Documente Academic
Documente Profesional
Documente Cultură
[Bergmann, Jan]
On: 8 June 2007
Access Details: [subscription number 778304179]
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
1. Introduction
The carpenterworm Chilecomadia valdiviana (also known as butterworm) is a
polyphagous insect native to Chile. It is associated with bushes and trees, among
them economically important species like eucalyptus or avocado trees. The larval stage
feeds on the wood of the host species, boring galleries of up to 27 cm length and 1 cm
diameter into the stem [1], weakening the bole and making it more susceptible to wind
breakage. Studies of other cossid species revealed that larvae commonly produce fatty
acid derivatives, similar to the sex pheromone compounds produced by adult females
[24]. In the course of a study aimed at the identification of the sex pheromone of
C. valdiviana, we therefore also analyzed the composition of volatile compounds
produced by the larvae.
474
J. Bergmann et al.
Table 1.
No.
Compound
1
2
3
4
5
6
7*
8
9*
10
11
12
5-Dodecenyl acetate
7-Dodecenyl acetate
11-Dodecenyl acetate
Dodecyl acetate
Tetradecatrienyl acetate
(Z )-5,13-Tetradecadienyl acetate (1)
7,13-Tetradecadienyl acetate
(Z )-5-Tetradecenyl acetate (3)
7-Tetradecenyl acetate
9-Tetradecenyl acetate
13-Tetradecenyl acetate
Tetradecyl acetate
Relative percentage
1.6
0.1
1.5
37
0.1
44
Aprox. 0.1
14
Aprox. 0.6
0.2
0.2
1.1
*Identified in DMDS-derivatized extract; co-elutes with previous peak in analysis without derivatization.
majority (82%) of the material extracted and consisted of straight-chain acetates, while
in fraction 2 about 1% of the crude extract was recovered, corresponding to straightchain alcohols. The remaining material did not elute from the column under the chosen
conditions.
One of the major components in fraction 1 was identified as dodecyl acetate, by
comparison of the analytical data with those of an authentic standard. The remaining
compounds were mainly singly and doubly unsaturated acetates, as deduced from their
mass spectra. In order to determine the positions of the double bonds, the extract was
submitted to derivatization with dimethyl disulfide (DMDS). The formation of DMDS
adducts leads to prominent fragments in the mass spectrum, allowing the unequivocal
determination of double bond positions [5,6]. The results of these analyses are
summarized in table 1.
Fraction 2 contained five compounds, one of which was shown to be dodecanol by
comparison with an authentic standard. The remaining compounds were two
dodecenols, a tetradecenol, and a tetradecadienol. Upon comparison with the reference
material synthesized, the C14 compounds were identified as (Z )-5-tetradecenol (13) and
(Z )-5,13-tetradecadienol (9), while the remaining two C12 compounds are likely to be
the corresponding alcohols of 5-dodecenyl acetate and 11-dodecenyl acetate.
To determine the geometry of the double bonds in the two major unsaturated
compounds, 5,13-tetradecadienyl acetate and 5-tetradecenyl acetate, and in the
corresponding alcohols, reference material was synthesized. The general procedure is
shown in scheme 1. Key steps are the acetylenic coupling of protected 5-hexyn-1-ol (6)
with 8-bromo-1-octene and 1-bromooctane, respectively, and the selective partial
reduction of the triple bond to a double bond with the desired geometry.
Hydrogenation of tetradec-5-yn-13-en-1-ol (8) with Lindlars catalyst at 1 bar in
order to obtain (Z )-5,13-tetradecadienol (9), resulted, however, in a mixture of
products, with (Z )-5-tetradecenol as the main component. The terminal double bond is
apparently more susceptible to reduction than the internal triple bond, as the result was
not altered by shortening the reaction time to 10 min. Determination of the natural
compounds geometry, however, was still possible by using the synthesized (E ) isomer,
as this contained small amounts of the (Z ) isomer. Comparison of the analytical data of
the synthetic reference material with those of the natural compounds clearly showed the
475
a
OH
OTHP
(5)
(6)
R
OH
OTHP
(8) R = 7-Octenyl
(12) R = n-Octyl
(7) R = 7-Octenyl
(11) R = n-Octyl
O
8, 12
e
OH
(9) R = 7-Octenyl
(13) R = n-Octyl
O
(1) R = 7-Octenyl
(3) R = n-Octyl
O
8, 12
OH
(10) R = 7-Octenyl
(14) R = n-Octyl
O
(2) R = 7-Octenyl
(4) R = n-Octyl
476
J. Bergmann et al.
In the species C. cossus and Z. pyrina, the compounds produced by adult females are
different from those identified from the larvae. The sex pheromone of C. cossus consists
of (Z )-5-dodecenol, (Z )-5-dodecenyl acetate, and (Z )-5-tetradecenyl acetate [8], while
in Z. pyrina (E,Z)-2,13-octadecadienyl acetate, (E,Z)-3,13-octadecadienyl acetate,
(Z,Z)-2,13 octadecadienyl acetate, and (Z )-13-octadecenyl acetate are biologically
active compounds produced by females [9]. There is no information about volatile
compounds of C. moorei, however, these are likely to be different as well, as none of the
compounds present in larvae were found in the pupae [4]. Apparently, biosynthetic
pathways are different in larval and adult stage, respectively. It is interesting to note,
however, that the preferred positions of insaturations are at carbons 5 and 13, both in
adults and larvae. Identification of the compounds produced by adult C. valdiviana
might reveal more coherences.
3. Experimental section
3.1. General experimental procedures
Solvents and chemicals were purchased from Merck (Darmstadt, Germany) and
Sigma-Aldrich (St. Louis, USA). Chemicals were of highest available purity and used as
supplied, solvents were dried and distilled prior to use.
Silica gel for column chromatography was from Merck (silica gel 60, 63200 mm;
silica gel 60, 3263 mm for flash chromatography).
Gas chromatographyMass spectrometry (GC/MS) analyses were carried out on
a Shimadzu GC-17AGCMS-QP5050A combination. The GC was equipped with
a 30 m 0.25 mm HP-5 fused silica capillary column (0.25 mm film thickness). Mass
spectra were acquired at 70 eV.
Proton NMR spectra were acquired on a Bruker AMX400 at 400 MHz. Chemical
shifts are expressed in ppm relative to the internal standard tetramethylsilane
( 0 ppm).
477
478
J. Bergmann et al.
43 (44), 55 (66), 67 (48), 68 (35), 79 (100), 81 (35), 94 (28), 97 (38), 111 (15), 112 (10),
121 (2), 124 (2), 135 (2), 138 (2), 153 (1), 166 (2), 192 (1), 210 (M, <1); 1H-NMR
(400 MHz, CDCl3): 3.68 (t, 2H, J 6.3 Hz, H-1), 2.232.13 (m, 4H), 1.721.64
(m, 2H), 1.621.52 (m, 3H), 1.501.42 (m, 2H), 1.401.22 (m, 10H), 0.88 (t, 3H,
J 6.6 Hz, H-14).
479
Synthesis of (E )-5-tetradecenyl acetate (4). The synthesis was essentially the same as
for 3. Acetylation of 100 mg (0.47 mmol) 14 with 0.50 mL (0.54 g, 5.3 mmol) acetic
anhydride yielded 110 mg (92%) of a colorless oil; purity (GC): 94% (E ), 6% (Z ); MS
(EI, 70 eV): m/z 41 (50), 43 (100), 54 (50), 55 (52), 61 (3), 67 (80), 68 (54), 81 (62), 82
(73), 95 (43), 96 (49), 109 (12), 110 (14), 123 (8), 124 (10), 138 (10), 151 (2), 166 (5), 194
(12), 254 (M, <1); 1H-NMR (400 MHz, CDCl3): 5.465.30 (m, 2H, H-5, H-6),
4.05 (t, 2H, J 6.9 Hz, H-1), 2.04 (s, 3H, CH3CO), 2.071.93 (m, 4H, H-4, H-7),
1.661.56 (m, 2H), 1.451.36 (m, 2H), 1.361.20 (m, 12H), 0.88 (t, 3H, J 6.9 Hz,
H-14).
Synthesis of 1-(20 -tetrahydropyranyloxy)-tetradeca-5-yn-13-ene (7). The synthesis was
essentially the same as for 11. 2.50 g (13.7 mmol) 6, 8.75 mL (14 mmol) butyllithium
(15% solution in hexane), and 2.35 mL (2.67 g, 14 mmol) 8-bromo-1-octene yielded
3.15 g (77%) of a colorless oil; MS (EI, 70 eV): m/z 41 (30), 55 (16), 67 (35), 85 (100),
95 (16), 101 (4), 109 (4), 121 (2), 135 (2), 181 (4), 219 (3), 292 (M, <1); 1H-NMR
(400 MHz, CDCl3): 5.80 (ddt, 1H, J 17.2, 10.4, 6.2 Hz, H-13), 4.99 (dd, 1H,
J 17.2, 1.8 Hz, H-14a), 4.92 (dd, 1H, J 10.2, 1.8 Hz, H-14b), 4.624.55 (m, 1H,
H-20 ), 3.903.82 (m, 1H), 3.74 (dt, 1H, J 9.8, 6.5 Hz), 3.533.46 (m, 1H), 3.40 (dt, 1H,
J 9.8, 6.7 Hz), 2.202.10 (m, 4H, H-4, H-7), 2.082.00 (m, 2H), 1.831.22 (m, 18H).
Synthesis of tetradeca-5-yn-13-en-1-ol (8). The synthesis was essentially the same as for
12. Treatment of 2.97 g (10.2 mmol) 7 yielded 1.64 g (77%) of a colorless oil; MS (EI,
70 eV): m/z 41 (50), 55 (58), 67 (88), 68 (36), 79 (100), 81 (34), 93 (25), 111 (13), 121
(3), 135 (6), 137 (4), 151 (3), 165 (3), 179 (1), 193 (2), 207 (1), 208 (M, <1); 1H-NMR
(400 MHz, CDCl3): 5.80 (ddt, 1H, J 16.6, 10.4, 6.6 Hz, H-13), 4.99 (dd, 1H,
J 17.1, 1.8 Hz, H-14a), 4.92 (dd, 1H, J 10.2, 1.8 Hz, H-14b), 3.67 (t, 2H, J 6.3 Hz,
H-1), 2.222.10 (m, 4H), 2.072.00 (m, 2H), 1.711.25 (m, 13H).
Synthesis of (E )-5,13-tetradecadienol (10). The synthesis was essentially the same as
for 14. Reduction of 180 mg (0.87 mmol) 8 using 300 mg (7.91 mmol) lithium aluminum
hydride in 10 mL dry diglyme yielded 110 mg (60%) of a colorless oil; MS (EI, 70 eV):
m/z 41 (84), 55 (90), 67 (100), 68 (49), 81 (62), 82 (38), 95 (36), 96 (24), 109 (9), 110
(10), 121 (9), 135 (8), 149 (2), 163 (1), 179 (1), 210 (M, <1); 1H-NMR (400 MHz,
CDCl3): 5.81 (ddt, 1H, J 16.8, 10.3, 6.5 Hz, H-13), 5.42-5.36 (m, 2H, H-5, H-6),
4.98 (dd, 1H, J 17.0, 1.8 Hz, H-14a), 4.92 (dd, 1H, J 10.2, 1.8 Hz, H-14b), 3.64
(t, 2H, J 6.8 Hz, H-1), 2.07-1.93 (m, 6H, H-4, H-7, H-12), 1.61-1.52 (m, 2H), 1.45-1.22
(m, 11H).
Synthesis of (E )-5,13-tetradecadienyl acetate (2). The synthesis was essentially the
same as for 3. Acetylation of 55 mg (0.26 mmol) 10 with 0.25 mL (0.27 g, 2.65 mmol)
acetic anhydride afforded 50 mg (76%) of a colorless oil; purity (GC): 97% (E ), 3%
(Z ); MS (EI, 70 eV): m/z 41 (78), 43 (100), 54 (52), 55 (70), 61 (3), 67 (90), 68 (38), 79
(34), 80 (38), 81 (55), 82 (28), 93 (16), 94 (17), 95 (26), 96 (16), 107 (12), 110 (11), 121
(10), 135 (9), 149 (5), 163 (2), 192 (1), 252 (M, <1); 1H-NMR (400 MHz, CDCl3):
5.81 (ddt, 1H, J 17.1, 9.9, 6.4 Hz, H-13), 5.465.29 (m, 2H, H-5, H-6), 4.99 (dd,
1H, J 17.1, 1.4 Hz, H-14a), 4.93 (dd, 1H, J 9.9, 1.4 Hz, H-14b), 4.05 (t, 2H,
480
J. Bergmann et al.
J 6.6 Hz, H-1), 2.081.94 (m, 6H, H-4, H-7, H-12), 2.04 (s, 3H, CH3CO), 1.661.58
(m, 2H), 1.441.24 (m, 10H).
Acknowledgements
Jan Bergmann would like to thank the Direccion de Investigacion of PUCV for a
research grant (DI 125.789). Katya Lopez thanks MECESUP (Chile) for a doctoral
fellowship. The support of Corporacion Nacional Forestal (Vina del Mar, Chile) is
acknowledged.
References
[1] J.T. Kliejunas, B.M. Tkacz, H.H. Burdsall Jr, G.A. DeNitto, A. Eglitis, D.A. Haugen, W.E. Wallner.
Pest risk assessment of the importation into the United States of unprocessed Eucalyptus logs and chips
from South America. Gen. Tech. Rep. FPL-GTR-124, U.S. Department of Agriculture, Forest Service,
Forest Products Laboratory, Madison, WI (2001).
[2] R. Trave, L. Garanti, A. Marchesini, M. Pavan. Chim. Ind., 11, 1167 (1966).
[3] A. Marchesini, L. Garanti, M. Pavan. Ric. Sci., 39, 874 (1969).
[4] J.A. Garbarino, V. Gambado. Bol. Soc. Chil. Qum, 33, 129 (1988).
[5] H.-R. Buser, H. Arn, P. Guerin, S. Rauscher. Anal. Chem., 55, 818 (1983).
[6] M. Vincenti, G. Guglielmetti, G. Cassani, C. Tonini. Anal. Chem., 59, 694 (1987).
[7] G. Cahiez, A. Alexakis, J.F. Normant. Tetrahedron Lett., 21, 1433 (1980).
[8] A. Capizzi, C. Tonini, E. Arsura, G. Guglielmetti, P. Massardo, P. Piccardi. J. Chem. Ecol., 9, 191 (1983).
[9] P.L. Castellari. Boll. Ist. Ent. Univ. Bologna, 40, 239 (1986).
[10] A.O. Angulo, T.S. Olivares. Gayana Zool., 56, 181 (1992).