This article was downloaded by:[Bergmann, Jan]

[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

Natural Product Research

Formerly Natural Product Letters
Publication details, including instructions for authors and subscription information:
http://www.informaworld.com/smpp/title~content=t713398545

Identification and synthesis of some fatty acid

derivatives from larvae of Chilecomadia valdiviana
(Lepidoptera: Cossidae)
To cite this Article: Bergmann, Jan, Lopez, Katya and Buono-Core, Gonzalo ,
'Identification and synthesis of some fatty acid derivatives from larvae of
Chilecomadia valdiviana (Lepidoptera: Cossidae)', Natural Product Research,
21:5, 473 - 480
To link to this article: DOI: 10.1080/14786410601129986
URL: http://dx.doi.org/10.1080/14786410601129986

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf
This article maybe used for research, teaching and private study purposes. Any substantial or systematic reproduction,
re-distribution, re-selling, loan or sub-licensing, systematic supply or distribution in any form to anyone is expressly
forbidden.
The publisher does not give any warranty express or implied or make any representation that the contents will be
complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses should be
independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims, proceedings,
demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or
arising out of the use of this material.
Taylor and Francis 2007

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

Natural Product Research, Vol. 21, No. 5, 1 May 2007, 473480

Identification and synthesis of some fatty acid derivatives from

larvae of Chilecomadia valdiviana (Lepidoptera: Cossidae)
JAN BERGMANN*, KATYA LOPEZ and GONZALO BUONO-CORE
Instituto de Qu mica, Pontificia Universidad Catolica de Valpara so,
Avda Brasil 2950, Valpara so, Chile
(Received 25 January 2006; in final form 17 May 2006)
Larvae of Chilecomadia valdiviana (Lepidoptera: Cossidae) were extracted and the extract was
fractionated by chromatography on silica. As shown by gas chromatographymass spectrometry, the major fraction contained saturated and unsaturated straight-chain acetates, with
(Z )-5,13-tetradecadienyl acetate and dodecyl acetate as the main components, while in a minor
fraction the corresponding alcohols were detected. The identification of the compounds and the
synthesis of some reference material are presented.
Keywords: Chilecomadia; Cossidae; Larvae; Acetates; DMDS; GC/MS

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.

2. Results and discussion

Larvae of C. valdiviana were homogenized and extracted with hexane. The extract was
filtered and concentrated to give the crude extract, which was fractionated by flash
chromatography on silica gel, yielding two fractions. Fraction 1 contained the vast

*Corresponding author. Tel.: 56-32-273172. Fax: 56-32-273422. Email: jan.bergmann@ucv.cl

Natural Product Research
ISSN 1478-6419 print/ISSN 1029-2349 online 2007 Taylor & Francis
http://www.tandf.co.uk/journals
DOI: 10.1080/14786410601129986

474

J. Bergmann et al.

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

Table 1.

Straight-chain acetates identified from larvae of C. valdiviana.

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

Fatty acid derivatives from larvae of C. valdiviana

475

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

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

a: DHP, pTsOH, RT; b: BuLi, 8-bromo-1-octene or 1-bromooctane, THF, HMPT, 30C;

c: pTsOH, MeOH, RT; d: H2, Lindlar's catalyst, hexane, RT; e: Ac2O, DMAP, pyridine, RT;
f: LiAlH4, diglyme, 200C
Scheme 1.

Synthesis of reference material.

natural compounds to present (Z ) geometry. Pure (Z )-5,13-tetradecadienyl acetate has

been obtained before by copper-catalyzed carboncarbon coupling [7].
Similar compounds have been found in larvae of other cossid species. 5,13Tetradecadienol, 3,5,13-tetradecatrienol, and 4,6,13-tetradecatrienol, together with the
corresponding acetates have been identified from Cossus cossus larvae, without
determining the geometry of the double bonds [2]. In larvae of Zeuzera pyrina, dodecyl
acetate, 11-dodecenyl acetate and 5,13-tetradecadienyl acetate were identified [3].
Larvae of Chilecomadia moorei, a species closely related to C. valdiviana, produce
dodecyl acetate, (Z )-5-dodecenyl acetate, (Z )-7-dodecenyl acetate, 11-dodecenyl
acetate, tetradecyl acetate, (Z )-4-tetradecenyl acetate, (Z )-5-tetradecenyl acetate, and
(Z )-5,13-tetradecadienyl acetate [4]. A common feature in all species investigated, is the
production of 5,13-tetradecadienyl acetate, which is also the main component in C.
valdiviana. Probably, the enzymes involved in the biosynthesis of these straight-chain
acetates, are conserved in the family Cossidae, thus leading to secretions similar in
composition. The function of these secretions is not known. It can be speculated that
they might possess antimicrobial properties or that they are used by gravid female
adults at the moment of choosing an oviposition site. This would explain the fact that
infestations with C. valdiviana occur concentrated in a small area within a bigger area of
available host plants.

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

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).

3.2. Insect material

Larvae of C. valdiviana were collected from infested trees in Parque Nacional La
Campana (Region de Valpara so, Chile) and other sites around Valpara so.
Identification was done according to reference [10].

3.3. Extraction and fractionation procedure

100 g larvae (all instars) were homogenized and stirred with 500 mL of hexane overnight
at ambient temperature. The resulting mixture was filtered and dried over anhydrous
magnesium sulphate. The solvent was evaporated to give 12.0 g of crude extract, which
was fractionated by flash chromatography on 200 g of silica gel, using a mixture of
hexaneethyl acetate (85 : 15) as the eluent. Two fractions were collected; fraction 1
(9.92 g) and fraction 2 (0.09 g). These fractions were submitted to analysis as described.

Fatty acid derivatives from larvae of C. valdiviana

477

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

3.4. Derivatization with DMDS

In a gas-tight vial, 50 mL of carbon disulfide, 5 mL of iodine solution (5% in diethyl
ether), and 50 mL of DMDS were added to 50 mL of the extract. The vial was placed in
an oven at 50 C for 4 h. Sodium thiosulfate solution (10%) was added to destroy
excess iodine; the organic phase was carefully removed, concentrated, and analyzed by
GC/MS.

3.5. Syntheses of reference compounds

Synthesis of 1-(20 -tetrahydropyranyloxy)-5-hexyne (6). To a stirred solution of 4.00 g
(40.8 mmol) 5-hexyne-1-ol in 20 mL dry dichloromethane were added 150 mg
p-toluenesulfonic acid and 3.72 mL (3.44 g, 41 mmol) 3,4-dihydro-2H-pyrane at 0 C.
The reaction mixture was allowed to warm to room temperature and hexane and sat.
sodium bicarbonate were added. The aqueous phase was extracted with hexane; and
the combined organic phases were dried (MgSO4) and concentrated. Purification of the
crude product by column chromatography yielded 7.41 g (99%) of 6 as a colorless oil;
MS (EI, 70 eV): m/z 41 (52), 56 (45), 67 (28), 79 (35), 85 (100), 101 (22), 111 (4), 125
(2), 140 (1), 181 (1), 182 (M, <1); 1H-NMR (400 MHz, CDCl3):  4.574.53 (m, 1H,
H-20 ), 3.863.79 (m, 1H), 3.72 (dt, 1H, J 9.8, 6.4 Hz), 3.503.43 (m, 1H), 3.38
(dt, 1H, J 9.8, 6.3 Hz), 2.20 (dt, 2H, J 7.0, 2.4 Hz, H-4), 1.92 (t, 1H, J 2.7 Hz, H-6),
1.831.45 (m, 10H).
Synthesis of 1-(20 -tetrahydropyranyloxy)-tetradeca-5-yne (11). A solution of 2.50 g
(13.7 mmol) 6 in 15 mL THF and 15 mL of HMPA was cooled to 30 C. 8.75 mL
(14 mmol) butyllithium (15% solution in hexane) was added and the reaction mixture
was warmed to 0 C. After 15 min, 2.43 mL (2.70 g, 14 mmol) 1-bromooctane were
added, and the reaction mixture was stirred for 1 h at room temperature. After addition
of hexane and water, the aqueous phase was extracted with a 9 : 1 mixture of hexane
ethyl acetate. The combined organic phases were washed with brine, dried over
anhydrous MgSO4, and concentrated. The crude product was purified by column
chromatography. Yield: 3.59 g (89%) colorless oil; MS (EI, 70 eV): m/z 41 (21), 55
(30), 67 (32), 85 (100), 95 (22), 101 (5), 109 (5), 111 (5), 121 (2), 138 (1), 167 (1), 181 (5),
195 (1), 221 (7), 235 (1), 294 (M, <1); 1H-NMR (400 MHz, CDCl3):  4.604.56
(m, 1H, H-20 ), 3.903.82 (m, 1H), 3.74 (dt, 1H, J 9.9, 6.5 Hz), 3.543.46 (m, 1H), 3.40
(dt, 1H, J 9.8, 6.6 Hz), 2.222.10 (m, 4H, H-4, H-7), 1.881.22 (m, 22H), 0.88 (t, 3H,
J 6.8 Hz, H-14).
Synthesis of 5-tetradecynol (12). To a solution of 3.37 g (11.5 mmol) 11 in 20 mL
methanol, was added a catalytic amount of p-toluenesulfonic acid and the mixture was
stirred at room temperature. After 4 h, saturated sodium bicarbonate solution was
added and most of the methanol was evaporated. To the residue was added ethyl
acetate and water, the phases were separated, and the aqueous phase was extracted with
ethyl acetate. The combined organic phases were washed with water, dried over
anhydrous MgSO4 and concentrated. The crude product was purified by column
chromatography. Yield: 1.77 g (73%) colorless oil; MS (EI, 70 eV): m/z 41 (68),

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

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).

Synthesis of (Z )-5-tetradecenol (13). A mixture of 10 mL hexane, 500 mg Lindlars

catalyst, and 50 mL quinoline was stirred for 45 min in hydrogen atmosphere. 1.15 g
(5.48 mmol) 12 was added and stirring was continued for 5 h in hydrogen atmosphere.
The mixture was filtered and the solvent evaporated. The crude product was purified by
column chromatography. Yield: 1.09 g (94%) colorless oil; MS (EI, 70 eV): m/z 41
(43), 43 (30), 55 (52), 67 (100), 68 (78), 81 (47), 82 (60), 95 (18), 96 (26), 109 (10), 123 (4),
124 (4), 138 (5), 152 (1), 166 (2), 194 (3), 212 (M, <1); 1H-NMR (400 MHz, CDCl3):
 5.415.30 (m, 2H, H-5, H-6), 3.64 (t, 2H, J 6.6 Hz, H-1), 2.091.94 (m, 4H, H-4,
H-7), 1.651.53 (m, 2H), 1.461.38 (m, 2H), 1.361.23 (m, 12H), 0.88 (t, 3H, J 6.7 Hz,
H-14).

Synthesis of (Z )-5-tetradecenyl acetate (3). 300 mg (1.42 mmol) 13 and a catalytic

amount of 4-(dimethylamino)pyridine were dissolved in 5 mL pyridine. 1.00 mL (1.08 g,
10.6 mmol) of acetic anhydride was added and the mixture was stirred at room
temperature for 2 h. Saturated sodium bicarbonate solution and hexane were added and
stirring was continued for additional 10 min. The aqueous phase was extracted with
hexane. The combined organic phases were washed with water and brine, dried over
anhydrous MgSO4, and concentrated. The crude product was purified by column
chromatography. Yield: 330 mg (92%) of a colorless oil; purity (GC): 80% (Z ), 20%
(E ); MS (EI, 70 eV): m/z 41 (53), 43 (100), 54 (43), 55 (43), 61 (3), 67 (60), 68 (40), 81
(38), 82 (53), 95 (27), 96 (28), 109 (8), 110 (8), 123 (4), 124 (5), 138 (5), 152 (1), 166 (3),
194 (5), 254 (M, <1); 1H-NMR (400 MHz, CDCl3):  5.425.28 (m, 2H, H-5, H-6),
4.05 (t, 2H, J 6.8 Hz, H-1), 2.091.94 (m, 4H, H-4, H-7), 2.04 (s, 3H, CH3CO),
1.671.60 (m, 2H), 1.451.36 (m, 2H), 1.351.23 (m, 12H), 0.88 (t, 3H, J 6.7 Hz,
H-14).

Synthesis of (E )-5-tetradecenol (14). 850 mg (22.4 mmol) Lithium aluminum hydride

was added to a solution of 600 mg (2.86 mmol) 12 in 35 mL dry diethylenglycoldimethylether, and the mixture was heated to 180 C. After 5 h, the mixture was cooled to
0 C, hexane was added and the excess hydride was hydrolyzed by careful addition of
water. The aqueous phase was extracted with a 1 : 1 mixture of hexaneethyl acetate.
The combined organic phases were washed with water and brine, dried over anhydrous
MgSO4, and concentrated. The crude product was purified by column chromatography.
Yield: 210 mg (35%) of a colorless oil; MS (EI, 70 eV): m/z 41 (100), 43 (50), 55 (84),
67 (85), 68 (60), 81 (46), 82 (68), 95 (28), 96 (35), 109 (9), 123 (4), 124 (4), 138 (5), 151
(1), 166 (2), 194 (2), 212 (M, <1); 1H-NMR (400 MHz, CDCl3):  5.455.37 (m, 2H,
H-5, H-6), 3.64 (t, 2H, J 6.5 Hz, H-1), 2.041.92 (m, 4H, H-4, H7), 1.611.52 (m, 2H),
1.461.37 (m, 2H), 1.361.19 (m, 12H), 0.88 (t, 3H, J 6.9 Hz, H-14).

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

Fatty acid derivatives from larvae of C. valdiviana

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,

Downloaded By: [Bergmann, Jan] At: 18:58 8 June 2007

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).