Agricultural and Biological Chemistry

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3S-(+)-3,7-Dimethyl-1,5,7-octatriene-3-ol in the
Essential Oil of Black Tea

Yoichi Nakatani, Sumiko Sato & Tei Yamanishi

To cite this article: Yoichi Nakatani, Sumiko Sato & Tei Yamanishi (1969) 3S-(+)-3,7-
Dimethyl-1,5,7-octatriene-3-ol in the Essential Oil of Black Tea, Agricultural and Biological
Chemistry, 33:6, 967-968, DOI: 10.1080/00021369.1969.10859406

To link to this article: https://doi.org/10.1080/00021369.1969.10859406

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 Short Communication

[Agr. Bioi. Chern., Vol. 33, No. 6, p. 967-968, 1969]

3S-( + )-3,7-Dimethyl-1,5,7-octatriene-3-ol m the Essential

Oil of Black Tea"

Sir: relative retention time to that of linalool was

Extensive studies on the neutral fraction of
the essential oil 21 from black tea have been
carried out by Yamanishi et al. with fractional
distillation, silica-gel column chromatography
and gas chromatography*
In this paper we wish to report the isolation
of a component with a very sweet and flowery
aroma, which has never been reported as a
constituent of black tea up to date. 31
The compound seems to be one of the im-
portant constituents of black tea flavor. The
1.27 on the column of Carbowax 20M, and
the IR, NMR and mass spectra were com-
pletely identical with those of authentic 3, 7-
dimethyl-1,5,7-octatriene-3-ol, which was re-
cently isolated from the essential oil of Ho-leaf
by Muraki. 4 ' However, the former has the
specific rotation + ll.9°, while the latter has
[a]~-15.2°
In order to determine the absolute configu-
rations* at C-3 of these compounds, (- )-linalyl
acetate (l), [a]t0 -10.8°, was transformed into

100
90
,.,--, ... --- -
.s" 70 :'
"'"' 60
''
~ 50
E
40
:!
~,J
0~ 30
20
10
4000 3600 3200 2800 2400 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600
1
\\'a\'e numher I em )

FIG. 1. Infrared Spectra of Natural and Synthetic 3R-(- )-3, 7-dimethyl-1 ,5, 7-octatriene-3-ol (neat film).
Full line: Natural one
Broken line: Synthetic one

* Experimental parameters of GLC were as fol- 3) T. Yamanishi, Eiyo to Shokuryo, 21, 227 (1968).
lows; 4) S. Muraki, The 11th Symposium on the Chemis-
Column: 3 mm X 187 em stainless steel, try of Terpenes, Essential Oils and Aromatics, Matsu-
Carbowax 20M 2396 on Chromosorb W yama, Japan, Oct., 1967, p. 30.
60/80, 5) G. Ohloff und E. Klein, Tetrahedron, 18, 37 (1962).
Carrier gas: Helium, 20 mlfmin, 6) R. S. Mulliken, ]. Chern. Phys., 7, 121 (1939).
Column Temp.: 15ooc. * After this article was accepted, T. Yoshida et al.
1) T. Yamanis~i, A. Kobayashi, H. Nakamura, reported the determination of the configuration of
A. Uchika, S. Mon, K. Osawa and S. Sasakura, Agr. (- )-trans-Hotrienoi: T. Yoshida, S. Muraki, H. Kawa-
Biol. Chern., 32, 379 (1968). mura and A. Komatsu, Agr. Biol. Chern., 33, 343
2) T. Yamanishi, T. Kiribu~hi, M. Sakai, N. (1969).
Fujita, Y. Ikeda and K. Sasa, tbtd., 27, 193 (1963).
968 Y. NAKATANI, S. SATO and T. YAMANISHI

OCOCH, " OCOCH, = OCOCH, ~ OCOCH,

Nss+n+n+n

B~ ~BrBr~
I
(R -configuration) (R -configuration l

6'"/
~Oil
nOCOCH,

~ --:K:-:'O'""H----'""

II
(R- configuration) (R- configuration) (R- configuration)

FIG. 2. Synthesis of 3, 7-Dimethyl-1 ,5, 7-octatriene-3-ol.

HO-Leaf Oil tion (!-form; .{~'.?xH 230 mp, log s4.4 and d-form:
A:;;~: 230 mp, log s4.3) of these compounds in-
dicate that their conjugated double bonds exist
in the S-trans conformation.
It is very interesting that both linalool and
(3R)-(-) (3R)-(-) 3, 7-dimethyl-1 ,5, 7-octatriene-3-ol in black tea
have 3S-configuration, while those in Ho-leaf
Black Tea
have 3R-configuration. This fact as well as the

~·------• ~OH easy transformation described above indicates

(3S)-( +) (35)-(+)
FIG. 3. Probable Biosynthetic Pathway of 3,7-
Dimethyl-l ,5, 7-octatriene-3-ol.
(- )-3,7-dimethyl-1,5,7-octatriene-3-ol (II), [a)~
-3.0°, via a mixture of bromides (Figs. 1, 2).
Since I was shown to be 3R-configuration on
alkaline hydrolysis to 1-linalool (III), [a]~ -
10. 7o, it is concluded that II has 3R-configu-
ration and the corresponding (+)-form has
3S-configuration. This is also the first synthesis
of this structure to our knowledge.
Furthermore, the intensities of UV absorp-
that these 3,7-dimethyl-1,5,7-octatriene-3-ols
were respectively derived from the correspond-
ing linalools in the manufacturing process or
in plants themselves (Fig. 3).
The authors wish to thank Mr. Shigeru
Muraki (Takasago Perfumery Co. Ltd.), Pro-
fessor Akio Kobayashi (Tohoku University)
0 and Dr. Y oshiaki Tanahashi (U niversite de
Strasbourg) for their valuable discussion.
Yoichi NAKATANI
0
Sumiko SATO
Tei YAMANISHI
Laboratory of Food Chemistry
Ochanomizu University
Bunkyo-ku, Tokyo
Received March 22, 1969