Insect pheromones and their analogs. LXI. Synthesis of 4E,10Z-tetradecadien-1-ylacetate, a component of the Lithocolettis ringoniella sex pheromone

Article abstract of DOI:10.1023/A:1012590612393

A new scheme for synthesizing 4E,10Z-tetradecadien-1-ylacetate, the principal component of the apple leaf miner (Lithocolettis ringoniella) sex pheromone, is developed using a highly stereoselective Claisen rearrangement.

Full text of DOI:10.1023/A:1012590612393

Chemistry of Natural Compounds, Vol. 37, No. 3, 2001
INSECT PHEROMONES AND THEIR ANALOGS. LXI. SYNTHESIS
OF 4E,10Z-TETRADECADIEN-1-YLACETATE, A COMPONENT
OF THE
SEX PHEROMONE
Lithocolettis ringoniella
R. N. Shakhmaev,1 R. R. Vakhidov,1
V. V. Zorin,2 and V. N. Odinokov3
UDC 542.91+547.473+639.936.2
A new scheme for synthesizing 4E,10Z-tetradecadien-1-ylacetate, the principal component of the apple leaf
miner (Lithocolettis ringoniella) sex pheromone, is developed using a highly stereoselective Claisen
rearrangement.
Key words:
Lithocolettis ringoniella, synthesis, sex pheromone, 4E,10Z-tetradecadien-1-ylacetate.
The principal component of the sex pheromone of the apple leaf miner (Lithocolettis ringoniella) is 4E,10Z-
1
1
tetradecadien-1-ylacetate ( ) [1]. A synthesis of has been described in which the double bonds of E- and Z-configuration are
introduced using the Wittig reaction [1].
1
We developed a synthesis of that is based on a stereospecific thermal Claisen rearrangement that was used previously
to synthesize pheromones of (E)-configuration [2-5].
O
HO
HO(CH ) Br
2 5
THPO
THPO(CH ) Br
2 5
OEt
OH
4
5
3
2
O
O
O
OEt
6
OEt
7
OR
1: R = Ac
8: R = H
2
3
The starting material is 5-bromopentan-1-ol ( ). Reaction of its tetrahydropyranyl ether ( ) in a Grignard reaction with
4
acrolein gave the key synthon, alkenyl secondary alcohol . The thermal Claisen rearrangement occurs smoothly on heating
4
with triethylorthoacetate in the presence of catalytic amounts of propionic acid. Acid hydrolysis gives the ethyl ester of 10-
4
5
hydroxy-4E-decenoic acid ( ). Formation of exclusively the E-configuration for the -bond was confirmed by capillary GLC
and IR and H NMR spectroscopies. In particular, an absorption band for the C C deformation is present at 965 cm whereas
the absorption at 780 cm-1 that is characteristic of a Z-double bond is absent.
-1
1
Then alcohol 5 was oxidized by pyridinium chlorochromate to the corresponding aldehyde 6, which underwent a Wittig
reaction with the phosphorus ylide generated from butylbromide. Hydride reduction of the resulting ethyl ester of 4E,10Z-
tetradecadienoic acid (7) gave 4E,10Z-tetradecadien-1-ol (8), acetylation of which gave the target compound 1.
1
According to capillary GLC, 1 is at least 99% pure. The structure was confirmed by H NMR and IR spectroscopies.
1) Scientific-Research Institute of Fine Chemicals and Reagents, Ufa; 2) Ufa State Petroleum Technical University;
3) Institute of Petroleum Chemistry and Catalysis, Academy of Sciences of the Republic of Bashkortostan, Ufa. Translated from
Khimiya Prirodnykh Soedinenii, No. 3, pp. 240-241, May-June, 2001. Original article submitted May 21, 2001.
0009-3130/01/3703-0282$25.00 ©2001 Plenum Publishing Corporation
282

EXPERIMENTAL
1
IR spectra were recorded on a Beckman Microlab 620 MX instrument as thin layers. H NMR spectra were obtained
on a Tesla BS-587A spectrometer (working frequency 80 MHz) in (CD ) CO. Chemical shifts are given on the scale with
3 2
HMDS internal standard. GLC analysis was performed on a Chrom-5 instrument with a flame-ionization detector, 3500×3 mm
column, stationary phase of silicone SE-30 (5%) on chromaton N-AW-DMCS (0.16-0.20 mm), working temperature 50-250oC,
and He carrier gas (30 mL/min). Compounds 1, 5, and 8 were analyzed on a Carbo Erba instrument with glass capillary column
(20 m × 0.2 mm), working temperature 50-200oC. TLC was carried out on Silufol UV-254 plates with fixed SiO layers.
2
1-(Tetrahydropyran-2-yl)oxy-5-bromopentane (3). A mixture of 2 (6.0 g, 35.9 mmole), TsOH (0.02 g), and
diethylether (50 mL) was cooled (15oC), treated with dihydropyran (12.1 g), and stirred on a magnetic stirrer for 1 d (TLC
monitoring). The reaction mixture was washed successively with saturated NaHCO and NaCl solutions, dried over Na SO ,
3
2
4
and evaporated. Yield 7.2 g (80%) of 3, bp 90-92oC (1 mm).
1-(Tetrahydropyran-2-yl)oxy-7-octen-6-ol (4). Grignard reagent prepared from 3 (7.0 g, 27.9 mmole) and Mg
(0.73 g, 30 mmole) and dry diethylether (100 mL) was cooled, treated dropwise with acrolein (1.75 g, 28 mmole) in absolute
diethylether (20 mL), stirred for 1 h, and treated with cold water (20 mL). The aqueous layer was separated and extracted with
diethylether (3×20 mL). The combined organic layer was dried over Na SO . The solvent was evaporated. The residue was
2
4
chromatographed over silica gel. Yield 5.02 g (79%) of 4.
IR spectrum ( max, cm-1): 3500 (OH), 1640 and 970 (CH CH ). PMR spectrum ( , ppm, J/Hz): 1.2-1.6 (14H, m, CH ),
2
2
3.6-4.2 (5H, m, CH –O, CH–O), 4.8 (1H, m, O–CH –O), 5.2-5.5 (2H, m, CH C), 5.6-5.9 (1H, m, CH C).
2
2
2
Ethyl Ester of 10-Hydroxy-4E-decenoic Acid (5). A mixture of 4 (4.12 g, 18.1 mmole), triethylorthoacetate
(8.76 g, 54.2 mmole), and propionic acid (0.02 g) was heated on an oil bath at 138oC for 1 h. The ethanol formed was distilled
through a condenser. The mixture was cooled, treated with diethylether (100 mL), washed with saturated NaHCO and NaCl
3
solutions, dried over Na SO , and evaporated. Unreacted triethylorthoacetate was vacuum distilled from the residue. The
2
4
residue was dissolved in diethylether (100 mL), treated with TsOH (0.2 g), stirred at room temperature for 24 h (TLC
monitoring), treated with saturated NaHCO and NaCl solutions, dried over Na SO , and evaporated. The residue was
3
2
4
chromatographed over silica gel. Yield 2.02 g (52%) of 5.
IR spectrum ( max, cm-1): 3500 (OH), 1740 (C O), 1650 and 965 (E-CH CH). PMR spectrum ( , ppm, J/Hz): 1.12
(3H, t, J = 6, CH ), 1.2-1.6 (6H, m, CH ), 1.8-2.1 (6H, m, CH C CH , CH COO), 3.7-4.1 (5H, m, CH –O, OH), 5.2-5.5 (2H,
3
2
2
2
2
2
m, CH CH).
Ethyl Ester of 10-Oxo-4E-decenoic Acid (6). A suspension of pyridinium chlorochromate (14.9 g, 8.34 mmole) in
dry CHCl (100 mL) was treated dropwise with 5 (1.54 g, 7.12 mmole), stirred for another 30 min, diluted with diethylether
3
(100 mL), and pased over a silica-gel column (15 cm layer). The resulting solution was washed successively with NaHCO
3
and NaCl solutions, dried over Na SO , and evaporated. The residue was chromatographed over silica gel. Yield 1.13 g (64%)
2
4
of 6.
IR spectrum ( max, cm-1): 1740 (C O), 1650 and 965 (E-CH CH). PMR spectrum ( , ppm, J/Hz): 1.12 (3H, t, J = 6,
CH ), 1.25-1.5 (4H, m, CH ), 1.8-2.2 (8H, m, CH C CCH , CH C O, CH COO), 3.7-4.1 (2H, m, CH O), 5.2-5.5 (2H, m,
3
2
2
2
2
2
2
CH CH), 9.27 (1H, s, CH O).
Ethyl Ester of 4E,10Z-Tetradecadienoic Acid (7). Butylbromide (0.59 g, 4.34 mmole) and PPh (1.14 g,
3
4.34 mmole) were heated under Ar at 160oC for 8 h, cooled to -20oC, treated with absolute THF (50 mL) and carefully with
t-BuOK (0.49 g, 4.34 mmole), stirred for 30 min, cooled to -70oC, treated with 6 (0.92 g, 4.34 mmole), again stirred at -70oC
for 2 h, left overnight, diluted with hexane (50 mL), filtered to remove Ph PO, evaporated, and chromatographed over a silica
3
gel column. Yield 0.69 g (62%) of 7.
IR spectrum ( max, cm-1): 1740 (C O), 1650 and 965 (E-CH CH), 780 (Z-CH CH). PMR spectrum ( , ppm, J/Hz):
0.88 (3H, t, J = 6, CH ), 1.12 (3H, t, J = 6, CH CH O), 1.25-1.5 (6H, m, CH ), 1.8-2.3 (10H, m, H CC C, CH COO), 3.7-3.9
3
3
2
2
2
2
(2H, q, J = 6, CH –O), 5.2-5.5 (4H, m, CH CH).
2
4E,10Z-Tetradecadien-1-ol (8). A mixture of LiAlH (0.08 g, 2.1 mmole) and absolute diethylether (20 mL) under
4
Ar was treated dropwise with 7 (0.43 g, 1.68 mmole), stirred for 2 h, cooled to 0oC, and treated dropwise below 5oC with water
(5 mL). The organic layer was separated. The aqueous layer was extracted with ether. The combined organic layer was dried
over Na SO and evaporated. Yield 0.27 g (71%) of 8.
2
4
IR spectrum ( max, cm-1): 3500 (OH), 1650 and 965 (E-CH CH), 780 (Z-CH CH). PMR spectrum ( , ppm, J/Hz): 0.88
283

(3H, t, J = 6, CH ), 1.2-1.5 (8H, m, CH ), 1.8-2.1 (8H, m, H CC C), 3.7-4.0 (3H, m, CH –O, OH), 5.2-5.5 (4H, m, HC CH).
3
2
2
2
4E,10Z-Tetradecadien-1-ylacetate (1). A mixture of 8 (0.08 g, 0.38 mmole), absolute pyridine (1 mL), and Ac O
2
(0.35 mL) was held at room temperature for 24 h, diluted with diethylether (10 mL), washed with HCl (5 mL, 10%) and
saturated NaCl solutions, dried over Na SO , evaporated, and chromatographed over silica gel. Yield 0.06 g (86%) of 1.
2
4
IR spectrum ( max, cm-1): 1740 (C O), 1640 and 965 (E-CH CH), 780 (Z-CH CH). PMR spectrum ( , ppm, J/Hz):
0.88 (3H, t, J = 6, CH ), 1.2-1.5 (8H, m, CH ), 1.8-2.1 (11H, m, H CC C, CH COO), 3.6-3.8 (2H, m, CH –O), 5.2-5.5 (4H,
3
2
2
3
2
m, HC CH).
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3.
4.
5.
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