WO2017171674A1 - Synthesis of attractant of pistachio twig borer (kermania pistaciella) - Google Patents

Synthesis of attractant of pistachio twig borer (kermania pistaciella) Download PDF

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WO2017171674A1
WO2017171674A1 PCT/TR2017/000040 TR2017000040W WO2017171674A1 WO 2017171674 A1 WO2017171674 A1 WO 2017171674A1 TR 2017000040 W TR2017000040 W TR 2017000040W WO 2017171674 A1 WO2017171674 A1 WO 2017171674A1
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acetoxy
bromo
dodecane
heptadecene
optically active
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PCT/TR2017/000040
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French (fr)
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Sirit ABDULKADIR
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Abdulkadir Sirit
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

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  • the invention relates to the stereoselective synthesis (2S,12Z)-2-acetoxy-12-heptadecene secreted by female pistachio twig borer and can be used as attractant for determination of the number of male individuals in monitoring area, mass trapping and mating disruption.
  • the pistachio twig borer (Kermania pistaciella) is one of the most important insect pests in plantations of pistachio in Middle East, particularly in Turkey and Iran. After mating, females lay eggs close to shoot tips and fruit clusters and larvae bore into and feed on terminal buds and in twigs and shoots formed the previous year. Larval feeding causes abscission of fruit buds and die-back of twigs and may directly damage fruit clusters (1 ). Pistachio trees are treated annually with insecticides to reduce damage caused by K. pistaciella larvae. The use of chemicals called insecticide are not effective and leave residue on fruit that is harmful to the environment and human health. The use of a pheromone or an attractant which ensures minimizing the use of insecticide or can be used instead of themis of great importance in recent years.
  • Monitoring technique is used to determine whether the presence of adult moths in a monitored area, date of first appearance in season if available, level of infestation and the correct timing of control measures.
  • the aim of mass trapping method is to attract and trapthe greatest possible number of insects which reduce the number of male and female species.
  • the insect's mating chances are reduced and the possibility of laying eggs gradually decreases which hinder production of new generations of pests.
  • Mating disruption is aimed to control pests by saturating the air with synthetic sex attractants or substances with a similar action and mask naturally occurring pheromones or saturate the receptors in the insect causing confusion and disruption of natural reproductive means. This prevents the insects mating.
  • Pheromones and attractants incorporated into an inert carrier such as paraffin, vegetable wax, beeswax, silica, alumina, cellulose, polyethylene, polyvinyl chloride, natural and synthetic rubberthus made as a controlled releasing capsule are widely used in Integrated pest management (IPM).
  • IPM Integrated pest management
  • (2S,12Z)-2-acetoxy-12-heptadecene a natural compound secreted by female pistachio twig borer, was reported by Gries et al. (2) as major sex pheromone component of pistachio twig borer, Kermania p; ' sfac/ ' e//a.WO2007079563A l discloses a couple of synthetic methods for the preparation of (2S,12Z)-2-acetoxy-12-heptadecene.One of the methods includes the preparation of racemic (12Z)-2-hydroxy-12-heptadecene by the reaction of (11Z)-hexadecenal with methyl magnesium halide, the resolution of racemic (12Z)-2-hydroxy-12-heptadecene by immobilized lipase (Novozyme 435) and acetylation of unreacted isomer (2S, 12Z)-2-hydroxy- 12-heptadecene, other is
  • the other method for scale up production of (2S,12Z)-2- acetoxy-12-heptadecene includes firstly the conversion of (Z)-9-tetradecenol into corresponding mesyl derivative with methanesulfonyl chloride, then corresponding bromide derivative with lithium bromide, the obtained (Z)-1 -bromo-9-tetradecene is converted into Grignard reagent with metallic magnesium in dry THF then reacted with (S)-propylene oxide to give (2S,12Z)-2- hydroxy-12-heptadecene.
  • (2S,12Z)-2-acetoxy-12-heptadecene is prepared by acetylation reaction with acetic anhydride at the last step.
  • the present invention comprises novel methods for the preparation of (2S, 12Z)-2-acetoxy-12- heptadecene with great enantiomeric purity and key intermediates therefore which uses readily available and cheap starting materials and is economical to practice.
  • This compound can be used as an attractant for the determination of the number of male K. pistaciella in a monitored area, mass trapping and mating disruption.
  • FIG. 1 illustrates a scheme for the stereoselective synthesis of (2S,12Z)-2-acetoxy-12- heptadecene.
  • FIG.2 illustrates a scheme for the synthesis of (2S,12Z)-2-acetoxy-12-heptadecene by the kinetic resolution of rasemic (2RS,12Z)-2-acetoxy-12-heptadecene.
  • Grignard reaction shown in second step of the Figurel was carried out with rasemic propylene oxide, with the obtained rasemic compound all reactions were repeated as in Figure 1 and target molecule (RS-7) was prepared in rasemic form.
  • the kinetic resolution of rasemic (2RS,12Z)-2-acetoxy-12-heptadecene was performed in the presence of immobilised lipase and dipotassium phosphate buffer (pH7) to give enantiomerically pure (2S,12Z)-2- acetoxy-12-heptadecene along with R-alcohol (R-8) ( Figure 2).
  • (2S, 2Z)-2-acetoxy-12-heptadecene was synthesized in the following manner.
  • a solution of (S)-2-acetoxy-12-bromo dodecane (5.0 g, 16.3 mmol) and triphenylphosphine (4.3 g, 16.3 mmol) in 50 mL dry acetonitrile was heated at reflux for 16 h.
  • the solvent was removed under reduced pressure and the residue was extracted with 600 mL hot diethyl ether.
  • the obtained phosphonium salt was used without further purification.
  • Dipotassium hydrogenphosphate buffer solution (0.1 M, pH 7, 7.5 mL), (2RS,12Z)-2-Acetoxy- 2-heptadecene (0.4 g, 1.35 mmol) and 62.5 mg lipase acrylic resin (Candida antarctica, Sigma-Aldrich) were stirredfor 24 h at room temperature.
  • the mixture was extracted twice with a mixture of 25 mL Et 2 0-pentane (10:90), and the extracts were washed with 25 mL brine and dried over MgS0 4 .

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present invention relates to the stereoselective synthesis (2S,12Z)-2-acetoxy-12-heptadecene secreted by female pistachio twig borer and attract male individuals.

Description

SYNTHESIS OF ATTRACTANT OF PISTACHIO TWIG BORER (KERMANIA PISTACIELLA)
FIELD OF THE INVENTION
The invention relates to the stereoselective synthesis (2S,12Z)-2-acetoxy-12-heptadecene secreted by female pistachio twig borer and can be used as attractant for determination of the number of male individuals in monitoring area, mass trapping and mating disruption.
DESCRIPTION OF THE PRIOR ART
The pistachio twig borer, (Kermania pistaciella) is one of the most important insect pests in plantations of pistachio in Middle East, particularly in Turkey and Iran. After mating, females lay eggs close to shoot tips and fruit clusters and larvae bore into and feed on terminal buds and in twigs and shoots formed the previous year. Larval feeding causes abscission of fruit buds and die-back of twigs and may directly damage fruit clusters (1 ). Pistachio trees are treated annually with insecticides to reduce damage caused by K. pistaciella larvae. The use of chemicals called insecticide are not effective and leave residue on fruit that is harmful to the environment and human health. The use of a pheromone or an attractant which ensures minimizing the use of insecticide or can be used instead of themis of great importance in recent years.
Monitoring technique is used to determinewhether the presence of adult moths in a monitored area, date of first appearance in season if available, level of infestation and the correct timing of control measures.
The aim of mass trapping method is to attract and trapthe greatest possible number of insects which reduce the number of male and female species. Thus, the insect's mating chances are reduced and the possibility of laying eggs gradually decreases which hinder production of new generations of pests.
Mating disruption is aimed to control pests by saturating the air with synthetic sex attractants or substances with a similar action and mask naturally occurring pheromones or saturate the receptors in the insect causing confusion and disruption of natural reproductive means. This prevents the insects mating.
Pheromones and attractants incorporated into an inert carrier such as paraffin, vegetable wax, beeswax, silica, alumina, cellulose, polyethylene, polyvinyl chloride, natural and synthetic rubberthus made as a controlled releasing capsule are widely used in Integrated pest management (IPM).
(2S,12Z)-2-acetoxy-12-heptadecene, a natural compound secreted by female pistachio twig borer, was reported by Gries et al. (2) as major sex pheromone component of pistachio twig borer, Kermania p;'sfac/'e//a.WO2007079563A l discloses a couple of synthetic methods for the preparation of (2S,12Z)-2-acetoxy-12-heptadecene.One of the methods includes the preparation of racemic (12Z)-2-hydroxy-12-heptadecene by the reaction of (11Z)-hexadecenal with methyl magnesium halide, the resolution of racemic (12Z)-2-hydroxy-12-heptadecene by immobilized lipase (Novozyme 435) and acetylation of unreacted isomer (2S, 12Z)-2-hydroxy- 12-heptadecene, other isomer (2R,12Z)-2-acetoxy-12-heptadeceneis converted into the target molecule after a series reaction, while (2S,12Z)-2-acetoxy-12-heptadecene is prepared after a series of chiral and synthetic transformation by using 11 -bromo-1-undecene and 1-hexyne as starting materials in other method. The other method for scale up production of (2S,12Z)-2- acetoxy-12-heptadecene includes firstly the conversion of (Z)-9-tetradecenol into corresponding mesyl derivative with methanesulfonyl chloride, then corresponding bromide derivative with lithium bromide, the obtained (Z)-1 -bromo-9-tetradecene is converted into Grignard reagent with metallic magnesium in dry THF then reacted with (S)-propylene oxide to give (2S,12Z)-2- hydroxy-12-heptadecene. (2S,12Z)-2-acetoxy-12-heptadecene is prepared by acetylation reaction with acetic anhydride at the last step.
SUMMARY OF THE INVENTION
The present invention comprises novel methods for the preparation of (2S, 12Z)-2-acetoxy-12- heptadecene with great enantiomeric purity and key intermediates therefore which uses readily available and cheap starting materials and is economical to practice. This compound can be used as an attractant for the determination of the number of male K. pistaciella in a monitored area, mass trapping and mating disruption.
DRAWINGS
FIG. 1 illustrates a scheme for the stereoselective synthesis of (2S,12Z)-2-acetoxy-12- heptadecene.
FIG.2 illustrates a scheme for the synthesis of (2S,12Z)-2-acetoxy-12-heptadecene by the kinetic resolution of rasemic (2RS,12Z)-2-acetoxy-12-heptadecene. DETAILED DESCRIPTION OF THE INVENTION
Stereoselective synthesis of (2S, 12Z)-2-acetoxy-12-heptadecene is disclosed by applying two different methods using readly available 1 ,9-nonandiol as starting material. As shown in Figure 1 , 1 ,9-nonanediol wasfirst reacted with hydrogen bromide (HBr, 48 %) in toluene according to the procedure reported by Kock et al. (3) to afford 9-bromo-1 -nonanol. Bromo alcohol was converted into corresponding Grignard reagent with metallic magnesium after alcohol hydrogen of this compound is removed with methyl magnesium bromide in dry THF under nitrogen atmosphere. Copper I iodide (Cul) was added to Grignard reagent and the mixture was reacted with (S)-propylene oxide at - 20 DC to give stereoselectively {S)-1 ,11 -dodecanediol (S-3) in 98 % enantiomeric excess. Primary alcohol group of the diol (S-3) was firstly converted to mesyl derivative using methanesulfonyl chloride in the presence of triethylamine then the mesylate was reacted with lithium bromide in dimethylsulfoxide to afford (S)-12-bromododecane-2-ol (S- 4). After secondary alcohol group of the bromo alcohol was acetylated by using acetic anhydride in pyridine at room temperature, the acetate (S-5) was reacted with triphenylphosphine in acetonitrile to provide corresponding phosphonium salt (S-6), (2S,12Z)-2- acetoxy-12-heptadecene (S-7) was stereoselectively synthesized by a Wittig reaction of valeraldehyde with the prepared (S)-2-acetoxy dodecyl phosphonium bromide (S-6) in the presence of sodium bis(trimethylsilyl)amide (NaHMDS), only cis isomer of the alkene was obtained. Alternatively, Grignard reaction shown in second step of the Figurel was carried out with rasemic propylene oxide, with the obtained rasemic compound all reactions were repeated as in Figure 1 and target molecule (RS-7) was prepared in rasemic form. The kinetic resolution of rasemic (2RS,12Z)-2-acetoxy-12-heptadecene was performed in the presence of immobilised lipase and dipotassium phosphate buffer (pH7) to give enantiomerically pure (2S,12Z)-2- acetoxy-12-heptadecene along with R-alcohol (R-8) (Figure 2).
EXAMPLE # 1
9-Bromononanol was synthesized in the following manner.
In a 500 mL round bottom flask fitted with a Dean-Stark apparatus 1 ,9-nonanediol (Sigma- Aldrich) (20 g, 0.125 mol) was dissolved in toluene (500 ml). To this solution was added 21 mL hydrobromic acid (48 %, 188 mmol) and the mixture was heated for 30 h at reflux. The water formed during the reaction was removed using a Dean-Stark trap. The progress of the reaction monitored by thin layer chromatography (TLC) indicated that all starting materials reacted with HBr. After cooling to room temperature, the mixture was washed with 1 M HCI (100 mL), 1 M NaOH (100 ml), 100 mL water and finally with 100 mL brine. The organic layer was dried over anhydrous magnesium sulfate, and concentrated in vacuo. The crude oil obtained was fractionally distilled to give 9-bromononanol in 94 % yield. B.p.: 124-128 !lC/2 mmHg (lit: 125- 126 DC/2 mmHg). EXAMPLE # 2
(S)-1 , 1 1-dodecanediol was synthesized in the following manner.
To an oven dried flask fitted with reflux condenser were introduced 9-bromononanol (15.0 g, 67.2 mmol) in 60 mL dry THF and 22.5 mL methyl magnesium bromide (3M in Et20, 67.5 mmol) was added dropwise to the reaction mixture under nitrogen at a temperature of 60 DC or below.After completion of the dropwise addition of the Grignard mixture, the reaction mixture was stirred for additional 1 hour at 60 DC to prepare a solution of a magnesium alcoholate. Separately, 1.8 g of metallic magnesium (74 mmol) in 30 mL dry THF and 2 drops of dibromoethane as a reaction initiator were introduced into another dry reaction flask into which the above prepared magnesium alcoholate solution was added dropwise at 60 to 70 DC. After completion of the dropwise addition, the reaction mixture was further stirred for about 6 hours and then cooled to 20 DC. Thereafter, 0.88 g copper I iodide (4.5 mmol) were added to the mixture and, after several minutes of agitation, a mixture of 2.7 g (S)-propylene oxide (46.5 mmol; Sigma-Aldrich ) in 30 mL dry THF was added dropwise to the mixture. After completion of the dropwise addition, the mixture was further agitated for 15 minutes at 20° C. and then 100 mL of an aqueous solution containing 5% of NH4CI and 5% of HCI were added thereto dropwise. The organic solution taken by phase separation of the mixture was dried over anhydrous magnesium sulfate, and the solvent was removed in vacuo. The crude product was purified by flash chromatography (Si02, hexane/EtOAc) to give (S)-1 ,11-dodecanediol. Yield: % 77. FT-IR: 1060, 1470, 2850, 2925, 3390 cm"1. [a]20 D = +5.12° (c=1.0; CHCI3). GC (HP-5MS) tR: 10.36 min (FID: 240°C; temp.prog: 1 min 50°C de, then 20°C/min to 280°C). MS: m/z: 55 (% 100 ), 69, 82 123, 140, 151 , 169, 187, 201. 1H-NMR (400 MHz, CDCI3): δ 1.18 (d, J=6Hz, 3H), 1.21 -1.65 (m, 20H), 3.64 (t, J=6.5Hz, 2H), 3.70-3.87 (m, 1 H). 3C-NMR (100 MHz); 23.24, 25.71 , 29.39, 29.46, 29.54 (2), 29.60 (2), 32.60, 39.19, 62.54, 67.86.
EXAMPLE # 3
(S)-12-bromo dodecane-2-ol was synthesized in the following manner.
A solution of triethylamine (8.0 g, 79.07 mmol) and (S)-1 ,11-dodecanediol (10.0 g, 49.42 mmol)was prepared in 70 mL of dry dichloromethane. Methanesulfonyl chloride (6.4 g, 55.84 mmol) was added dropwise at 0 DC. The reaction mixture was allowed to warm to room temperature after stirring for 30 min at 0 nC, then pure water (80 mL) was added and phases were separated, organic phase was washed with water and brine, dried over anhydrous magnesium sulfate. The solvent was removed in vacuo to yield a yellow oil. The residue was dissolved in 130 mL dimethyl sulfoxide and treated with lithium bromide (12.88 g, 148.26 mmol). The reaction mixture was stirred at 40 GC for 3 h, then 250 mL hexane and 250 mL were added to the mixture. The phases were separated and organic layer was washed with water (4x50 mL) and 50 mL brine, dried over anhydrous magnesium sulfate and the solvent was removed in vacuo to yield a yellow oil. The crude product was purified by flash chromatography (Si02, hexane/EtOAc) to afford (S)-12-bromo dodecane-2-ol. Yield: % 83, FT-IR: 1463, 2853, 2924, 3348 cm"1, [oc]20 D= + 3.08° (c=1.1 ; CHCI3), GC (HP-5MS) tR: 10.90 min (FID: 240°C; temp, prog : 1 min to 50 °C, then 20 °C/minto 280 °C), MS: m/z: 55/57 (% 100 ), 67/69, 81/83, 95/97, 135/137, 148/150, 162/164, 218/220, 249/251 , 263/265 (M+), 1H-NMR (400 MHz, CDCI3): δ 1.11 (d, J=6Hz, 3H), 1.21 -1.42 (m, 17H), 1.74-1.81 (m, 2H), 3.32-3.35 (m, 2H), 3.68-3.74 (m, 1 H), ,3C-NMR (100 MHz); 23.48, 25.75, 28.15, 28.74, 29.40, 29.44, 29.54, 29.60, 32.81 , 34.07, 39.33, 68.15.
EXAMPLE # 4
(S)-2-acetoxy-12-bromo dodecane was synthesized in the following manner.
(S)-2-acetoxy-12-bromo dodecane (10.77 g, 41 mmol), acetic anhydride (5.6 g, 55.3 mmol) and pyridine (5.5 g,69 mmol) were mixed in a flask, stirred at rt for 18 h. The residue was purified by flash chromatography (Si02, hexane/EtOAc) to afford (S)-12-bromo dodecane-2-ol. Yield: % 86, FT-IR: 722, 1044, 1733, 2853, 2925, 2974 cm-1 , [a]20 D= + 1 .45° (c 1.07; CHCI3), GC (HP-5MS) tR: 17.06 min (FID: 240°C; temp. Prog.: 1 min to 50°C, then 20°C/min to 280°C), MS: m/z: 55, 69, 87 (%100), 111 , 148/150, 162/164, 204/206, 246/248, 265/267, 307 (M+), 1 H NMR (400 MHz): CDCI35: 1.15-1.21 (m, 3H), 1.20-1.30 (m, 12H), 1.36-1.48 (m, 3H), 1.50-1.61 (m, 1 H), 1.78-1.89 (m, 2H), 1.96-2.07 (m, 3H), 3.39 (t, J = 6.6 Hz, 2H), 4.84-4.88 (m, 1 H), 13C-NMR (100 MHz): 20.0, 21.4, 25.4, 28.1 , 28.7, 29.4 (3C), 29.5, 32.8, 34.1 , 35.9, 71.0, 170.8.
EXAMPLE # 5
(2S, 2Z)-2-acetoxy-12-heptadecene was synthesized in the following manner. A solution of (S)-2-acetoxy-12-bromo dodecane (5.0 g, 16.3 mmol) and triphenylphosphine (4.3 g, 16.3 mmol) in 50 mL dry acetonitrile was heated at reflux for 16 h. The solvent was removed under reduced pressure and the residue was extracted with 600 mL hot diethyl ether. The obtained phosphonium salt was used without further purification. In a round-bottom flask , (S)-2- acetoxy dodecyl phosphoniumbromide (5.8 g, 1.0 mmol) was dissolved in dry THF (50 ml). Sodium bis(trimethylsilyl)amide (NaHMDS) (1 mL, 1.0 M, 1.0 mmol) was added dropwise at OnC, and the mixture was stirred for 45 min at 0 C. The bright orange solution was cooled to - 78 C, and valeraldehyde (0.9 g, 1.0 mmol)in 50 mL dry THF was added slowly dropwise. After stirring for 1 h at -78 C, the mixture was allowed to warm to r.t. Water (50 mL) was added and the reaction mixture was extracted with 50 mL NH4CI and twice with 25 mL Et20, organic phase was dried over anhydrous magnesium sulfate and the solvent was removed in vacuo. The crude product was purified by flash chromatography (Si02, hexane/EtOAc) to afford (2S,12Z)-2- acetoxy-12-heptadecene. Yield: % 71 , FT-IR: 1737 cm-1 , [n V + 0.72 (c 4.0°; CHCI3), GC (HP-5MS) tR: 12.05 dk (FID: 240°C; temp. Prog.: 1 min to 50°C, then 20°C/min to 280°C), MS: m/z: 55 (%100), 68, 82, 96, 109, 123, 138, 152, 166, 194, 207, 236 (M-60 ), 1H NMR (400 MHz, CDCI3): δ0.87 (t, J = 7.0 Hz, 3H), 1.18 (d, J = 6.3 Hz, 3H,), 1.21-1.38 (m, 18H), 1.39-160 (m, 2H), 1.95-2.05 (m, 7H), 4.86 (m, 1 H), 5.33 (m, 2H), 13C NMR(100 MHz), 13.9, 19.9, 21.3, 22.3, 25.3, 26.8, 27.1 , 29.2, 29.4, 29.5, 29.7, 31.9, 35.9, 71.0, 129.8 (2), 130.2(2), 170.7.
EXAMPLE # 6
The kinetic resolution of rasemic (2RS,12Z)-2-acetoxy-12-heptadecene.
Dipotassium hydrogenphosphate buffer solution (0.1 M, pH 7, 7.5 mL), (2RS,12Z)-2-Acetoxy- 2-heptadecene (0.4 g, 1.35 mmol) and 62.5 mg lipase acrylic resin (Candida antarctica, Sigma-Aldrich) were stirredfor 24 h at room temperature. The mixture was extracted twice with a mixture of 25 mL Et20-pentane (10:90), and the extracts were washed with 25 mL brine and dried over MgS04. After removal of solvent on a rotary evaporator, the residue was purified by flash chromatography (Si02, Et20/pentane) to afford the unreacted (2S, 2Z)-2-acetoxy-12- heptadecene (S-7) in 87 % yield with 99.0 % enantiomeric excess (ee). The ee % was determined by GC-MS (Agilent 7890B GC-5977A MSD) fitted with chiral column (Cyclodex-B; 30 m x 0.25 mm ID). GC tR: 35.08 min (FID: 240°C; temp. Prog. : 1 min to 100°C, then 10°C/min to 180°C).
REFERENCES
(1) Mart, C, Celik, M.Y. ve Yigit, A. (1995) Biological Observation and chemical control of pistacio twig borer, K. Pistaciella Ams. (Lep. Dinophilidae), injurious in pistachio orchards in Turkey. Acta Horticulture 419: 373-378. (2) Gries, R., Khaskin, G., Daroogheh, H, Mart C, Karadag, S., Er, M.K., Britton, R., Gries, G., (2006) (2S,12Z)-2-Acetoxy-12-heptadecene: Major Sex Pheromone Component of Pistachio Twig Borer, Kermania pistaciella. J. Chem. Ecol., 32: 2667-2677.
(3) Grube, A., Timm, C. ve Kock, M., (2006) Synthesis and Mass Spectrometric Analysis of Cyclostellettamines. Eur. J. Org. Chem., 1285-1295.

Claims

1. A process for the stereoselective multi-step synthesis of (2S, V2Z)-2-acetoxy-12-heptadecene, secreted by female pistachiotwig borer (Kermania pistaciella) and attract male individuals, the chemical structure represented by Formula S-7.
Figure imgf000008_0001
S-7
2. A process for producing optically active (2S, ^Z^-acetoxy-^-heptadecene as claimed in claim 1 , which comprises dissolving (S)-2-acetoxy dodecyl phosphonium bromide in dry THF.adding sodium bis(trimethylsilyl)amide (NaHMDS) to this solution at 0 °C and stirring for 45 min.then adding a solution of valeraldehyde in dry THF after cooling the solution to -78 °C and stirring for 1 h at -78 °C, allowing the mixture to warm-up to room temperature, extracting the resulting mixture with ethyl acetate and purifying by flash chromatography to yield (2S, 12Z)-2- acetoxy-12-heptadecene.
3. A process for producing optically active (S)-2-acetoxy dodecyl phosphonium bromide as claimed in claim 2, which comprises dissolving (S)-2-acetoxy-12-bromo dodecane in acetonitrile and refluxing with triphenyl phosphine for 16 h to convert into (S)-2-acetoxy dodecyl phosphonium bromide.
4. A process for producing optically active (S)-2-acetoxy-12-bromo dodecane, which comprises acetylating (S)-12-bromo dodecane-2-ol with acetic anhydride in pyridine to convert into (S)-2- acetoxy-12-bromo dodecane as claimed in claim 3.
5.A process for producing optically active (S)-12-bromo dodecane-2-ol, which comprises converting (S)-1 ,11 -dodecanediol to corresponding mesyl derivative by reacting with methanesulfonyl chloride and triethyl amine at 0 DC, followed by treatment with lithium bromide dissolved in dimethyl sulfoxide to afford (S)-12-bromo dodecane-2-ol as claimed in claim 4.
6. A process for producing optically active (S)-1 ,1 1-dodecanediol, which comprises converting an alkoxide prepared by removing an alcohol hydrogen of 9-bromo nonane-1-ol with an alkyl magnesium halide to a Grignard reagent, reacting with (S)-propylene oxide and a catalytic amount of copper (I) iodide or lithium tetrachlorocuprate to yield (S)-1 ,1 1-dodecanediol as claimed in claim 5.
7. A process for preparing (RS)-1 ,1 1 -dodecanediol which comprisesusing racemic propylene oxide according to the process in claim 6.
8. A process for converting (RS)-1 ,11-dodecanediol as claimed in claim 7 to (RS)-12-bromo- dodecane-2-ol according to the process in claim 5.
9. A process for converting (RS)-12-bromo-dodecane-2-ol as claimed in claim 8 to (RS)-2- acetoxy-12-bromo dodecane according to the process in claim 4.
10. A process for converting (RS)-2-acetoxy-12-bromo dodecane as claimed in claim 9 to (RS)- 2-acetoxy dodecyl phosphonium bromide according to the process in claim 3.
11. A process for converting (RS)-2-acetoxy dodecyl phosphonium bromide as claimed in claim 10 to (2RS, 12Z)-2-acetoxy-12-heptadecene (RS-7) according to the process in claim 2.
Figure imgf000009_0001
RS-
12.A process for producing optically active (2S, 12Z)-2 acetoxy-12-heptadecene as claimed in claim 1 , which comprises stirring (2RS, 12Z)-2 acetoxy-12-heptadeceneas claimed in claim 1 1 with dipotassium hydrogen phosphate buffer (pH 7) and lipase acrylic resin (Candida antarctica, Sigma-Aldrich) for 24 h at room temperature, extracting the mixture with Et20-pentane, drying organic phase with magnesium sulfate, evaporating solvents in vacuo, purifying the residue by flash chromatography.
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