A new synthesis of (Z,E)-undec-5-enoic acids, the sex pheromone of the varied carpet beetle Anthrenus verbasci

Article abstract of DOI:10.1007/s11172-005-0169-8

A new synthesis of (Z,E)-undec-5-enoic acids with the natural isomer composition Z/E = 85 : 15, the sex pheromone of the varied carpet beetle Anthrenus verbasci was developed based on co-metathesis of cycloocta-1,5-diene and ethylene.

Full text of DOI:10.1007/s11172-005-0169-8

2650
Russian Chemical Bulletin, International Edition, Vol. 53, No. 11, pp. 2650—2652, November, 2004
A new synthesis of (Z,E )ꢀundecꢀ5ꢀenoic acids, the sex pheromone
of the varied carpet beetle Anthrenus verbasci
V. I. Bykov,aꢀ A. R. Goletiani, T. A. Butenko, and E. Sh. Finkelshtein
b
a
a
aA. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences,
2
9 Leninsky prosp., 117912 Moscow, Russian Federation.
Fax: +7 (095) 230 2224, Eꢀmail: bykov@ips.ac.ru
b
Iv. Dzhavakhishvili Tbilisi State University,
1
prosp. I Chavchavadze, 380028 Tbilisi, Georgia.
Fax: +7 (883 2) 22 1103
A new synthesis of (Z,E)ꢀundecꢀ5ꢀenoic acids with the natural isomer composition
Z/E = 85 : 15, the sex pheromone of the varied carpet beetle Anthrenus verbasci was developed
based on coꢀmetathesis of cyclooctaꢀ1,5ꢀdiene and ethylene.
Key words: olefin metathesis; pheromones; 1,5ꢀcyclooctadiene, ethylene, undecꢀ5ꢀenoic
acids, varied carpet beetle.
The varied carpet beetle Anthrenus verbasci is a highly
major product, together with an Eꢀstereoisomer impurity
(0.3—1.2%).
In this study, in order to prepare the exact replica of
4
,5
dangerous pest damaging stuffed insects and animals in
1
entomological and zoological museums. The sex pheroꢀ
mone (SF) of this insect is a mixture of (Z,E )ꢀundecꢀ5ꢀ
enoic acids 6 in the ratio Z/E = 85 : 15. Its synthetic
analog with the stereoisomer ratio Z/E = 75 : 25 was
obtained using the Wittig reaction. Later, Harada and
Mori attained a stereoisomer ratio, Z/E = 82 : 18, closer
the pheromone of varied carpet beetle Anthrenus verbasci,
we used both stereoselective and nonstereoselective verꢀ
sions of the coꢀmetathesis between 1 and 2.
2
The ratio of geometric isomers in decaꢀ1,5,9ꢀtriene 3
formed upon metathesis with almost complete converꢀ
sion of 1 was found to approach the thermodynamically
equilibrium value (Z/E = 16 : 84). At a temperature of
20 °C and an ethylene pressure of 10 atm, the degree of
conversion of 1 is 99.5% after 48 h and the ratio of the
triene isomers Z/E = 21 : 79. At a lower degree of converꢀ
sion (80%), this ratio is 99 : 1. Thus, using triene samples
obtained with different degrees of conversions of 1, it
is possible to obtain a mixture with the composition
Z/E = 85 : 15. Mixing of two triene samples with Z/E 99 : 1
and 21 : 79 (10 and 2.18 g, respectively) gave sample 3
with Z/E = 85 : 15, required for the synthesis of an exact
replica of the natural pheromone (Scheme 1). It is noteꢀ
to the natural one, by performing the Wittig reaction with
3
2
ꢀhydroxytetrahydropyran.
Previously, we synthesized the (Z )ꢀ5ꢀ (Z )ꢀ7ꢀmonoꢀ
4
enoic components of the lepidopterous SF and also
(
Z )ꢀtricosꢀ9ꢀene (the SF of the house fly Musca
domestica) and (Z )ꢀ7,8ꢀepoxyꢀ2ꢀmethyloctadecane (the
5
SF of gypsy moth Limantrya dispar). As the key reaction,
we used the (Z )ꢀstereoselective coꢀmetathesis of
cyclooctaꢀ1,5ꢀdiene (1) with ethylene (2) (Scheme 1). In
the presence of MoCl /SiO —SnMe under mild condiꢀ
5
2
4
5
,6
tions and with incomplete conversion of 1 (23—87%),
Z )ꢀdecaꢀ1,5,9ꢀtriene (92—68%) is formed as the
(
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2540—2542, November, 2004.
066ꢀ5285/04/5311ꢀ2650 © 2004 Springer Science+Business Media, Inc.
1

Synthesis of (Z,E )ꢀundecꢀ5ꢀenoic acids
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004 2651
worthy that this isomer ratio did not change throughout
the subsequent steps of the synthesis.
mixture was stirred until the precipitate dissolved. Then the
mixture was allowed to warm to room temperature and stirred
for 1 h. The mixture was then cooled to –20 °C, solutions of
MeONa (4.8 g, 89.6 mmol) in MeOH (50 mL) and I2 (22.7 g,
Triene 3 was subjected to partial regioselective hydroꢀ
7
boration–iodination using 9ꢀBBN as the hydroborating
8
9.6 mmol) in THF (80 mL) were successively added dropwise.
agent. (Z,E )ꢀUndecaꢀ1,5ꢀdiene (5) was prepared by crossꢀ
coupling of (Z,Е )ꢀ10ꢀiododecaꢀ1,5ꢀdiene (4) with lithium
After removal of the solvents, the residue was extracted with
hexane and the extract was washed with water and dried with
8
9
dimethylcuprate. Hydroboration—oxidation of diene 5
furnished (Z,E )ꢀundecꢀ5ꢀenꢀ1ꢀol (6) in a high yield; this
was oxidized to aldehyde1 and then to (Z,E )ꢀundecꢀ5ꢀ
MgSO . The removal of hexane and distillation in vacuo gave
4
8.3 g (35%) (E,Zꢀ10ꢀiododecaꢀ1,5ꢀdiene, b.p. 125 °C (15 Torr).
0
1
H NMR (CDCl ), δ: 1.30—2.20 (m, 10 H, CH ); 3.18 (t, 2 H,
3
2
1
0
enoic acid (7). Note that the Moffatt oxidation, which
we have used earlier to prepare unsaturated aldehydes,
gives nearly quantitative product yields.11 Further oxidaꢀ
tion of the product with 30% hydrogen peroxide in the
same reaction vessel for 48 h gave acid 7 in 50% yield.
Thus, we proposed a new, convenient synthesis of the
sex pheromone of the varied carpet beetle Anthrenus
verbasci through coꢀmetathesis of readily available cycloꢀ
octadiene and ethylene.
CH2—I, J = 7.4 Hz); 4.9 (m, 2 H, CH2=CH—); 5.40 (t, 1.7 H,
ZꢀCH=CH—, J = 6.0 Hz); 5.42 (m, 0.3 H, EꢀCH=CH—); 5.80
(m, 1 H, —CH=CH ).
2
(
Z,E )ꢀUndecaꢀ1,5ꢀdiene (5). A suspension of CuBr (5.2 g,
3
6 mmol) and LiCl (3.12 g, 72 mmol) in THF (120 mL) was
stirred at ~20 °C until a homogeneous solution formed. This
solution was cooled to –70 °C, and methyllithium (1.6 g,
7
2 mmol) was added. After stirring for 1 h, (Z,E )ꢀ10ꢀiododecaꢀ
1,5ꢀdiene (4) (7.9 g, 30 mmol) was added. The mixture was
heated to ~20 °C, stirred for 2 h, and hydrolyzed with 30 mL of
5
% aqueous HCl. The organic layer was separated, neutralized
with K CO , washed with water, and dried with MgSO . The
2
3
4
Experimental
removal of the solvents and vacuum distillation gave 3.04 g
67%) (Z,E )ꢀundecaꢀ1,5ꢀdiene (5), b.p. 188 °C (760 Torr),
(
2
0
The purity of solvents, starting compounds, and reaction
products was checked and the reactions were monitored by GLC
using a LKhMꢀ8MD chromatograph with a flame ionization
detector (a 50 m × 0.2 mm quartz capillary column) with the
nD 1.4383, impurity content ~2%. MS, m/z (Irel (%)): 152 [M]
(2), 124 [M – 28] (4), 110 [M – 42] (12), 96 (14), 81 (44),
1
67 (64), 55 (78), 41 (100). H NMR (CDCl ), δ: 0.85 (m,
3
3 H, CH —CH ); 1.29 (m, 6 H, CH —CH ); 2.15 (m, 6 H,
3
2
2
2
SKTFP or SEꢀ30 stationary phases and H as the carrier gas.
CH —CH=); 4.90 (m, 2 H, CH =CH—); 5.39 (t, 1.7 H,
2 2
2
The analyses were carried out with linear temperature programꢀ
ZꢀCH=CH—, J = 6.0 Hz); 5.41 (m, 0.3 H, EꢀCH=CH); 5.80
–
1
ming (12 °C min ) from 35 °C to a temperature 100 °C below
(m, 1 H, CH=CH ).
2
1
13
the boiling point of the compound. H and C NMR spectra
were recorded on a Bruker MSLꢀ300 spectrometer in CDCl3
(Z,Е)ꢀUndecꢀ5ꢀenꢀ1ꢀol (6). Diene 4 (3.04 g, 20 mmol) was
added at 12 °C to a stirred suspension of dimeric 9ꢀВВN (2.44 g,
10 mmol) in anhydrous THF (20 mL). The mixture was stirred
at 12 °C for 1 h and at 25 °C for 1 h and cooled to 6 °C.
Methanol (30 mL), 3 M NaOH (5 mL), and 30% H O (20 mL)
relative to Me Si. IR spectra were measured on a Specord IRꢀ75
4
instrument in thin films. Mass spectra (EI) were run on a Finigan
MAT 95 XL mass spectrometer at 70 eV. The stereoisomer comꢀ
2
2
1
13
position was determined by GLC and H NMR and C NMR
spectroscopy. All reactions were carried out under highꢀpurity
were added at such a rate that the temperature did not exꢀ
ceed 20 °C. The volatile components were distilled in vacuo and
the residue was extracted with hexane. The extract was washed
argon; the solvents were distilled from LiAlH under argon.
4
6
(
Z,Е )ꢀDecaꢀ1,5,9ꢀtriene (3). The catalyst MoCl /SiO2
with water, dried with MgSO , concentrated, and distilled to give
5
4
(
1
50 g, 12.5 mmol of Mo) and cyclooctaꢀ1,5ꢀdiene 1 (Fluka,
35 g, 1.25 mol) were charged into a steel autoclave equipped
3.1 g (91%) of (Z,E )ꢀundecꢀ5ꢀenꢀ1ꢀol, b.p. 108 °C (12 Torr),
2
0
1
nD 1.4526, impurity content ~1%. H NMR (CDCl ), δ: 0.90
3
with a stirrer, a manometer, and a sampling device, and the
(br.s, 3 H, CH —CH ); 1.31 (br.s, 8 H, CH —CH ); 1.51 (m,
3
2
2
2
pressure of ethylene 2 was brought to 10 atm. A solution of
2 H, —CH —CH —O); 1.99 (br.s, 4 H, (CH —CH=CH);
2 2 2
Me Sn (Fluka, 5.34 g, 30 mmol) in toluene (93 mL) saturated
with ethylene at 12 аtm was added from a special vessel. After
2.24 (br.s, OH); 3.52 (m, 2 H, —CH —O); 5.29 (br.s, 2 H,
2
—CH=CH—). C NMR (CDCl ), δ: 13.9 (CH —CH ); 22.9,
3 3 2
4
13
4
8 h (20 °C), the reaction mixture was separated from the cataꢀ
26.6, 29.3, 29.9, 30.3, 31.8, 32.6 (7 CH ); 62.4 (CH —O); 129.9
2 2
lyst and fractionated to give 46 g of triene 3 (Z/E = 21 : 79),
(ZꢀCH=CH); 130.1 (EꢀCH=CH).
2
0
yield 27%, b.p. 170 °C (760 Torr), nD 1.4487. Purity 99.0%.
(Z,Е )ꢀUndecꢀ5ꢀenoic acid (7). Pyridinium trifluoroacetate
(0.5 g) in 10 mL of DMSO was added to a mixture of
(Z,Е )ꢀundecꢀ5ꢀenꢀ1ꢀol (6) (3.1 g, 18.2 mmol), DMSO (1.6 g,
20.5 mmol), and DCC (4.2 g, 20.6 mmol) in toluene (30 mL),
and the mixture was stirred for 4 h. A 30% solution of H O
+
+
1
MS, m/z (Irel (%)): 136 [M] (3), 41 [M – 95] (100). H NMR
CDCl ), δ: 2.15 (m, 8 H, CH —CH=); 4.90 (m, 4 H,
(
3
2
CH =CH—); 5.39 (t, 0.42 H, ZꢀCH=CH—, J = 6.0 Hz);
2
5
.42 (m, 1.58 H, EꢀCH=CH—); 5.80 (m, 2 H,—CH=CH ).
2
2
2
1
3
C
NMR (CDCl ), δ: 27.0 (CH —CH=CH); 34.0
(40 mL) was added, the reaction mixture was stirred at room
3
2
(
(
(
CH =CH—CH ); 114.8 (CH =CH); 129.6 and 130.2
temperature for 48 h, and 40 mL of H O was added. The organic
layer was separated and the aqueous layer was extracted with
2
2
2
2
CH=CH);
138.5
(CH =CH).
IR,
ν/cm–1
:
730
2
ZꢀH—C=C—H); 950 (ЕꢀH—C=C—H); 1640 (C=C).
Z,E )ꢀ10ꢀIododecaꢀ1,5ꢀdiene (4). Triene 3, Z/E = 85 : 15
12.18 g, 89.6 mmol) was added at 6 °C to a suspension of
hexane. Drying (MgSO ), removal of the solvents, and distillaꢀ
4
(
tion in vacuo gave 1.9 g (50%) of (Z,Е )ꢀundecꢀ5ꢀenoic acid (7),
2
0
(
b.p. 138 °C (2 Torr), n
1.4502, impurity content about 5%.
D
1
dimeric 9ꢀBBN (10.9 g, 44.7 mmol) in THF (40 mL), and the
H NMR (CDCl ), δ: 0.89 (m, 3 H, CH —CH ); 1.34 (m, 6 H,
3
3
2

2652
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004
Bykov et al.
CH —CH ); 1.82—2.11 (m, 6 H, —CH —); 2.31 (t, 2 H,
6. V. I. Bykov, T. A. Butenko, E. Sh. Finkel´shtein, USSR
Pat. 1225833, Byul. izobret., 1991, 46.
2
2
2
CH —COOH, J = 7.0 Hz); 5.29 (br.s, 2 H, —CH=CH—); 11.1
2
(
br.s, 1 H, OH).
7. H. C. Brown, M. W. Rathke, and M. M. Rogic, J. Am. Chem.
Soc., 1968, 90, 5038.
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Received July 8, 2004;
in revised form September 9, 2004