Straightforward preparation of (2E,4Z)-2,4-heptadien-1-ol and (2E,4Z)-2,4-heptadienal

Article abstract of DOI:10.1081/SCC-120023447

A concise synthesis of (2E,4Z)-2,4-heptadien-1-ol and (2E,4Z)-2,4-heptadienal is presented. Commercially available (Z)-2-penten-1-ol was converted to ethyl-(2E,4Z)-2,4-heptadienoate by reaction with activated MnO₂ and (carboethoxymethylene)triphenylphosphorane in the presence of benzoic acid as a catalyst. Ethyl-(2E,4Z)-2,4-hep-tadienoate was converted to (2E,4Z)-2,4-heptadien-1-ol with LiAlH₄. The alcohol was partially oxidized to (2E,4Z)-2,4-heptadienal with MnO₂. The title compounds are male-specific, antennally active volatile compounds from the Saltcedar leaf beetle, Diorhabda elongata Brulle (Coleoptera: Chrysomelidae) and have potential use in the biological control of the invasive weed saltcedar (Tamarix spp).

Full text of DOI:10.1081/SCC-120023447

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
Õ
SYNTHETIC COMMUNICATIONS
Vol. 33, No. 18, pp. 3233–3241, 2003
Straightforward Preparation of
(2E,4Z )-2,4-Heptadien-1-ol and
(2E,4Z )-2,4-Heptadienal
Richard J. Petroski*
#
USDA, REE, Agricultural Research Service,
National Center for Agricultural Utilization Research,
Crop Bioprotection Research Unit,
Peoria, Illinois, USA
ABSTRACT
A concise synthesis of (2E,4Z)-2,4-heptadien-1-ol and (2E,4Z)-2,4-
heptadienal is presented. Commercially available (Z)-2-penten-1-ol
was converted to ethyl-(2E,4Z)-2,4-heptadienoate by reaction with
2
activated MnO and (carboethoxymethylene)triphenylphosphorane
*
Correspondence: Richard J. Petroski, Research Chemist, USDA, REE,
Agricultural Research Service, National Center for Agricultural Utilization
Research, Crop Bioprotection Research Unit, 1815 N. University St., Peoria,
IL. USA 61604; Fax: (309) 681-6693; E-mail: petrosrj@ncaur.usda.gov.
#
Names are necessary to report factually on available data; however, the USDA
neither guarantees nor warrants the standard of the product, and the use of the
name by USDA implies no approval of the product to the exclusion of others that
may also be suitable.
3
233
DOI: 10.1081/SCC-120023447
Copyright & 2003 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
234
Petroski
in the presence of benzoic acid as a catalyst. Ethyl-(2E,4Z)-2,4-hep-
tadienoate was converted to (2E,4Z)-2,4-heptadien-1-ol with LiAlH4.
The alcohol was partially oxidized to (2E,4Z)-2,4-heptadienal
2
with MnO . The title compounds are male-specific, antennally
active volatile compounds from the Saltcedar leaf beetle, Diorhabda
elongata Brulle (Coleoptera: Chrysomelidae) and have potential use
in the biological control of the invasive weed saltcedar (Tamarix spp).
Key Words: Ethyl-(2E,4Z )-2,4-heptadienoate; (2E,4Z )-2,4-hepta-
dien-1-ol; (2E,4Z )-2,4-heptadienal; Oxidation-Wittig reaction;
Saltcedar leaf beetle; Diorabda elongata Brulle (Coleoptera:
Chrysomelidae).
[
1]
The title compounds, (2E,4Z )-2,4-heptadien-1-ol (1) and (2E,4Z)-
[
2]
2
,4-heptadienal
compounds from the Saltcedar leaf beetle, Diorhabda elongata Brulle
Coleoptera: Chrysomelidae) (personal communication from Dr. Allard
Cosse). This beetle is being used for the biological control of saltcedar
Tamarix spp), which is an invasive bushy tree found along rivers in the
(2), are male-specific, antennally active volatile
(
(
[3]
western United States. The compounds are likely to be part of the
pheromone of the Saltcedar leaf beetle and, if so, have potential use in
monitoring dispersal of the Saltcedar leaf beetle from sites of release.
Compound 1 is also a key synthetic intermediate in the synthesis of the
pheromone of the European grapevine moth, Lobesia botrana Den. and
[
4]
Schiff, an important pest of vineyards.
Previously reported synthetic pathways to 1, or similar compounds,
involve either multistep preparation of Z-enynols, such as (Z)-4-hepten-
[
5,6]
2-yn-1-ol, followed by stereoselective reduction of the triple bond,
multistep preparation and thermal prototropic rearrangement of b-
allenic esters to give (2E,4Z)-dienoic esters followed by reduction to the
[7]
alcohols, or a lengthy strategy involving a combination of a zirconium-
mediated
[2,3]
Wittig rearrangement and Peterson elimination as key
[8]
steps.
The synthetic pathway leading to 1 could be shortened substantially
i f Z( )-2-penten-1-ol could be partially oxidized to (Z)-2-penten-1-al,
converted to ethyl-(2E,4Z)-2,4-heptadienoate by Wittig or Horner-
Wadsworth-Emmons chemistry, then reduction of the ester with
LiAlH would give compound 1. Unfortunately, Z-allylic aldehydes,
4
such as (Z)-2-penten-1-al, are known to isomerize to the more thermo-
9]
[
dynamically stable E-isomer. This is probably why more lengthy routes
to 1 have been reported. A recent report of the oxidation of allylic

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
(
2E,4Z )-2,4-Heptadien-1-ol/(2E,4Z)-2,4-Heptadienal
3235
alcohols, in the presence of stabilized Wittig reagents to directly generate
a,b-unsaturated esters, solves the isomerization problem by trapping the
Z-allylic aldehyde as it is formed.
[
10]
The synthetic pathway leading to 1 would have to be shortened sub-
stantially if the compound, along with 2, were to be used as part of a
biological control strategy to manage Saltcedar. In this article, I report
the application of in situ oxidation-Wittig reaction methodology to the
straightforward preparation of 1 in just two steps and the subsequent
mild oxidation of 1 to 2.
RESULTS AND DISCUSSION
A preliminary experiment (0.4 mmol scale) was conducted to deter-
mine if (Z)-2-penten-1-ol could be oxidized with activated MnO to
2
(
Z)-2-penten-1-al then immediately converted to ethyl-(2E,4Z)-2,4-
heptadienoate by a Wittig reaction using (carboethoxymethylene)triphe-
nylphosphorane in the presence of benzoic acid as a catalyst. Oxidation
of (Z)-2-penten-1-ol resulted in a mixture of (Z)-2-penten-1-al (93%)
and (E)-2-penten-1-al (7%). The minor isomer was identified by
GC/MS comparison with (E)-2-penten-1-al, obtained from Aldrich.
Immediate conversion of the aldehyde mixture by a Wittig reaction
resulted in ethyl-2,4-heptadienoate containing 8% of unwanted ethyl-
(2E,4E)-2,4-heptadienoate. By comparison, the use of in situ oxidation-
Wittig reaction methodology resulted in less than 2% of the unwanted
(
2E,4E)-isomer.
Benzoic acid was added as a catalyst to enhance the 2E-isomer
[11]
stereoselectivity.
A pilot reaction, run on a 1 mmol scale, with and
without benzoic acid (0.2 mmol) yielded ethyl-2,4-heptadienoate with
E/2Z isomer ratios of 11.0 and 5.7 respectively. The minor isomer was
assigned the Z double-bond configuration on the basis of nearly identical
2
[
12,13]
mass spectra to the major product and earlier GC retention times.
The assignment of 2E,4Z geometry for the major isomer of ethyl-2,4-
heptadienoate is based on observed coupling constants of J2–3 ¼ 15.2 Hz
and J4–5 ¼ 10.7 Hz. Other evidence also supports the assignment of 2E,4Z
1
3
13
geometry. Our observed C NMR data matched published C NMR

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
236
Petroski
[
data for ethyl-(2E,4Z)-2,4-heptadienoate. In addition, the observed
7]
13
C
chemical shift was 139.3 for C-3, 142.5 for C-5 and 21.5 for C-6. This
1
data compares better with ethyl-(2E,4Z)-2,4-octadienoate with C che-
3
mical shifts of 139.5 for C-3, 141.3 for C-5 and 30.2 for C-6 than for
1
ethyl-(2E,4E)-2,4-octadienoate with C chemical shifts of 145.0 for C-3,
3
[
44.4 for C-5 and 35.0 for C-6. The observed upfield shifts result from
14]
1
the steric effect of the cis form.
[
7,14,15]
Ethyl-(2E,4Z)-2,4-heptadienoate was readily converted to 1 with
LiAlH . The amount of unwanted 2Z-isomer decreased to only 0.5%
4
after the reduction because the reaction conditions caused some isomer-
ization of the Z-double-bond to the thermodynamically more stable E-
[13,16]
configuration.
The assignment of 2E,4Z geometry for the major
isomer is based on observed coupling constants of J2–3 ¼ 15.2 Hz and
J4–5 ¼ 10.8 Hz.
The oxidation of 1 to 2 with MnO resulted in some isomerization of
2
the 4Z double bond to the 4E isomer (ca. 6%). This amount of isomer-
ization during the oxidation of 1 to 2 with MnO was observed pre-
2
[7]
viously. The assignment of 2E,4Z geometry for the major isomer is
based on observed coupling constants of J2–3 ¼ 15.2 Hz and J
¼
4–5
10.7 Hz. The minor isomer was identified as (2E,4E)-2,4- heptadienal
by GC/MS comparison with reference material.
In summary, a very straightforward preparation of compounds 1 and
has been presented. The reactions are very easy to do and the reagents
2
are readily available. The compounds are important synthetic intermedi-
ates and natural products that may play a role in the biological control of
Saltcedar.
EXPERIMENTAL
General Details
Kugelrohr boiling points are given as the oven temperature at which
the product begins to distil. Organic chemicals were purchased from
Aldrich (Milwaukee, WI) unless otherwise stated.
Preparation of Ethyl-(2E,4Z )-2,4-heptadienoate
To a 500-mL round-bottomed flask was added CH Cl (200 mL),
2
2
(
carboethoxymethylene)triphenylphosphorane (8.36 g, 24 mmol), (Z)-2-

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
(
2E,4Z )-2,4-Heptadien-1-ol/(2E,4Z)-2,4-Heptadienal
3237
penten-1-ol (1.72 g, 20 mmol), benzoic acid (0.49 g, 4 mmol), and acti-
vated MnO (17.4 g, 200 mmol). An argon atmosphere was introduced.
2
The resulting reaction mixture was stirred at RT for ca. 72 h until
GC/MS analysis indicated that the reaction was complete. The mixture
was filtered and the filter cake, containing mainly MnO , was washed
2
with CH Cl (100 mL). The resulting solution was evaporated in vacuo
2
2
to give a mixture containing mainly ethyl-(2E,4Z)-2,4-heptadienoate,
triphenylphosphine oxide and benzoic acid. The mixture was extracted
with hexane (40 mL Â 5), filtered and the solution was placed in the
ꢀ
freezer (À20 C) overnight to precipitate most of the remaining triphe-
nylphosphine oxide. The mixture was filtered, then the filtrate was
washed with saturated aqueous NaHCO solution (50 mL Â 2) and satu-
3
rated aqueous NaCl solution (50 mL). The combined washings were
back-extracted with hexane (40 mL) and the combined hexane extracts
were dried over anhydrous MgSO . After filtration, the volume of the
4
solution was measured (190 mL) and anhydrous ether (10 mL) was
added. The solution was passed through a short column of silica gel
(
6 g, slurry prepared in hexane) and the column was washed with 5%
ether in hexane (50 mL) to ensure complete elution of the product. Trace
amounts of benzoic acid, unureacted (Z)-2-penten-1-ol and by-product
triphenylphosphine oxide were thus removed. The solvent was evapo-
rated in vacuo to give a pale yellow oil. The crude product from two
preparations was combined and distilled (Kugelrohr), to afford a clear,
colorless liquid (3.89 g, 63% isolated yield). Purity was checked by gas
chromatography (GC) and found to be >95% ethyl-2,4-heptadienoate
before distillation and >99% ethyl-2,4-heptadienoate after distillation,
composed of isomers: 89% (2E,4Z), 9.0% (2Z,4Z) and 1.8% (2E,4E).
The (2E,4E)-isomer was identified by GC/MS comparison with ethyl-
(
2E,4E)-2,4-heptadienoate, prepared by the same Wittig reaction from
E-2-pentenal (Aldrich). The order of GC retention times for the various
isomers was the (2Z,4Z)-isomer; then the (2E,4Z)-isomer, and finally
ꢀ
the (2E,4E)-isomer, b.p. 38 C at 0.3 mm Hg. MS m/z (% base) 154
þ
(
(
(
M , 49), 125 (58), 109 (51), 97 (98), 81 (100), 79 (53), 67 (11), 53
1
24), 41 (20), 39 (21). H NMR ꢀ 0.71 (3H, t, J ¼ 7.5, CH ), 1.04
6
–7
3
3H, t, J ¼ 7.1, OCH CH ), 1.92 (2H, dt, J ¼ 7.8 and J ¼ 7.5,
2
3
5–6
6–7
CH ), 4.11 (2H, q, J ¼ 7.1, OCH CH ), 5.51 (1H, dt, J ¼ 10.7
2
2
3
4–5
and J ¼ 7.8, olefinic, H-5), 5.88 (1H,dd, J ¼ 12.4 and J ¼ 10.7,
5
–6
3–4
4–5
olefinic, H-4), 5.98 (1H, d, J ¼ 15.2, olefinic, H-2), 7.89 (1H, ddd,
2
–3
1
3
J2–3 ¼ 15.2, J ¼ 12.4 and J ¼ 1.1, olefinic, H-3). C NMR ꢀ 13.9
3–4
3–5
(
CH ), 14.3 (OCH CH ), 21.5 (CH ), 60.1 (CH CH ), 122.0 (olefinic,
3 2 3 2 2 3
C-2), 126.2 (olefinic, C-4), 139.3 (olefinic, C-3), 142.5 (olefinic, C-5),
66.8 (ester carbonyl).
1

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
238
Petroski
Preparation of (2E,4Z )-2,4-Heptadien-1-ol (1)
A solution of ethyl-(2E,4Z)-2,4-heptadienoate, containing ca. 9%
Z,4Z-isomer, in dry ether (10 mL) was added dropwise to a solution
2
of LiAlH (25 mmol) in ether (85 mL) at 0 C in an argon atmosphere.
ꢀ
4
ꢀ
After stirring at 0 C for 1 h, the reaction was quenched by the dropwise
addition of ice water. Anhydrous Na SO was added to absorb excess
water and the mixture was filtered. The filter cake was washed with ether
2
4
(
(
50 mL) and the solvent was evaporated in vacuo to give a pale yellow oil
2.59 g). The crude product was distilled (Kugelrohr), to afford a clear,
colorless liquid (2.21 g, 80% isolated yield). Purity was checked by gas
chromatography (GC) and found to be >95% 2,4-heptadien-1-ol before
distillation and >99% 2,4-heptadien-1-ol after distillation, composed of
isomers: 97% (2E,4Z), 0.5% (2Z,4Z) and 2% (2E,4E). The order of GC
retention times for the various isomers, from earliest to latest, was the
(
b.p 58 C at 3.0 mm Hg. Lit., b.p. 120 C at 10 mm Hg. MS m/z (% base)
2Z,4Z)-isomer; then the (2E,4Z)-isomer, and finally the (2E,4E)-isomer.
ꢀ
[6]
ꢀ
.
þ
1
12 (M ,36), 94 (30), 83 (100), 79 (56), 68 (64), 55 (96), 41 (65), 39 (45).
1
H NMR ꢀ 0.92 (3H, t, J6–7 ¼ 7.5, CH ), 1.42 (1H, s, OH), 2.10 (2H, dt,
3
J5–6 ¼ 7.6 and J ¼ 7.5, CH ), 3.92 (2H, d, J ¼ 5.3, CH OH), 5.39
6–7
2
1-2
2
(
1H, dt, J ¼ 10.8 and J ¼ 7.6, olefinic, H-5), 5.63 (1H, dt,
1–2 3–4
4
–5
5–6
J2–3 ¼ 15.2 and J ¼ 5.3, olefinic, H-2), 6.02 (1H, dd, J ¼ 11.3 and
J4–5 ¼ 10.8, olefinic, H-4), 6.53 (1H, dd, J ¼ 15.2, J ¼ 11.3, olefinic,
2–3
3–4
1
H-3). C NMR ꢀ 14.4 (CH ), 21.3 (CH ), 63.2 (CH OH), 125.9 (olefinic,
3
3
2
2
C-3), 127.9 (olefinic, C-4), 132.9 (olefinic, C-2), 133.7 (olefinic, C-5).
Preparation of (2E,4Z )-2,4-Heptadienal (2)
A mixture of activated MnO2 (1.7 g, 19.5 mmol), 1 (250 mg,
.23 mmol) and CH Cl (20 mL) was stirred at RT in an argon atmosphere
2
for 48 h. An additional 1.8 g (20.7 mmol) of activated MnO was added in
2 2
2
portions over the first 30 h. When GC/MS analysis indicated that the
reaction was complete, the mixture was filtered. The filter cake, containing
mainly MnO , was washed with CH Cl (10 mL). The resulting green solu-
2
2
2
tion was passed through a short column of florisil (1 g, slurry prepared in
CH Cl ) to remove colored impurities then the solvent was evaporated
2
2
in vacuo to give the product (230 mg, 94% yield). Purity was checked by
gas chromatography (GC) and found to be >99% 2,4-heptadienal,
composed of 94% (2E,4Z) and 6% (2E,4E) isomers. Authentic (2E,4E)-
2,4-heptadienal (Aldrich) was available for GC/MS comparison. The
(
2E,4E)-isomer had a greater GC retention time than the corresponding

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
(
2E,4Z )-2,4-Heptadien-1-ol/(2E,4Z)-2,4-Heptadienal
3239
(
base) 110 (M , 23), 95 (6), 81 (100), 79 (15), 67 (15), 53 (24), 41 (19), 39 (22).
2E,4Z)-isomer. The other possible isomers were not detected. MS m/z (%
þ
1
H NMR ꢀ 0.75 (3H, t, J6–7 ¼ 7.5, CH ), 1.83 (2H, dt, J ¼ 7.8 and
3
5–6
J6–7 ¼ 7.5, CH ), 5.46 (1H, dt, J ¼ 10.7 and J ¼ 7.8, olefinic, H-5),
2
4–5
5–6
5
.76 (1H, dd, J ¼ 11.5 and J ¼ 10.7, olefinic, H-4), 5.98 (1H, dd,
3
–4
4–5
J2–3 ¼ 15.2 and J ¼ 7.8, olefinic, H-2), 6.88 (1H, ddd, J ¼ 15.2, J
¼
1–2 2–3 3–4
1
1
1.5 and J ¼ 1.1, olefinic, H-3), 9.45 (1H, d, J ¼ 7.8, HC ¼ O).
3
–5
1–2
3
C NMR ꢀ 13.7 (CH ), 21.6 (CH ), 126.4 (olefinic, C-2), 132.4 (olefinic,
3 2
C-4), 143.7 (olefinic, C-3), 145.1 (olefinic, C-5), 192.5 (aldehyde carbonyl).
Analysis of Reaction Products
All reactions were monitored by GC using a Hewlett-Packard (HP)
890 Series II instrument equipped with flame ionization detector and
5
interfaced to a HP ChemStation data system. The oven temperature was
ꢀ
ꢀ
programmed from 50 to 250 C at 10 C/min; the programmable cool on-
ꢀ
column inlet temperature was always 3 C hotter than the oven tempera-
ꢀ
ture and the detector temperature was 250 C. A DB-1 capillary column
(
15 m  0.25 mm, 0.25-mm film thickness, J&W Scientific, Folsom, CA)
was used with 1-mL sample injections.
Electron impact mass spectra (70 eV) were obtained with an HP 5973
MSD instrument, equipped with a splitless injector. The oven temperature
ꢀ
ꢀ
was programmed from 50 to 250 C at 10 C/min; the injector temperature
ꢀ
ꢀ
was 250 C and the detector temperature was 250 C. An EC-1 capillary
GC column (30 m  0.25 mm, 0.1 mm film thickness, Alltech, Deerfield, IL)
1
13
was used with 0.3-mL sample injections. H NMR, C NMR and
2
D NMR spectra (CDCl ) were obtained on a Bruker (Bellerica, MA)
3
Advance 400 spectrometer at 400 MHz. Chemical shifts are referenced
to tetramethylsilane; coupling constants (J) are in hertz.
The E/Z-isomeric ratio of all reaction products was calculated by gas
chromatography/mass spectrometry (GC/MS) and the stereochemistry of
the major isomer was confirmed by NMR analysis. The E-isomer of all
the products had a greater GC retention time than the corresponding
Z-isomer.
ACKNOWLEDGMENTS
I thank Bruce W. Zilkowski and Robert J. Bartelt for acquiring mass
spectral data, David Weisleder for acquiring NMR spectra, and Robert J.
Bartelt for helpful discussions.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
3
240
Petroski
REFERENCES
1
2
3
. Registry Number 70979-88-3.
. Registry Number 4313-02-4.
. Stelljes, K.B.; Wood, M. Foreign agents imported for weed control.
Agric. Res. 2000, March, 4–9.
4
5
. Henrick, C. The synthesis of insect sex pheromones. Tetrahedron
1977, 33, 1845–1889, and pertinent references therein.
. Cassani, G.; Massardo, P.; Piccandi, G. New simple synthesis
of internal conjugated (Z)-enzymes. Tetrahedron Lett. 1979, 20,
633–634.
6
. Descoins, C.; Lettere, M.; Linstrumelle, G.; Michelot, A.;
Ratovelomanana, V. Steroselective synthesis of (E)-7,(Z)-9-dodeca-
dien-1-yl acetate. Synth. Commun. 1984, 14 (8), 761–773.
. Tsuboi, S.; Masuda, T.; Takeda, A. Highly stereochemically con-
trolled synthesis of esters with alumina catalyst. Its application to
total synthesis of flavor components and insect pheromones. J. Org.
Chem. 1982, 47, 4478–4482.
7
8. Kuroda, S.; Katsuki, T.; Yamaguchi, M. Stereoselective synthesis of
(
2E,4Z)-dien-1-ols; key intermediates for synthesis of sex phero-
mones of silk worm and of grape vine moth. Tetrahedron Lett.
987, 28 (7), 803–804.
1
9. Xiao, X.; Prestwich, G.D. Minimizing geometric isomerization dur-
ing oxidation of allylic alcohols to aldehydes. Synth. Commun.
1990, 20 (20), 3125–3130.
1
1
1
0. Wei, X.; Taylor, R.J.K. In situ alcohol oxidation-wittig reaction.
Tetrahedron Lett. 1998, 39, 3815–3818.
1. Johnson, W.A. Ylides and Imines of Phosphorous; John Wiley &
Sons, Inc.: New York, 1993; p238, and pertinent references therein.
2. Petroski, R.J.; Weisleder, D. Improved Horner-Wadsworth-
Emmons preparation of a-ethyl-a,b-unsaturated esters from alde-
hydes. Synth. Commun. 2001, 31 (1), 89–95.
13. Bartelt, R.J.; Weisleder, D.; Plattner, R.D. Alkyl branched tetraene
hydrocarbons. J. Agric. Food Chem. 1990, 2192–2196.
1
4. Sakai, T.; Seiko, K.; Tsuji, A.; Utaka, M.; Takeda, A. A new synth-
esis of a-benzoyloxy aldehydes. Application to the stereoselective
synthesis of conjugated (E,E)dienoic esters. J. Org. Chem. 1982,
47, 1101–1106.
1
5. Dorman, D.; Jautelat, M.; Roberts, J.D. Carbon-13 nuclear
magnetic resonance spectroscopy. Quantitative correlations of the
carbon chemical shifts of acyclic alkenes. J. Org. Chem. 1971, 36,
2757–2766.

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
(
2E,4Z )-2,4-Heptadien-1-ol/(2E,4Z)-2,4-Heptadienal
3241
16. Petroski, R.J.; Weisleder, D. Improved preparation of sap beetle
coleoptera: nitidulidae) aggregation pheromones. In Synthesis and
Chemistry of Agrochemicals VI; Baker, D.R., Fenyes, J.G., Lahm,
G.P., Selby, T.P., Stevenson, T.M., Eds.; ACS Symposium Series
800, American Chemical Society: Washington, DC, 2002; 231–237.
Received in the USA March 18, 2003

MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
©
2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.

Copyright of Synthetic Communications is the property of Taylor & Francis Ltd and its content may not be
copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written
permission. However, users may print, download, or email articles for individual use.