The resulting residue (126
mg) was purified through silica gel 60 (10 g, 1 cm id x 10 cm l)
with benzene-ethyl acetate (9*1) as eluent. Fractions of 100 drops
(2 ml) were collected. The residue from combined fractions 26-45 (60
82
mg) yielded crystalline material, which was further recrystallized from
ethanol. It gave the following datas mp 149-150°C; [ o G ^ D -118° (c 3*7,
CHCl^); ir (CHCl^) indicated no free hydroxyl hands and signals at vmax
1760-17*1-0 (acetate), 1675, I605, 1375, 1250, 1050 , 995, 910 , 900 cm"1 ;
1H-nmr (CDCl^, 90 MHz, figure 5&) had signals at 6 (ppm): 1.25-1.84
(methylene protons at C-6, C-7), 1.46 (s, 3H» CH^ at C-4), 2.10, 2.03
(x2), 2.00, 1.97 (5 acetates), 2.38 (m, 1H, H at C-9), 2.50 (m, 1H, H
at C-5), 4.20-3.70 (two multiplets for protons base of acetates at C-8
and sugar bases), 4.88-5.16 (protons base of acetate plus glucosidic
proton), 5*40 (d, J 1.9 Hz, H at C-l), 5-94 (s, 1H, H at C-3). The
mass spectrum (figure 57 ) has a molecular ion at 542 (0.72^). The

13C-nmr (CDCl^) is presented in table 5, figure 58 • Analysis calculated
for C ^ H ^ O ^ : C, 55-35^: H, 6.32??. Found: C, 55-84??; H, 6 .34#.
Emulsin Hydrolysis of Strictoside.
Strictoside (50 mg) was dissolved in 2 ml of water and emulsin
(11 mg) was added to this solution. The reaction mixture was kept at
room temperature for 24 hours. Tic indicated the presence of a compound
having an Rf 0.59 (silica gel, solvent system I) which corresponds to
strictoside aglycone. The reaction mixture was evaporated to dryness
and extracted with a hot mixture of equal parts of chloroform-methanol-
ethanol-ethyl acetate. The extract was then evaporated to yield 60 mg
of an oily residue which was adsorbed on 0.5 g of silica gel # 1 and
applied on the top of a silica gel # 5 column (lOg, 1 cm id x 10 cm 1),
with solvent system I as eluent. Fractions of 50 drops (1 ml) were

collected. Tubes 21-30 contained the aglycone (10 mg) which had the
same Rf value as above. Its ^H-rrmr (iyr-d^, 90 MHz) indicated the
presence of the following signals at 6 (ppm): 6.34 (br.s., H at C-3)»
5-50 (d, J 5.4 Hz, H at C-l), 1.55 (br.s., 3H, CH^ at C-4), no sugar
13
moiety was apparent. The C-nmr (Ryr-d^.) indicated the presence of
nine carbons at 6 (ppm): (1) 93*9» (3) 136.1, (4) 112.9» (5) 37 *8 , (6 )
29 .1, (7) 34.3, (8 ) 74.9, (9) 16.6.
Acetylation of Strictoside Aglycone.
The aglycone of strictoside (10 mg) was dissolved in 0.5 ml of
pyridine and 0.5 ml of acetic anhydride was added. The reaction mixture
was kept at room temperature for 12 hours, then methanol and toluene
were added followed by evaporation. An oily residue was obtained which
was purified on silica gel ^ 2 5 4 ^ cm id x 8 cm l), with
hexane-ethyl acetate (4:1) as eluent. Fractions of 20 drops were
collected. From tubes 28-33 the acetate of the aglycone was obtained
(3 mg). It had the following properties: Rf 0.36 (hexane-ethyl acetate
4:1): *H-nmr (CDClî figure 59 ) presented signals at 6 (ppm): 6.18 (d,
J 4.0 Hz, H at C-l), 6.00 (br.s., H at C-3), 5 .00 (m, H at C-8 ), 2.60
(m, H at C-5), 2.35 (m, H at C-9), 2.03 ( Ac), 2.12 (Ac), 1.58 (s, 3H,
CH^ at C-4).
84
Purification of Glucoside X .
The combined fractions 69-88 (1.3 g) from the non-phenolics
n-butanol solubles column, were dissolved in methanol and adsorbed on
3 g of silica gel § 1, and applied at the top of a florisil column (100
g, 60-100 mesh, 2.5 cm id x 40 cm l). Two liters of chloroform,
followed by three liters of chloroform-methanol (9s1) were used as
eluent. Fractions of 1000 drops (15 ml) were collected with an automa
tic fraction collector. The combined fractions I56-I86 (0.2? g)
contained glucoside X. Further trials for purification were unsuccesful.
Acid Hydrolysis of Glucoside X .
Glucoside X (5 mg) was dissolved in 1 ml of 0.5 N sulfuric acid.
The reaction mixture was then heated at 95°C for 90 minutes, then calcium
hydroxide (20 mg) was added. The reaction mixture was filtered and the
filtrate was evaporated to dryness. Glc analysis of the TMS-derivative
of the residue was carried out as described for 7-chlorodeutziol. The
presence of glucose was determined from this analysis.
Column Chromatography of The Water Solubles Fraction.
The aqueous fraction obtained from the fractionation scheme of
Mentzelia decapetala (40 g) (figure 2), was dissolved in 50 ml of water
and poured into a charcoal column (250 g of activated charcoal alkaline,
Norit A, Fischer Sci. Co.; 10 cm id x 10 cm 1, scintered glass column).
Increasing amounts of ethanol in water were used as eluent (table 2).
This eluent was forced out of the column by the use of a water vacuum
pump. The different fractions obtained were collected according to the

85
vanillin-hydrochloric acid test for iridoids. Fractions 7-13 gave a
positive iridoid test and were further purified on silica gel 60 column.
Column Chromatography of The Water Solubles-Irldoid Fraction.
An iridoid positive fraction (18.5 g) from the water solubles-
charcoal column was dissolved in methanol and adsorbed on 37 g of silica
gel # 1 and applied on the top of a silica gel column (1kg, particle
size 0.063-0.2 mm, EM Reagents, 7*5 cm id x 60 cm l). Chloroform-
methanol (9si) was used as eluent. Fractions of 170 ml were collected
after an initial 1.7 liter of hold-up volume. The fractions were
combined according to the tic analysis with solvent systems I and II,
and to the weight profile. The resulting fractions are presented in
table 3*
Purification of Decaloslde.
The combined fractions 124— 143 (1.0 g) of the iridoid-water solubles
column were dissolved in methanol and adsorbed on 2 g of silica gel # 1,
and applied to the top of a silica gel 60 column (100 g, 0.063-0.200 m
mesh, 2.2 cm id x 48 cm 1). Ethyl acetate-methanol (6sl) was used as
eluent. Fractions of 900 drops (14 ml) were collected. Tic analysis
indicated the presence of decaloside in fractions 61-130.
Physiscal and Spectral Data for Decaloslde.
Decaloside was obtained as a white crystalline hygroscopic material
It had a mp 190°C (lit. 193°C); Its Si-nmr (DgO, figure 60 ) had the
following signals at 6 (ppm): 6.25 (br.s., H at C-3), 5.88 (br.s., 2H,

86
H's at C-7 and C-8), 5-*3 (d» J 7-3 Hz, H at C-l), 2.69 (m, H's at C-5
13
and C-9). The C-nmr (i^®) presented is tahle 4.
Acetylation of Decaloside.
Decaloside (130 mg) wa-s dissolved in 2 ml of pyridine and 2 ml of
acetic anhydride was added. After two hours on a steam hath, methanol
and toluene were added and the mixture was evaporated to dryness. An
oily dark "brown material was obtained which was dissolved in chloroform.
and upon addition of ethanol a crystalline material was obtained. Upon
filtration and recrystallization from ethanol 53 nig of decaloside
hexaacetate were obtained. Its mp 164-5°C is comparable with that of
the literature (162-4°C). The ^H-nmr (CDCl^, figure 61 ) is superimpos-

13
sable with that of decaloside hexaacetate. The C-nmr (CDCl^) is
presented in figure 62 t table 5-
Purification of Glucoside V .
The combined fractions 158-194 (3 g) from the iridoid water soluble
column, yielded a white amorphous precipitate which tends to decompose
upon exposure to the light. Purification of this fraction through
activated charcoal (? g) with water and methanol used as eluents,
yielded a syrup (2.8 g). A sample of this syrup (2 g) was dissolved in
methanol and adsorbed on 5 g of florisil and applied on the top of a
florisil column (65 g, 100-200 mesh, 2.5 cm id x 30 cm l). With
chloroform-methanol (3*1) used as eluent. Fractions of 999 drops were
collected. The combined fractions 111-160 yielded glucoside V as a
hygroscopic, white amorphous powder (210 mg). The compound presents one
87
homogeneous spot both in tic and paper chromatography.
Spectral data for Glucoside V .
Glucoside V could not be obtained as a crystalline material. Its
*H-nmr (CD^GD, figure 6 3 ) presented the following signals at 6 (ppm):
6.47 (br.s., H at C-3), 5-91 (br.s., 2H, H's at C-7 and C-8), 3.10-4.60
(protons base of hydroxyl functions), 2.77-2.94 (m, H's at C-5 and C-9).
13
Its ^C-nmr (lÔ* figure64 ) had the following signals at 6 (ppm): (1)
98.4, (3 ) 141.2, (4) 113.4 , (5 ) 44.5, (6) 80 .8 , (7) 135.9, (8) 133-9,
(9) 47.5, (10) 69.9, (1') 101.7, (2») 73.7, (3’) 76.8, (4') 70.2, (5’)
76.3 , ( 6') 6 1 .3 , (1") 99.4, (2") 73.3, (3") 76.5, (4") 70.2, (5") 76.3,
(6") 61.3 . No mass spectrum could be obtained since the compound is
not volatile enough.
Acid Hydrolysis of Glucoside V .
Glucoside V (5 mg) was dissolved in 1 ml of 0.5N sulfuric acid.
The reaction mixture was heated at 95°C for 90 minutes. The material
began to turn black at 70°C. After 90 min. calcium hydroxide (20 mg)
was added, then the reaction mixture was filtered and the filtrate was
evaporated to dryness. Preparation of the TMS-derivative and glc
analysis was carried out in the same conditions described for 7-chloro-
deutziol. From this analysis the sugar moiety was identified as glucose.
88
Acetylation of Glucoside V .
Glucoside V (113 mg) was dissolved in 1 ml of pyridine and 1 ml of
acetic anhydride was added. After one hour on a steam hath methanol and
toluene were added to the reaction mixture. Evaporation of the excess
reagents yielded an oily residue (180 mg) which was adsorbed on silica
gel # 1 (1 g) and applied on the top of a silica gel 60 ^ 23^ column
(I2gf 1 cm id x 25 cm l) with hexane-ethyl acetate (1:1) as eluent.
Fractions of 100 drops (2 ml) were collected. From combined fractions
63-67 a crystalline material was obtained. It had the following
physical and spectral data: mp. 153-5° C; |[of]2^D -128° (c 2.8, CHC1^)»
the ir (CHCl^) showed no signals for free hydroxyl groups and vmax at:
1?60, 1660, 1380, 1220, 1040 cm-1. The ^H-nmr (CDCly 90 MHz, figure 65)
presented signals at 6 (ppm): 6 .3I (br.s., H at C-3)» 6.05 (dd, J 6Hz,
H at C-6), 5.89 (dt, J 6Hz, H at C-7), 5.63 (m, H at C-6), 5.34-4.81
(signals for protons base of acetates and glucosidic protons), 4 .36-
3.74 (remaining primary acetates and H's at C-10), 3*07-2.79 (two m, H's
at C-5 and C-9), 2.08-1.99 (acetate signals, integrates for 9 acetates).

13
The C-nmr (CDCl^, figure 66 ) had the following signals: (l) 96.2,
(3) 1^0.3, (4) 111.3, (5) ^ . 2 , (6) 81.9, ( ? ) 132.0 , (8) 136.1 , (9 )
47.0, (10) 69.3, (1 *) 96.4, (2’) 70.8, (3*) 72.8, (4') 69.3, (5*) 72.2,
(6‘) 6 2 .0 , (1") 100.1, (2 ") 71.5, (3”) 72 .0 , (4”) 69.3 , (5”) 73.1, (6")
62.0, plus acetate signals at ~ 170 and ~ 20 ppm.
Hydrogenation of Glucoside V .
Rhodium on charcoal (50 mg, 5% MCB), was suspended in 4 ml of
ethanol and saturated with hydrogen for a six hour period, then a
solution of glucoside V (200 mg) in 1 ml of water was added and the
reaction was maintained under a hydrogen atmosphere at 20°G for 3*5
hours. The suspension was then filtered through a scintered glass
funnel and the residue was washed with methanol. The filtrates were
concentrated under vacuo and the residue (200 mg) was adsorbed on 2 g
of silica gel # 1 and applied on the top of a silica gel G column (20g,
1 cm id x 25 cm l). Methanol-chloroform (1 :3 ) was used as eluent.
Fractions of 250 drops were collected. Combined fractions 81-160
yielded 110 mg of 3i4-7»8 tetrahydro-glucoside V. It had an Rf 0.1 in
chloroform-methanol (3:1)» silica gel plates. Its ^H-nmr (Dg0 )
following signals at 6 (ppm) 5*09 (br.s., H at C-l), 4.47 ( H at C-l')»
4.28-3-16 (protons base of the hydroxyl groups), 1 .18-2.07 (protons for
C-4, C-6 and C-7).
Emulsin Hydrolysis of 3,4-7.8-Tetrahydro-glucoside V .
The tetrahydrocompound (50 mg) was dissolved in 0.5 ml of distilled
water and 20 mg of emulsin was added. After eight days at room
temperature, the reaction mixture was evaporated to dryness and extracted
with a hot mixture of equal parts of chloroform-methanol-ethanol-ethyl-
acetate. Evaporation of the extract gave a residue (53 mg) which wan
dissolved in methanol and adsorbed on silica gel # 1 and applied on the
top of a silica gel # 5 column (I5g» 1 cm id x 19 cm l) with chloroform-
methanol (3*1) used as eluent. Fractions of 50 drops were collected.
The combined fractions 3 1 - 6 0 contained 15 mg of the aglycone ^4 which
had an Rf 0.62 in chloroform-methanol (3*l)» silica gel plates. The
*H-nmr (Ryridine-d^) presented the following signals at 6 (ppm): 5.36

90
(d, J 4 Hz, H at C-l), 4.63 (m, H at C-6), 4.15-4.41 (complex signal
for H's at C-10), 4.07 (m, H's at C-3), 2.75. 2.54 (m, H's at C-5 and
C-9), 1.70-2.26 (m, H's at C-4, C-6 and C-7)* The *^C-nmr (pyr-d*.)
had the following signals at 6 (ppm): (l) 95-9, (3) 63.5. (4) 25.7, (5)
42.0, (6) 75.3, (7) 33.5, (8) 37-3, (9) 46.7, (10) 61.8.
Acetylation of Aglycone 54
Aglycone j>4 (15 ms) was dissolved in 1 ml of pyridine and acetic
anhydride (1 ml) was added. The reaction mixture was maintained on a
steam bath for two hours. Evaporation of the reaction mixture, after
this time produced a residue which was dissolved in hexane-ethyl acetate
(65:35) and applied on the top of a silica gel 60 TF254 c°lUII,in (5 g,
5 cm id x 10 cm l). Hexane-ethyl acetate (65:35) was used as eluent.
Fractions of 1 ml were collected. Combined fractions 9-13 yielded the
triacetate 55. » which had an Rf O .63 in hexane-ethyl acetate (1:1) as
eluent in silica gel plates. The ^H-nmr (CDCl^, figure 67 ) had the
following signals at 6 (ppm): 6.01 (s, H at C-l), 5»i3 (d, J 4.4 Hz, H
at C-6 ), 4.40-3.40 (complex signal for H's at C-3 and C-10), 2.50-2.23
(m, H at C-5 and C-9), 2.12, 2.06, 2.03 (3 Acetates singlets), 1.25-
1.90 (H's at C-7 and C-8 ).
Acetylation of Tetrahydro-glucoside V .
Tetrahydro-glucoside V (30 mg) was dissolved in 1 ml of pyridine and
acetic anhydride ( 1 ml) was added. The reaction mixture was maintained
on a steam bath for one hour, then methanol and toluene were added and
the solution was evaporated to dryness. The resulting acetate had the
91
following datas 1H-nmr (CDCl^) had the following signals at 6 (ppm):
5.63 (t, H at C-6), 5.24-4.75 (m, for protons base of acetates),
4.18-4.14 (m, H's at C-10), 2.15-2.02 (for 9 CH^-CO), 1.87-1.64 (m,
for H's at C-4, C-7, C-8 ).
Acid Methanolysis of Tetrahydro-glucoside V .
Tetrahydro-glucoside V (95 mg) was dissolved in 1 ml of spectra
grade methanol and added to a 50 mg sample of cation exchange resin
(AG 50W-X12, 200-400 mesh, hydrogen form-sulfonic acid, Bio-Rad lab),
which was previously washed with 1 ml of spectra grade methanol. The
reaction mixture was stirred in an anhydrous environment for one hour,
then filtered through 50 mg of Amberlite CG-4B (100-200 mesh, weakly
basic, polyamine-phenol formaldehyde type, anion exchange resin, RNH* OH
Mallinckrodt). The resin was washed with methanol and the obtained
filtrates were concentrated under vacuo. The residue (105 mg) was then
dissolved in 1 ml of solvent system I and applied at the top of a silica
gel 60 ^ 2 5 4 c°lumn (6 g, 0.5 cm id x 20 cm l) . Solvent system I was
used as eluent. Fractions of 50 drops were collected. The combined
fractions 21-25 (16 mg) contained l-0-methyl-10-glucosyl-decaloside
which had an Rf 0.19 in solvent system I and silica gel plates. The
H-nmr ( ^ O ) indicated the presence of the following signals at 6 (ppm):
5.33 (s, H at C-l), 4.20-3.30 (glucosyl residue), 3.25 (s, OCH^), 1.47-
1.98 (complex pattern for H's at C-3, C-6 and C-7). The mass spectrum
indicated the presence of M+ - OCH^ at 332 (1.6$); M+_ OCH3- Glu at 171
(14 %) among other fragments.

92
Acetylation of l-()-Methyl-10-Glucosyl-decaloside (j>6).
Compound ^ 6 ( 8 mg) was dissolved in 0.2 ml of pyridine and acetic
anhydride (0.2 ml) was added. The reaction mixture was maintained on
a steam hath for two hours. After this time the reaction mixture was
evaporated to dryness. The residue (15 mg) was dissolved in 1 ml of
hexane-ethyl acetate (is) and applied on the top of a silica gel 60
column (10 g, 1 cm id x 12 cm l) with hexane-ethyl acetate (1:1)
as eluent. Fractions of 50 drops (1 ml) were collected. Combined
fractions l?-25 (5 mg) contained 1-O-methyl-lO-glucosyl-decaloside
pentaacetate j?7. It had an Rf 0.37 in hexane-ethyl acetate (1:1) with
silica gel plates. The ^H-nmr (CDCl^) presented the following signals
at 6 (ppm): 5*53 (m, H at C-l), 5*1^-^*81 (complex signal of protons
base of acetates), 3*36 (s, OCH^), 2.16-2.02 ( singlets for acetates,
integration five acetates), 1.99-1*21 (m, for H's at C-4, C-6, and C-7).
Permethylatlon of Tetrahydro-glucoside V.
Tetrahydro-glucoside V (30 mg) was dissolved in 1.2 ml of
dimethyl sulfoxide (distilled over calcium hydride and kept under
molecular sieve), and to this solution 0.5 ml of dimethylsulfinyl anion
was added - prepared by warming sodium hydride (750 mg) in the presence
of dimethyl sulfoxide ( 15 ml) at 50°C for one hour under stirring in a
nitrogen gas flow - The reaction mixture was stirred at 26°C for 1.5
hours.. This solution was then cooled at 20°C and methyl iodide (1 ml)
was added. The reaction mixture was left at 25°C for 15 minutes. After
this time, distilled water (20 ml) was added and the mixture was
extracted with 4-5 ml portions of chloroform. The chloroform extracts

93
were washed with water and concentrated under vacuo. The residue (10
mg) presented two spots on tic. Rf 0.40, O .38 with benzene-ethanol-water
ammonium hydroxyde 200:47:15*1 as solvent and silica gel plates. No
starting material was evident.
Hydrolysis of the Permethylated Product.
The above residue (10 mg) was dissolved in 0.16 ml of sulfuric
acid (72^) at 0°C, and the reaction mixture was allowed to stay at 0°C
for one hourj then the reaction mixture was diluted with 1.44 ml of
water and the temperature was raised to 100°C. The solution was kept
at 100°C for four hours, then the reaction was cooled and extracted
with chloroform. The chloroform extracts were evaporated under vacuo.
Glc analysis of this residue was done under the following conditions:
column: 5% neopentyl-glycol succinate on chromosorb-w (60-80 mesh),
4 mm x 1.58 mj column temperature 180°C, carrier gas He (20 psi);
detector temperature 250°C; injector temperature 200°C. From this
analysis 2,3»4,6, tetra-O-methyl-D-glucopyranoside was detected . It had
a retention time (min) 5*3 (3 )» ?•! (<*)> as compared with an authentic
sample prepared by permethylation and hydrolysis of glucose and of
maltose.
Isolation of Glucoside VII.
The combined fractions 158-194 ( 3 g) from the iridoid-water
solubles column were passed through activated charcoal (as in isolation
of glucoside V). A sample (0.8 g) from the obtained syrup was adsorbed
on silica gel # 1 (2 g) and applied to the top of a silica gel 60

94
column ( bOO g, 4.3 cm id x 63 cm l) with chloroform-methanol (3:1) as
eluent. Fractions of 999 drops were collected. Combined fractions 151“
180 yielded glycoside VII (180 mg) as an amorphous white precipitate.
Spectral data for Glycoside VII.
Glycoside VII could not be obtained as a crystalline material.
Its *H-nmr (D2°» figure 68) presented the following signals at 6 (ppm):
6.32 (br.s., H at C-3), 5.94 (br.s., 2H. H's at C-? and C-8), 2.94-3.28
(complex signal for protons base of alcoholic functions), 2.71 (m, H's
at C-5, and C-9), 1.17-2.00 ( a complex signal for a methylene group,

13
The J C-nmr (DgO, figure 6 9 ) had the following signals at 6 (ppm):
(1) 98.3. (3) 141.2, (4) 113.3, (5) 44.4, (6) 80.7, (7) 133-9, (8) 135-8,
(9) 47-5, (10) 64.2, (1‘) 102.0, (2') 73-2, (3') 76.8, (4’) 70.1, (5‘)
76.2, (6') 61,2, six carbons corresponding to a deoxy-sugar at : 99 . 2 ,
7 5 . 5 , 7 1 -0 , 73-2, 6 9 .8 , and 34.8.
Acetylation of Glycoside VII.
Glycoside VII ( 50 mg) obtained from fractions 144-157 of the
iridoid-water solubles column, was dissolved in 2 ml of pyridine and
acetic anhydride (2 ml) was added. The reaction mixture was maintained
on a steam bath for two hours. Evaporation of the excess reagent
yielded a brown syrup (90 mg) which was adsorbed on silica gel 60 (1 g)
and applied to the top of a silica gel # 6 column (10 g) with benzene-
ethyl acetate (3:1) as eluent. Fractions of 50 drops were collected.
The combined fractions 26-40 yielded 74 mg of material which was
further purified through silica gel 60 (8 g, 1 cm id x 8 cm 1) with

95
hexane-ethyl acetate (1«1) as eluent• Fractions of 50 drops were
collected. Combined fractions 81-100 yielded 43 mg of glycoside VII-
octaacetate which was crystallized from chloroform-ethanol. The
ocatacetate 60 had a mp. 152-3°C ; [a]23D -103° (c 4.3, CHCl^); the ir
(CHCl^) indicated the absence of free hydroxyl functions and the
presence of acetate bands at vmax 1?60 era-* . The *H-nmr (CDCl^, figure
7 0 ) presented signals at 6 (ppm): 6.30 (s, H at C-3), 6.09 (dd, H at
C-7), 5*93 (dd, H at C-8 ), 5*60 (m, H at C-6 ), 5.23-4.?8 (signals for
the protons base of acetates and glycosidic protons), 4.43-3*73
(remaining primary acetates and H's at C-10), 3*07, 2.78 ( 2 m , for H's
13
at C-5 and C-9), 2.08-2.00 ( 8 acetate signals). The C-nmr (CDCl^,
figure 71) had the following signals: (l) 96.5, (3) 140.2, (4) 111.6 ,
(5) 40.4, (6 ) 82.2, (7) 132.2 , (8 ) I36.O, (9) 47.0, (10) 68.8, (1‘)
9 6 .5 , (2') 70.9, (3') 72.8, (4') 69.6 (5 ') 72.3, (6') 6 2 .0 , the signals
for the deoxy sugar appeared at : 100.5 , 71*7, 32.9, 70.9, 68.8, 6 5 .5 ,
plus acetate signals at ~ 170 and ~20 ppm. Analysis calculated for
C37Hw 02 1 : C, 53.62#; H, 5.84^. Found: C, 53*83^1 H, 5*9256.
Acid Hydrolysis of Glycoside VII.
Glycoside VII (4.4 mg) was dissolved in 2 ml of 2.ON hydrochloric
acid and the reaction mixture was heated on a steam bath for 45 min.
A black tar appeared upon heating. The reaction mixture was then
filtered through polyamide (1 cm^), and the adsorbent was washed with
distilled water. The combined filtrates were concentrated under vacuo
and dissolved in 0.05 ml of distilled water. Paper chromatography was
carried out with ethyl acetate-pyridine-water I2s5«4 as eluent. After

96
development and evaporation of the eluant* the chromatogram was
sprayed with a 1% solution of p-anisidine hydrochloride in n-butanol.
The chromatogram was then heated at 100°C for 5 minutes. Two spots
were present for the hydrolyzate: the first one Rf 0.45 corresponded
to glucose, as compared with a reference sample. The second one Rf 0.55
belongs to the deoxy sugar.
Cleavage of Glycoslde-VII-Ocatacetate.
Glycoside-VII octaacetate (32 mg) was dissolved in one ml of ethyl
ether-acetic anhydride mixture (1:1), and boron trifluoro ethereate (0.2
ml) was added. The mixture was stirred at 0°C and slowly allowed to go
to room temperature (during a period of 12 min.). The mixture was then
cooled and pyridine (1 ml) and a 5% solution of sodium bicarbonate (1 ml)
and ice was added. The reaction mixture was stirred on an ice bath for
15’ » and then it was extracted with 3-5 ml portions of ethyl ether and
chloroform. The organic extracts were combined and dried. Tic analysis
of the residue indicated the presence of decaloside hexaacetate (Rf 0.72
ether; Rf 0.38, hexane-ethyl acetate 1:1), as well as a spot with Rf
0.93, ether; Rf 0.64, hexane-ethyl acetate (1:1), that corresponds to
the deoxy sugar acetate.
Isolation and Identification of Scopoletin.
Scopoletin crystallized out upon concentration of the methanol
solubles (figure 2) of the partition scheme. The crystalline material
was filtered and recrystallized from methanol to yield 122 mg of
colorless needles. It had a mp. 204°C (Lit. 204°C), [ofP^D 0.0 (c 1.6,
CHÔH). The uv (CHÔH, c 0.48#) had the following signals at Xmax
(log 6): 345 (4.07), 298 (3.68), 262 (3-63). 252 (3-68), 229 (4.11).
(CHÔH-NaOMe): 390 (4.36), 278 sh (3*64), 242 (4.03. The 1H-nmr
(CDÔD, 60 MHz, figure 72 ) presented the following signals at 6 (ppm)i
7.82 (d, J 10 Hz, H at C-3), 7.10 (s, H at C-5), 6.75 (s, H at C-8 ),
6.18 (d, J 10 Hz, H at C-4), 3*90 (s, OCH^). The mass spectrum had a
molecular ion peak at M+ 192 (0.8$) alongside with M-15 m/e 177 (0.3$),
M-29 m/e I65 (0.4$), M-43 m/e 147 (100$), 118 ( 35% ). All of these
data are in agreement with the reported literature values (mp, uv, ms)
for scopoletin.
Separation of the Tertiary and Quaternary Alkaloidal Fractions.
The ethanolic extract (1.1 kg), obtained after percolation of 6 kg
of M. decapetala tops with 300 liters of ethanol, was concentrated
under vacuo using a steam-heating distillation apparatus followed by a
rotary evaporator. Prom this extract, 1.1 kg was dissolved in 2$ citric
acid solution ( 5 liters) and filtered. The filtrate aqueous solution
was extracted with 4-5 liters portion, of ethyl acetate. The ethyl
acetate solution was concentrated to a small volume, then washed with
2$ citric acid solution and dried with anhydrous sodium sulfate.
Concentration of the ethyl acetate yielded 28 g of residue.
The remaining acid solution was extracted with 2-6 liter portions
of chloroform. The chloroform extracts were washed, dried and
concentrated as above yielding 1.6 g of chloroform solubles.
The aqueous phase was brought to pH 8 with ammonium hydroxide
solution (250 ml) and extracted with chloroform. The chloroform residue
constitutes 3 g of tertiary alkaloidal fraction.
The aqueous solution remaining after the isolation of the tertiary
alkaloids was acidified with glacial acetic acid to pH 4, and 2 liters

98
of a 2% ammonium reineckate solution were added. The precipitate
formed was collected and-dried, yielding 32 g of reinecke salts. The
reinecke salts were dissolved in 50$ aqueous acetone and filtered. The
filtrate solution was poured into an ion exchange resin column (454 g,
Amberlite IRA-410 GP, Mallinckrodt). The filtrate was passed through
the column five times, then it was dried under vacuo. Quaternary
alkaloids (14 g) in the chloride form were obtained.
Column Chromatography of the Tertiary Alkaloids.
The tertiary alkaloids (3 g) obtained from the above fractionation
scheme, were dissolved in methanol and adsorbed on silica gel # 1 , then
applied on the top of a silica gel 60 ^ 2 5 4 co^-UInn ( ^ 0 S t 4.6 cm id x
70 cm 1 ) with chloroform, and increasing proportions of methanol in
chloroform used'as eluent. Fractions of 75 ml were collected. From
fractions 22-30 (eluted with chloroform) a crystalline material was
obtained which was identified as scopoletin. No further data was
obtained from this column.
Column Chromatography of The Quaternary Alkaloids.
The quaternary chlorides (11.4 g) were adsorbed on siljca gel # 1
(20 g) and applied to the top of a silica gel 60 PF^ ^ column (1.3 kg»
8.6 cm id x 70 cm 1 ), with chloroform and increasing amounts of methanol
in chloroform used as eluent. Fractions of 150 ml were collected.
From fractions 187-213 (eluted with chloroform-methanol 4:1) choline
was obtained. It was identified on the basis of the ir and nmr spectra
as compared with those of a reference sample, and tic and co-tlc
analysis (Rf 0.50, silica gel, ethyl acetate-acetic acid-water 1:1:1 ;
and Rf 0.46, silica gel, n-butanol-acetic acid-water 4:1:1).

Pharmacological Studies on the Extracts and Isolated Compounds.
Hypotensive_activity
In a typical experiment, dogs of either sexes weighing 7.5-12.5 kg
were utilized. The dogs were anesthetized with 35 ®g/kg of sodium
pentobarbital,iv . The trachea was cannulated as well as the right

carotid artery and the arterial blood pressure was recorded via a
linear core transducer (Narco Bio-System, Inc.) connected to a
physiograph. The femoral vein was isolated and cannulated for the
administration of the test solution.
The mean blood pressure was determined as follows: Mean blood
pressure (MBP) = diastolic blood pressure (DBP) + 1/3 pulse pressure
(PP). Pulse pressure (PP)= systolic pressure - diastolic pressure.
A change of -50 units in the mean arterial pressure of dogs was
obtained when a dose of 8.3 mg/kg of an ethanolic extract of quaternary
chlorides was injected into the animal. A similar effect was observed
when a dose of 1 mg/kg of choline chloride (in 0.9% saline solution)
was administered. The different iridoid glycosides were admininstered
in doses as high as 10 mg/kg without any visible change in the mean
arterial pressure.
The hypotensive activity in rabbits was studied using animals of
either sex with average weight 2.5 kg, using as anesthetic nembutal, ip.
The blood pressure was determined in a similar manner to that described
in the experiments for dogs.
A change of -25 units in the mean arterial pressure of rabbits was
observed when a dose of 10 mg/kg of the water soluble extract of
M. decapetala (in 0.9 % saline solution) was administered. The
different iridoid glycosides did not show any apparent change in the
mean arterial pressure at the same dose level.

100
Antibiotic Assay.
Antibacterial testing for plant extracts was carried out using the
agar dilution assay. For this purpose, a 0.2 ml ethanolic solution
containing 10 mg of the sample were mixed with 10 ml of sterilized
tripticase-soy agar medium and poured into a Petri dish. The plates
were allowed to set and the test organisms were streaked upon the plates.
The presence of growth of the organisms after 2*4- hours in the media
indicated no antibacterial activity at a 100 jig/ ml level.
The test organisms used were:
Staphylococcus aureus Smith strain ATCC 13709 (gram positive)
Escherichia coli 9637 (gram negative)
Salmonella gallinarum 918*4- (gram negative)
Klebsiella pneumoniae AD 10031 (gram negative)
Mycobacterium smegmatis 607 B 607 (acid fast)
Candida albicans (yeast)
A positive and a negative control were used alongside with the
following samples! ethanolic extract of M. decapetala; rutin, scopoletin.
Under the above conditions the samples tested produced no activity
at a 100 (ig/ml level.
Antifungal_Activity.
Cladosporium assay s Tic assay,- The sample (0.2 mg) was dissolved in
methanol and spotted on a 5 x 20 silica gel plate and developed with
chloroform-methanol (3si). After developing, the plate was dried
throughly and it was sprayed with an aqueous suspension of Cladosporium
aucumeles spores, until the plate was damp . Then the plate was
101
sprayed with molten potato dextrose agar (made up at ■§■ the normal
concentration). The plate was then light incubated at 2 2 ° C in a
moisture chamber, to allow for spore germination. After ?2 hours the
plate was removed and allowed to dry, then it was examined for signs of
inhibition of spore germination. When the isolated iridoid glycosides
of M. decapetala were tested, no inhibition zones were evident for
all of the samples.
Phytophtora zoospore assays The iridoid samples were dissolved in
water, and then mixed with molten sucrose-asparagine media and poured
into 3*5 cm petri dishes, then inoculated with a 0.1 ml of a zoospore
suspension. Final concentration of the sample s 200 ppm. Spore
germination was counted after three hours. Sporangia counts were made
after k days, representing the number of sporangia per field at 2l0x
magnification. The sporangia counts in the iridoid containing plates
did not show any difference to those of a negative control. It was
concluded that the iridoid samples did not have any antifungal activity
under the above conditions.
Antifeeding Test.
Briefly, the test consisted of measuring the extent of feeding by
third-instar insects on a diet composed of the ethanolic plant extract
residue admixed with cellulose, agar, and water. The extracts that
gave diets acceptable to the insects corresponded to host plant material.
For example, red oak (Quercus rubra L.) leaves, which are readily fed
on in the field, gave acceptable extracts. Residues yielding unaccepted
diets could be divided into three distinct groups on the basis of the
feeding response observed when the extract was tested In combination
with the red oak diet. Those that did not inhibit feeding were
classified as neutral. Extracts that reducing feeding were classified
as inhibitory or deterrent, while the third group which produced an
increase in diet consumption above the red oak response were called
synergistic (31).
An ethanolic extract of M. decapetala indicated no feeding
inhibition. The extract tested at 1.0 gm gave 29% feeding, but when
0.25 gm was admixed with 1.0 gm of red oak extract 119^ feeding
resulted. The low feeding on the extract alone indicated lack of
feeding stimulants in M. decapetala.

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+
1. M.L. Femald, "Manual of Botany" 8 Ed. American Book Company,
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103
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20. J.W. Comforth, R.H. Comforth, and K.K. Mathew, J. Am. Chem. Soc.,
112 (1959).
21. H. Inouye, S. Ueda, and Y. Nakamura, Tetrahedron Lett., No. 43,

5229 (1966).
22. M.L. Scarpati, and P. Esposito, Gazz. Chim. Ital., ££,1209 (I967).
23. P.A. Sanford, and H.E. Conrad, Biochemistry, £, 1508 (1966).
24. T. Endo, and H. Taguchi, Chem. Pharm. Bull., 21:12, 2684 (1973).
25. C.A. Bliss, and E. Ramstad, J. Am. Pharm. Assoc.. 46:1, 15 (1957).
26. Z. Kowalewski, 0. Schindler, H. Jager, and T. Reichstein, Helv.

Chim. Acta., 4^:161, 1280 (i960).
27. M.M. Ballantyne, P.H. McCabe, and R.D.H. Murray, Tetrahedron, 27,
871 (1971).
28. S.S. Popov, J.C. Ivanov, P.P. Panov, Compt. Rend. Acad. Bulg. Sci.,
2£:9, 1225 (1972).
29. H. Inouye, K. Uobe, M. Hirai, Y, Masada, K. Hashimoto,

J. Chromatogr., 118, 201 (I976).
30. T.J. Mabry, K.R. Markham, and M.B. Thomas, "The Systematic
Identification of Flavonoids", Springer-Verlag, New York, (1970).
31. R.W. Doskotch, T.M. ODell, and P.A. Godwin, Qiviron. Eiitomol., 6,
563 (1977).
104
SPECTRA APPENDIX
105
Figure 12. IR Spectrum of Rutin (KBr).
MeOH
.— MeOH-NoOMe
OH
HO
HO
MeOH—NaO Ac
+ HCI H0BO
V.
Mi
wm
»:
Figure *3* UV Spectrum of Rutin.

3.0 3.0 4.0 5.0 7.0 0.0 9.0
os
OH
OH
HO
Rutinosyl
HO
7.0 6.0 5.6 > P M(i) 4.0 3.0 3.0 1.0
Figure 14, H-NMR Spectrum of Rutin (CDÔD) .

IS 13
097880988879888798787
t kami mi spon
Mm mo MO
Figure 15• IR Spectrum of 7-Chlorodeutziol (KBr).

o
VO
HQ CH.
HO OGIu
Lnii1111 11 1111111 11 11 1 1 1 1 1 i i . 1 11 1 11 1. 1 1 1 1 i i 1 1 1 1 . . I , i 1 1 i , 111111. 1 1 . . i «1 ................. I ..........................I

10- 9 .0 8 .0 7 .0 6 .0 5 .0 ^ , ) 4 .0 3 .0 2 .0 1 .0 0
Figure 16. *H-NMR Spectrum of 7-Chlorodeutziol (Dg0 )*
110
OGIu
Im iln iiliin lin ilim l U »nliiiiliiiiliiiiliiiiliiiil » „ i|i„ il m illiiil„„i,l..|....i....|....i....|.... ..... .
2 0 0 190 1 80 170 160 150 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
PPM ( < 1
Figure 17. ^C-NMR Spectrum of 7-Chlorodeutziol (DgO).

CH.
AcO OGIu (Ac)
VA.
JL A. ^ _________
u -*'jl u i I | H I I I I I t.l l l I > 1 I i i i L i m liiii I I I I I 1 I ! I I I I I n l! I I t l m I I m I I l h l I I I I ill i l l !

8 0 7 .0 6 .0 5 .0 , 4 .0 3J0 2 .0 1 .0 0
rrM ( I )
Figure 18. ^H-NMR Spectrum of 7-Ghlorodeutziol-Hexaacetate (CDGl^).

AcO OGIu( A c ) 4
- A .
___________I
.......... ■ ■ l . . , . l . n . L . n l i m l . n i l n n l m i l n i i l i m l i m l i m l i m l i m l i i i i l i i i i l i i i i J
2 0 0 190 180 170 160 150 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
rrMi t )
13
Figure 19« C-NMR Spectrum of 7-Chlorodeutziol-Hexaacetate (CDCl^).
o
o
INTENSITY
ID
o 4 0 0 5 0 0 6 0 0
io
REL.
in
(\i
I i i i i 1 ll^ U l i* f 1 1 1 ^ i 1 1 I i i | i i f f t r 1111 m 11r i i i i 11111 r m t pr t n
100 200 3 0 0 4 0 0 5 0 0 6 0 0
M/E
Figure 20. Mass Spectrum of 7-Chlorodeutziol Hexaacetate.
HQ
HO OH
I I I I I LL> I I L l I I I I I L- L 1 1 I I I I I I I I L I I 1 I t . » 1 I I 1 I I 1 I t 1 l I I m I l l i l I l n l I I I l l I I H I I I H I I I.L 1 t.J

•-0 7 .0 6 .0 5 .0 4 .0 3J0 2 .0 1.0
ffM ( I )
Figure 21. ^H-NMR Spectrum of 7-Chlorodeutziol Aglycone (CDÔD).

HQ CH
Clf
OH
■i *•<
I I ' ' MI ' " Ti ^ (flffI r n *"1 ' PTnf ‘ j ," ': r (- | - i i ? i ,
HIHHiliml Imilitului .1.1.il l.l .l

liiiilimtniilinilin
200 160 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 SO 4 0 3 0
P T M (< )
13
Figure 22. C-NMR Spectrum of 7-Chlorodeutziol Aglycone (Acetone-d^).
AcO CH
AcO OAc
l-t-L I I I L I I I I .. I _i_L I-l.JLJ.J-Lj-)- L )- L J.

8.0 7 .0 6.0 5 .0 4 .0 3 .0 1.0
Figure 23. *H-NMR Spectrum of 7-Chlorodeutziol Aglycone Triacetate (CDCl^).

o
INTENSITY
REL.
CM "
0 100 200 300
M/E
Figure 24. Mass Spectrum of 7-Chlorodeutziol Aglycone Triacetate.
00
OGIu
LI l l m i l n n I m i l i i n l n u U n i l i . n l . ■ LI I I. H 1 L ... 1 I I . I I ■ I I I 1 H I I I LI I I I M l I I I m l
•-0 7 .0 6 .0 S .0 4 .0 3J0 2 .0 1 .0 0
PfM( I )
Figure 25. 1H-NMR Spectrum of 3,^-Dihydro-7-Chlorodeutziol (CDÔD).

CH
AcO OGIu (Ac)
1 1
8.0 7 .0 6.0 5 .0 4 .0 3J0 2.0 1.0
Figure 26. H-MMR Spectrum of 3i^~Dihydro-7-Chlorodeutziol-Hexaacetate (CDCl^)*

100
INTENSITY
75
50
REL.
25
Figure 2?. Mass Spectrum of 3 ,4-Ditydro-7-Chlorodeutziol Aglycone.
T2T
H0
O G Iu
li^l 11I 1IIIIIIII

II 11 Ii III1 IIM 1 IIIIIn 11 IItII I1 1 ..I■iliIili1 1.iii1n ii1iiiiIiii!» n n Iiin In iiIiiiiI
,a 9 0 8 0 7 .0 6 .0 5 .0 p w ( |, 4 .0 3 .0 2 .0 |. 0 0
Figure 28. 1H-NMR Spectrum of Mentzeloside (DgO).
122
HO ch3
>Glu
PPM( I )
Figure 29. l3C-NMR Spectrum of Mentzeloside (DgO).

K>
Ac q
G lu(A c)
L u l l L A I I I 11 I 1 t I I I 1 I I I L I I I l_L L l i i i I h i i I I I Li I i I I I I I i LI I I i I I I I I I i 1 ui, n I i i.i tl n n l

M 7 .0 6 .0 SO ^ « W 1.0 0
Figure 30 • H-NMR Spectrum of Mentzeloside Pentaacetate (CDCl^).

o
O G I u( A c )4
*|inivmfpTmwfpTvnimfmmiiii|iiiiim i|tiiiiiii>|iiiwwH|iim ii>i|iiii iiwi| iiiiitm ]ii n n i i M 'i iiinnm|m iiinnminm |ninmn»mnnnnmnn|nmwimmnnn
190 IS O 170 160 IS O 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 SO 4 0 3 0 2 0 10 0
PPM(I)
Figure 31. ^C-NMR Spectrum of Mentzeloside Pentaacetate (CDCl^).

S WAVHEHCTH
ANSMISSION
W A V M M k H CMT*
Figure 32. IR Spectrum of Loasaside (KBr). ^

tv>
ON
O
o
INTENSITY
in
i>
o
in
REL.
0 100 2 0 0 3 0 0 4 0 0 5 0 0
M/E
Figure 3 3 . Mass Spectrum of Loasaside.
CH
Glu
lu IIII III II IIIIII II II II»I IIIII III I II1 II III IIIH I lIlIIIIlII 11 .III I II IIIII II|.... I... I|| II. |IIn I1 IIII
1 a 9 0 8 0 7 .0 6 .0 5J0 4.0 3 .0 2 .0 1 .0 0
Figure 3*f. 1H-NMR Spectrum of Loas aside (D20) ’

CH
Glu
l i i u l l l l l l l l f c i l i i u l n l l l l I f l l i l l l l l l l l l m l i l t t L l i l l H I i l l 11 llim lia id A IiiL .il I . . . . I n n l H u l n n h m l m i t m t l u n l n n l n n t n n l m i t i l i i l m i ^ m li» n l* » til» » » » l l i i i i n l t l m i U m l l l n l
2 0 0 190 100 170 160 IS O 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
rm< < I
Figure 35. -'C-NMR Spectrum of Loasaside (D20).

AcO CH
Glu (Ac)
7 .0 6.0 5 .0 4 .0 3 .0 2.0 1.0
Figure j6. H-NMR Spectrum of loasaside Pentaacetate (CDCl^),

Glu(Ac)4
2 0 0 190 IS O 170 160 150 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
PPM 1 1 )
Figure 37. ^C-NMR Spectrum of Loasaside Pentaacetate (CDCl^).

L n j 11 1 n i I » m 1 11 11 1 1 11 1 1 i i i . I i 11 i 1 1 . 11 I i n 1 1 11 . . I . i i i | . n 1 1 . 11 i | 11 1 1 1 1 i i . i . . . . I . i 1 1 1 i 11 . 1 . i i i i .« i i I
10. 9 .0 a .0 7 .0 6 .0 5 .0 ffM (, J 4 .0 3 .0 2J0 1 .0 0
1 H
Figure 38. H-NMR Spectrum of 7,8-Dihydro-Loasaside (DgO). ^
GlulAc*4
J
Jl
l l i l l l l t . l l l l t l _ l L l l l l l I I I I I I I II l l l l l l ■!«« Ill l l l l l l l l a l ! | | || l l l ! l t l l , 111l , ^ l l ^ « | | | p

I a 9 0 W 7 .0 6 .0 5 .0 r p M ) n 4 .0 3 .0 2.0 1.0
Figure 39. *H-NMR Spectrum of 7 ,8-Dihydro-Loasaside Pentaacetate (CDCl^)§

CH.
HO
— I—
*-*■>. 11i .... I ■t i . i L u i l i l t !■<■]
• ° 7 .0 6 .0 5 .0
PTM| I )
4 .0 1.0 o
Figure 40. ^H-NMR Spectrum of 6,7-Isoloasaside (Do0). »-»

2 ^
0 ^ 0
OGIu
Lllu h iii Ii iiil m M m iiI ii iiI ni i ii, 11111111.i, 11,1.1.. 1 ....... ..........1.... 1. ....... .
9.0 8.0 7.0 6.0 5.0 2.0
4 .0 3 .0 1.0
Figure 41. Sl-NMR Spectrum of Sweroside (DgO).

I... I"...I-... l"*"*"T""""|llllllll>|,,IHII|l|,l,l,lln|,llllllllllllllllll|lllllllll|ll|m |ll||||m w |»wwHmmnim|munMmmnim miim|iiiiiiiim iiinim
2 0 0 190 IS O 170 160 1 50 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
PPM ( I )
Figure ^2. ^C-NMR Spectrum of Sweroside (DO).

0 ^ 0
O G I o ( A c )4
JU
LlJ-l »l I Ll Llllll ll J i I 1 I 1.1 it II l i I I I I l I n n I l l 1 1 I 1 1 . i I i l I l I i I i 1 1 . t i i I . . i i I i n i I . i i . I . . i i I t n . I i i i 1 1 . i ii 1

'A 9 .0 8 0 7 .0 6 .0 5XJ n u ( l ) < 0 3 .0 2 j0 1 .0 0
Figure 1+3. H-NMR Spectrum of Sweroside Tetraacetate (CDCl^).

Vo)
OGIu(Ac)
u ttMtmjLx ^ A .i>i- aJoi fikMm

^Yt vW w TwT^ T T W F f W l f ^ ^ ^
piwfiiii|n iiiiiii|inmiii|i iiiii|iiinwii[iiiiiiiii|imiiin|iiiiinii|iiiiiiiii[imniii[

iii|iiiiiiiih iiiiiiiii|iih >iiif|fTTTTTITTpHlfIT
2 0 0 190 180 1 70 1 6 0 |5 0 --- 1---
140 30 -
120 110 100 9 0 80 70 6Q 5'
0 4Q 3Q 20 10
PPM ( * 1
Figure *i4. ^C-NMR Spectrum of Sweroside Tetraacetate (CDCl^).

INTENSITY
Po .
4 0 0 5 0 0
ID ~
REL.
0 100 200 300 500
M/E
Figure 45. Mass Spectrum of Sweroside Tetraacetate.
0 ^ 0
Glu(Ac)4
VT l - A ^
JU
U I I l l I 11 i l l I I | I I I I I h I I 1. 1 I I I t I I 1X1,1J I I I I I I 1 1 1 I I I l I i I 1 I I i I i l l . I I i I 11 I I I . i n I . . . . I . . . I I I . . . I . . . I .
3.0 2.0 1.0
,a 90 80 70 6-° 50 »TM(< I 40
Figure lv6. Si-NMR Spectrum of 8,10-Dihydro-Sweroside Tetraacetate (GDGl^).

HOCK OGIu
L l i 111 I I I I I I I I U I I I I I I I I 1I I l i I I I l I l I l l 11 I i i l i 1 I I . . 11I lI I m 11. n I I I I i I I I I i I I I H I I I i I I 11 I 1I I n 11 I I n i I

,a 9 0 * -0 7.0 6 .0 5 .0 4 .0 3 .0 2 .0 1 .0 0
Figure 47. H-NMR Spectrum of Decapetaloside (D_0).

2 »-*■
■c-
O
O
INTENSITY
in
o
o
in
REL.
1111
5 0 0
M/E
Figure 1*8 . Mass Spectrum of Decapetaloside.
CH3
HOCH 2 OGIu
ilnllb.li
W m m
|iiiniiii|iiiii iii|iiiiiini|iiiiiiiii|iiNinii|MiitHii|umimnmmn|iimnn|iiu
2 0 0 190 180 170 160 150 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
PPM( I)
13
Figure 49 • C-NMH Spectrum of Decapetaloside (DO).
6
1
AcOCH
L i . i n H n i li 1 1 1 11 i 11 11 .1 1 1 1 1 I . I I 1 1 I I .. I. I 1 1 II I .... I.. I I I n . 1 1 .... i .. 1 . 1 . 1 I I I .... I .. .1 Li 1 . .1.. II I. m I

la 9.0 S.0 7.0 6.0 5.0 ppM( , , 40 3.0 2.0 1.0 0
Figure 50* ^H-NMR Spectrum of Decapetaloside Pentaacetate (CDCl^).

INTENSITY
in "
REL.
0 100 200 3 0 0 4 0 0 5 0 0 6 0 0
M/E
Figure 51. Mass Spectrum of Decapetaloside Pentaacetate.
£
A c OC H2 O G I u ( A c )4
j l I mfc I f tf^grvJ
|irHiiiii|iiiiiiw [iiiiHii»|wm iiii|iiiiiiw | im iiiM|iiiiiHM|iiiiiiiit|iiiiiiiii|iiiiw ii|iim iiii|iHiHiii|Hiiw ii|iiiiiiiii|iiHHin |in iin ii|Hin iim m n n in iiinnM| nn m m
2 0 0 190 180 170 160 IS O 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
PPM( 11
Figure 52. C-NMR Spectrum of Decapetaloside Pentaacetate (CDCl^).

L l i 1 1 11 l i . i J -1 u . i h i 11 1 1 ■i 11n i «I 1 11 i I .. . i I n 111.. ■. I . i 111 . i ■ ■I . . . ■ I ■. i ■ I I . . . . 11 . . . I . i 1 1 1 . 111 I
10. 9 .0 a .O 7 .0 6 .0 5 jO ffM (, ( 4 .0 3 .0 2 .0 1 .0 0
Figure 53. 1H-NMR Spectrum of Strictoside (DgO).

o
o
INTENSITY
in
o
in
REL.
iT v r i | i i i* i i i i i i
3 0 0 4 0 0
Figure 5**. Mass Spectrum of Strictoside.

OH OGIu
I" | llll|ll|l|| | | | | » » ||m*»ii|i*iiHiii|M>H n»|iin iiiii|iiiiiiiii|iiiiiiiii|iiiiiiiii|iiiiiiiii| iiiiiiiiijiiiinrin iiiiiiiii|iiiiiim |iiiiiiiii|iiiiiiiii|iiiiiiiii|iin iiiin»iiiin r

200 190 180 170 160 150 MO 130 120 110 100 90 80 70 60 50 40 30 20 10
P fM ( I )
Figure 55* ^C-NMR Spectrum of Strictoside (DÔ).

° * e O G I u ( A c )4
l i 11 i i i m 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 n 1 1 1 11 n l m i i m . I . i i 1 1 . 1 1 1 1 i i . 1 1 1 1 1 1 1 1 1 1 . 1 . . . . 1 11 ■ 1 i ■ ! 1 . 1 1 1 1 1 1 . i n I
,a *0 7.0 6.0 5 0 rm{t) < 0 3.0 2.0 l.o 0
Figure 5^« H-NMR Spectrum of Strictoside Pentaacetate (GDGl^).

INTENSITY
REL.
CM ~
0 100 200 3 0 0 4 0 0 5 0 0
M/E
Figure 5 7 , Mass Spectrum of Strictoside Acetate.
ch3
AcO OGIu(Ac)
|iiuuHipuniiiiHmniiHimmnHnmin|iiiiiiiiinniminiiiiiiiii|iiiiiiiinmiiiiiniiiiiiiii|iiiiiiiii|iiiiiiiii|iiiiiininmiiiiniiiinnniiiiiiiii|Hiiiiin|iiiiiiiiniiiiiiii>
2 0 0 190 180 170 1 6 0 IS O 140 130 120 110 1 0 0 9 0 8 0 7 0 6 0 SO 4 0 30 2 0 10 0
PPM( I»
jo
Figure 58* C-NMR Spectrum of Strictoside Pentaacetate (CDCl^)•
OAc
OAc
n i | ii ii T i n i j i ITT i i i t t | i i i i i i i 1 1 111 n i i i i i 11 111 11 i n - [ 1 1 rri i m 111m i i n~| 11 ii 111 it

&o 7 .0 6 .0 5 .0 PPM ! I ) 4 .0 3 .0 2 .0 1 .0
Figure 59* H-NMR Spectrum of Strictoside Aglycon Diacetate (CDCl^).

OGIu
I n l ll l 1 1 l I i li I I U-J-l ll .1 I I U n 1 I I n I i . il 1 i i l i I h . . I . i I i I 1 l i i I . ■ ■ i I I I i i I . i i . I . 1 1 . I .m 1 i . . . I I . i . I ,JJUj
10. 9 .0 8 .0 7 .0 6 .0 5 .0 . . . . . . .
rr*»(11 4 .0 3 .0 2 .0 1 .0 0
Figure 60. Spectrum of Decaloside (DgO).

OGIu ( Ac )4
Figure 61. *H-NMR Spectrum of Decaloside Hexaacetate (CDGl^)^

O G Iu ( A c )4
#** W mmwmy
|i i i i i i i i i |m i ii ii i|i ii ii in i | iiiiii> in iiiiiiii i |i ii ii ii i n i m im i |i i i i i i m ]n » in iiin m i ii ii |ii ii ii ii n iiiiiin i|» iiiiiiin i ii ii iii n i ii m i i i |i i Mn n

2 0 0 190 180 170 160 IS O 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 SO 4 0 3 0 2 0 10 0
PPM( 11
Figure 62. *^C-NMR Spectrum of Decaloside Hexaacetate (CDCl^).

HO
OGIu
I n i III l u l i i i i l n n 1 1 II 11 II i 1 1 1 II i 1 I. II I 1 1 111 II I . I. i i i I . 1 1 1 1 ■I » I I ■■ ■■ I H I I I « » » I 1 1 ... I m 1 1, i II I

10. 9 .0 8 .0 7 .0 6 .0 5 .0 M ( , , 4 .0 3 .0 2 .0 1 .0 0
Figure 63. ^H-NMR Spectrum of Glucoside V (10-0-P-glucosyl-decaloside) (CD^D).

HO
OGIu
i
niiinii»|m inimmm'inmiii|,i|ii|ii|iiHniniin|m |i|ui|im i|l,Tliii|i'i|Hiiim n'l'|m im |m m i'll'|n|"lH|iiii'm|iii'inii|.. ... 1... 1...
2 0 0 190 180 170 160 150 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
PPM! I )
13
Figure 6^, C-NMR Spectrum of Glucoside V (10-0-p-glucosyl-decaloside) (D 0),
2
Ac O
JUL
I i I. i I. ». i I i i 1 1 1« « i i I m > I n i i I ■» ■ i I n n I ■ ■■ » I« i « i I « 11 1 1 . «i ■ I ■■ « « I « ■ i i « « i n I «. n 1 1 ■ ■« I . m l
9 .0 9 .0 7 .0 6 .0 5 .0 4 0 3 0 2 .0 1 .0 0
Figure 6 5 . *H-NMR Spectrum of Glucoside V-Nonaacetate (CDCl^).

C H 2 O G I u ( A c)4
O G I u ( A c )4
pim T m pm tTm jrtm rm jr i|iiiiinii|IIITflTII T|1I1H IIII|H

T T T iiHiiiiiiin|iim iiii[iiiiiiiii|iiiiniiniiniiiiHiiiiiiiii|iiiiiii'i|im iniH
2 0 0 190 IS O 170 160 IS O 140 130 1 2 0 110 1 0 0 9 0 > 0 7 0 6 0 SO 4 0 3 0 2 0 10 0
PPMI11
Figure 66. ^C-NMR Spectrum of Glucoside V-Nonaacetate (CDCl^).

AcO
OAc
I . .. . h i m I . n i 1 1 i ii 11 . 1 11 n . . 1 «m I . . ii I it 11 Im . 1 1 1i i I m i l i 11 i I i i i l l ij-I 11» i.iilji 11 11 m l 11 n li u II

ia 9.0 B.O 7.0 6.0 5.0 frM<4, 40 30 20 >0 0
Figure 67. 1H-NMR Spectrum of Tetrahydro-glucoside V-Aglycone Triacetate (GDGl^).

6.0 5 .0
Jl 11 ■1 .
4 .0 3 .0 2.0 1.0
1
Figure 68. H-NMR Spectrum of Glycoside VII (D20). m
piiiiiiii|innnii[iiiiiiiiniiiiiiiinmniin|iiiiiiiii|iiiiiiiii|iiiiiiiii[iiiiiin>|iiiiiiiinimiiinniiiiiiii|iiiiiiiiniiiiiiiii|»ii'i'i||i|l»ii|'l|lllllllll|lllll,lllllll,llllllllllllllll
2 0 0 190 180 170 160 IS O 140 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 SO 4 0 3 0 2 0 10 0
ffM( I )
Figure 6 9 . *^C-NMR Spectrum of Glycoside VII (DÔ).

vA l a /
vj *'r v
L l i I I I I I . H. I H I I I I I I I I I i l l 111 I I I I I 1 I I H I I I I I I I I I I I I I . I I I I I I I I I . I . I I I I I I I I I I I I . I I I I I I I I I I I I , I , I M I . , , I I
>0- 9 .0 S O 7 .0 6 .0 5 .0 4 .0 3 .0 2 .0 1.0
i n r
PfM(* )
Figure 70. *H-NMR Spectrum of Glycoside VII- Octaacetate (CDCl^).

pHiwii»piiiHiiipiniiiiipiiiiiiiip iiiiiiiipim i» ipiiinn>| tiiHH»qHwiiiii|n n n iiip iiiniiip tm »iipnwnnpiiw n i| iiiMnu|uiin w p n nmnpm iim piiiin n p n iinTH
2 0 0 190 1 80 170 160 IS O 1 4 0 130 1 2 0 110 1 0 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 10 0
PPM! 11
Figure ?!• *^C-NMR Spectrum of Glycoside VII- Octaacetate (CDCl^)•
o\
3.0 4.0 3.0 m«(T» 6.0 7.0 0.0 9.0
«o
0.0 7.0 6.0 S.0 ffM(i) 4.0 3.0 3.0 1.0
Figure 72. ^H-NMR Spectrum of Scopoletin (GDÔD).

PART II. IRIDOIDS.- A REVIEW.
167
168
INTRODUCTION
Iridoids represent a large and still expanding group of cyclopentan-
(c)-pyran monoterpenoids. They are found as natural constituents in a
large number of plant families, usually, but not invariably, as
glucosides. In some instances the presence of iridoids have been used
to support a defined botanical classification (1).
The name iridoid is a generic term derived from the names
iridomyrmecin, iridolactone, and iridodial, compounds isolated from some
species of Iridomyrmex, a genus of ants, in which they occur as defensive
secretions (2). Although the name iridoid is now generally accepted,
these compounds have been referred to as pseudoindicans, due to the blue
coloration that some of them develop upon hydrolysis. They have also
been referred to as aucubin glucosides.
Iridoids were first isolated in the latter part of the nineteenth
century, but it was not until 1958 that 0. H a l p e m and H. Schmid (3)
proposed the basic skeleton of the iridoids in their investigation of
the structure of plumieride.
Several reviews which dealt with the iridoid group include those of
Bobbitt and Segebarth (U), 1969, a comprehensive review which also
included physico-chemical data; Plouvier and Favre-Bonvin ( 5 ) , 19?1,
which stressed the distribution, structure, properties and biosynthesis;
Buchbauer (6), in 1974 discussed the pharmaceutical significance of the
iridoids; Sticher and Junod-Busch ( 7 ) , 1975, presented a study of their
isolation proceedures; Jensen, Nielsen and Dahlgren ( 1 ) , in 1975 dealt

169
with their botanical distribution; Van Der Sluis and Labadie (8) in 1978
reviewed the secoiridoids; and finally in 1978, Jahodar (9)» Rimpler (10)
and Sticher (11) presented three approaches dealing with the isolation
and structure elucidation of the iridoid glucosides. From the
biosynthetic point of view, Inouye and coworkers have discussed this
subject on several occasions [1971 (12), 1978 (13* 1^)3*
The present review is a presentation of a complete listing of the
iridoids and secoiridoids that have appeared in the literature through
January 1980, with their physical constants: melting point, specific
rotation, ultraviolet, infrared, proton and carbon magnetic resonance,
as well as mass spectral data. The intent of the review is to provide
the researcher, who has just managed to isolate an iridoid compound, with
a quick means of deciding whether his compound is known or new, as well
as allowing him to establish a structural hypothesis by comparison of
the physical data.
Included in this listing are iridoid glycosides, secoiridoids, and
non-glycosidic iridoids. We have chosen not to include nitrogen
containing iridoids: neither the simple product of the substitution
of oxygen with nitrogen (upon ammonia treatment of the iridoid), nor the
large and important group of alkaloids with an iridoid part i.e.
ajmalicine, catharanthine and ibogamine type, which by themselves
constitute a clear and defined group.
The material has been divided into ten groups: iridoid glycosides
with a C-8, C-9» and C-10 carbon skeleton constitute the first three
groups. The C-9 group is separated into two subgroups, depending on the
position of the ninth carbon which is either on C-4 or C-8. Increasing

170
oxidation state of carbons 10 and 11 mark the sequence in these groups.
The secoiridoids constitute the next three groups: Group IV contains the
simple secoiridoids, whereas group V contains secoiridoids which are
conjugated with a terpene type moiety, and in group VI secoiridoids
which carry a phenolic moiety as a substituent are presented. Group VII
contains the bis-iridoids and bis-secoiridoids. The non-glycosidic
iridoids constitute the last three groups: with miscellaneous structures
in group VIII, tetracyclic non-glycosidic iridoids of plumiera type
are in group IX, and finally the valeriana compounds constitute group X.
In all cases, an increasing oxidation state was used as a guide for the
presentation of the different structures.
The numbering of the skeleton is according to figure 1_. If C-10
is not present, then C-ll takes its number. In the cases in which an
aromatic ring is present, the numbering system of the ring is as
pictured in figure When bis-iridoid glycosides are presented, the
iridoid part is denoted as a , and the secoiridoid part as b .
a b c
Figure 1. Numbering system for: a) iridoids, b) secoiridoids, and

c) aromatic ring.
1?1
For each compound the following information is provided when
available: the structure, molecular formula and calculated molecular
weight (mass spectrum); melting point in °C; CoG (with concentration and
solvent); for uv data the \ max is given in nm (log €); the ir data is
given in cm ; the H-nmr and C-nmr chemical shifts are in 6 (ppm
scale) units, and the coupling constants in Hz. The *H-nmr data have
been rounded to the second decimal point; the ^ C - n m r data have been
rounded to the first decimal. The m/e data of mass spectra is given.
Every data is followed by the corresponding reference number.
Because of the increasing number of compounds identified through
the acetate derivative, the melting point and optical rotation for this
derivative are stated when available. When more than one acetate is
reported, the one with the highest number of acetates was chosen.
Moreover, when the *H-nmr data is available only for the derivative
this data is then presented.
The family and in some instances the generic source from which the
compound was characterized is stated, and when possible other sources
in which the compound is present are given.
Some abreviations used through the text ares Glus glucose, Xyl:
xylose, t: trans, Me: methyl, p: para, Ac: acetate, 0 : phenyl.
A cross index and molecular weight tables are presented.

Iridoid Compounds
I. - Iridoid glycosides: Eight carbon basic skeleton
1.- UNEDOSIDE
C14H2 o V 332.1107
MR: 232-4° ( 15)
[a]D: -112.4° ( * )
DERIVATIVES: Aglucon acetate:

OGIu
H-NME: 5-6 (d, J=9-5. Hj), 5-0 (H3)
^•9 (q, H6), 3.6 (d, J=2.8 ,
H? & 8^ ( )
SOURCES: Ericaceae: Arbutus (15)
Verbenaceae: Stllbe ( 16, 17 )
2.-STIISERIC0SIDE
HO
OH C14H2 0 °1 0 ! 34 8 - 1056
[a]2^ : -61.5 (c=0.2, H20) ( 16)
UV: («20) 197 (3.97) ( 16)
IR: 1645 (16)

OGIu *H-NMR: (16)
MS: m/e: 186, 185, 169, 168, 167,
163, 162, 157, 151, 150, 149,
145, 139, 134, 127, 123, 121,
114, 109, 97, 91, 87, 8 5 , 83,
81, 73, 71. 6 9 , 6 1 , 6 0 , 5 7 , 55.
53, 51. 45, 4 3 , 41, 39 (16)
DERIVATIVE: Hexaacetate:
MP: 144-6° ( 16 )
SOURCES: Verbenaceae: Stllbe ( 16 )

Ila. - Iridoid glycosides: Nine carbon basic skeleton (C-9 in C-4 ) 173
3.- STRICTOSIDE
C^Ôg: 332.1471
^H-NMR: DgO, 90 MHz (18)
13C-NMR: D20, (1) 95.4, (3) 133.4, (4)
116.1, (5) 35.7, (6) 27.6, (?)

0-5.14(d J 3.5)
OGIu 32.8, (8) 74.7, (9) 50.6, (10)
15.4, (1*) 99.1, (2') 73*3, O')

76.7, (4') 70.2, (5') ?6.3, (6‘)
61.3 (18)
DERIVATIVE t Fentaacetate:
MPi 146-8° (18)
[V p D . -118° (c=3*7, CHC13 ) (18)
SOURCES: Loasaceaei Mentzella (18)
IS 4
4.- LOASASIDE
HO CH
C15H22°8i 330.1314
317
S.94 b r i MP: 216-220° d (18)
[ a ] 23D: -150° (c = 1 .3 , H20) (18)

-3.00
UV, (CHÔH) 207 (3-55) (13)
Glu IR: KBr, 3400, 1650, 1610, 1350, 1150, 1050
(18)
MS: M+330, n/e: 168, 15J, 133, 122, 85 (18)
^-NMR: D20, 90 MHz (18)
13C-NHR: D20, (1) 97.7, (3) 135.7, (4) 114.5,
(5) 48.4*, (6) 81.2, (?) 134.7,
(8) 134.9, (9) 46.9*, (10) 15.4,
(!') 99-3, (2') 73-5, (3’) 77.0,
(4’) 70.4, (5') 76.5, (6’) 61.5
(18)
DERIVATIVE: Pentaacetate:
MP: 153-6° (d, unstable) (18)
SOURCES: L oaaaceae: Mentzella (18)

174
5.- DEUTZIOL
C15H2i*°9* 348.1420
MP» 108-110° (19)
4 75-5JO S0-2.15
[a]25®! -150° (c=0.6, CHÔH) (19)
1.50-23
UV: (CH3OH) 218 (2.97) (19 )
5 4 3(d,J.tS ) IR: KBr, 1650 (19 )
O G Iu 1H-NMRi D20 ( 19)
SOURCES: Saxlfragaceae (Hydrangeaceae 1
Deutzla (19)
V60(d, JO 5) 6 .- MENTZELOSIDE (DEUTZIOSIDE)
C15H22°91 >6.1263
119m
6 13m MP; 266-270° ( 20 )
3.34 m
-101° (c-1 .021, H20 ) ( 2 0 )
3.S0(d.J2 73l|4 6 , (d-J,°) W: 203 (3.53) (20 )

OG Iu IP: KBr, 3420, I665 ( 20 )
1H-NMR: DMSO-dg, 100 MHz (20)
13c-nmr, d2o, (1) 96.7 , (3) 135.6 , (4)
113.4 , (5 ) 42.5* (6) 78.4,(7 )
56.4, (8) 59.6, (9) 41.0?
(10) 15.8 , (1*) 99.8, (2’)
73.4, (3’) 77.0, (4*) 70.2,
(5’) 76.4, (6') 61.2 ( 18)

DERIVATIVE1 Pentaacetate:
MP: 199° (20 )
D O 26* -103.3° (c=0.974, CHCLj) (2 0 )
SOURCES: Doaaaceae: Mentzella (20 )
Saxlfragaceae: Deutzla (21 ) . ( 2 1 6 3

1671
7.- 7-CHL0R0DEUTZI0L 175
QH CH
C15H2309C1« 382.1030
397
Cl*. MP: 126-8° d (18)
3 * y - 334
[aipD: -132° (c=1.0, H20) (18)
OH OGIu
UV, (CHÔH) 205 ( 3.5 ) (18)
IR KBr, 3400, 1670, 1620, 1090, 890 (18)
1H-NKR: D20, 90 MHz (18)
13C-NKF, D20, (1) 95-2, (3) 135-3, (4)
U5.7, (5) 46.4*. (6) 82.1, (7)
70.9, (8) 78.1, (9 ) 41.5*, (10)
16.8, (I1) 100.3, (2*) 74.6, (3’)
7 7 .6 , (4') 71 .6 , (5') 77.3. (6*)
62.8 (18)
DERIVATIVE: Hexaacetate,
MP, 124-5° (18)
[a]20D: -125° (c=2.6, CHC13) (18)
SOURCES, Loasaceae , Mentzella (18)
16 J d . J 1.0) 8.- SCABROSIDE

CH,
C15H22010‘ 362.1213
370-390 6 IS q MP, 218-220° ( 22)
[a]15D, -8O .5 (c=0.5, CHÔH) ( 22)
UV, 208 (3 .6 ) ( 22)

OGIu
IR, 1670 (22 )
1H-KMR, D20 (22 )
SOURCES: Saxlfragaceae: Deutzla (22 )

176
9-- DECAIOSIDE
c15H22°9 i 3^6.1263
QH
MP: 193° (23 )
6 34
SI3 [aJ^D: -137.9° (c=0.4?5, CHÔH) (23)
UV: 204 (3.68) (23 )

S 13
IR, 3390, 1658 (23 )
OGIu
*H-NMR: DMSO-dg (23 )
13C-NMR: D20, (1) 97.7. (3) 139.0, (4)
116.4 , (5 ) U7.5* (6 ) 80.9,(7)
133.8, (8 ) 135.8, (9) 43.4*,
(10) 61.3, (!’) 99.1, (2 ’)
73*3, (3') 76.7, (4') 71.9,
(5 ‘) 7 6 .3 , (6 *) 61.2 ( 18 )
MP: 162-4° ( 23)
[a]2^ : -127.62°
7.62° (c=1.144, CHClj) (23 )
SOURCES: Loasaceae: Mentzella ( 23)
lib. - Iridoid glycosides: Nine carbon basic skeleton (C-9 in C-8 )
10.- 6,10 BISDEOXYAUCUBIN
c 15h 22°7i 31^•13^5

CH
OGIu Sl-NMR: D20 {2M-)
DERIVATIVE: Tetraacetate:
MP: 137-8° (25)
[aipD: -142° (c=0.5, CHCl^) (25)
SOURCES: Synthesis (24, 25)

177
11.- AOTIRRIDE
C15H22°8 ‘ 330.131U
3 SOlbr.J
7'3?< ^ i637dd HP: 85-7° (26) , 83-4° ( 27 )
[aD^Di -116° (c=0.42, Dioxane)( 26),

S«Hd,J30) -124° (c=0.4, Dloxane) (2?)
OGIu UV: 206 (3.6) (-27 )
IR: (KBr) 1665. 1670 ( 27 )
^-NMR: T20, 100 MHz (27)
MP: 154-5° { 26 ), 152-3° ( 27 )
[oG2^D: -142° (c=0.64, Dloxane) (27),
QO^D: -I580 (c=1.05, Dloxane) (26)
SOURCES:Scrophularlaceae: Llnarla
( 26 ), Antirrhinum ( 27 ).
12.- LINARIDE (10-DEOXYAUCUBIN)
C15H22°8 : 330.1314
Amorphous powder
s o Sdd
UV: 204 (3 .7 ) (28)
IR: KBr, 1660, I650 (28 )

.o
S5 4(d,J 3.0) *H-NMR: D20 , 90 MHz (2 8 )
O G Iu DERIVATIVE: Pentaacetate:
MP: 122-3° (2e )
[a]10D» -176° (c=3.3. Dloxane) (2 8 )

SOURCES: Scrophularlaceae: Llnarla (28).
13.- GLUROSIDE
C15W 332 •1U?1

Amorphous powder
[c0 20D j -178.5° (K20) (29 )
UV: (H20) 190 (3.8) (29 )
IR: KBr, 1653 ( 29)
^H-NMR: D20, 100 MHz (29 )
MP: 113-11**° ( 29 )
[a]20D: -12**. 1° (CHC13) (29)
SOURCES: Iabiatae: Galeopsls (29 )
1*+.- 6-DESOXY-HARPAGIDE
C15H2**°9! ^ BAU20
Amorphous powder
[a]20D: -158.**° (H20) ( 29 )
UV: (H20) 189 (3-9) (29 )
IR: KBr, 1655 (29 )

1H-NMR: DgO, 100 MHz ( 29)
DERIVATIVES: Tetraacetate:
MP: 188-9° ( 29 )
[aJ^D: -133.**° (CHC13) (2 9 )
Pentaacetate:
MP: 127-8° (29 )
[a]2°D: -112.7° (Acetone) (29)

SOURCES: Labiatae: Galeopsls ( 29 )
15*- MIOPOROSIDE
C15H2**°9i 3UBAUZ0
Amorphous powder
[a]25D: -175° (c=1.0, CH30H) (30 )
UV: (CMjOH) 20** (3-51) ( 30)
IR: KBr, 1660 (30 )

*H-NMR: D20, 60 MHz (30 )
MP: 17**-5° ( 30 )
SOURCES: Myoporaceae: Mvoporum (30 )
16.- REPTOSIDE
C1?H26°10S 390.1526
Hygroscopic, Amorphous powder
[a]27D: -hS° (c-0.7, CH30H) ( 31 )
UV; (CH30H) 205 (3.7) ( 31)

IR: KBr, 1710, I65O (31)
^H-NMR; D20, ( 31 )
DERIVATIVE; Pentaacetate:
MP: 127-8° { 31 )
C<027D! -114° (Acetone) (31 )
SOURCES; Labiatae: Ajuga, Galeopsls
17.- GLUCOSIDE VII
c 17H26°10‘ 390.1526
Amorphous powder
[rD^D: -42° (CH30H) ( 29 )
UV; (H20) 205 (3.7) ( 29)
IR: KBr, 1710, I65O ( 29 )

1H-NMR; DgO, 100 MHz ( 29 )
DERIVATIVE; Pentaacetate;
MP: 125-7° ( 29 )
[ o] 20D; -105° (CH30H) (29)
SOURCES : labiatae: Galeopsls ( 29
18.- AJUGOL
C1?Zk°9' 3W . 1&20
Amorphous powder
[a^D: -169° (c=2 . CH^H) (32)

1H-HMR: D20 (32)
DERIVATIVE; Pentaacetate:
MP; 127-8° (32)
O j 18D; -168° (c=2 ,Acetone) (32)
SOURCES: labiatae: A.juga, Mellttls,
Leonurus. ( 32 )
19*- AJUGOSIDE (LEONURIDE)
^TÎO* 390.1.526
4.1 6.3244 Amorphous powder
a.22
[a]17D: -115° (c=2, CH3OH) ( 32 )
UV1 (CHÔH), 206 (3 •6 )( 32 )

AcO CHg o G tu
2.09k 1.47k IR: (KBr) 1705, 1655 ( 32 )
*H-NMR: D20 ( 32)
MP: 172-3° (32)
[q318D: -93° (c=2. Acetone) (32)
13C-imR: (1) 94.0, (3) 140.4, (4) 102.8.
(5) 3 8 .0 , (6 ) 77.9, (7)45.3,
(8 ) 87.1, (9) 48.3, (10) 22.1,
(!') 95.?. (2 ') 70.7, (31) 72.7,
(4') 68.7, (5') 7 2 .0 , (6 *) 62.0
(33)
SOURCES: Labiatae: A.juga, Helittls.
Leonurus ( 32, 34)
20.- CALIRIDOSIDE
266 S S4(d,J *2) C15H22°9! >i6-1263

6.9 0(d,J62) MP: 189-192° (35)
[a]23!: -78° (c=0.99, HgO) (35 )

_5.95<d,J 6.2) UV: (H20) 189-5 (4.18) ( 3 6 )
r (d,j6.a>|
CH3 OGIu IR: KBr, 1663 (36 )
2.01k
*H-NMR: D20, 100 MHz (36)
MP: 130-2° ( 36)
[cO^D: -60° (c=1.05, CHClj) (36 )
SOURCES: Labiatae: Leonurus (31) ,
Galeopsls (36 ), Ajuga (31) .

181
21.- LATERIOSIDE
OH 47 2
C24H30°10' **78.1838
6.2 4 dd
[V]20D: -68.9° (c=0.83, CHÔH) ( 37 )
9 7 d.J I UV: (BtOH) 207 (4.06), 218 (4.13), 224

CinnamoylO
726-766 3 O G Iu (4.06), 279 (4.31) ( 37 )
IR: KBr, 1690, 1655, 1635, 1580, 1495. 1430
( 37 )
*H-NMR: CDÔD ( 37 )
13C-NMR: CD30D, (1) 94.6, (3) 141.3, (4)
104.1, (5 ) 41.6, (6) 76.8b, (7)
48.8, (8 ) 90.1. (9) 49.4, (10)
23.0, (1') 100,0, (2’) 74.6, (3')
7?.8b, (4*) 7 1 .5 , (5 *) 77.8b, (6 ‘)
6 3 .0 , (1") 135.6 , (2 ") 129.8°, (3 ")
129.0, (4") I3 1 .3 , (5 ") 129.O, (6 ")
129.8, (a) 145.7, (3) 120.1, (CO)
I6 8 .5 ( 37 )
MP: 157-9° ( 37 )
[a]20D: -8 9 .2 (0=0 .5 6 , CHC13) ( 37 )
SOURCES: Scrophularlaceae: Scrophularia ( 37 )
22.- IRIDOID A
I OH C15H24°10’ 36U*1369
6.4S
MP: 198-9° (38 )

* CH 3 [o ]20D: +10° ( CHC13) (3S)
1.2 4
OGIu
UV: 218 (38 )
IF: 1650 (38 )
1H-NMR: (38 )
SOURCES: Gentianaceae: Gentlana (38 )
23.- HARPAGIDE
36<*-1369
Amorphous powder
[alpD: -154° (c=1.135. EtOH) (39 )
IF: 1655 (39 )

V n MR i D£0 (39 )
DERIVATIVE: Heptaacetate:
MP: 185-190° (39 )
[a]22D: -118° (c=0.99t CHC13) (39 )
13C-NMR: For Hexaacetate: (1) 94.1, (3)
141.7, (4) 107.3. (5) 71.5.
(6) 77.7, (7) 43.6, (8) 86.1,
(9) 54.8, (10) 22.2, (1') 96.5,
(2') 71.2, (3') 72.1, (4*) 68.7
(5') 72.1, (6') 6 2 .0 ( 33 )

SOURCES: Labiatae: A.juga, Galeopsls,
Mellttls. Stachys. Teucrlum. ( 4 )
Pedaliaceae: tfarpagophytum ( 1 ) ,
Scrophularlaceae: Scrophularla (40 ).
24.- 8-ACETYL HARPAGIDE
C17H26°ll' 4o6-i475
MP: 154-6° ( 41 )
£a]17D: -132° (c=l .04, CH^H) (41)
UV: 210 (3.6) (4)
1H-NMR: D20, 60 MHz (41)
MP: 185-190° (39)
[cJ^D: -118 0 (c=0.99, CHC13) (41)
SOURCES: Labiatae: Mellttls, A.juga,
Galeopsls, Stachys. Teucrlum. (4,41).

183
25 •“ HARPAGOSIDE
c24H30°n' 4 9 4 *1788
Amorphous powder
[oO^D: -42.6 (c=0.99, CH^H) (39)
UV: 216(4.19), 222 (4.12), 2?6 (4.36)
(39)
IRi 1690, 1635, 1580, 1500 ( 39)
Sl-NMR. D2o (39 )

DERIVATIVES! Pentaacetate-.
KP: 213-4° ( 39 )
0 3 22D:-60.2° (c=0.?6, CHCIj ) (39 )
13C-NHR: (1) 94.1, (3) 141.5, (4) 107.3
(5) 71.5, (6 ) 77.6, (7) 43.3,
(8 ) 8 6 .2 , (9) 54.9, (10) 2 2 .2 ,
(1’) 96.4, (2’) 71.0, (3') 72.1,
(4') 68.7, (5’) 72.1, (6 *) 61.9,
(1") 134.5 . (2 ") 128.8 , (3 ")127.9 ,
(4") 130.2 , (5") 127.9, (6")128.8,
(8) 119.1, (0.) 144.5, (CO) 166.0,(33)

SOURCES: Lablatae; Lamlum ( 4 ),
Pedaliaceae: Harragophytum (1 ),
Scrophulariaceae« Scrophularla ( 40)
26.- 8-(O-METHYL-p-C0UMAR0YL) HARPAGIDE
C25H32°13! 54°.1842
Isolated as a mixture with harpagoside,
structure determined by hydrolysis,
and analysis of the acetylated hydrolyzate
( 42)
SOURCESi Scrophulariaceaei Scrophularla (42)
184
2?.- PROCUMBIDE
Cl / 22° 10' 362'1213

MPi 210-1° (43 )
H(?: U
OHn 4 9 5 (d,J6 .5 ) [a]20D! -?8° (c=l.0, BtOH) (43 )
»' X V
6.5 "(d,J6.5)
1H-NMR: DgO (43 )
13C-NMR: CDÔD, (1) 95*6, (3) 144.1

i(d j.) J S4°(d-J»>
(4) 104.5, (5) 80.0, (6) 77.7
CH3 OGIu
1 5 It (7) 65.8 , (8) 66.8, (9) 52.9
(10) 17.6 (46)
KP: 173-4° (43 )
[a]3°D: -59° (c=0.57, CHCLj) (43)
SOURCES: Pedallaceae: Harpagophyture (43)
28.- ANTIRRINOSIDE
OH C15H22°10 : 362.1213
H 4 99 d, J 6 5>
Amorphous powder
669 (d.J 65)
[a]l6D: -78° (c=0.5, Dioxane) (45 )
UV: (EtCH) 207 (3-4) (45)

J6.5, 5(d. J 6.5)
73 OGIu IR: (KBr) 3487(tr), 2900 (br),l658,
i.sit
1230 (26)
1H-NMR: D20, 60 MHz (45 )
13C-NMR: CD3OD, (1) 94.6, (3) 142.9 ,
(4) 107.5, (5) 74.5, (6 ) 77.3.
(7) 6 6 .0 , (8 ) 64.2, (9) 52.7,
(10) 17.5 (46 )
MR: 173-4° (45 )
LcGl6D: -170° (Dioxane) (45 )
SOURCES: Scrophulariaceae: IAnarla
(26 ), Antirrhinum (45 ).

185
29. - 5-O-0-G1UCOSYL-ANTIRRINOSIDE
IOld,J 6.1)
4.30(d,J
66 3(d.J 6.1) C21H32°15: 524.1741
3 6 0(d,Jl.
[o]Di -35° (c=0.7. CH3OH) ( 47 )
: s.otdjmj 4 4(d i 7.2) uv, 208 (3.5) ( 47 )
CH3 OGIu 1H-NMR: D20 (47 )

isi »
DERIVATIVE! Acetatei
[ajD: -73° (c=0.5, Dioxane) (47)
SOURCES: Scrophulariaceae: Antirrhinum (4?)
30.- LINARIOSIDE
HO
OH s, 3dd
34 0-4 C15H23°10Cl! 398.0980
6 36td,J651
Unstable, hygroscopic
340-4
[a]11D: -51° (c =0.98, Dioxane) (26 )
HCT : I570br»
IR: KBr, 3450, 2960, I663, 1238 ( 26)
CH3 {)GIo
1.311 *H-NMR: D20, 60 MHz (26 )
DERIVATIVES: Heptaacetate:
HP: 148-150° (26 )
[a]1AD: -107° (c=0.62, Dioxane) (26)
SOURCES: Scrophulariaceae:
Linaria (26 ), Cymbalaria ( 48 )•
31.- BARTSIOSIDE
23-27 5 02td,J 6.0)
3.01 C15H22°8' 330.1314
16.3 2 dd
MP: 118-120° ( 24 )
S.I6
[oG^Di -89° (c=0.3. CH30H) ( 24 )
I ’* ’ UV: (EtOH), 209 (3.2) ( 24 )
H0CH2 OGIu
4.3 9 IR: (KBr) 1660 ( 24 )
lH-NMR: D20, 90 MHz ( 24 )
MP: 108-9° ( 24 )
D O 25D: -105° (c=0.14, Acetone) ( 24)
SOURCES: Scrophulariaceae1 Bartsia (24)

186
32.- AUC'JBIN (AUCUBOSIDE, RHINANTHIN)
l2 dd C15H22°9 : 3^6.1263
•^^6.3 2 dd MP: 180-2° (25)
[a]l5D: -162° (c=1.98, H20) (4)

S23ld,JSO) UV: (H20), 210 (3.4) (4)
O G Iu IR: Nujol, 1655 ( 25 )

1H-NKR: D20 ( 49 )
13C-MR: D20, (1) 99.2, (3) 140.5, (4)
106.0 , (5 ) 43.7, (6) 81.6,(?)

129.5. (8) 147.5, (9) 47.2,
(10) 60.4, (l*) 9 6 .5 , (2’)
73.7. (3‘) 77.1, (4‘) 70.5,
(5’) 76.6, (6’) 61.7, ( 50 )
KP: 128° ( 25)
[a]15D: -156.6 (c=3.012, CHCl^j) (49)
SOURCES: Apocynaceae, Buddlelaceae,
Callltrichaceae, Cornaceae,
Globulariaceae, Hippurldaceae,
Lentlbulariaceae, Loganiaceae,
Orobanchaceae, Plantaglnaceae,
Scrophulariaceae, Euconuniaceae,
Verbenaceae (51,1* 25).

18?
3 3 .- lO-O-6-CLUCOSn.-AUCUBIN
S I6 d d
6.35 dd C2lH32°l4! 5° 8 - 1792

6.0 4 m MP: 248-250°d (52 )
5.27(d,JS) [a]21D: -122° (e-l.O.H.,0) (52)

GluOCH 2 OGIu 1H-NMR: ( 52)
4.60m
SOURCES: Scrophulariaceae: Linaria (32)
34.- SCROPHULARIOSIDE
OH 507 dd C24H28°10! 4 7 6 ' 1682

[a]20D: -93° (c=0.7^, CH3OH) (210)
6.30 dd
UV: (CH3OH) 204 (4.26), 216 (4.19) ,
4.79(d,J7) 222 (4.11), 277 (4.29) (210)
*'t n 2 O G I u (6-Cinnamoy|) IR< KBr, 3400, 1710, 1655. 1640, 158O,

4.15*4.24
1495, and 1450 (210)
1H-NMR: CDÔD, 360 MHz (210)
^C-NMR: CDÔD, (1) 98.2, (3)141.6, (4)
105.8, (5) **6.5. (6)82.9, (?)
130.7, (8)147.8. (9)47.9. (10)
61.5, (1*)100.0, (2')?4.8,(3’)
77.7, (4')71.7, (5')75«6, (6*)
64.6, (r')135.6, (2")130.l\
(3")129.3*. (4")131.6, (5”)129.3
(6")130.1, (a)146.5, (8)118.7,
(CO) 168.4 (210)
DERIVATIVES: Pemtaacetate:
MP: 173-5° (210)
SOURCES: Scrophulariaceae: Scrophularla (3 7 )

188
35.- ACMJSIDE
OH
C2 lH26010‘ 43B- 1525
KP. 145-6° ( 53 )
[oG 20D: -91.5° (EtOH) (53)

UV: (H20), 258 (4.15), (OH") 299(33)
pOH-BenzoylOC H,
OGIu IR: (Nujol) 1708 ( 53)
MP: 126° ( 53 )
SOURCES: Verbenaceae: Vitex. (53)
36.- MELAMPYROSIDE
C22H26°10* 450.1525
MP: 108-110° (54); 84-5° (5 5 )
CcG^D: -50° (c=0.3, Acetone) (55 )
Glu 1H-NMR: Acetone-dg, 60 MHz (55 )
13C-NKR: (1)97.8, (3)141.6, (4)105.5t (5)
46.0, (6)82.7, (7)132.6, (8)142.4
(9)48.4, (10)64.0, (1 ')100.1 , (2 ‘)
74.7, (3')78.0*, (4 *)7 1 .3 . (5 ')
77.7*, (6 *)6 2 .6 , (1")131.0, (2”)
130.5, (3")129.6, (4")134.4, (5 ")
129.6, (6")130.5, (00)167.7 (211)

MP: 74-5° (55 )
[cG ^ D : -94° (c=0.33, Acetone) (55)
SOURCES: Scrophulariaceae: Melanpyrum
(55 )1 Odontites , Euphrasia ( 5^ ).

37.- CATALPOL
189
C15H22010i 362.12X3
6.6 i dd MP i 203-5° (56)
D O 22,5!)! -102°(c=0.98, 90% BtOH) (56)

9(d,JM UVi (H£0) 193 (3-9) (4)
H°CH 2 OGIu
IR« 1665 (**)
^-NMRs D20, 60 MHz ( 56 )
13C-HMRi (1) 93.2, (3) 140.2, (4) 103.2,
(5) 36.6, (6) 76.3,(7) 6 0 .6 ,
(8) 64.7, (9) 42.0, (10) 58.9,
(1’) 97.7. (2') 73-3, (3')
77.3, (4*) 70.1, (5') 77.1,
(6*) 6 1 .2 , (57)
DERIVATIVES Hexaacetates
MPs 140° (56 )
(VpDs -88° (c=1.46, CHCl^) ( 56 )
SOURCES: Bignoniaceae, Buddleiaceae,
Callltrichaceae, Globulariaceae,
Hippurldaceae, Lentibulaxiaceae,
Plantaginaceae, Scrophulariaceae (4 ).
38.- GLOBULARIDIN
4 16(d.J
W l l ' U* - ' ?aa
[a]20!), -57.65 (0.0.51. OHjOH) (50 )
P
UVi (CHÔH) 216 (4.02), 221sh * 278
lO(d.J|)
Cinnamoyl-OCHg OGIu (4.46) ( 58)
4 95-4 2 4
(d,J 13) IR: KBr, 3410, 1705, 1635, 1580,
1500, 1450 (58 )

*H-NMR 1 CDjOD, 100 MHz (58)
13C-NMR: (1) 98.1, (3 ) 6 2 .8? (4) 2 3 .8 ,
(5) 38.1, (6) 73.0, (7) 6 2 .2 ?
(8) 6 3 .3 , (9) 43.3, (10) 64.3,
plus glucose and cinnanoyl
signals ( 58 )
SOURCES 1 Globulariaceae» Globulaxia (5 8 )

190
39.- GLOBULARIN (SCUTELLAROSIDE-l)
c 24h 28°i i ‘ U92*1631

Amorphous powder
[a]Di -?3° (c=1.0, EtOH) (59 )
UVi 278 (**.30) (59 )

t-CinnamoytOCH2 Glu
7.4 5 ,6.4 S( J 16) IR: Nujol, 1686, 1634 (59 )
1H-NMRi D20, 60 MHz (59 )
DEM VATIVE: Pentaacetate:
MP: 14?-9° (58 )
laf°5?8: -103.3 (c=l.0, CHC13) (59 )
13C-NMR: (1) 94.2, (3) 140.9, (4)101.9,
(5) 35.0, (6 ) 79.6, (?) 5 8 .6 ,
(8 ) 6 3 .0 ,(9) 41.9, (10) 61.3,
(1 ’) 96.7, (2 ') 70.7, (3*)
72.5, (4*) 6 8 .2 , (5') 72.2,
(6 ') 61.3, (1") 134.5, (2 ")
128.7, (3") 128.0, (4”) 130.O,
(5") 128.0, (6 ") 128.7, (a)
144.5, (P) 117.7, (CO) 165.9
( 59)
SOURCES: Globulariaceae: Globularia
( 58 )i Labiatae: Scutellaria ( 59 )
40.- KUTKOSIDE
C23H28°13s 512’ 1530

Amorphous powder
[a]D: -145° (c=1.0, EtOH) ( 60 )

4*5-5.2 5
IR: KBr, 3600-3200, 1?00, 1630, 1655,
VanilloylOCH2
4.50 1590, 1500 ( 60 )
1H-NMR: Acetone-dg (60 )
MP: 173° (60)

SOURCES: Scrophulariaceae: Picrorhlza (60).
191
^l.-pICROSIDE-I
QH
4*0-5.20
190-360 C24H280ll' *92.1631
Hygroscopic unstable compound.
[a]Di -82° (c=1.0, CHÔH) (61 )

3.20
h o £ h^2 O G Iu- 6 -C i nnam oyl
IR: Nujol, >00-3200, 1705, I636,
4.35-360 1660, 1605, 1580, 1495 (61 )
(d, J 13)
*H-NMR: D20, 100 MHz (61 )
[n]Di -83° (c=l.0, CHC13) (61 )
13C-NMR: (1) 9^.1. (3) 1W.0, W 101.9.
(5) Jk.9, (6) 79-6, (7) 58.6,
(8) 6 2 .6 , (9) W.6, (10) 61.5,
(1 *) 9 6 .6 , (2 *) 70.7,(3*)72.5.
(4>) 68.5. (5‘) 72.3.(6')6 2 .1 .
(1") 13^.2 , (2") 128.2, (3")
128.7, (**") 130.3. (5") 128.7,
(6") 128.2, (a) 145.5, (8)H7-3.
(CO) 166.2, (33 )
SOURCES: Scrophulariaceae: Plcrorhlza (61),
42.- O-METHYL-CATALPOL
C16H24°10‘ 3 7 6 •1369
540 6 .SO(d, i4) MP: 236-8° ( 56 )
[<x]2 2 -5D: -122° (c=1.64, EtOH) ( 5 6 )

1S00
IR: 1650 ( 56)
HOCHj OGIu
4.3 2(d.Jl3) ^-MMR: D20, 60 MHz (56)
DERIVATIVE: Hexamethyl ether:
MP: 79° ( 36)
[cG2 3 -5D: -91° (c=1.96, CHCl^) ( 56)
X-RAY: ( 56 )
SOURCES: Buddleiaceae: Buddlela (5 6 )

43.- SCUTEIAARIOSID-II
C24H28°12' 508- 1580

Amorphous powder
-80.1 (c=0.5, EtOH) (5 7 )
DERIVATIVE, Hexaace tate1

p ^ o u m a ro y l-O C H 2 OGIu
HP: 153-4° (57 )
[aJP°57Bi -94° (c=1.0t CHCl^) (57)
13C-KMRi (1) 94.1, (3) 141.0, (4) 102.0
(5) 34.9, (6 ) 79.6, (7) 5 6 .6
(8 ) 6 2 .8 , (9 ) 41.9, (10) 6 1 .3
(I1) 96.7, (2 ') 70.7, (3’)72,5
(4’) 68.2, (5*) 72.2, (6')6l.3
(1") 132.3 , (2 ") 129.3. (3")
121.9, (4") 152.0, (5") 121.9,
(6”) 129.3. (a) 143.8, (8)
118.0, (CO) I6 5 .8 (57 )
SOURCES: Lafclatae: Scutellaria ( 57 ).
44.- VERPR0SIDE
ProfocatechuoylO
C22H26°13* ^98.1373
IR, KBr, 1655 ( 62 )
1H-HHR, ( 62 )
HOCH2 OGIu
3.M- 4.1• MS, M+ 792 ( 62 )
SOURCES, Scrophulariaceae1 Veronica (

193
45.- VEKKINQSIDE
Caffeoyl c2 f * W v ' 524*1530

Amorphous substance
6 3 4( d.J S)
3 69 [a]20D« -180.8° (c=0.7, CHÔH) ( 6 3 )
UVs (CH3OH), 328 (4.02), 295 (3-90)

I3 (d,i9 )
hoch2 sh, 243 (3.81), 213 (3.93) ( 6 3 )
IRi KBr, 3400, 1700, 1655, 1632 ( 6 3 )
1H-NMRi CDÔD ( 63 )
13C-NMR: (1) 95-1, (3) 142.1. (4) 102.9
(5) 36.5, (6 ) 81.0,(7) 60.2
(8 ) 6 6 .7 , (9) 42.9, (10) 6 1 .2
(1*) 99.6, (2*) 74.6, (3') 78.1
(4*) 71.4, (5*) 77.3. (6 ') 62.7
(1") 127.4, (2”) 115-3, (3“)
146.4, (4") 149.3. (5") 114.4
(6 ") U 6 .5 , (a) 147.5, (P)
123.2 , (CO) 168.8 ( 63 )
DERIVATIVE. Heptaacetatei
MPi 93.6° ( 63)
[cO^Di -101.97 (c=0.71, CHCl^) (6 3 )
SOURCES! Scrophulariaceae! Veronica (63).

**6.- SPECIOSIDE
C24H2B°12! -508.1580
MP: 244-5° ( 64)
[aJ21D: -203.3° (c=0.4, CHÔH) ( 64)
UV: (CHÔH) 230 (3-82), 315 (4.15) ( 64)
IR: KBr, 3415, 1?15. 1615, 1520, I5OO,
1080 ( 64)
PMR: CDÔD, 90MHz (64)
1H-NMR: CD^D, 90 KHz (64)
l3C-NHR: CÔD (1) 95.2, (3)142.4
(4) 103.0, (5) 36.8, (6 ) 81.4
(7) 6 0 .3 , (8 ) 6 6 .9 , (9) 43.3
(10) 61.3, <1‘) 99.9, (2')
74.9, (3') 78.7, (4') 71.8,
(5’) 77.8, (6 ') 6 3 .O. (1")
136 JB, (2 ") 131.3, (3" * 5")
117.0, (4") 161.7, (6 ") 131.3
(a) 147.3. (S) 11U*5 (CO)

161.6 (64 )
DERIVATIVE: Acetate:
MP: 174-5° (64 )
[a]2Z,D: -113° (c=2.0, CHCl-j) (64 )
SOURCES: Bignonlaceae: Catalpa (64 )

Benzoyl
4?.- VERONICOSIDE 195
509
W n ' 466•1475
6SCKd.j7)
3.S6-454 MP, 167-9° ( 65)
UV« (CH3OH) 205 (1+.09), 232 (4.18),

•-56 4
HOCH2 OGI o 275 (3.02) ( 65)
316-4.54
IRi KBr, 3380, 1?15, I655 (6 5 )
1H-NMR: ftrcldine-d^ (6 5 )
13C-NMR: Fyridine-dy (l) 94.4, (3 )
141.4, (4) 102.0, (5) 36.2
(6 ) 81.0, (7) 59.2, (8 ) 66 .8
(9) 42.9, (10 ) 6 0 .0 , (1 *)
99.8, (2') 74.6, (3‘) 78.5,
(4') 71.2, (5’) 77.9, (6 *)
62.4, (1") 133.4, (2") 129.8
(3") 128.6, (4") 129.9, (5”)
128.6, (6 ") 129.8, (CO) 166.2
( 65 )
MP: 172° (65 )
[VpD: -104.96 (c=0.64, CHCl.j) ( 6 5 )
SOURCES: Scrophulariaceae: Veronica (65)

196
48.- MINECOSIDE
IsoferulovlO C25H300i3' 538‘1686

MP; 142° ( 63)
[a320Di -182° (e=0.64, CHÔH) ( 63)
UV; (CH3OH), 204 (4.13), 244 (3-98),
298 (4.09), 328 (4.18) ( 6 3 )

HOCH2 OGIu
IH; KBr, 3320, 1720, 1655, 1635 ( 63 )
H-NMR: CD30D (6 3 )
13c-nmhi (l) 95 .1 .(3) 1^2 .5 , (4 )103.0
(5) 3 6 .8 ,(6 ) 81.4, (?) 60.3
(8 ) 66.9, (9) 43.3. (10) 61.4
(1*) 99.8, (2 *) 74.9, (3’)
78.7, (4’) 71.9, (5') 77.8,
(6 ’) 6 3 .0 , (1-) 1 28.9 , (2 ")
114.9, (3") 148.1, (4") 151.7
(5") 112.6, (6 ") 114.9, (OCHj)
56.5, (a) 147.3, (6 ) 123.0,
(CO) 168.8 (63 )
MP: 105.5° ( 63)
[a]2^ ; -101.27 (c=0.31, CHCl^) (63 )
SOURCES; Scrophulariaceae; Veronica (6 3 )

197
49.- catalposide
V9-7.9
pOH-Benzoyl C22H26°12!
5.4 MP: 215-7° ( u )

64 d
[a]2 3 ,2D: -184° (c=0.87, CHÔH) (4)
UV: (EtOH), 260 (4.27) (OH-) 303 ( 4 )
IR: (KBr) 1655. 1705 ( 4 )

HOCH2 OGIu
5.0 1H-HMR: D20, 60 MHz ( 66,67 )
13C-NMR: Acetone-dg, (1) 99.8, (3)
142.4, (4) 103.0, (5) 36.8,(6 )
81.6, (7) 60.3. (8 ) 66 .9 , (9 )
4 3 .3 . (10) 61.3. (1') 95-2 .
(2 1) 74.9, (3‘) 78.6, (4*)
71.8, (5’) 77.8, (6 ') 62.9 .
(1 ") 121.9, (2 ",6 ") 132.9, (3".
5") U 6 .2 , (4") 136.7 , (7")
167.9 (64 )
MP: 142-3° (66)
-106 (c=0.75, CHCl^) ( 4 )
SOURCES: Blgnonlaceae, Scrophulariaceae,
Globulariaceae (66,4).
198
50.- AMFHICOSIDE (PICROSIDE II)
V a n iI C23K28°1 3 ! 512.1530
MP: 214-5° (6 6 )
[a]20Di -115° (EtOH) (6 8 )
UV: (EtOH), 223, 268 (68)
IR: (KBr) 3400, 1725,1280.1655,1230,
1610, 1530, 1460,765 (6 8 )
MP: 168-170° (66 )
^-NMR: CDCly 60 MHz, 7.74 (ArH),
7.69 (AxH), 7.13 (ArH), 6 .3 6
(H3), 3.9 (0CH3). 2.70 (H5 ,H9)
2.34-2.04 (Ac), ( 6 8 )
13C-NMR: (1) 94.3. (3) 141.2, (4) 102.0,
(5) 35.3. (6 ) 80.2, (7) 58.9 ,

(8 ) 62.7, (9)41.8, (10) 61.2,
(1') 96.3, (2*) 70.7, (3’) 72.7,
(4') 68.3, (5') 72.4, (6 ') 62.3,
(1”) 128.1, (2 ") 113.6, (3")
151.2, (4") 144.1, (5“) 122.9,
(6 ") 122.9, (CO) 165.7, (OCRj)
5 6 .2 ( 33 )
SOURCES: Bignoniaceae: Amphlcome ( 69 )

51.- 6 -a-L-RHAKNOPYRANOSYL CATALPOL 1-99
C21H32°14! 50BA?9Z
[a]2°589i -124.5° (c=0.1, CH,OH) ( 40)
I3c-NHR: (1) 93.2, (3 ) 140.4, (4)
102.5, (5) 35.7. (6 ) 81.5
(7) 57.5, (6 ) 65.3, (9) 41.2
(10) 58.9, (1’) 97.9, (2 *)
73-5, (3*) 77.4, (4-) 70.3
(5*) 76.5, (6 ') 61.4, (l")
98.9, (2")70.6, (3") 70.3,
(4") 72.0, (5") 68.9, (6 ”)
17.9 (40 )
DERIVATIVE: Octaacetate :
MP: 217° (40 )
[cd2^ : -7.2° (c=0.1, CKCl-j) (40)
SOURCES: Scrophulariaceae:
Scrophularla (40 )
52.- MONOKELITTOSIDE
ci j ! W 362-1213
Amorphous powder
[a]18D: -180° (c=0.7, H?0) (69 )

1H-NMR: T20, 60 MHz (69 )
13C-NMR: (1) 93*6, (3) 142.4, (4) 108.4,
(5 ) 72 .8 , (6 ) 80.5, (7) 127.7.
(8 ) 148.3, (9) 53-6, (10) 60.8,
(1') 99.4, (2’) 74.4, (3') 78.2,
(4') 71.6, (5')77.4. (6 ')6 2 .6 , (211)

MPi 169-170° ( 69 )
SOURCES: labiatae: Mellttls (69 )

200
p-Coumaroyl O 53-- ODOf.’TOSIDE
C24H2B012! 5 0 8 •1580
MP: 1^5-7° { 70)
[a]2°D: -92° (c=0.1, EtOK) ( 7° )

HOCH 2 OGIu UV: 2 3 2 (3 -6 6 ), 273 (2 .61), 282 (2 .5 6 )
(70 )
SOURCES: Scrophulariaceae: Odontites (70)
54.-MELITT0SIDE
OGIu C21H32°15! 52U'm i

MP: 167-8° ( 49 )
J64)
[a]1?D: -29° (c=1.6, HgO) (49)
UV: (EtOH) 209 (3-57) (49 )
'■"2 OGIu IRt 1655 (^9 )

4.3° .
H-NMR: D20 , 60 MHz (49 )
DERIVATIVE: Decaacetate:
MP: 149-150° (49 )
SOURCES: Labiatae: Mellttls (49)
53.- MACFADIENOSIDE
QH
H S03(d,j6 )
Id.JliU 22 C15H2 2 ° U ! 378.1161
6.4l(d,J 6 )
3 6S(d,J1 Hygroscopic substance
[aH28D: -30° (c=0.2, CH30H) (71 )
UV: (CHÔH) 204 (3.4) (71)

HOCH 2 OGIu
4 .3 5 IR: KBr, I65O ( 71)
(d.J 1 25)
1H-NMR: D20, 100 MHz (?1 )
MP: 153-6° ( 71 )
[a328D: -35° (c=0.2, Acetone) ( 71 )
SOURCES:Signoniaceae: Macfadyena (71)

201
56.- GLOBULARIMIN
OH
6 2ldd C24H30O12' 510-1?36
HO** (VpD. -105.97 (c*0.6^,CH30H) (72)
4<d. JS)
UVs (CH-jOH) 217 (4.08), 223sh, 278
(**•38) ( 72 )
t-CinnamoylOCH 2 OGIu
4.56 4.32 IRs KBr, 3400,1702, I638, 1580, 1495,
( d , J 13)
1450 ( 72 )
1H-NMR: CD3OD, 100 MHZ ( 72 )
13C-NMR! CRjOD, (1) 93-3, (3) 140.5
(4) 105-8, (5) 38.4, (6)83.8
(7) 85.4, (8 ) 80.2, (9) 48.9
(10) 66.4 (72 )
DERIVATIVES: Hexaacetate:
Ca]20D: -81.08 (c=0.63, CHCl^ (72)

SOURCES: Globulariaceae: Globularia (72)
57.- CLOBULARININ
C24H30°12' 510‘ 1736

S 12dd
• 4-251 [a]2^ : -84.4? (c=0.64, CH^H) (72 )
6.3ldd
UVS (CH30H) 217 (4.08), 223sh, 278
HO
(**•38) ( 72 )
5 2 (Id 16)
IR: KBr, 3400, 1702, I638, 1580, 1495,
♦-CinnamoylOCHg OGIu
4. 5 5 - 4.34 and 1450 (72 )
( d . J 12 )
1H-NMR: CD30D, 100 MHz ( 72 )
13C-NMR: CD30D, (1) 96.3. (3) 141.6,
(4) 106.4 , (5 ) 38.9, (6 )
78.6, (?) 78.6, (8 ) 81.4,
(9) 44.6, (10) 69.0 ( 72 )
DERIVATIVES: Hexaacetate:
[a]20D! -9 7 .0 6 (c=0.6l, CHC13) (72 )
SOURCES! Globulariaceae 1 Globularia (72)

202
Ill• * Iridoid glycosides: Ten carbon basic skeleton
58.- LAMIOSIDE
C18H28°ll’ 4 2 0 - 1631
Amorphous powder
2 " OH ^ 3
l a f ?Li -133° (c=0 .5, CH30H) ( 7 3 )
6.1 7(q ) ,J )
[tx]l6D: -125° (c=0.5» Dioxane) (73)
UV: 208 (3.6) (73)

96(d JOS)
*H-NMR: D20, 60 MHz ( 73 )
3 OGIu
1.4 2 DERIVATIVE: Isopropylldene:
MP: 194-5° ( 73 )
SOURCES: Labiatae: Lamlurn (73 )
59-- LAMIOL
O H q ^ i C l ^ i .57 ( d , j 1 . 3 ) C16H26°10! 378.1526

Amorphous powder
,6.0»(q,JI3)
I .90 [oG D: -153 (c=0.46, doxane) ( 7 3 )
►
*H-NMR: D20, 60 MHz (73)
HO (d.Jo.l)
DERIVATIVES: Pentaacetate:
.?,3 OGIu
MP: 168-170° ( 73)
-119° (c=0.78, Dioxane) (73)

SOURCES: Labiatae1 Lamlurn ( 73 )
I 36 <
60.- DECAPETALOSIDE
C16H26°8’ 3^6*1627
5.9 Obr
*H-NMR: D20, 90 MHz (18)
13C-NMR: D20, (1) 97-0, (3) 133.9. (4) 115.8,

-490<d,J4)
HOCH, (5) 44.?, (6 ) 29.8, (7) 27.4, (8 )
»7-?42ddO G *«
38.4, (9) 42.8, (10) 65.9, (11) 15.6,
(1 *) 99.1, (2 ') 73.3. (3') 76.7,
(4’) 70.1, (5') 76.3, (6 ’) 61.2, (18)
MP: 114-5° (18)
jV p D : - 90° ( 0= 3 . 7 . CHCI3) ( 1 8 >
SOURCES: Loasaceae: Mentzella (18)

203
61.- V1LL0SIDE
C16H26°9! 3U6- 1627

IR: 3350, 1740, 1720, 1150 ( 74)
HP: 112-3° (74 )

CH
[a]31D: 0° (c=0.5, CHÔH) ( 74)
[a]31405: +36° (c=0.5, CHÔH) (74)
1H-NMR: CDCly 1.18 (d, J=6 , CH^) (74 )
SOURCES: Valerianaceae: Patrlnla (74).
4.J*
62.- RONTINIOSIDE
H2OXyl
57 Old,J 1 1
C21H32C12: 4?6-1893
[a]20D . . U4° (c=l.2, CHjOH) ( 75 )
s : s(d,J 9 ) UV: (CH3OH) 251 (4.0) ( 75 )
OGIu *H-WMR: D20, 90 MHz ( 76 )
13C-NMR: D20, (1) 103.6, (3) 145.0, (4)
110.2, (5) 135-3. (6) 123.1,
(7) 40.7, (8) 38.1, (9) 53-1,
(10) 19.3 , (11) 67.4, (l1)
99.5, (I") 102.3, (2,3,4 of
both glucosyl units) 73.4, 76.4,
70.1 respectively: (5*) 76.7,
(5M) 65.7. (6*) 61.3 ( 76 )
SOURCES: Montlniaceae: Montinla ( 76 )
6 3 ,- VALEROSIDATE
* 15: C21H34°11! 4 6 2 •2101

CH2 OGI u HP: 152° ( 77 ) : 78-80° ( 78 )
fe»Old 1 1) [cfpD: -93° (c=l.0, CHÔH) (77)
'ji/0D: -102° (H20) ( 78 )

6 JS(d JISI
IR: 3400-3350, 1748, 1670, 1455, 1375,
CH30H Ol&ovoleroyl
u»» 1255, 1100 ( 77)
1H-:.’HR: D20, 60 MHz (77)
SOURCES: Valerianaceae: Valeriana ( 78 )

V H 2O C H 3 20 k
64.- SYRINGENONE
C17H24°9' 372.1420
MS: M 372, m/e: 210, 192, 182 ( 79 )
OGIu SOURCES: Oleaceaei Syrlnga. Phylllnea

<79 ).
65.- SYRINGOXIDE
O CHgOCHg
V » ° i o ' 388'13‘9
SOURCES: Oleaceaes Syringa, Phylllnea
( 79 ).
3 OGIu
6 6 .- PATRINOSIDE
CH2 O G I u
C21H34°ll' **6 2 -2101
Colorless prisms
HP: 97-8° ( 80 )
[a]25D: -45.4° (c=1.63, CH30H) ( 80)

HOCH2 O ls o v a le ro y l
IR: KBr, 3370, 1740, 1660 ( 80 )
X-RAY: ( 80 )
HP: 130-2° (81 )
[a]D: -45.7° (EtOH) ( 81 )

*H-NMR: 6.25 (d, J=1.5. H^), 5-86
(d, J=6, Hj), 4.05-4.20 (H1q,
Hu ), 2.7-3*2 (H5), 2.2 (Hfi)
1.95-2.10 (Ac), 0.96 (d, J=6 ,
CH3) (81 )
SOURCES: Valerianaceae: Patrlnla,
Valeriana (81 )
205
67.- OPULUS IRIDOID I
Isolated as a mixture
1H-NHKi 90 MHz ( 82 )
13C-NMR: CDC13 , (1) 89.5, (3) 139-9,

AcO OAc CH24 (4) 113.4, (5 ) 3 1 .9 , (6 ) 34.8
6.45 (7) 80.5, (8 ) 81.1, (9) 44.0
(10) 67.0 , (11) 68.6 , (1 -)

f T 7 ** |*30Cd.i 4) 97.0, (2’) 70.2, (3’) 71.4,
AcOCH^Qm ^ « 2 - M e - b u t y ric
4.34 ■3- M e - b u t y ric (4')6 6 .2 , (5,)74.1.(6')62.2 ( 82)
SOURCES: Caprifoliaceae: Viburnum (82 )
6 8 .- 0FJLUS IRIDOID III
1H-NMR: D20, 90 MHz ( 82)
13C-NKR: D20, (1)91.3. (3) 139.8, (4)
U5.8, (5)30.7, (6)36.9, (7)

X ylO
AcO OAc 7 8 .6 , (8)82.3, (9)44.5, (10)
CH2 4 36
68.5, (U)70.0, (l')97.8,
HOi (2')71.2, (3*)71.2, (4')74.5*

4«0\ 1 O
(5')74.2? (6 *)6 l.l, (1")104.7
6 3 0(d,J 31
AcOCHjOH Q« 2- M e - b u t y r i c (2")73.8, (3")76.5, (4")70.0
4.36 « 3- M e - b u t y r i c (5 ") 6 6 .0 ( 82)
SOURCES: Caprifoliaceae:Viburnum ( 82)
69.- OPULUS IRIDOID II
*H-NMR: CDClj, 90 MHz ( 82 )
13C-NMR: CDCly (1)90.0, (3) 139.8,
(4)113-7, (5) 32.3, (6 ) 34.8

AcO OAc
6.4 3 (7)80.5, (8 ) 82.3,(9)43.9, (10)
AcO
64.2, (11) 68.4, (l1) 97.0 ,
>->• d , J 5 (2*)70.0, (3') 71.1, (4’)65.7.

HOC • 2“ M e-butyric
• 3- M e - b u t y r i c (5') 73-9. (6 *) 62.1 (82 )
SOURCES: Caprifoliaceae: Viburnum ( 82 ).

?0.- OPULUS IRIDOID IV 206
.13C-NMR: D20, (1) 91.4, (3)139.6, (4)
115.8, (5)31.0, (6)37.1. (7)
78.6, (8 )8 3 .6 , (9)44.0, (io)

AcO OAc
6 5 .2 , (11)70.0, (l')97.8,
(2')71.1, (3')71.1, (4’)74.2
(5') 74.2, (6 ')6 l,2 , (1")

HOCH2 f t u * « 2 - M e-butyric
OH ° « 3- M e - b u t y r i c 104.7, (2")73.B, (3")76.6,
(4")70.0, (5 ") 66.0 ( tz )
SOURCES: Caprifoliaceaes: Viburnum (82)
CH jO GIu 71.- PENSTEMDE
C21H30°10‘ 442.1838
UV: 214 (4.33) (83 )
IR: 1750. 1665 (83 )
1H-NMR: DgO, 60 4 100 MHz ( 83 )

HOCHg O lsovaleroyl
13C-NMR: (1) 102.1, (3,10) 140.4, 130.4,
(4) 115.8 , (5.9,8) 46.4. 3 6 .8 ,
2 6 .1 , (6 , 7 ) 43.7, 37.3. (8 )
69.1, (11) 6 0 .5 , (a) 142.0,
(2CH3) 22.5 ( 83 )
SOURCES: Scrophulariaceae1 Penstenon (8 3 )

Revised s t r u c t u r e =(212)
CHO 72.- BOSCHNALOSIDE
C16H24°8! 3W*-1 W
SOURCES: Orobanchaceae: Boschnlakla
( 12 ).
3 OGIu
73.-IXOROSIDE
cl6H24°9‘ 360.1^20
Amorphous powder
[aft. -102.6 (c=0.64, CHÔH) ( 84)

3(d,J3.5)
HO 3 UV: (CH^H) 249 (4.09) ( 84)
OGIu
132t IR: KBr, 3400, 1?30, 1640 (34 )
L20 ( 84)
DERIVATIVE! Pentaacetate:
MP: 93-6° (84)
[oG36D! -102.2 (c=0.69, CHC13) ( 84 )
SOURCES: Rubiaceae: Ixora (84).
74.- TARENN0SIDE
9.31
H=0 C16H22°9 ! 358' 1263
[aH^D: 442.1 (c=1.06, CHÔH) ( 85)
7 5«(d,J5S)
UV: (CHÔH) 250 (4.10) ( 85)
S3! IR: KBr, 3400, 1660-1630 ( 8 5 )

HOCH
Glu 1H-NMR: DgO, 60 KKz ( 85)
HP: 127-9° ( fi5)
[cO^D: -2.3 (c=0.6, CHCl^) (85 )
SOURCES: Rubiaceae: Tarenna (85 )
75." TECOMOSIDE
CH=Q
240-3.1 S C16H24°108 37 6 ' 1369
7.1 21
Amorphous powder
43 6
\afhx -118° (c=0.2, CHÔH) ( 8 6 )
.27 d J 1.5
dd
UV: (EtOH) 241 (4.01) ( 86)
OGIu
1.33 d J a s IR: KBr, 2760, 1670, I63O (86 )
*H-NMR: D20, 100 MHz ( 86 )
MP: 124-5° (86)
SOURCES: Bignoniaceae: Tecoma ( 8 6 )

?6.- GARDOSIDE 208
COOH
°16»22V 37“'m 3
[aj22!)! -33-6° (c=0.9, CH3OH) (8? )
HO
UV, (CH3 OH) 235-5 (3-98), ( 8?)
CH IR: KBr, 3300, 1675, 1625 ( 87)
1H-NMRi D20 ( 87)
MP: 209-211° ( 87)
[cG ^ D . -59.9 (c=0.57, CHC13) (87 )
SOURCES: Rubiaceae: Gardenia (87 ).
77.- BISDESOXYDIHYDROMONOTROPEIN
COOH (DESOXYLOGANIC ACID)
Cl6H29°9! 360.1920
MP: 113-5° ( 86)
UV: 231 (3-29) ( 8e)

CH OGIu IR: 1653, 1678, 1635 ( 88 )
MS: 198 (m«) (88 )
^H-NMR: For Methyl Ester:
Deoxyloganln ( 88 )
SOURCES: Labiatae: Physostegla (83)
78.- DEOXYLOGANIN
COOCH (BISDESOXYDIHYDRO-MONOTROPEIN METHYL ESTER)
7.4 (d, J 1 )
c17H26°9 s 379.1577
MP: 157-8° ( 88 )
[c020D: -90° (c=0.295< EtOH) ( 88 )

M(d,J 4.5)
CH3 OGIu UV: 236 (9.03) ( 88 )

«-Md J6)
IR: 2990 b, 1710, 1690b, 1690 ( 8 8 )
1H-NMR: CD30D, 60 MHz ( 88 )
Derivative: Tetraacetate:
MP: 115-6° ( 89 )
SOURCES; Loganlaceaes: Stxychnoa (89)
Apocynaceaes: Vinca (89), Menyantheaceae:
Menyanthes ( 89 ).
79.- BRASGSIDB
209
5.1 7
C16H22°9* 338,1263
7.41 d J 15
[a]22©, -1?0° (c=0.97, EtOH) (9 0 )
UV« (CH3OH) 233 ( 90 )

| 5 7,
IRi 1735 ( 90 )
CH OGIu
1 .0 l' lH-NMR, 1)20 , 90 MHz ( 90 )
DERIVATIVEi Tetraacetate*
MP, 185-7° { 91 )
SOURCES, Verbenaceae, Verbena ( 91 )
80.- DIHYDR0C0RNIN
COOCH>
3.«1J
C17H26°10' 39°*1526
7.41 MP, 90-100° ( 92)
[a]20D, -126° (c=0.5, EtOH) (92 )
UV, (EtOH) 238 (4.05)( 92 )

n^3 OGIu Sl-NMR, DjO, 100 MHz ( 92 )
DERIVATIVE, Pentaace tate,
MP, 166-8° (92 )
[of]20D: -115° (c= 0.5, EtOH) ( 92 )
SOURCES: Cornaceae, Cornus ( 92 ).
81.- IOGANIC ACID

COOH
C16H24°10* 376.1369
Amorphous compound
HOi
DERIVATIVE, Pentaacetate,
KP, 163° ( 93)

CH
OGIu
I.OSd UV, (EtOH) 230 (4.2), 234 (3-97)( 93)
IR, CHClr 1750, 1715, 1645 ( 93 )
VNMR, 7.45 (s, H3), 1.05 (d. J=7 ,
V (” )
SOURCES, Loasaceae, Mentzella (94 )
Loganlaceae, Strychnos (95 ),
Centlanaceae, Swertla (93 )•

210
82.- lOGANIJf (LOGANOSIDE)
OOCH C^ Z 6 ° 1 0 ! 390•1526
7.»0 MPj 220-2° (96 )
HO [a]D« -62.B° ( 4 )
UV: 237-8 (9.03) { 4 )

CH S-NMR: DgO (96 )
0.90
13C-NHFi D20, (1) 97.6, (3 ) 151.8 ,
(9) II3 .9 , (5 ) 3 0 .7 , (6)41.3,
(7) 74.9, (8 ) 41.0, (9 ) 4 5 .8 ,
(10) 12 .9 , (11) 170.6 , (och3)
5 2 .6 , (1 *) 99.5. (2 ‘) 7 3 .6 ,
(3') 7 6 .6 , (4') 70.5, (5’)
77.2, (6 1) 61.6 (97 )
KP: 140-1° (96)
[cf)D: -79-6° (CHCl^) ( 96 )
IR: 1750, 1705. 1640 (96 )
x - ray ( 9e )
SOURCES: Apocynaceae: Vinca,
Caprifoliaceae: Lonlcera, Cornaceae:
Mastlxla. Loganiaceae: Strychnos.
Henyanthes: ( ^ ).
83.- MUSSAENOSIDE
C17H26°10! 390.1526
3.75>
Amorphous powder
OOCH3
[a]3°D: -106° (c=0.6l, CHyDH) ( 99 )
7.4 fttd.J I)
UV: (CH30H) 238 (4.04) ( 99 )
IR: KBr, 3400, 1695, 1640 ( 99 )

HO ssca.j33)
OGIu ^-NMR: D20, 60 MHz (99)
1.33
MP: 124-6° (99 )
[a]3°D: -92.5° (c=1.18, CHC13) (99)
SOURCES: Rubiaceae: Mussaenda (9 9 ).

84.- LADROSIDE 211
362
cooch3
C26H32°13‘ 55 2 - 18"2
7.3 7 [a]2^ : -6 8 .9 3 (c=0.72, CH^H) (10° )
UVi (CHÔH) 221 (4.07), 236 (4.09), 328
J 5 19 d, J 6 (3.99) ( 10°)
”*3 O G I u ( 6 - C a f f e o y l ) IR: KBr, 1635, 1642, 3400 (100 )
• 6 79-702
6 2 3 , 7 53
1H-NMRi CDÔD, (100 )
13C-NMR: CD-jOD, (1) 95.6. (3) 152.0, (4)
112.7, (5) 32.9, (6 ) 3 0 .6 , (7)
39.6, (B) 81.0, (9) 51.6, (10) 25.0,
(11) 169-3, (1*) 99.4, (2 ') 74.5,
(3') 77.4, (4') 71.4, (5') 75.3,
(6 f) 64.0, (1”) 127.3, (2 M) 115.1,
(3") 146.3, (4") 149.2, (5") 116.4,
(6 ") 123.0, (OCH3) 51.8, (a) 147.1,
(0) 114.6, (CO) 168.9, 169.3 (10° )
MP: 106-8° (10° )
[a]20D: -12.5° (c=0.62, CHCl-j) (100 )
SOURCES: Scrophulariaceae1 Veronica (100 )
8 5 .- KETOLOGANIN (7-OXOLOGANIN)
OOCH C17H24°10! 388.1369
MP: 194-7° ( 10$
UV: (EtOH) 234 (4.02) (101)
IR: Nujol, 3500-3000, 3080, 1745,

CH OGIu 1680, 1615, 1300 (101)
DERIVATIVE1 Tetraacetate:
MP: 107-9°, and 145-7° (101)
[cl)25D: -147 (c=1.0, CHCl.j) (101)
VNMR: 1.13 (d, J=10, HJ0), 2.57
(■, H6), 3.6? (OCH3), 7.35
(d, J=2, H3), 2.06-1.88 (Ac)
( 101)
SOURCES: Gentlanaceae: Swertla (101)
Loganiaceae: Stiychnoe (i02).

8 6 .- VERBENALIN (VERBENALOSIDE) (CORNIN)
37*
COOCH-
C17H24°10' 388.1369
7.5 I (d.J 15) MP: 182-3° ( 103)
[a]Dt -173° (c =3.98, H,0) (103)

53l(d,J 5.5) UVi (EtOH) 290 (2.02) (4 )
IR: KBr, 1?30, I68 5 , 1640 (103)
^H-NMR: D20 ( 103)
13C-NMR: D20, (1) 99-9. (3) 15^.3.
(4) 104.6, (3) 43.4*, (6 )
218.9. (?) 43.8, (8 ) 29.6,
(9) 44.9*, (10) 19.9, (11)
169.7. (D 97.0, (2') 73.5

(3’) 77.1, (4*) 70.4, (5')
76.6, (6 ') 61.5, (OCH3) 52.9( 30 )
MP: 133° (103)
SOURCES: Comaceae: Cornua ( 1 ),
Verbenaceae: Verbena (1°3).
3.7 5 87*- HASTAT0SIDE

COOCH,
OHl C17H24°11: W > 1318
71 5 ( V p D , -320° (H20) (104)
,c.O UV: (H20 ) 234 (3 .98 ) (104 )
IR: KBr, 1620 (lo2*)

OG Iu
1H-NMR: D?0 (104)
13C-NMRi D20| (1) 95.0, (3) 157.0, (4) 105.6,
(5) 74.4, (6 ) 215.4, (7) 40.7, (8 )
26.3, (9) 52.1, (10) 19.4, (11) 168.2,
(och3) 52.7, (1 *) 100.1 ( 105)
MP: 180-2° ( 104)
MS: M+ 572 (104)
SOURCES: Verbenaceae: Verbena (91 )

213
8 8 .- SYRINGOPICROSIDE
C2UH30°ll' 4 9 4 • 1788
Amorphous powder
[a]14*8Di -115° (c=1.0, H20) (106)

IP j 3UOO, 1730, 1685. 1630 . 850 (106 )
1H-NMRi D20 ( 10^
DERIVATIVES: Pentaacetate:
MP: 156° ( 106)
[a]2 0 ,6D: - U 6 .5 (c=l.0, CHC13) ( 106)
SOURCES: Oleaceae: Syrlnga (106)
89.- IPOLAMIIDE
C17H2 6 ° U ! 406-14?5
MP: 194-5° (107)
[a]13D: -136° (c=0.5, Dioxane) (10?)
UV, (CHÔH.) 229 (4.03) (107)
IR: KBr, 1700, 1640 (107)
1H-NMR: D20 (10?)
13C-NMR: D 0, (1) 99.3. (3) 152.9, (4)

^ «
114.0, (5) 71.5, (6 ) 39.4,
(7) 3 8 .0? (8 ) 6 1.6 , (9) 55.2,
(10) 22.8, (11) 169.1, (OCH^)
52.5, (1’) 94.5, (2 ') 73-3 .
(3’) 77.1, (4’) 70.5, (5‘)
76.2, (6 *) 60.7 (108)
MP: 143-5° (107)
l a ? ?V, -77° (c=0.6, Dioxane) (107 )
SOURCES: Lablatae: Iamlum (107),
Verbenaceae 1 Stachytarpheta ( 108).

90.- IPOLAMIIDOSIDE 214
3«0 >
OOCH3 C19H28°12' khQA^°
^ r.tn [aJl6D: -60° (c=0.?, Dioxane) (109)
UV: (CH30H) 229 (3-90) ( 10S5

6 tabr. 1 . IBs KBr, 1720sh, 1705, I63O { 109 )
OGIu *H-NMR: (109)
KPi 144-5° (109)
[cJ*8D: -76° (c=0.5. Dioxane) ( 10$i)
SOURCES: Lablatae: lamiiuin (109).
91.- SKANZHISIDE
OOH
Cl6H240i r 392’1318
^ 7 1 a1
MF: 82-90° ( HO)
[a]D: -81.7° (EtOH) (HO)

55 aidja)
UV: 229 (4.04) (110)
OGIu
IR: 3600-3200, 1650, 1510 (110)
1H-NMR: D20 ( 110)
MP: 111-2° ( 110)
[a]D: -82.4° (EtOH) ( 110)
SOURCES: Rubiaceae: Gardenia (HO).
92.- SHANZHISIDE METHYL ESTER

371
COOCH3 C17H2 6 ° u ! U06'lk73
Amorphous powder
7.4• (d,J 1 )
[a]3°D: -110.8° (c=0.42, CHÔH) ( 99)
UV: (CHÔH) 238 (3-93) (99 )
IR: 3400, 1690, 1640 ( 99) .

Glu
*H-NMR: Dz0 ( 99)
MP* 173-5° (99 )
M 30D: -111.9 (c=0.67, CHC1 ) (99)

3
SOURCES: Rubiaceae: Mussaenda (99)
C O O C Ho 93-- CARYOPTOSIDE (5-DESOXY-LAMIIDE)
U06.1475
DERIVATIVE: Pentaacetatei
MP: 137-9° (HI)

CH3 O G Iu MSs jn/£ 269, 139 (111)
^H-NMRs CDCly 60 MHz: 1.20 (CH-j)
3.68 (0CH3), 7.30 (H-3),
1.90-2.05 (Ac) (111)
SOURCES: Verbenaceaei Caryopterls (1)
94.- GENTIOSIDE
COOCH3
C17H2^°11:
DERIVATIVE: Pentaacetate s
MP: 191-2° ( 38)
[aJ^Di -102° (CHCI3) ( 38)

CH3 O G Iu
UV: 209, 219, 243, 251. and 269 ( 38)
IR: 3500, 1715, 1615 ( 38 )
1H-NMR. 3.75 (0CH3), 5.60 (h6), ?.4O
(H3). 1.26 (H10) (38)
SOURCES: Gentianaceae: Gentlana (38 ).
3 73 95." BARLERIN
OOCH-
C19H26°12' ^ 6AU2k
MP: 180° (112 )
HOi
[ c tlp D i -1 0 2 ° (CH30H) (112 )
sea Id.J > UV« 235 (3-76) (112)
OG Iu
iso IRi 1695, 1640 (112)
1H-NMRi (112)
DERIVATIVE! Hexaacetatei
MPi 182° (112)
[a^Di -96° (CHClj) (II2)
SOURCESi Acanthaceae: Barlerla (112).

216
96.- ACETYL BARLERIN
3.7 J
OOCH, C21H28°13l W 8 -153°
IRi 1695. 1640 (112)
UVi 235 (3.76) (112)
*H-NMR. (H2)
3 10 5 9 0( d, J 3 )
DERIVATIVE . Hexaace tatei
"*3 OG Iu
1.5 0 »
MP. 182° (H2)
[a]2^ : -96° (CHClj) (112)

SOURCES: Acanthaceae: Barlerla (112).
97.- FULCHELLOSIDE I
C17H26°12!
422.1424
OOCH Amorphous powder
[a]21D: -148° (c=0.97. EtOH) ( 113)
UV: (CHÔH) 233 ( 113)
IR: KBr, 1687, 1625 ( 113)
OGIu ^H-NMRt D20, 60 MHz (113)
MP: 166-9° ( 113 )s 171-4° ( 90 )
[cf|21D: -91.5° (c=0.3 , EtOH) ( 90 )
SOURCES: Verbenaceae: Verbena (113 )
98.- PULCHELLOSIDE-II
C17H26°12« 422<1"24
OOCH MP. 150-3° ( 114)
CaU21D. -95° (c=1.01, EtOH) ( 114)
UV: (CHÔH) 233 (11*$
71 d,J 1* IR. KBr, 1687, 1625 ( 11*$
1H-NMR: ( 90 )
C *j3 . O G Iu
l .i odTJ 6 *
MP. 132° (114 )
[cO^D: -88.7° (c=0.56, EtOH) ( 90 )
SOURCES: Verbenaceae. Verbena (114 )

99." LAMIIDE 217
COOCH- c17h2 6°12> 422.1424
Amorphous powder
7 3 31
[a]22D: -127 (c=l.l, CHÔH) (107)
UVi (EtOH) 229 (4.02) (107)
OGIu IF I KBr, 1700 (107)

1.0It
Vnmri d2o (107)
DERIVATIVE •. Pentaacetate i
HP: 186-8° (107)
[a]1^ : -83° (c=0.8, Dioxane) (10?)
SOURCES 1 Labiatae: Lamlum (107 ),
Phlomls (115 ). Verbenaceae 1
Chascanum ( 116) , Duranta (H7).
100.- LAMIID0SIDE
HO f OOCH3
7.5 1»
C26H32°14! 56B.1792
pO H - t-C innam oy Amorphous powder
7 6 5-640
[a]18Di -80° (c=0.34, CHjOH) (115)
(0.J16)
UVi (CH30H) 311 (4.18), 227 (4.22,
OGIu
II• 212sh (1 1 5 )
IRi KBr, 1710-1690, 1633, 1605, 1595,
1520, 1440 , 840 ( 115)

1H-NMRs D20 , 60 MHz (
DERIVATIVE: Pentaacetate!
MP: 199-200° ( 113
SOURCES: Labiataei Phlomls (115)
101.- DURANTOSIDE-III
HO COOCH3
2.33 - 25 ■
C28H36°15‘ 612‘ 2053
D i-O -M e-C affeoylO Amorphous substance
4 55-4.9 7
UV: (H20 ) 311 (4.16), 226 (4.31),
191 (4.34) (117)

O G Iu
III
IR: KBr, 1700, 1630, 1510 (11?)
1H-NMR: CD30D, 60 MHz ( 117)
MS: 822 ( 117)
SOURCES: Verbenaceae: Duranta (117)

HQ C O O C H 3 102.- DURANTOSIDE-II
233-760. 582.1948
O -M e-C oum aroylO
4.S3-S.00 Amorphous substance
UV: (H20) 310 (4.30), 228 (4.29),
O G Iu 189 (4.29) (117)

1 It
IR: KBr, 1700, 1630, 1600, 1510, 1040,
840 (117)
2H-NMR: CDÔD, 60 MHz (117)
MP: 161-6° (117)
MS: 792 ( 117)
3*2 103.- DURANTOSIDE-I

C O O CH -
HO C26H32°13’ 552*1842
2 3 0-2.6.
Amorphous substance
f-C innam oyl O
460-
7J3-MJ UV: (H20) 282 (4.29), 224 (4.24) (117)
IR: 3010, 1700, 1630, 1600, 1500,

OGIu
1.20 1290, 873. 780, 695 (11?)
PMR: CDÔD, 60MHz (11?)
MP: 199-204° (117)
MS: 762 (117)
31 2 104.-LAMALBID (la mi rid os id e )

OH OOCH
4.10 V ” 7 c17H26°12‘ k 2 Z ' l k Z k
7,53
HO [aJ20D: -124° (H20) (118)
3 72
UV: (CH3OH)235 (3.96) (118)
CH. IR: KBr, 1695. 1635 ( H 8 )

Glu
1.
27'
^K-NMR: D2 0, 60 MHz (118)
MP: 189-190° (119 ). 195° (118)
SOURCES: Labiataei lamlurn (118).

105.- PHLOMIOL
ooch 3 C17H26°13: ^38.1373

4.2 I(d,J 4
HP! 150-1° (120)
HO
3.76(J,J4 5) [a^D: -112° (c=0 .5 , CH30H) (120)
5.9 2 br 1 UVi (C H ^H ) 231 (3.83) (12°)
OGIu IR: 1?0 5 , I635, 1300 (120)
1.21
*H-NMR: D20 (120)
DERIVATIVE: Heptaacetatei
HP: 202-3° (120)
SOURCES! labiatae! Phlomls (120)
106.- ADOXOSIDE
COOCH3
‘W W w - 1* 6
MPi 140.5. 141.5° ( 121 )

[ a ^ D : -63° (c=2.0, CHClJ (121 )
HOCH
OGIu 1H-NHR: CDC13, 90 MHz, 7.40 (br. s. H3)
3.73 (0CH3), 2.90 (m, H5), 5.18
(d, J=4.0, Hj), 1.95-2.10 (Ac)
(121 )
SOURCES: Adoxaceae: Adoxa (121 )
107.- GENIPOSIDIC ACID

COOH
C16H22°10 S 37^ 1213
7.5 6»
[cG24D: +19.3 (c=1.01, CH30H) ( 84)
UV: (CH30H) 237 (3.6*0 (64)

5.2 5(0,J 7)
IR: KBr, 35OO, 1680, I63O ( 84)
HOCH2 OGIu
^-NMR: D20 ( 84 )
SOURCES: Rubiaceae: Ixora (84),
Genlpa (122) ,
108.- GENIFOSIDE
3.7 S
C17H24°10S 388 • 1369

HP-. 163-4° (123)
7.5 5(d,Jl )
[a]2^ : +7.5° (EtOH) (123)
UV: (EtOH) 236.5 (4.08) (123)
HOCH IP: Or, 3400, 1710, 1700, 1640 (123)

OGIu
4.2 2 m
^-HMR: D20, 60 MHz (123)
MP: 137-8° (123)
[a]20D: +11° (EtOH) (123)
SOURCES: Rubiaceae: Gardenia (123)

Comaccao: Comug (124)
3.7*1
COOCH. 109. CENIPIN-1-0-8-GENTI0BIOSIDE
C23H34°15 550.1897
7 6 6(<J,J 1.5 )
595m MP: 227-9 ° (123)
[a]22D: 0 (c=l.0, CH30H) (123)

5 3 3(dJ7)
HOCH UV: (EtOH) 238 (4.11) (123)
O G Iu-G lu
6 - 1” IR: KBr, 1710, I690, 1640, (123 )
Sl-NMR: D20, 100 MHz (1 2 3 )
DERIVATIVE: Ocatace tate:
MP: 167-9° (123)
[alpD: 0 (c=0.5, CHÔH) (1 2 3 )

SOURCES 1 Rubiaceae1 Gardenia (123)
110.- flumieride
C21H26°1 2 ! 4 7 0 •1423
COOCH, MP: 224-5° (3 )
M 16D: -114° (c=0.54, H20) ( 5
[a] D: -80° (CH_0H) (3 )
UV: (EtOH) 216 (4.2) (3 )
IR: 1700, 1650, 1630 (3 )

« G|U
CH.
MP: 149-150° (3 )
-.20
M D: -138° (c=0.9, CHC13) ( 3 )
SOURCES: Apocynaceae: Pluwlerla (3 )

111.- THEVESIDE 221
COOH
3.2 Is C 16H22°11! 390.1161
10 11
6 22 Amorphous powder
UVi (EtOH) 231 (3-85) (125)

7d J 6
hoch2 IR: KBr, 2700-2300, 16?0, 1634 (125)
4 .6 5 I OGIu
1H-NMR: D20, 100 KHz (126)
[a^Di -34.3 (c=2.18, CHCLj) ( 125)
SOURCES: Apocynaceae: Thevetla ( 125),
Cerbera ( 127).
4 25
COOCH 112.- THJEVIRIDOSIDE
HO
3 2 ti
C17H24°11! 388.1369
6 [a]D: -23° (H20 ) (128)
UV: 233-4 (3.9) (128)

HOCH OGIu IR: KBr, I698, 1678, 1621 (128)
1H-NKR: D20, 100 MHz (128)

MP: 122-123° ( 12f5
[cfpD: -15-5° (c=2.28, CHC^) (125 )
SOURCES: Apocynaceae: Thevetla (128 ),
Cerbera (1 2 7 ) •
113.- DEACETOi-ASPERULOSIDIC ACID

OH COOH
C16H22°11’ 390-1161
7.70<d,J I) MP: 138-1^5° (softening) ( 129 )
6,0 Sin
[a]D: +33-5 <H20) ( 129 )
IR: 2700-2400, l?00b, 1640 ( 44 )

HOCH, ,
° gi« ^H-NMR: D20 (44 )
13C-NMR: CDÔD, (1) 101.5, (3) 155.6,
(4) 108.3, (5) 42.6, (6 ) 7 5 .3 ,
(7) 129.9, (8 ) 151.3. (9)45.7,
(10) 6 1 .6 , (11) 170.9 (46 )
SOURCES: artefact formed during extraction
of asperuloslde (44 ). Rubiaceae (129).

222
114.- SCANDOSIDE
QH OOH Cl6H22°ll! 39°-1161

MP: 139-143° <13°)
51 S [a]30D: -33-3 (H20) (130)
UV-. 233 (4.16) (130)

HOCH IR: 3330-320 0 , 1690, 1635 (13°)
OGIu
1H-NMRi D20 (130)
13C-NMR: CDÔD, (1) 98.8, (3) 154.0
(4) 111.0, (5 ) 47.0, (6 ) 82.4
(7) 129.9, (8 ) 147.3, (9)45.9,

(10) 61.1, (11) 172.1 (46 )
DERIVATIVES: Methyl-ester:
Iff: 134° (130 )
SOURCES: Rubiaceae: Paederia (130)
115.- ASPERULOSIDIC ACID

OH COOH
cieH24°i2! ^ 2-1267
MP: 127-131° (44)
[V)22D; +8.6 (c=0.9e,CHÔH) (44)
AcOCH UV: (EtOH), 234 (3.95) (44)

OGIu
IR: (KBr) 2700-2400, 1700, I63O (44)
^-NMR: D20, 60 MHz (44 )
SOURCES: Product obtained from hydrolysis
of Asperuloside ( 44 ) Rubiaceae 1 Galluro ( 21 3 )
116.- 6 -EFI-PAEDEROSIDIC ACID
C18H24 ° U S* ^8.1039
Iff: 85-91° ( 44)
HO COOH
[a]23D: +26.4 (c=0.58, CHÔH) ( 44 )
UV: (EtOH) 233 (3.91) ( 44 )
IR: KBr, 2700-2350, 1700, 1640 ( 44)
1H-NMR: D2 0, 60 MHz (44)
SOURCES: Product obtained upon heating

Paederoside (44).S t r u c t u r e ( 2 1 4 )
117.- 10-ACETYX SCANDOSIDE
OH COOH
C18H24°12! **32.1267
.7 .SKd.JtO) MP, 133-7° (44)
3.94m
[a]22!): -17.1° (c=l.02, CHÔH) (44)
3 36(03.0)
UV: (EtOH), 233 (3.97)C^)
A cO C H 2 o G Iu
2.1S» 4.13m IR: (KBr), 2700 2400, 1700, 1672,
1630. (4U)
1H-NKR: D20, 60 MHz (44 )
DERIVATIVE: Pentaacetate Methyl Ester:
MP> 133-5° (41+)

SOURCES: Product obtained upon
extraction of Asperuloside. (44 ).
118.- paederosidic acid

OH :o o h
C18H24°llSi ***'11039
7 7Old J 1.5) MP: 124-9° ( 44 )
[a]24D: +28.2 (CHÔH) (13° )

2.701
[ a f b , +54.4 (CH30H) ( 44 )
O G Iu
UV: 233 (4.04) (130 )
IR: 3550, 2750, 2450, 1690, 1635 (130)

1H-NMR: D£0 (130)
SOURCES: Rubiaceae: Paederia ( 130 )
Also reported as an artefact formed
upon extraction of Paederoside ( 44 )

S t ru c t u r e ( 2 1 4 )
119.- SCANDOSIDE METHYL ESTER

375
COOCH C17H24°11‘ 404-1318
[aJ^D: -56.11 (c=2.42, CH^H) (87)
7S0(d,J 3)
3J i m UV, (CHÔH) 236(3.89) (87)
IR, Nujol, 1695, 1635 t87 )

15 3 t(d,J 4.51
1H-NMR- D20 (87)
'2 OGIu
MP: 132-4° ( 87)
Ca]33D: -87.6 (c-1.01, CHC^) ( 87)
SOURCES, Rubiaceae: Gardenia ( 8 7 )

224
120.- FERETOSIDE
37 S »
COOCH3 C17H2^°11*
DERIVATIVE! Hexaacetate:
74 5
5.5 5 MPs 133-4° ( 50 )
,5.9 Old [c J^ D : -78° (CH-jOH) ( 30 )

H O CH 2 £ g 1u uvs (ch3oh) 233 (3.8) ( 50 )
4.7 51
IRi KBr, 1745, 1700, 1645 ( 50 )
1H-NMR: CDC13 , 1.90-2.10 (Ac), 3-25
(m, H5, H9), 3-75 (OCH3),
4.75 (m, H10), 5.55 (m, H?),
5.90 (in, H j ) , 7.1*5 ( « . H? ) (50 )
13C-NMR: CDC13 , (1) 95-5. (3) 151-3 .
(4) 109.4, (5) 39.8, (6) 81.6,
(?) 129.0, (8) 142.9, (9) 46.3,
(10) 61.2, (11) 166.7, (OCH3)
51.4, (11) 96.7, (2') 70.9 .
(3') 72.6, (41) 68.5, (5')
72.6, (6’) 61.8, (50 )
SOURCES: RuUlaceae: Feretla (50 )
121.- DAPHYLLOSIDE
3 75 C19H26°12'
OH COOCH3 MPi 94-8° (131)
7.7 d [a]18D: +19.7° (c=1.42, HgO) (131)

6.01
UV, (c k 3o h ), 235 (3-95) (131)
IR: (KBr). 1730, 1710, 1635 (44)

AcOCH
O G Iu *H-NMRi D20, 60 MHz ( 131)
DERIVATIVE: Pentaacetate,
MP, 58° (131)
[a]l6D, +51-3 (c=0.78, EtOH) (131)
SOURCES! Daphnlphyllaceae! Daphnlphyllum
(131)1 artefact formed upon methanolysis
of asperuloside ( 44 ).
225
122.- DEACETYL-ASPERULOSIDE
Cl6H20°10! 372.1056
7 .2 0 KPi 118-120° ( 44 )
5.6 7
-88.3° (EtOH) (130)
[ttJ24Di -119.4° (c=0.5, CHÔH) (44 )

HOCH
4.2 3'
OGIu UV: 239 (3.66) (130 )
IR> 1655. 1735 (130)
1H-NMR: D20 (130)
HP: 154-5° (130 )
[cG 17D: -128.6° (c =0.65, EtOH) (130)
SOURCES: Rubiaceae: Paederla (130)
Asperula ( 132 ). also formed as an
artefact upon extraction of asperuloside (44).
123.- ASPERULOSIDE
C18H22°11 ‘ 4 1 4 - 1161
MP: 131-2° ( 4 )
7 41
[aJ16D: -200 (c=l.4, H20) (4 )
UV: (EtOH) 234.5 (3-83) ( 4 )
IR: (KBr) 1664, 1757, 1745 ( 4 )

AcOCH
2.2 7
OGIu
4 6S 1H-HMR» D20 , 60 MHz (133)
13C-NMR: D20, (1) 99.4, (3) 150.6, (4)
105.6 , (5) 3 6 .8 . (6 ) 86.9,(7)
128.8 , (8 ) 143.2, (9) 44.5,
(10) 62.1, (U) 173.8, (r)
93.6, (2 ’) 73.6, (3’) 77-2,
(4 ') 7 0 .6 , (5 ’) 76 .6 , (6 *)
61.8, (CO) 174.0, (50)
DERIVATIVE 1 Tetraacetate:
MP: 154-5° (4)
-128.6° (c=0.65 , EtOH) (4 )
SOURCES: Daphniphyllaceae, Ericaceae.
Globularlaceae, Harunamelldaceae,
Rubiaceae (133, 134, 4)

124.- FAEDEROSIDE
C18H22°10Sl 430-°” 3
MP: 122-3° ( 130)
[cfJ^D: -195.6 (CHÔH) (130)
UV: 235 (4.02) (130)
IRs 3350, 1740, 1710, I63O (130)
MP: 153-5° (130)
1H-NMK: CDC13 , 7.23 (d, J=2, H3),
5.72 (d. J=2, Hj). 5-80 (H?)
4.82 (H10), 2.36 (Ac-S), 2.11-
2.00 (Ac) ( 130 )

SOURCES: Rubiaceae: Paederla (130)
Structure ( 2 1 4 )
125-- MONOTROFEIN
C 0 • 390.1161
16 22 11 J
MP: 161-3° (CRjOH), 170-3° (H20) (135)
0 ] l6D: -130.7 (c=l.04, H20) (135
UV: (EtOH) 235 (3.98) ( 135)
IR: 3580, 2800-2500, 1700, 1675.
1645, 1615 (133
X-RAY: ( 136 )
DERIVATIVE: Pentaacetate-methyl-ester
MP: 147-8° (135)
[a]26D: -17.8 (c=0.43, EtOH) ( 135)
-NMR: CDC13 , 7.32 (H3), 6.2 (dd, Hg)
5.61 (Hp), 4.52 (d, J=3. Hj)
4.15 (H10), 3-70 (OCH3), 3.50
(H5), 2.66 (q. H9) (135)
SOURCES: Ericaceae: Vacclnlum.
Clobularlaceae: Globularla.
Hammamelldaceae1 Llquldambar.
Monotropaceae: Monotropagture■
lyrolaeeae: Chlmaphlla. Pyrola, Monotropa
Rubiaceae: Galium, Asperula ( ^ ) .

22?
126.- VACCINIOSIDE
COOH C25H28°13‘ 536.1530

MP: 150-3° (137)
746
5.67- 5.64 ^
|V)17D: -75.2 (c=1.0, H„0 ) (137)
P
I614 {d, J 16) 1H-NMRj D20 (138)
P-C oum aroyl-O C H jO H § G|u IR: KBr, 3400-3200, I685, 1605 (138)
6 62-7.32 4.23 br. i
DERIVATIVE 1 Pentaacetate1
MP: 110-2° (138)
SOURCES: Ericaceae: Vacclnluin (138).
127.- MONOTROPEIN-METHYL ESTER

OOCH
C17H24°11! W A -1318
13C-NMR: CD30D, (1) 95-2, (3) 152-5.
(4) 110.5. (5)38.8, (6)
HOH0C i. 137.5. (7) 133.7, (8) 85-9 ,

OGIu
(9) 45.4. (10) 68.3. (11)
169.0, (OCH^) 51.6 ( ^ )

MP: 147-8° (135)
[a]18D: -76.25° (c=0.e, EtOH) ( 13$
SOURCES: ( 135)
128.- NYCTANTHOSIDE
C O OC H 3 C17H26°12' liZ2'll*2li
7.55td.J 1.5) DxD^D, -65.1° (CHÔH) (139)

HO
UV: (H20) 237 (3-84) (139)
5.3 S(d J4.5) IR: KBr, 1695. 1635 (139)
HOCH2 t> G ,u
^H-NMR: D20 (139)
SOURCES: Ver'benaceae 1 Mycthantes (139)

129.- GARDENOSIDE 228
COOCH, C17H24°ll’
HP: 64-5° ( 50 )
[ a ] 20D: -70.5° (c=1.0, CHÔH) ( 5 0 )

HO UV: (CH30H) 233 (3-5) (50 )
IR: KBr. 1760.1720, I65O (50)

*H-NMR: CDCl^, 1.80-2.05 (Ac), 2.80
(dd, H?), 3-68 (OCH3), 5.90
(d, H^,), 6 .0 7 (d, Hj), 6.3 6
(dd, H6), 7.35 (H3) (50 )
13C-NNR: (Free Compound); CD3OD, (1)
94.4, (3) 152.0, (4) 111.6,
(5) 38.9, (6 ) 135.8* (7)
135-9? (8 ) 86.3, (9) 52.**,
(10) 67.2, (11) 169.7, (0CH3)
51.6 (l^)
SOURCES: Rubiaceae: Feretla ( 50)
Gardenia ( 87 )
130.- forsythide
COOH Cl6H22°ll‘ 390.1161

Amorphous powder
7.53 (d,J 0
[o]3°D: -64.7° (c=1.0, CH30H) (l1^ )
UV: (CH30H) 234 (4.06) (140 )

wJ Ts.3 3(d.i5
IR: Nujol, 3500-3100, 2800-2500, 1685,
HOOC OGIu
1630 ( 140)
*H-NMR: DgO, 60 MHz (140)
MP: 253-5° (1U0)

SOURCES: Oleaceae: Forsythla (140 ).
229
131.- FORSYTHIDE METHYL ESTER

COOH
Cl?H24°ll' i*o 4 ‘ 1318
Amorphous powder
[a]32D: -51.9 (c=1.0, CHÔH) (140)
UV.- (CH30H) 233-5 (4.05) (l40 )
IRr KBr, 3500-3000, 2800-2500, 1710,
1690, I63O (140)
1H-HMRi D20, 60 MHz (LUO )
MP: 191-3° (l40)
[a332D: -54.7 (c=1.0, chci 3) (140 )
SOURCES: Oleaceae: Forsythla (l40 )
132.- 1XOSIDE
COOH
C16H20°11‘ 388'1005
Amorphous powder
7.03ini
[a]3^ : +33-6 (e-1.15. H20) ( 84 )
7(dJ5 ) UVi (H20) 219 (4.16) ( 84 )
HOOC OG Iu IR: KBr, 3400, 1700, 1620 (84 )
1H-NMRi D20 ( 84)
HP: 236-7° (84 )
[cG35D! -3.2° (c=0.28, CH30H) ( 84)
SOURCES: Rubiaceae: Ixora (84 )

133.- GRISELINOSIDE
C 18H24°12! ^ 2 . 1 26 ?
D O 21* -117° (c=0.3, CHÔH) ( 105)
UVi (CH3OH) 235 (9.0) ( 105)
1H-NMR: D20 , 90 MHz (105 )
13C-NMRi D20 (1) 96.9, (3) 159.6, (9) 109.0
(5) 90.7, (6) 215*5, (?) 37.9,
(8) 39.8, (9) 99.0, (10) 176.3
(11) 169.2, (OCH3) 53.9, (1*)
100.3 ( 105)
MP: 188-9° ( 105 )
[a]21L: -122° (c=0.3, CHC13) (I0 5 )
DERIVATIVE: Enol-pentaacetate:
MP: 179-6° ( 105)
[c024D: 9.9° (c=0.6, CHC13) ( 105)
SOURCES: Comaceae: Grlsellnla ( 105)
!>+•- ARA1IDI0SID3
C18H29°131 **8- 1216

[dU^D: -211° (c=0.3, CH30H) (105 )
UV: (CH-jOH) 232 (3.99) (105 )
1H-NMR: D20, 90 MHz (105 )
13C-NMR: D20, (1) 95-3. (3) 157.5, (9) 105.9,
(5) 79.0, (6) 212.0, (7) no recorded
(8) 36.2, (9) 97.1, (10) 175.9, (11)
167.9, (OCH3) 53-9, 52.8, (1') 100.2
(105 )
MP: 188-190° ( 1°5)
[cG 25D: -232° (e=0.5, CHC13) (105 )
SOURCES: C o m a c e a e : Aralldlurn ( 105 )

231
IV. - Secoiridoid glycosides: Simple
135.- LONICEROSIDE ( SECOLOGANIN)
WvPio' 388‘1369
[a]Ds -105° (c=l.l, CHÔH) (141)
UV: (EtOH) 236 (3*99) (1 W )
IR: Neat, 3400, 1700, 1623 (141)
COOCH, 13C-NMRs D20, (1) 97.6, (3 ) 154.0, (4)
109.6 , (5 ) 27.5, (6) 44.6, (7)
20 6 .8 , (8) 133.6, (9) 44.6, (10)
121.6, (11) 169.8, (0CH3) 52.6,
OGIu (I1) 99.6, (2') 73.5. (3') 76.6,
(4’) 70.5, (5‘) 77.2, (6*) 61.6

(9? ).
MP: 115-6° ( 141)
[a]D: -102° (c=1.0, CHC1,) (i4l)
1H-NHR: CDC13 , 9-67 (H?), 7.38 (H^,
3-66 (OCH3) ( 141 )
SOURCES: Caprlfollaceae: Lonlcera

( 141), Synthesis (142 )•
136.- SVERTIAMARIN (SWERT1AMAR0SIDE)
C16H22°11s 390.1161
Si-NMR: D20, 60 MHz (143)
MP: 190-1° (143)
UV: 206 (3.2), 234(4.0) (143)

57S(d. J1.5)
IR: 350e, 1697, 1618, 840 (14^
O G Iu 13C-NMR: CDC13, (1) 97.7, (3) 150.7 , (4)
109.9, (5) 63.1, (6) 3 2 .6 , (7 )
64.6, (8) I3 I.5 , (9) 5 0 .8 , (10)
121.3, (11) 164.8. (I1) 97.0,

(2*) 70.7, (3’) 72.4, (4‘) 68.2
(5*) 71.9, (6*) 61.6 ( 90)

SOURCES: Gentianaceae: Swertla (12)
232
137.- SWEROSIDE
C16H22°9' 358.1263
Amorphous powder
[a]2^ : -236° (H20) (144)
UV: 246 (3.92) (144)

jL O
1H-NMR: D20, 60 MHz (144)
ft,. O G Iu 13C-NKRi D20, (1) 98.4, (3) 154.2, (4)
105-6 , (5) 27.3, (6 ) 24.8, (7)
70.4, (8 ) 132.2, (9) 42.5, (10)
121-5. (11) 170.2, (1’) 99.2,
(2*) 73-5, (3’) 76.4, (4') 70.4,
(5*) 72.1, (6 ’) 6 1 .6 ( 97)

MP: 167-8° (144)
[d]27D: -250° (CHCI3) (144)
[a]D: -173° (CHCLj) (145)
Loganiaceae: Antboclplsta ( 4 ).
Stereochemistry ( 1^*6 )
Loasaceae 1 Ment2ella (18)
138.- EUSTQSIDE
OH C16”23°11C1‘426,0928 233
7.6 9 Hygroscopic, bitter tasting, white powder
[aJ^Dt -100° <c=1.0, CHÔH) ( 147)

HO,
UVi (CH30H) 237 (3.86) (147)
3-4*
Glu IR: KBr, 3350, 1685, 1610 (147)
1H-NMF: D20 , 60 MHz (147 )
MP: 158-160° (147)
[a^D: -81° (c=1.0, CHCl^) ( 147)
13C-NMR: CDCLj, (1) 94.7, (3) 150.5,
(4) 110.5, (5) 62.9, (6 ) 31.5.
(7) 6^.2 , (8 ) 69.9, (9) **5.8,
(10) *43-6, (11) 16*4.0, (1*)
96.9, (2 ') 70.6, (3') 71.6 ,
(V) 68.2, (5*) 72.3, (6 *)
6 1 .6 (1*7)
SOURCES: Gentianaceae: Eustoroa (14? )

139.- EUSTOMOSIDE
c w 0 : 390.1161
16 22 11
Amorphous, colorless bitter principle
OH
1.13-2.4 3 [a]2^ : -123.2° (c=1.01, CHÔH) (147)
7.7 3
UV: (CH3OH) 235.5 (3-94) (lU?)
2.70-30! IR: KBr, 3*400, 1695, 1620 (147)
1H-NMR: D20, 60 MHz (14? )
MP: 201-3° (147)
[a]*0D: -101.8° (c=1.01, CHC13) (14?)
13C-NHR: CDC13 , (1) 95.8, (3) 150.0,
(*4) 110.0, (5) 63.5, (6 ) 32.0,
(7) 6*4.6, (8 ) 49.1, (9) 49.0,
(10) 45.0, (11) 164.4, (1*)
96.7, (2‘) 70.6, (3 ’) 71.6,
(4*) 6 8 .0 , (5') 72.3, (6 ')
6 1 .4 (1^7)
SOURCES: Gentianaceae: Eustoma (147 )

zy+
140.- eustomorusside
OH C16H24°12' 408-126?
2.00-2.21
770
Hygroscopic, bitter tasting, white powder
HO, [a]20Di -72.9° (c=l.l, CH^H) ( 14?)
UV: (CHÔH) 236.5 (3.76) (W)

OGIu
IRt KBr, 3350, 1690, 1615
^H-NHR: D20, 60 MHz (14?)
MP: 142-4° (147)
[a]23D: -67.9° (c=l.0, CHCl^) (147 )
13C-NMR: CDC13, (1) 94.5, (3) 150.3,
(4) 110.6, (5) 62 .6 , (6 ) 31.1
(7) 64.3, (6 ) 68.5, (9) 47.0
(10) 62.4, (11) 164.0, (1')
9 6 .8 , (2 ’) 70.6, (3’) 71.6,
(4*) 68.1, (5’) 72.4, (6 ')
61.4 (14? )
SOURCES: Gentianaceae: Eustona (147)
141.- SECOLOGANIC ACID
HO
C16H22°10’ 374' 1213
Amorphous powder
UV: (CHÔH) 241 (*48)
UV: 241.5 (3 .9 ) (145)

OGIu
^H-NMR: CDCly 7.58 (d, J 2.5, H3),
6.64-6.40 (m, H^, 5.46-4.^
(He ,l0), 5.35 (d, Hj), 2.17-
1.95 (Ac) (146)
MS: m/e: 584, 526, 525, 524, 482, 395,
331, 237, 177, 169, 139, 127, 109,
97, 81 (146)
SOURCES: Loganiaceaei Anthocleista (146).

11*2.- GENTIOPICROSIDE
235
C16H20°9! 356.1107
MP: 122° (118-121 hydrated) (1^*9)
[a]D: -196° (H20) hydrated (149)
MP: 190° (anhydrous) (149)
OO^D: -217.6° (c=1.0, CH3OH) (149)
UV: (EtOH) 24?sh (3.84), 255sh (3-93).

OGIu
270 ( 3-97) (149)
IR: Nujol, 3533. 3460, 3267, 1712,
1677, 1612, 931. 772 (149)

13C-NMR: D2o , (1) 98.5. (3) 150.4,
(4) 104.4, (5 ) 125.2 , (6)
117.8, (7) 71.2, (8) 133.9.
(9) 45.4, (10) 119.5, (CO)
167.5, (1*) 99.6, (2') 73-3
(3*) 76.5, (4’) 70.3, (5')
77.1, (6*) 61.6 (150)

MP: 140° (149)
[a]25D: -I5 9 .I (c=1.0, CHCI^) (149)
SOURCES: Gentianaceae: Swertla (^51)

Stereochemistry (152 )
143.- VOGELOSIDE
C17H26°10' 390.1526
Amorphous powder
UV: (CH30H) 241 (148)
MP: 153° (I4 8 )

OGIu
1H-NMR: 7.58 (d, J 2.5, Hj). 5-31 (d, Hj),
5-37 (H?), 5.52-4.90 (Hg(H10)
3.54 (OCH3), 1.96-2.10 (Ac) (148)
MS: 556, 526, 525, 496, 483. 482, 394,
361, 3 3 1 , 26 9 . 209, 169, 139, 127,
109 , 97 , 81 (148)
SOURCES: Loganiaceae: Anthoclelsta (140).

144.- MORRONISIDE
C17H26°11*
[a]D: -72° (o=1.0, EtOH) (153)
IR: 1700, 1640 (153)
*^C-NMR: DÔ, ?a and 76 Morroniside:
(1) 96.2, (3) 154.9, (4) 110.2a
110.93, (5) 31-la, 26 .8 6 , (6)
3 6 .1a, 33-46, (7) 95-9a, 91.66,
(8) 73.8a, 65.93, (9) 38.7a,
39.33, (10) 19.6, (CC) 169.8,
(0CH3) 5 2 .6 , (1*) 99.5. (2’)
?3-6, O') 76.8, (4*) 7 0 .5 ,
(5’) 77.1. (6') 61.6 (150 )

MP: 148-151° (153)
[a]D: -73-5° (c=0.97, CHCl^) (153)
*H-NHR: CDCI3> 7.40 (H3), 3-73 (OCH^
(153 )
SOURCES: Caprifollaceae: Lonlcera
(153) , SanPucus (15^ ).
145.- KINGISIDE
C17H24°11! 404-1318
[a]D: -91° (c=0.7, EtOH) (153)
IR: 3350, 1740,1640 ( 153)
V nm R: CDC13, 7.44 (H3), 3.73 (OCH3)
1.96-2.10 (Ac) (153 )
SOURCES: Caprifollaceae: Lonlcera
(153 )• Configuration ( 155 )

23?
146.-SECo GALIOSIDE
COOCH3 C17H2*°12' '*2 0 - ‘ 267

3.10-1.49 *5, Amorphous foam
S.(Odd
[a]2^ : -82° (c=0.2, EtOH) (150)
UV: (EtOH) 238 (4.05) (*50 )

5.651
OGIu 1H-NMR: D20, 90 MHz (I50)
13c -nkri d 2o , (1 ) 9 6 .3 , (3) 151.1 . (4)
109.8, (5) 25.2, (6 ) 34.6,
(?) 103.3. (8 ) 78.9, (9) 37.2,
(10) 96.7, (CO) 169.5. (OCH3)
52.7, (1*) 100.4, (2’) 73-6,
(3’) 76.7, (4>) 70.4, (5’)
77.1, (6 ‘) 6 1 .6 (130 )
MP: 171-172.5° (150 )
[a^D: -73° (c=0 .3 , CHCl3) (150 )
SOURCES: Rubiaceae: Galium (150 )
147.- GENTIOFLAVOSIDE
GluO. r H 0 1 374.1213
16 22 10 J
MP: 126-8° (156)
[a^D: -108° (chci3) (136)
IR: 3080, 1755, 1715, 1615 (156)
UV: 210, 219. 243, 252, 269 (156 )
^H-NMR: 5.60 (H6), 7.45 (H3), 1.20
(d, ch3) (156)
SOURCES:Gentianaceae: Gentlana ( 156)

238
V. - Secoiridoid glycosides: terpene conjugated
148.- FOLIAMENTHIN
OH C26H36°128 5t>0-2206
MP: m - 6° (15?)
[a]Di -63° (CHÔH) (1-57)
1H-NMR: C&jOD, 100, 220 MHz (145 )

I.A5
7.57 DERIVATIVEi Pentaacetate:
[a]D: -55° (1*5)
530
UV: 228 (^,24), 245sh (1^*5 )
OGIu SOURCES: Menyanthaceae: Menyanthes (145)
149.- MENTHIAFOLIN
OH
C26H36°12‘ 5'*0’2206
MP: 186° (157)
[a]D. -68° (CH30H) (157)
UV| 228, 245sh (157 )
IR: 1740-1685 (157)
MS: M+ 708, and m/e 693, 525, 361,
331 (157)
OGIu 1H-NMR: CDC13 , 100-220 MHz, 7.60 (H3),
6 .6 5 0^), 5-91 (H?,), 6 .9 4
(H3 .). 1.87 (H10.), 1.32 (H9<),
2.30-2.10 (Ac) ( 157 )
SOURCES: Menyanthaceae: Menyanthes (157)

239
150.- DIHTDROFOLIAMENTHIN
C26H38°12’ *42.2363
OH
[a]Di -65° (CHÔH) (157)
UV* 245 (157)
IR: 1740, 1710 (15?)
KS: 732 (157)
VnKR; CDCIy 7.60 (d, H3), 6.60 (m, H?)
4.31 (d, Kg), 1.75 (m, H9), 1.22

OG Iu
(d, H10.) (157)
SOURCES: Menyanthaceae: Menyanthes (157)
151.- JASMININ
OH
C26H38C12! ^ 2 -2363
DERIVATIVE: Aglucone ethyl ether:
MP: 139-141° ( 158)
[a]26D: -49.1° (c=2.1B, CHCl^) ( 158)
UV: 23B (4.0) ( i5e)
IR: CCI4 , 3550, 1730, 1710, 1630, 825 ( 158)
SOURCES: Oleaceae: Jasminurn ( 158)

OGIu
. - Secolrldoid glycosides: phenolic conjugated
152.- LIGSTROSIDE
C25H32°121 52U-1893
\ ( J \ O 37* -180° (c=0.23, 95% EtOH) (159)
H O ' ^ ///^ S' C O O C H 3 *H-NMR: D20 (159)

7.3 A - * .( 3 I I
rj4 DERIVATIVE: Pentaacetate:
I O -127° (C=0.3. CHC13) (159)
604r ^ SOURCES: Oleaceae: Fraxlnus (159).
1* odd OGIu LIgustrum (160).

153*- 10-HYDROX Y-LICSTRD31DE 240
C23H25°13! 512.1530
HO COOCH
13C-NKR: (1) 92.5, (3) 152.2, (4)108.1,
(5 ) 3 0 .e, (6 ) 39.6, (?) 170.0,
HO (8 ) 124.0, (9) 130.9, (10) 60.4,
(CO) 165.9, (0CH3) 51.1*, (r)

Glu
9 6 .8 , (2 ') 70.6, (3 ‘) 7 2 .3 ,
(to*) 6e.O, (5 ') 7 2 .1 , (6 ') 6 I.5
( 150 )
SOURCES: Oleaceae: LIrustrun ( 161)
154•- 10-ACET0XY-LICUSTR03IDE
C27H34°14! 5S2.194B
Lq]18D: -1^3-9 (CJLjOH) (162 )
UV: (CHÔH) 228 (4.26), 279 (3.3?.

HO'
COOCH
255 sh (3 .32 ) (162)
IR: Nujol, 1730, 1705, 1633 (162)
1H-N”R: CDÔD (I62 )

Ac O
OGIu
[aJ^D: -128.6° (c=1 .0 , CHC13) ( 16^
SOURCES: Oleaceae: Osranthus (162 )
155.- CENTAPICRIN
400-4.30
*2?2B°l 2l 52°-1581
7.6 4 MF: 234-7° (163)
3.7S-3.10
(a.j 3)
[aH^D: -213° (c= 0.5, Pyridine) (163)
UV: (CH30H) 237 (4.32), 303 (3-55) (163)

HO,
IP.: KBr, 3500-3300, 1750, 1?25, 1705,
c0 1620, 1460, 995. 905 (163)
1H-NMR: ?yr-d5 , 100 MHz (I63)

• 04 DERIVATIVE: Triacetate:
7.37
La]]2^ : -135° (c= 3 .0 5 , CHC13 ) (163)
OH SOURCES: Gentianaceae: Brythrea (163)
241
156.- OLEUROPEIN
C25H32013» 5^0.1842
.17
MP: 87-9° ( 164)
1 3 0 0 " COOCH [a^D: -168° (c=0.6?, CH^H) ( 155 )
64 1- 6.7» [aJ^D: -147° (c=1.0, H20 , EtOH, or Acetone)
mutarotatlon; DO^°D* -127° (after 9 hours)

1.66
( 1*0
UVi (CH3OH) 23 3 .5 (4.20), 284 (3.48) (155)
OGIu
IR: 3420, 1710, 1640, 1450, 1390, 920,
1075, 862 ( 164 )
1H-KMR: CD30D, 60 MHz (155)
MP: 58-9° ( 164)
[a> -62° (c=l,0, AcOH) ( 164)
SOURCES: Oleaceae,: Plea ( I6 5 )
Stereochemistry ( 166 )
157.- 10-ACET0XY-0LEURCPEIN
HO.
C27H34°15: 598.1897
371
[a}21!): -191° (CH30K) ( 162 )
HO OO CH UV: (OTjOH) 235.5 (4.2), 283-5 (3-47)
7.3 0 ( 162)
IR: Nujol, 1740, 1705, 1635 ( 162)
AcO 1H-NMR: CD-jOD ( 162 )

a.oj
[a^D: -117.4° (c=1.0, CHC13) ( 162 )
SOURCES: Oleaceae: Osmanthus (^ 2 )

158.- AMAROPANIN (DEOXYAMAROGENTIM ) 242
C29H50°12'
HPs 178° (167)
3 60- 36 0 LcG26* 101.25 (C=0.474, CHjOH) (167)
UV: (CK30H) 210 (4.39), 315 (3.48),

HO 240sh ( 167)
HO '
HO IR: KBr, >U00P 1680, 1580, 1430, 980,
930, 890, 810, 783, 700 (167)

HO *H-NKR: Acetone-d^ (1 6 7 )
666-6 94
MP: 79° (167 )
MS: M+?60, m/e: 213, 109, 169. 229 .
253. 289, 297, 501, 5*0, 583.
696. 738 ( 167)
SOURCES: Gentianaceae; Gentiar.a (167)
Radix (168 ).
159.- AMAROGENTIN
C29H30°13 ! 58 6 .16S6
MP: 229-230° (169 )
[ct]20D: -116.6 (CHÔH) (169)
UV: 230 (4.46), 266 (4.07), 306 (3 .68 ) (169)

HO
IR: 1655, I58O ( l69 )
1H-NMR: (169 )
DERIVATIVE: Dihydjx-arcarogentln:
MP: 177-9° ( 169)
Radix ( 170), Gentlana ( 1711 168)

OH OH
O 160.- TRIF10R0SIDE
C35H^2°20' 782.2269
7.57 -122.8 (CH30H) ( 172)
UV, (CHjOH) 249(4.21), 325 (3-69) ( 172)

5.3 7
G lu
1470 . 995, 910 (172 )
I.M- 1.91 Ac 1H-NMR: CDCIy 60 MHa ( 172)
63 6-7.50
SOURCES: Gentianaceae: Gentlana (172).
2k3
161.- AKAROSVERIN
C29H30°li*’ 602.163**
i X
Amorphous powder
[ajDi -13° (CH30H) (169 )
IR: Nujol, 1685, 16**0, 1610 , 995 , 900 (169)
UV: (CRjOH) 227 (**.**6 ), 271 (**.03 ),
307 (3.65) (169 )

1H-NKRi CDÔD (169 )
O Q SOURCES:
Radix (170 )
Gentianaceae: Swertla (169 )
7.3* -611
162.- NUZHENIDE
C31H^ ° 17’ 688,2578

HO [af 50 : -151° (c=1.7, CH^H) (159)
3.69
P COOCH UV: (957s EtOH) 277 (3.3*0, 226 (**.13)
HO (139)
7.S4
^H-NMR: D20 ( 159)
HO
1^C-NKP: D20. (1) 95-7, (3) 155.6, (*0
1 SI4
OGIu 109.0. (5) 31.1, (6 ) **1 .0 , (7)
17**.**, (8 ) 125.7, (9) 129>, (10)
13 .6 , (11) 169.8, (om3) 5 2 .6 ,
lyrosoli (lb) 71.8, (2b) 35*3,
(3b) 131.1, (**b) 131.1, (5 4 7b)
1 16.3 , (6b) 155.2, (8b) 131.1 ,
Glucose: (1*) 100.5, 103 1, (2*)
73.8, 73.6, (3') 76.6, ?6.6 (**•)
70.3, 70.7. (5') 77.2, ?**.l, (6*)
61.5, 6**.8 (159)
SOURCES: Oleaceae: Fraxinus (159)

244
VII• - Bisglycosidic Iridoids and Secoirldoids
It 4 » 163.- SYLVESTROSIDE-III
QGCKj
C27H36°14l 584.2104
[a]20D: -65° (c=0.4, CH^H) (97 )
Q=HC
UV: (ch3oh) 237 (4 .25 ) (97 )
1H-NMRi Acetone-d6 ( 97)
13C-NMR: Acetone-d6 , b) (1) 96.9, (3)
133.0, (4) 109.9, (5) 27.3,

OGIu
(6) 44.8. (?) 201.7, (8)134.7
(9) 44.8, (10) 120./*, (11)
166.9, (1*) 99.7. (2') 74.2,
(3') 77.5, (4’) 71.2, (3')
77.5, (6l) 6 2 .6 .a ) (1) 96.4
(3) 153.0, (4) 111.4, (3)33.1
(6) 40.2, (7) 77.5, (8)41.1,
(9) 47.9, (10) 14.3, (11)
168.2, (OCH.j) 51.4 ( 97 )
DERIVATIVE! Pentaacetate:
[a]2^ , -81° (c=0.5, CHCI3) ( 97 )
SOURCES! Dipsacaceaes Dipsacus ( 97 )

I3 164.- SYLVESTROSIDE-IV
DERIVATIVE s Tetraacetate!
KP: 137-9° ( 97)

CH, [a]22!: -60° (c=0.4, CHCl^ ( 9 7 )
O >07fdJ7)
UVi (CH3OH) 233 (3-9?) (97 )
OGIu H-NMRs CDC13 ( 97)
13C-NMR: Acetone-d6, b) (l) 96.9,

(3) 153.3, 00 109.B, (5)
21.2, (6 ) 44.9, (7) 201.4
(8 ) 134.7, (9) 44.9, (10)
120.2 , (11) 166.8, (1 ')
99.7, (2 ') 73.4, (3*) 76.5
(4’) 7 0 .3 , (3*) 77.1, (6 ')
61.6, (a) (1) 69.9, (3)

169.8, (4) 52.2, (5) 37.2
(6 ) 41.8, (7 ) 7 9 .2 , (e)
38.7, (9) 42.7, (10) 13.4
(11) 169.5. (OCH3) 52.8 (9?)
SOURCES i Dipsacaceae» Dipsacus (97 )

246
I65.- CAUTLEYOSIDE
174
C33H**6°19' 7^ 2632
COOCH
M^D: -93° (c=0.6, CH3OH) ( 9? )
7.6 5
UV: (CH30H), 235 (**-3l) (9? )
D20 (1?3)
OHC 13C-NMF: D20, b) (1) 97.7, (3) 15**.2,

CH OGIu
(*0 109.8 , (5) 28.2, (6) UU.5*
(?) 206.7, (8) 133.9, (9)
45.1, (10) 121.6, (11) 168.9,
°) (1) 97.**, (3) 152.2, <*)
113.1, (5) 31.3, (6) **0.1, (?)
7 8 .8 , (8) 39.3, (9) **6 .3 , (10)
13 .2 , (11) 170.3 . (och3) 32.7,
(1') 99-6. (2‘) 73.5, (3')
76.6, {**’) 70.5, (5’) 77.2 ,
(6') 61.6 (double Intensity)( 97)
DERIVATIVE: Octaacetate:
MF: 1U6-80 ( 9 7 )
[a]22 Di -69° (c=0A, CHC13) (97 )•
SOURCES: Icacinaceaes: Cantleya ( 173)
Dipsacaceae: Dlpsacus (17** ).

247
166.- SYLVESTROSIDE-I
COOCH3
C33H^°19' ?^.2789
[exD21©. -106° (c=0.i*, EtOH) ( 9 7 )
UV: (EtOH) 236 (U.32) (9 7 )
*H-NMR: DgO ( 97)
I06 13C-NHRi P20, b) (1) 98.3, (3) 153-6
(*) 111.5. (5) 30.7. (6 ) 33-2,
(7 ) 60.8, (8 ) 1>.7, (9)
(10) 120.U, (11) 169.5. (!')
9 9 -6 , (2 ') 73-5. (3*) 7 6 .6 .
(^') 70.5, (5’) 77.2, (6 *) 61 .6
(sugar signals double Intensity)
a) (1) 97.U, (3) 152.2, (k)
113-2, (5) 31.1. (6 ) 1*0.2, (7)
7 8 .8 , (8 ) 39.3, (9) H6.k, (10 )
13-3. (11) 170.5, (OCH3 )52.7 ( 97 )
DERIVATIVE: Nonaacetate:
MP: 15^-5° (-97)
[a^D: -85° (c-O.k, CHCl^) (97 )
SOURCES: Dipsacaceae: Dipsacus (97)

248
3.76 167.- SYLVESTROSIDE-II

COOCH
m C3 5 W 790-289^
2.0 9
AcO C-O Colorless foam
a 20Di -99° (c 1.5, CHÔH) ( 97)

7 47
UVi (EtOH) 238 (4.38) ( 97)
CH3 OGI u
D20 (97 )
13C-NMfl: D20, b) (1) 98.0, (3) 153-7

OGIu
(4) iu.2, (5) 29.6, (6)31.1
(?) 64.3, (8 ) 134.6, (9)44.4
(10) 120.6 , (11) 168.9, (1 ')
9 9 -6 , (2 ') 73-5, (3') 76.6,
(4’) 70.4, (5')77.2, (6 ')6l.6
(sugar signals double Intensity)
a) (1) 97.4, (3 ) 152.2 , (4)
113.0, (5) 31.4, (6 ) 40.1, (7 )
78.6, (8 ) 39.5, (9) 46.4, (10)
13.5. (11) 170.1, (och3) 5 2 .6 ( 9 7 )
DERIVATIVE! Nonaacetates
MP: 154-5° (97 )
IVpD: -85° (c=0.4, CHC^) (97 )
SOURCES: Dipsacaceae: Dlpsacus ( 97)

2k 9
o 168.- CI-5
C42H54°2 2 ‘ 910.3107
M 25®, -185° (c=3-4, CHÔH) (159)
UVt (EtOH) 236 (4.30) (159)
IR: KBr, 3400, 1720, 1700, 1630, 1070
(159)
1H-NHR: D20 (159)
I3c-NMR: D20 , a: (1) 95.7, (3) 155-6,
(4) 108.9, (5) 31.2, (6 ) 40.9,
(?) 174.1, (8 ) 125.8, (9) 129.7
(10) 1 3 .8 , (11) 169.3 , (och3)
5 2 .6 | b: (1 ) 95.5. (3) 155.6,
(4) 108.9, (5) 31.2, (6 ) 40.7.
(7) 172.5, (8 ) 125.6 , (9) 129.4,
(10) 13 .3 , (11) 169.3 i Tyrosol
(lb) 6 6 .8 , (2b) 34.4, (3b) 137>
(448b) 131-2, (547b) 122.3 .
(6b) 150.0; Clucoses: (if) 100.7
(2 ’) 73-7. (3') 77.3, (4') 70.4,
(5 ') 7 6 .7 , (6 ’) 61.7 sugar signal
double Intensity (1 5 9 )
SOURCES: Oleaceae: Fraxlnus (159).

250
169.- GI-3
C48H64°27
■iu UVs (EtOH) 236 (4.36) (159)
IF: KBr, 3400, 1735. 170**, 1630, 1070
(159 )
1H-NMR: D20 (159 )
13C-NMR: D20| a: (1) 95-3. (3) 155-1. (4)
108.4, (5 ) 30-5. (6) 40.3, (7)

*.*5-7.3?
173.?, (8) 125.7. (9) 128.9, (10)
13.2 , (11) 169.0 , (och3) 5 2 .1 .
B; (1) 95.1, (3) 155-0, (4) 108.4,
(5) 30.5, (6) 40.2, (7 ) 172.4 ,
(8) 125.2 , (9) 128.9 , (10) 1 3 .1 ,
(11) I6 9 .O, lyrosol: (lb) 70.8,
(2b) 35.1. (3b) 137.2, (4b) 130.5
(5b,4 7b) 121.7, (8b) 130.5, (6b)
149.0, Clucoses: (1*) 100.1, 102.7,
100.1, (2>) 73.3, 73.1, 73.1, (3')
76.6, 76.6, 76.6, (4*) 70.0, 70.1,
69.8, (5*) ?6.0, 73.5, 76.0, (6’)

O
61.0,64.1,61.0 (15?
SOUFCES: Oleaceae: Fraxlnus (159)

251
VIII. Non-glycosidic lridoids: miscellaneous
170.-CENIPIC ACID
COOH C9H12V 184.0735
Amorphous powder
M^D: -105° <c=1.0, EtOH) (175)

,OH UV: 203 (3.45) (175)
4.3 0
IR: CHCly 1725 (175)
*H-NMR: CDC13 (175)
DERIVATIVES: Ammonium salt:
MP: 125-130° (175)
SOURCES: Rubiaceae: Genlpa (I7 5 )
171.- GENIPINIC ACID
COOH C11H15°6 ' 2^3.0868

Amorphous powder
COOCH3
[a^D: -126° (c=1.0, EtOH) (175)
4J4 UV* 203 (3-5) (175)

'H m
IR: CHC13 , 1750, 1725 (175)
1H-NMR: CDCl., (175)
SOURCES: Rubiaceae: Genlpa (175)
_ 172.- BOSHNIALACTOHE
( Y r C9H14°2 s ^ - 099U
\ C o l o r l e s s liquid
*
CH 105-112°/6 mm (176)
[a]21D: -18.2° (c=2.10, CHCl^) (176 )
IR« Neat, 1743, 1275: 1245, IO5 8 , IO3 3 ,
835 (176 )
^H-NMR: CCl^, 60 MHz (176 )
DERIVATIVE: 3R-cis-cis boshnlalic acid:
MP: 85° (176)
[apD: - 3 3 .7 (c=l.l, CHC13) (176)
SOURCES: Orobanchaceae: Boschnlakla (176)
Synthesis (176 )
173.- EUCOHMIOL 252
QH C9H1 6 V 108‘W B
Hygroscopic liquid
D O 25!)! -3 0 .5 (c=1.08, CHÔH) ( 17^

OH
UV, 206 (3 .8 ) ( 177)
4 64
IR: 33^0. 1665 (177)
KS: ir/e: 170, 152, 139, 122, 121,
109, 106, 105, 95, 9*». 93, 93,
91, 81, 80, 79. 77, 75, ?3, 6 0 ,
*+3.*+l 39, 31 (177 )
*H-NKR: D20, 60 KHz (177)
oil
M 25D: -20.7, (c=l.53, CH OH) (177)
SOURCES: EXicoirjriaceae: Euconr.la (177)
174.- VIBURTINA1
76 6 6 40
C10h6°2: 160.052^
0= CH HP: 93-5° (178)

UV: (CHÔH) 226 (*+.12), 243 (4.06),
251 (3-9*+), 287 (4.00), 424 (3 .85)
(178)
IR: 2780-2710, 1410, i390, 1370, 1634,
1050, 1025, 1005, 780, 760, 580
(178)
1H-NKR: (178)
SOURCES: Caprifollaceae: Viburnum,
Sambucus (178).
175.- 5-9 DEHYDRO-NEPETALACTONE

u • (d.J I)
CH
C10H12°2! 16*-0837
UV: (EtOH) 298 (179)
7.01
IR: 1710, 1640 (179)
1H-NKR: CDClj (179)
MS: m/e 164 (179)
SOURCES: Iamiaceae: Kepeta (1 7 9 )

176.- ERYTHROCENTAURINE 253
ci o ¥ y 176•c* 73
1
HPi 135-7° (180 )
43 9 Substance turns red on exposure to

3.6 0
sunlight (ISO)
UVt 223 (Jt*.3 ). 290 (3. 3) (180)

1 0 .1 6
IR: KBr, 1720, 1690, 1580 (iso)
MS:m/e: 176, 148, 131, 120, 119,
105. 91, 90, 63. 51. 39 (180 )
^H-NMRi (180 )
SOURCES1
. Loganlaceae: Anthoclelsta (180 )
177.- GEJTIOLACTONE
4 .5 4
C10H12°5: 212'o6&*
iafh: 0° (c=0.B55, CHÔH), 1 :365-589 (181)
4 90
UV: (CHÔH) 225-230 (3-74) (181)
'flo 150 -310m IR: KBr, 35OO, 1725, 1715. 1600 ( 181 )
3 60
MS: 212, 183, 168 ( 181 )
1H-NMR: CDC13 (iei )
13C-NHR: CDC13, (Ethyl) 7.7, 22.7,
(allylic methylene) 3 1 .0 , (methy
lene esters) 6 6 .7 , (CB0) 172.6,
161.6, (a and 8 ) 120, I53.i1,
(C-O) 72.3 (181)

X-RAY: ( 181 )
SOURCES: Gentianaceae: Gentlana ( 181 )
13 0 178.- matatabieteh
C10Hl6°! 152 -I201

37 m BP: 67°/l6mm (182 )
n16: 1.4771 (182)

I
t H 3 0.7 5 d ,J 7 [aD17D: -150° (182)
IR» 3100, 1675. 1085, 1045, 890 (182)
*H-NMRi (182)
SOURCES: Actinidiaceae , Actlnldla (182),
Synthesis (182).
179.- NEPETALACTONE 2&
C10H14°2! 166<099^
Oil
d25 : 1.0663 (1B3)

CH
B.P. 1 71-2° (183)
[aJ^Di +3-6° ( 183)
n25 : 1.4876 ( 183 )
CH DERIVATIVE: Nepetalic Acid:
MPs 73-75° (163 )
O 3 20D: +46.8 (c=l.l6, CHCl^) (183 )
SOURCES: labiatae: Nepeta (I83 )
180.- IRID0DIA1
C10Hl6°2 ! i6b-1150
BP: 90-2°/lnun ( 184)
CHlO
n19: 1.4782 (184 )
CHrO
d19: 1.001 (184)
CH
CH, OH D: +4.7 (c=1.15, Bensene) ( 184)
IR: CC1V 36IO, 3050, 1675. 852 ( 184)

DERIVATIVE: Iactol acetate:
BP: 115-120°/3mm (185 )
DERIVATIVE: Bis-dinltrophenyl hydrazone:

MP: 224-5° ( 184 )
SOURCES: ants: Irtdonyrnex (185 ) I

plants: Myopormr. (186 )
Syntheji* (u )
181.- IRIDOMYRMECIN
C10H16°2 ' 168-n 50

BP: 104-B°/l.5nun (184)
MP: 59-60° ( 184 )
[V)17D: +205° (c=0.223, CCl4 ) ( 184 )
1H-WMR: ( 187 )
[o]D: -199° (c=3.77, EtOH) ( 187 )
SOURCES: ants : Iridowyrniex ( 184 )(
Synthesis ( 187 )
25*5
182.- ISOIRIDOMYHMECIN (IRIDOLACTONE)
C10H16°2' 168*“ 50
KP: 58-9° (1&^ )
[a]17l)i -62° (c=1.01, CCl^) (IB'* )
DERIVATIVE: Hydxazide:
KP: 118-9° (IS'* )
SOURCES: ants: Irldoir-yrmex (18U )
Synthesis ( 187 )
183.- ISONEOKATATAEIOL
^10^18^2* 170.1306
V n’KR: (IS3 )
SOURCES: Actlnidiaceae : Actlnidia ( 18^.
CH, OH
o»o
18**.- NEOKATATABIOL
30-37 C10H16°2! 17° - 1306

BP: 95°/5miti (IBS)
[a]15D: + 21.3° (c=0.85) (IBB)

4. 3 0 d.J ■
CHo oh IR: 3400, 1070 (188)
1H-NHR: (188)
SOURCES: Actlnidiaceae : Actlnidia ( 188).
COOCH 185.- ELENOLIDE

HOOC
C11H12°5! zzU'o6Bk
KP: 155-6° (189)
QcQD: +369 (Acetone) (189)

OHC
IR: CH2C12 , 1792, 168**, I656, 16U5 ,
CH-
81**, 708 (189)
V n MR: CDC13 , 60 KHz (189 )
SOURCES: Oleaceae: Plea (189).

Structure (2 1 5)
186.- d-1 VERBEUALOL
OOCH 256
cn HiiPy
mpi 134° (190)
[a]D: -20° (EtOH) (190 )

CH OH SOURCES: Synthesis (191 )
37 J
187.- GENIF1N
COOCH3
C11H14°5' 226,0841
SI 6 MP: 120-1° (4 )
[a]D: +135° (OhjOH) ( 4 )

1(d.J *)
HOCH2 oh IR: CHC1,, 1693. 1630 (192)
4.2 »
1H-KMR: CDC13, 60 MHz (192)
SOURCES: Rubiaceae: Genlpa (192)

376 188.- SARRACENIN
C11H14°5! 226,0841
MP: 127-8° (*93)
UV: (EtOH) 232 (3-98) (*93)
3R: KBr, 2970, 1707, 1640, 1440, 1380,
92 0 , 860, 818 ( 193)

496
H-NMR cdci3 (193 )
13,C-NMR: CDCl-j: 18.7 , 22.1, 3 2 .4 , 3 5 .1
51.4, 69.0, 81.1, 91.7, 112.3
150.1, 166.8 (193 )
MS: M+=226, m/e: 41, 6 9 . 98. 109, 121,
137, 148, 165, 180 , 226 , 227 0-93)
X-Ray: (193)
SOURCES: Sarracenlaceae: Sarracenla

(193), Synthesis (194 ).
S.24 2-»0 189.- BALDRINA1
C12H10°4‘ 2 1 8 '-0579
MP: 112-3° (195)
UV: 227 (4.2), 244 (4.18), 287 (4.08)
VIS 425 (3.87) (195)

0
IR: KBr, 2800-2740, 1732, 1637 (195)
1H-HMR: CDClj, 100 MHz (195 )
SOURCES: Artefact formed from extraction
of Valtrate ( I9 5 )
190.- XYLOMOLLIN
COOCH
C12H18°7' 274-10-52
0 OCH 3
MP: 130-9° (EtOH) (196)
[a]24©: -44.3 (CH3OH) (197 )
IR: CHC1.J, 3600, 1733. 1720 ( 196)
1H-NMR: Pyr-d6 (196 )
^C-NMR: spectra In ref. ( 1 9 6 )
MS: M+1 275. Si/e 243 ( 196)
X-RAY: (197)
MP: 162-4° (197 )
SOURCES: Meliaceae: Xylocarpus ( 196 )
Synthesis (197 )
3.15 191.- FULVOPLUKIERIN

COOCH.
7.7 0 C14H12°4! 244•°735
7.16 MP: 151-2°d (4 )
UV: (EtOH) 270 (3.70), 366 (4 .56) ( 4
1H-NKR: CDCly 60 MHz (4 )

6.1 6
V4 k SOURCES: Apocynaceae: Plumerla (198)
. - Non-glycosidic lridolds: Plumlera type
1 9 2 .- PLUMERICIN
3.7 6
COOCH C15H14°6! 29°*°790
5.6 4 3.9 (I MP: 2 1 1 .5 -2 1 2 .5 ° (199)
7.4 0»
600
laf5I>s + 1 9 7 .5 ° (c= 0 .9 8 2 , CHC13 ) (199)
3.40 UV: (EtOH) 2 14-5 (4 .2 4 ) (199)
SAOl IR: 1757, 1751. 1705. 1715, 1655.

10 6 1622 (199)
7.14
1H-NMR: CDC13 (199 )
DERIVATIVE: O-Dihydxo:
MP: 191-2° (199)
DO^D: 4208.9 (c=0.892, CHCl3) (199)
SOURCES: Apocynaceae: Plunerla (199)

CO OH 193*- B-DIHYDRO PLUKERICINIC ACID 258
6 1Idi C14H14°6' 278.0790
7.441
S IOdd/-
KP: 189-190° (199)
3.40
IR j KBr, 1780, 1680, 1648, 1630 (199)
74.4 11 ^-NMRi CDC13 , 60 MHz (199 )
1.7S
SOURCES: Apocynaceae: Plumerla (199)
1.10
19**•“ ISOPLUMERICIN
COOCH.
3*1 C15H14°6' 290-0790
56 5
7.4 0»
to 0 KP: 2 0 0 .5-2 01.5° (199)
[a323D: +216.** (c=1.01, CHCl^) (199)

34 0
UV: (EtOH) 21**-15 (4.2**) (199)
4*4 4
IR: Nujol, 1751, 1757. 1715. 1705.
7.14
1655. 1622 (199)
2.0 6
1H-NKR: CDCl^, 60 MHz (199 )
SOURCES: Apocynaceae, Pluneria (199)
3.76 !95.- DIHYDROPLUMERICIN

COOCH,
C15H16°6 : 292.09**7
7.4 44 KP: 150-1° ( 199)
S.aodd
L a f 2 -5D: *257.5 (c=1.293, CHCl-j) ( 19$
UV: (EtOH) 240 (3.97) (199)
IR: Nujol, 1780, 1700, 165 5, 1622 (199)

1H-NKR: CDC13, 60 MHz (199 )
i.io
SOURCES: Apocynaceae: Pluinerla (199).
196.- ALLAKDIN
3 704
COOCH3 C15H16°6! 292-09U?
6.3 7 MP: 131-2° d (200 )
7.31 (d, J 3)
[aD21D. -35° (C=0.46, CHClj) (200)
UV: (EtOH) 238 (4.15), high end

5.0 0 d o
absorption (200)
O H «J0
1.121 IR: KBr, 3424, 3105. 3086, 2754, 1733,
2.26 q
1694, 1636, 1432, 1287, 1111. 1067
(200 )
1H-NMR: CDC13, 100 KHz (200)
X-RAY: (200 )
SOURCES: Apocynaceae : Allamanda (200)

259
197.- ALLAMANDIN
cooch 3
C15H160?' 308.0896
PH
MP i 212-5° (200)
[aJ21D: +15° (c=0.6, CKÔH) (200)
UV: (c HÔH) high end absorption (200)
IR: KBr, 3355. 2958. 1727, 1669, 1440,
1198, 1173. 1010 (2 0 0 )
MP: 173-7° P 00)
[VpD: +6 1 ° (c=0.36, CHC13) (200 )
*H-NMR: CDC1.J, 100 MHz: 5.51 (d, J 4.5,
Hj), 6.88 (d, J 8, H3), 2.89 (dd,
H^), 3.57 (m, H5), 5-97 (dd, Hg)
5.86 (dd, H?), 3.07 (dd, H9),
5.12 (d, J 1.5, H10), 7.22 (q, H ^ )
2.00 (d, J 7. Hli4), 3-70 (OCH3)
2.01 (Ac). (200 )
SOURCES: Apocynaceae: Allamanda ( 200)
3.7 0 198.- ALLAMANDICIN

O O CH
C15H16°7! 308.0896
SI 6 3» •
KP: 117-8° (200)
S.6I
[cO^D: +293° (c=0.42, CHCl^) (200)
3 .44(d,J 6) UVs (EtOH) 238 (4.06) (200)
464 IR: KBr, 3484, 3086, 2958, 1773, 1692,
1644, 1436, 1183, 1084 (200)

iso HO ^H-NMR: CDCly 100 MHz (200)
SOURCES: Apocynaceae: Allareanda (200)

260
3.7S 199.- ORUVACIN
OOCH. C21H18°8! 398•1002

dd
40 6
7.4 3 KP: 223° (201 )
[o]25D: 7193 (CHC13) ( 201 )

3.53
dd 5.63 (d,J 6) UV: (EtOH) 205 (4.05 ), 241 (4.06), 317sh
(3-8^), 3^8 (^.13) (201)
IR: Hujol, 3550, 1755, 1710, 1660, 1602 ( 201)
*H-NMR: CDC13, 100 MHz (201)
13C-NMR: CDC13, (1) 104.4, (3) 147.2, (4)

OCH,
3.9 2 112.7, (5) 39.7, (8)102.4, (9 )
51.7. (10) 82.3, (0CH3) 5*4.3 ,
(ax OCH3) 56.1, (CO) 166.6, (12)
169.9, (Oleflnic and aromatic C)
149.2, 152.9, 126.4, 126.5, 127.0,
141.0, 144.8, 115.2, 120.3, 126.0

(201 )
MS: m/e 369, 367, 366, 330, 337, 3 1 0, 309
(201 )
SOURCES: Rubiaceae: Morlnda (201 )
X. - Non-glycosidic iridolds: Valeriana type
20 0 .- desisovaleroxydidrovaltratum
CH
c 17H24C6! 324-1573
MP: 50° ( 202)
AcOi
[a]20D. -88° ( 202)
SOURCES: Valerlanaceae: Valeriana,

Oisovaleroyl
Centranthus (202)
261
4.77 - 4.6 2 201.- VA1TRATE

rw nA c
C22H30°8 * 4 2 2 -19^°
Oil
I s o va le r oy lO i
[a]21Dt +172.7 (CHÔH) (195)
J.96(d .J 102 UV. (CH30H) 204 (3.0), 256 (4.2) (195)
ilsovaleroyl
IR. Rujol, 1766, 1740, 1640, 1610 (19 5 )
*H-NMR: C0C13, 60 KHr ( 195)
SOURCES: Valerlanaceae. Valeriana,
Centrantbus (195) Stereochemistry (203 )
2 0 2 .- ISCVALTRAL
4-io*4.47^#0isoâ êr°y^ C H Or, 1 422.1940

22 30 8
r.0 KP: 80-1° (204)
’.»* Hi. ,
Oisovaleroyl1 UV. (CH30H) 277 (204)
IR: KBr (204 •)
AcO
4.9 s VlMR: CDC13, 60 MH2 (204)
KS: 39, 41, 43, 57 , 6 0 , 77, 8 5 , 91,
120, 147, 149, 164, 165, 166,
167, 260, 261, 321, 422 (204)
13C-NKR: C6D6: (l)100.5, (3) 190.1, (4)
127.5, (5) 159.9. (6 ) 134.6, (7)
144.1, (8) 94.e. (9) 57.3. (10)

72.8 , (11) 58.0 , (CO-lsoVal)
171.2. 172.4, (CH3-Ac) 20.8,
(CH-jiaoVal) 22.3, (CH-lsoVal)
25.7, (CHp-isoVal) 4 3 .O, 4 3 .3

(Co-Ac) 169.8 ( 204 )
SOURCES: Decomposition product of
Isovaltrate (204)
203.- IS0VA1TRATE 262
C22H3008 ‘ U22-19U0
13C-NMR: (1) 92.3. (3) 148.1. (4) 108.1

CHjOisovaleroyl
(3) 140.7, (6 ) 118.3 , (7) 83.1,
AcO (8 ) 64.0, (9) 42.9, (10) 60.2,
(11) 47.7, (CO-Ac) 169.6,
(CO-isoVal) 172.2, (CHÂc)

Isovaleroy!
20.8, (CH^-lsoVal) 22.1, (CH-
isoVal) 25.5, 25.7, (CH2 -lso-
Val) 42.9, 43.2 ( 204)
SOURCES: Valerlanaceae: Valeriana (204)

204.- VA1ECHL0RIHE
C22H31°8C1: 458.1707
CHjOAc HP: 79-80° ( 205)
[a]l6D: 104° (CHC13) (205 )

>valeroy! 0< <•-
UV: 200, 259 (205 )
IR: 1740, 1770, 1615, 1640, 3400 (205 )

CHÎ o-isovaleroyl
1H-NMR: CC14 ( 205)
SOURCES: Valerlanaceae: Valeriana ( 205)
4 * 3-4.39, 2 0 5 .- deox ydidrovaltrate

CH~0 Isovaleroy I
710 1 ^ C22H320?: 408.2148
A.42 HP: 66-70° (195)
UV: (CH30H) 204 (195)

jS.i i fd.JS)
IR: KBr, 3095-3075, 1750-1780, 1752,
j.43-734 Oisovaleroyl
1672, 665-895 ( 195)
1H-NHR: CDCI3, 100 HHs (195)
SOURCES: Valerlanaceae: Valeriana (195)

206.- HOKODIDROVALTRATE
isovaleroylOCf-^ C23H34°8! 438.2253

HP, 50-1° (195)
AcO
4.92 [VpD, -72° (CH30H) (195)
UV: 206 (ca 3) (195)

s j i i d . J s)
3.04-2J0 IR: KBr, 1766, 1733, 16?2 (195)
O i s o c a p ro y l
PMR: CDC13, 60MHz (19 5 )
SOURCES 1 Valerlanaceae: Valeriana (195)

20?.- DIDROVALTRATE 263
4.6« - 4 .4 2 C22H32°8 ! 424-209?
ChÔlsovoleroyl MP: 64-5° (195)
6J0(d,J IJ QaU21!)* -80.8 (CH3OH) (195)

AcO
o UVi (CHÔH) 206 (3 .0 ) (195)
J.l 1 d,J S3 IR: KBr, 1766, 1733. 1672 (195)
3.04-h0 O i s o vale royl 1H-NMR: CDClj (195)
13 C-NKR: C6 D6 , (1) 88.1, (3) 141.9. W
110.6 , (5 ) 3 9 -4 , (6 ) 35-1. (?)
75.6, (8 ) 64.0, (9) 32.5. (10)
6 3 .1, (11) 48.6, (CO-Ac) 169.3 .
(CO IsoVal) 170.6, 172.5, (CH^-
Ac) 20.9, (CH^-lsoVal) 22.4,
(CH-lsoVal) 22.5, 25.7. (CH2-
lsoVal) 43.1, 43.3 (
SOURCES: Valerlanaceae : Valeriana
(77 ) Stereochemistry (203 )
209.- ACEVALTRATE
C24H32010! 480.1995
S.34(dJ,
MP: 83-4° ( 195)
IsovaleroylO-
6 tf,J 2 W^D. +163.7 (CHÔH) ( 195)
**fd,J 10J
UVi (CH30H) 204 (3 .0 ), 256 (4.23) ( 195)
3.02-2,9 Oisovaleroyl ( 3 - A c ) IR: KBr, 1766, 1740, 1640, 1610 (195)
1 H-NKR: CDClj, 100 MHz (1 9 5 )
Centranthus (195).
209.- AHD-VALTRATE
470-4,0
HO C H 2 °Ac c24h34°ii* 498-2101
... MP: 107-8° ( 206)
isovaleroylO ^/ 'Nrl
y 4* i ' 00 IR‘ KBr* 3600-3300 , 3020 , 2960 , 2880,
odd, J 3 3) 1760-1730, 1665, 1470, 1380, 1243 (206 )

2 1 0 -2 1 2 O-isovaleroyl ( 2 A c ) ^-NMR: (206)
MS: M* 498, m/e 413, 397, 396, 339 (206 )
SOURCES: Valerlanaceae: Centranthus ( 206)

264
210.- HOMOACEVALTRATUM
C25Hy*°10' k9U'21^
I•
HP: 82-3° ( 2°2)
SOURCES« Valerlanaceaei Valeriana,
Centranthus ( 202).
211.- VALTRATE ISOVALEROXYHTDRIN
V W V 52U-2621
6 .6 5
IsovaleroylO-- MP: 105-7° (195)
5.6901 J3.«
[a]22D: +204.6 (CHÔH) (195)
HO » J 6.15 td.J 9..1
UV: (CHÔH) 256 (4.23) (195)
lsovaleroylOCH2 Oisovaleroyl
4.2 7 IR: 1762, 1735. 1702, 1640, 1610 (195)
1H-NKR: CCl^, 60 MHz (195)
SOURCES: Valerlanaceae: Valeriana (195)*
212.- 1VHD-VALTRATE
4.70-417 10 5
CH20Ac C27H40°118 540.2570
MP: 64-5° ( 207)
isovaleroylO
UV: 256 ( 20?)
06{d,J 2.1 ) IR: 3^90, 1250, 1750, 1640, 1612, 16?1 ( 20?)
1 .2- 3.11 0 isovaleroyl- ^-NMR: CDC13 , 100 MHz ( 207)
(2-isovalerOyl)
MS: m/e: 455 , 439 , 438. 8 5 , 57 ( 207)
NOTE: Valtrate and acetate groups are
exchangeable (20? )
SOURCES: Valerlanaceae: Centranthus (207)
C H j O isovaleroyl 213.- ISOVALTRATUM ISOVALEROXHYDRIN
C27H42^108 526.2778
AcO' MP: 92-3° ( 202)
isovaleroy!OCH2 O isovaleroyl Centranthus (202 ).

265
Compounds with no spectral or structural data:
214.- AUCUBIN ACETATE (203)
215.- CATALPOL MONOACETATE (208)
216.- ISOCATALFOL (209)
217.- IS0GENTIS1N (16 8 )
218.- METHYL CATALPOL MONOACETATE (208)
219.- ODOKTOSIDE ACETATE (208)
220.- HAEPAGCSIDE MCNOACETATE (? )
221.- VALERIDIKE (205)
Calculated molecular weight of lrldolds.
152.1201 C10Hl6 0 l 224.0684 C11H1205

Matatableter 178 Elenollde 185
154.0994 226.0841
W 2 C11H14°5
Boschnialactone 172 Genipln 187
Sarracenln 188
160.0524 c io He°2
174 Verbenalol 186
Vlburtinal
243.0868 Cn H1506
164.0837 C10H 12°2
Geniplc Acid 170
5-9 Dehydronepetalactone 175
244.0735
166.0994 c10hiUc2 C14H12°4
Fulvoplumlerin" 191
Nepetalactone 179
168.1150 C10Hl602 274.1052

C12H18°7
Xylomollln 190
Iridodial 180
Iridomyrmecin 181 278.0790 ClftH14D6
Isoiridonynnecln 182 8-Dihydroplumericinlc Acid 193
170.1306 c 10hi 8o 2 290.0790
C15H14°6
Isoneonatatablol 183 Isoplunerlcin 194
Neomatatabiol 184 Flumericin 192
176.0473 C10H8°3 292.0947

C15H16°6
Erythrocentaurine 176 Allamdin 196
188.1048 C9Hl60^ Dihydroplumericln 195
Euconmiol 173 308.0896 C15Hl60?
212.0684 °ioH 12°5 Allamandicln 198

Gentlolactone 177 Allamandin 197
218.0579 314.1365 £ ^ 22°?

C12H10°4
Baldrinal 189 6,10 Bisdeoxyaucubin 10
266
324.1573 C1?H2406 362.1213 C15H220 10

D e s ls o v a le ro x y d id ro v a ltra tu m 200 Antirrinoside 28
Catalpol 37
330.131^ c15h22o8
Honomellttoslde 52
Antlrrlde 11
Procumblde 27
Bartsioslde 31
Scabroslde 8
Llnarlde 12
Loasaalde 4 3S..I369 Cl j V > 1 0
332.1107 ClJfH2Q09 Harpaguide 23
llnedoside 1 Irldold A 22
332.1471 C15H2i+Og 372.1056 ci6h20o10

Cluroslde 13 D e a c e ty l-a s p e ru lo s ld e 122
Strictoslde 3
372.1420 C1?H2U09
3W».1471 Cl6H2408 S yrlngenone 64
Boschnaloslde 72
374.1213 cl6H22o 10
Cardoslde 76
346.1263 c15h22o9
Genlposidic Acid 107
Aucubin 32
Gentioflavoslde 14?
Oecaloslde 9
Secologanlc Acid 141
Galirldoslde 20
Mentzeloside 6 374.1577 c17h26o9
Deoxyloganln 78
>*6.1627 Cl6H26Oe
Decapetaloslde 60 376.1369 cl6H2Uo 10
Loganic Acid 81
Villoslde 61
O-Methyl Catalpol 42
348.1056 Cw H20010
Tecomoside 75
Stllberlcoslde 2
378.1161 Cl ^ 2ZOn
>*8.1420 C15H2409 Macfadlenoslde 55
Ajugol 18
378.1526 c l6H26o 10
6-Desoxy-harpagulde 14
Iamlol 59
Deutziol 3
Mioporoside 15 382.1030 C15H2309C1
7-Chlorodeutzlol 7
356.1107 ci6h20o9
388.1005 Cl6H20On
Gentloplcroslde 142
Ixoslde 132
358.1263 Cl6H2209
388.1369 c1?h24o10
B ra s o s id e 79
Cenlposlde 108
Sw eroslde 137
Ketologanln 65
T a re n n o sld e 74
Lonlceroalde 135
360.1420 Cl6H2/|09 Syringoxlde 65
B lsdesox y d ih y d ro m o n o tro pein ^ Thevlrldoslde 112
Ixoroslde 73 Verbenalln 86
267
390.1161 Cl6H22On 414.1161

C18H22°11
Desacetylasperulosidic Acid 112 Asperuloslde 123
Eustomoside 139 420.1267 C1?H2^0 12

Forsythlde 130 Secogalloslde 146
Monotropeln 125
420.1631 C18H20On
Scandoslde 114
Lamloslde 58
Swertianarin 136
Theveside 111 422.1424 C1?H26012
390.1526 c1?h26o10 lanalbid 104

laniide 99
Adoxoslde 106
Nyctanthoslde 128
Ajugoslde 19
Pulchelloslde-1 97
Dihydrocomin 80
Pulchelloside-II 98
Glucoside-VII 17
LoganIn 82 422.1940 C22H3OO0
Mussaenoslde 83 Isovaltral 202
Reptoside 16 Isovaltrate 203
Vogeloslde 143 Valtrate 201
3 9 2 .131B ci6h2ôu 424.2097 C22H32°8

Shanzhislde 91 Didrovaltrate 207
398.0980 426.0928
C15H23C10C1 Cl6H23°llC1
Linarioside 30 Eustoslde 138
398.1002 C2lH16°8 430.0933 C18H22°10S
Orwacin 199 Paederoslde 124
404.1318 C17H24°11 432.1267

C1BH2^°12
Feretoside 120 10-Acetyl Scandoslde 117
Forsithyde Methyl Ester 131 Asperulosldlc Acid 115
Gardenoside 129 Grlsellnoside 133
Gentioside 94
438.1373 C1?H260 13
Hastatoslde 87
Phlomiol 105
Kinglslde 145
Monotropeln Methyl Ester 127 438.1525 c21h26c10
Scandoslde Methyl Ester 119 Agnuslde 35
WS.M75 C,7H260u 438.2253 C^HÔg

8-Acetyl Harpaguide 24 Homodi drovaltrate 206
Caiyoptoside 93
442.1838 C21H30°10
Ipolanllde 89
Penstemlde 71
Morronlside 144
Shanzhislde Methyl Ester 92 446.1424 C19H26012
Barlerln 95
408.1267 Qaphylloslde 121
C16K24°12
Eustomorusslde 140
448.1039 ClBH24On S
408.2148 6-Epl-paederosidic Acid 116
C22H32°7
Deoxydldrovaltrate 205 Paederosldic Acid 118
268
1*48.1216 C18H2i|013 498.2101 C2i+K>+011
Aralldioslde 134 AHD-valtrate 209
448.1580 C19H28012 508.1580 C24H28012

Ipolamiidoslde 90 Odontoslde 53
Scutellarlosld-II 43
450.1525 C22H26010
Specioside 46
Melanpyroslde 36
508.1792 C21H320llf
458.1707 C22H3108C1
10-0-8-Glucosyl Aucubin 33
Valechlorine 204
6-a-L-Rhamopyranosyl Catalpol 51
462.2101
510.1736 c24h30o12
Patrinoside 66
Globularimin 56
Valerosldate 63
Globularlnln 57
466.1475 C22H2£On
512.1530 c23h28o13
Veronlcoslde 47
Arephlcoside 50
470.1423 C21H26012 Kutkoslde 40
Pluirderide 110
520.1581 C25H2B012
476.1682 C2i|H28O10 Centaplcrln 155
Scrophularioside 34
524.1530 c24h28o13
476.1893 C2lH32012 Veminoslde 45
Montinioslde 62
524.1741 C21H32015
478.1638 C24H30O10
5-0-6-Glucosyl Antlrrinoside 29
laterloside 21
Mellttoside 54
480.1995 C2t;H32O10
524.1893 C25H320 12
Acevaltrate 208
Ligstroside 152
482.1423 C22H260 12 524.2621 C2 ?^ O l0
Catalposide 49 Valtrate Isovaleroxhydrln 211
488.1530 C21H280 13 526.2778
Acetyl Barlerin 96 Isovaltratum isovaleroxhydrln 213
492.1631 C24H280 u 536.1530 c25h28o13
Globularin 39 Vaccinloside 126
Plcroslde-1 41
538.1686 C25H30O13
494.1788 c24h30ou Kinecoside 48.
Globularldin 38
540.1842 C25H320 1;j
Harpagoside 25
10-Hydroxy-ligstroslde I53
Syrlngoplcroside 88
Oleuropein I56
494.2151 c25h ^ o 10 O-Kethyl-p-couraaroyl Harpaguide 26
Homoacevaltratum 210 540.2206 C26H360 12
498.1373 C22H26° 13 Follamenthln 148

Verproslde 44 Menthlafolin 149
269
51*0.2570 c27nhoon 586.1686 C29H3Q013

IVHD-valtrate 212 Amarogentin 159
51*2.2363 c26h38o12 595.1897 ^27^34^15

10-Acetoxy-oleuropein 157
Dihydrofollamenthin 150
5112.2363 c26h33o12 602.1634 ^29^30^14

Jasminin 151 Amaroswerln 161
550. 1897 612.2053 C28H36015

Genlpln-l-0-8-gentiobloside 109 Durantoslde-III 101
552.181*2 C26H32013 688.2578

Durantoside-I 103 Nuzhenlde 162
Ladroside 84 746.2632 C33\ 6019
Cantleyoside I65
568.1792 C26H320li+
lamlldoslde 100 748.2789 C^gO^
Sylvestroslde-I 166
570.1737 c 29H30o 12
Amaropanin 158 7E2.2269 c35h42o20
Txlfloroside 160
790.2894 C35H50O20
582.1948
Sylvestroside-11 167
10-Acetoxy-ligustroside 154
Durantoslde-II 102 910.310? c42h ^ o 22
GI-5 168
584.2104 C27H36°14
Sylvestroside-III 163 1072.3635 Wtfz?
Sylvestroside-lV 164 GI-3 169
Names and synonyms of lrldolds cited in this review.
10-Acetoxy-llgustroslde 154 Asperulosidic Acid 115

10-Acetoxy-oleuropein 15? Aucubln 32
Acetyl Barlerin 96 Aucubin Acetate 214
8 -Acetyl Harpaguide 24 Aucuboside 32
10-Acetyl Scandoslde 117 Baldrinal 189
Acevaltrate 208 Barlerin 95
Adoxoslde 106 Bartsioside 31
Agnuslde 35 6 , 10 Bisdeoxyaucubin 10
AHD-Valtrate 209 Bisdesoxydihydromonotropein 77
Ajugol 18 Bisdesoxydihydromonotropein Methyl Ester 78
Ajugoside 19 Boschnaloslde 72
Allamandlcin 198 Boschnlalactone 172
Allamandln 19/ Brasoside 79
Allamdin 196 Cantleyoside I65
Amarogentin 159 Caxyoptoside 93
Amaropanln 158 Catalpol 37
Amaroswerin 161 Catalpol Monoacetate 215
Amphlcoside 50 Catalposide 49
Antirrlde 11 Centapicrin 1S5
Antlrrinoside 28 ?-Chlor$leutzlol 7
Aralldloside 134 Cornin 86
Asperuloside 123 Daphylloslde 121
/
270
Deacetyl-Asperuloslde 122 Ipolaniiidoside 90

Decaloside 9 Iridold A 22
Decapetaloside 60 Iridodlal 180
5-9 Dehydro-nepetalactone 175 Irldolactone 182
Deoxyamarogen tin 158 Iridorayrmecln 181
10-Deoxy Aucubln 12 Isocatalpol 216
Deoxydidrovaltrate 205 Isogenticin 217
Deoxyloganin 78 Isoiridomyrmecin 182
Leacetyl-asperulosldlc Acid 113 Isoneomatatablol 183
Desisovaleroxydidrovaltratura 200 Isoplumericin 194
6 -Desoxy-harpaglde 14 Isovaltral 202
Desoxyloganic Acid 77 Isovaltrate 203
Deutzloside 6 Isovaltratwr. Isovaleroxhydrln 213
5-Desoxy lanlide 93 IVHD-valtrate 212
Deutziol 5 Ixoroside 73
Didrovaltrate 207 Ixoside 132
Dihydxocomln 80 Jasninin 151
Dihydrofollamenthin 150 Ketologanln 85
Di hydroplumerlcin 195 Kingiside 145
g-Dihydro Plumericinlc Acid 193 Kutkoside 40
Durantoside-I 103 Ladroside 64
Durantoside-II 102 Lanaibid 104
Durantoside-III 101 Lamiide 99
Elenolide 185 Laniidoslde 100
6-Epi-paederosidic Acid 116 Lard ol 59
Erythrocentaurine 1?6 Ianioside 58
Eucomniol 173 Laterloside 21
Eustomoruside 140 Leonurlde 19
Eustomoside 139 Ligstroside 152
Eustoside 133 Llnaride 12
Feretoside 120 Linarioside 30
Folianenthln 148 Loganlc Acid 81
Forsythlde 130 Loganln 62
Forsythlde Methyl Ester 131 Loganoside 82
Fulvoplurcierin 191 Loniceroslde 135
Gallridoside 20 Loasaalde 4
Gardenoside 129 Macfadienoside 55
Gardoside 76 Matatabieter 176
Geniplc-acid 170 Melampyroside 36
Genipln 187 Mellttoside 54
Genip3n-l-0-g-gentiobloslde 109 Menthiafolin 149
Geniposide 108 Mentzeloside 6
Geniposidic Acid 107 Methyl Catalpol Monoacetate 218
Gentioflavoside 147 Minecoslde 48
Gentiolactone 177 Mioporoside 15
Gentiopicroside 142 Monomellttoslde 52
Gentioslde 94 Monotropeln 125
GI-3 169 Monotropeln Methyl Ester 127
Gl-5 163 Montinloside 62
Globularldln 38 Morronlslde 144
Globulazlnin 56 Mussaenoside 63
Globularin 39 Neoreatatabiol 184
Globularinin 57 Kepetalactone 179
Glucoside-VII 17 T.'uzhenide 162
5-0-g-Glucosyl-antirrinoside 29 Nyctanthoslde 128
10-0-6-Glucosyl-aucubin 33 Odontoside 53
Gluroslde 13 Odontoside Acetate 219
Crlsellnoside 133 Oleuropeln 156
Harpaguide 23 O-Methyl-Catalpol 42
Harpagoslde 25 8 -(O-aethyl-p-counaroyl)Haxpaglde 26
Harpagoslde Monoacetate 220 Opulus lxddoid-1 6?
Hastatoside 87 Opulus Irldold-11 69
Honoacevaltratun 210 Opulus Irldoid-IIl 68
Homodldrovaltrate 206 Opulus Irldoid-IV 70
10-Hydroxy-1igstroslde 153 Oruwacin 199
Ipolanlide 89 7 -Oxologanln 85
271
Paederoslde 124 Swertlamaxoslde 136

Paederosldlc Acid 118 Sylvestroside-I 166
Fatrlnoside 66 Sylvestroside-II 167
Penstemide 71 Sylvestroside-III I63
Phlomlol 105 Sylvestroslde-IV 164
Ficroside-I 41 Syrlngenone 64
Plcroside-II 50 Syringopicroslde 88
Plumerlcin 192 Syrlngoxlde 65
Pluraierlde 110 Tarennoslde 74
Procumbide 27 Teconoslde 75
Pulchelloside-3 97 Theveslde 111
Pulchelloslde-II 98 Thevlridoside 112
Reptoslde 16 Trifloroslde 160
6-a-L-Rhamnopyranosyl Catalpol 51 Unedoslde 1
Sarracenin 188 Vaccinloside 126
Scabroslde 8 Valechlorlne 204
Scandoslde 114 Valeridine 221
Scandoslde Methyl Ester 119 Valerosidate 63
Scrophularloside 34 Valtrate 201
Scutellariosid-I 39 Valtrate Isovaleroxhydrln 211
Scutellariosid-II 43 Verbenalin 86
Secogalioside 146 Verbenalol 186
Secologanlc Acid 141 Verbenaloslde 66
Secoloranln 135 Vermlnoside 45
Shanzhislde 91 Veronicoside 47
Shanzhislde Methyl Ester Verproside 44
Specicside 46 Viburtlnal 174
Stilberlcoside 2 Vllloside 61
Strictoside 3 Vogeloslde 143
Sweroside 137 Xyllomollin 190
Swertlamarin 136
272
Addendum
222.- GLOBULARIFOLIN
C22H26°11‘ 466*1^
6,2 6 (d,J 6) [a]20!). 122.8 (c=1.18, CH.jOH) (211)
*o UVi (CHjOH) 229 ('♦•I), 274 (2.9) (211)

fs.76(d,J 3.«)
IR: KBr, 3340, 1?20, 1655. 1602, 1585,
BenzoylOCH2
4.91 1454 (211)
1H-NKR: CDÔD, 100 KHz (211)
13C-NMR: (1)93-7. (3)142.3, (4)108.3, (5)
72.6, (6)80.2, (7)130*5. (8)142.6,
(9)54.1, (10)63 .2 , (l')99.3, (2')
74.2, (3’)77.8*, (4')71.3, (5’)
77.2*. (6 *)62 .6 , (1")130.8 , (2")
130.5*. (3") 129.5*. (4*’)134.3,
(5")129.5*. (6”)130.5* (CO)l67.2
(211)
M 20Di -138.8 (c=0.67, CHC13) (211)
SOURCES: Clobulaxiaceae: Clobularla (211)

273
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The following explanation of techniques is provided to help you understand

2. When an image on the Him is obliterated with a round black mark it is an

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EL-NAGGAR, LETICIA JIMENEZ

PART I: IRIDOID GLYCOSIDES FROM MENTZELIA DECAPTETALA.

The Ohio State University PH.D. 1980

PART II. IRIDOIDS.- A REVIEW.

Presented in Partial Fulfillment of the Requirements for

the Degree Doctor of Philosophy in the Graduate

School of The Ohio State University

Leticia Jimenez El-Naggar, B.S., M.S.

The Ohio State University

Reading Committee: Approved By

Prof. J.L. Beal

Prof. L.W. Robertson

Prof. D.D. Miller

My Parents s Ernesto & Reyes Maria

With my deepest gratitude to my adviser, Professor Jack L. Beal

for his invaluable teachings, continuous encouragement and care. It has

been an honor to work under his supervision.

Many times the author consulted with Professor Raymond W. Doskotch

was greatly appreciated.

Special thanks are due to Professor Larry W. Robertson and my fellow

My sincere gratitude to all my Family for their continuous moral

support and love.

I acknowledge the help provided by Dr. Jack Fowble and Librarians

preparation of this dissertation.

of my husband Dr. Sha'aban F. El-Naggar to whom I present my eternal love

February 1st., 1 9 5 1 ..................... B o m - Mexico, D.F., Mexico

July, 1973 .............................. B.S., in Pharmacy

March, 1975.............................. M.S., in Pharmacy

August, 1972-1973........................ Research Associate

1973~1975 .............................. Instructor, Cell Biology

1975-1980................................ Research Associate

Major Fields Pharmacognosy and Natural Products Chemistry.

B.S. dissertations Contribucion al Estudio de los Lipidos de Schistocerca

M.S. dissertation: Determinacion de las Estructuras de la Budleina A y

A. Romo de Vivar, C. Guerrero, E. Diaz, E.A. Bratoeff, and L. Jimenez.

L. J. El-Naggar, and J.L. Beal., Iridoids.- a Review., J. Natural

ACKNOWLEDGMENTS ................................................. iii

LIST OF ILLUSTRATIONS ....................................... xii

LIST OF TABLES ................................................ xvi

GENERAL INTRODUCTION ............................................. 1

PART I. IRIDOID GLYCOSIDES FROM MENTZELTA DECAPETALA .......... 2

OBJECTIVES OF RESEARCH .......................................... 6

ISOLATION OF IRIDOID GLYCOSIDES FROM MENTZELTADECAPETALA ____ 7

Glucoside VII ...................................... ^5

Scopoletin ........ .............................. .

Isolation of a Hypotensive Principle fromM . decapetala... ^8

Pharmacological Assays and Results ............... 50

Equipment and Services .................................... 52

Parity of Reagents and Solvents ........................... 53

Source of Plant Material ................ 5^

Extraction and Initial Partition Procedures ............... 55

Chromatographic Studies of the n-butanol and water solubles.. 55

Column Chromatography of the n-butanol Solubles on

Sephadex LH-20 and Isolation of Rutin ..................... 58

Identification of Rutin ................................... 58

Column Chromatography of the non-phenolic part of

the n-butanol solubles fraction .......................... 59

Purification of 7-Chlorodeutziol ........................ 59

Physical and Spectral data of 7-Chlorodeutziol ...... 60