Process for preparing (9e,11z)-9, 11-hexadecadienal

A technology of carbadienal and 11Z, which is applied in the field of preparation of -9,11-hexadecadienal, which can solve problems such as outbreaks

Pending Publication Date: 2019-10-29
SHIN ETSU CHEM IND CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Pest control of the hickory nut borer with insecticides can lead to outbreaks of secondary pests such as aphids, mites, and leaf miners because the insecticides also kill natural enemies of these secondary pests

Method used

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  • Process for preparing (9e,11z)-9, 11-hexadecadienal
  • Process for preparing (9e,11z)-9, 11-hexadecadienal
  • Process for preparing (9e,11z)-9, 11-hexadecadienal

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0100] Preparation of (8E,10Z)-1-chloro-8,10-pentadecadiene (1:X=Cl)

[0101] Magnesium (17.8 g, 0.733 gram atom) and tetrahydrofuran (198 g) were added to the reactor, and the resulting mixture was stirred at 60˜65° C. for 30 minutes. Then, (4E,6Z)-1-chloro-4,6-undecadadiene (5:X=Cl) (124g, 0.667mol) was added dropwise at 60-70°C, and the resulting mixture was heated at 70-75°C Stir for 6 hours to prepare (4E,6Z)-4,6-undecadienylmagnesium chloride. In another reactor was charged cuprous iodide (1.27 g, 0.00667 mol), triethyl phosphite (2.66 g, 0.0160 mol), 1-bromo-4-chlorobutane (131 g, 0.767 mol) and tetrahydrofuran ( 66.1 g), and the resulting mixture was stirred at 0-5°C for 30 minutes. Then, the solution of (4E,6Z)-4,6-undecadienylmagnesium chloride prepared above in tetrahydrofuran was added dropwise at 5˜15°C. After the dropwise addition was completed, the resulting reaction mixture was stirred at 5˜10° C. for 2 hours, and then the reaction was terminated by adding...

Embodiment 2

[0107] (9E,11Z)-1,1-diethoxy-9,11-hexadecadiene (3: R=C 2 h 5 ) preparation

[0108]Magnesium (7.82 g, 0.322 gram atom) and tetrahydrofuran (87.8 g) were added to the reactor, and the resulting mixture was stirred at 60˜65° C. for 30 minutes. Then, (8E,10Z)-1-chloro-8,10-pentadecadiene (1:X=Cl) (71.1g, 0.293mol) was added dropwise at 60~70℃, and then the resulting mixture was heated at 70~ Stir at 75°C for 2 hours to prepare (8E,10Z)-8,10-pentadecadienylmagnesium chloride. Then, toluene (136 g) and triethyl orthoformate (56.4 g, 0.380 mol) were added to the reactor at 75˜85° C., and the resulting mixture was stirred at 90˜100° C. for 17 hours. It was cooled to 0˜10° C., and then 20% by weight aqueous hydrogen chloride solution (40.5 g), water (43.9 g) and acetic acid (8.08 g) were added to the reaction mixture. After removing the aqueous layer from the resulting reaction mixture by liquid-liquid separation, the organic layer was washed with an aqueous solution of 8% by ...

Embodiment 3

[0114] Preparation of (9E,11Z)-9,11-Hexadecadienal (4)

[0115] Add (9E,11Z)-1,1-diethoxy-9,11-hexadecadiene (3:R=C 2 h 5 ) (146g, 0.469mol), tetrahydrofuran (469g), oxalic acid dihydrate (177g, 1.41mol) and water (469g), and the resulting mixture was stirred at 60-65°C for 3 hours. It was cooled to 40˜50° C., and hexane (138 g) was added to the mixture. After removing the aqueous layer from the resulting reaction mixture by liquid-liquid separation, the organic layer was washed with a solution of sodium chloride (4.27 g) and water (286 g). The organic layer was concentrated by evaporating the solvent in vacuo, and the resulting concentrate was distilled in vacuo to give (9E,11Z)-9,11-hexadecadienal (4) (93.0 g, 0.394 mol) in a yield of 83.9 %.

[0116] Characterization of (9E,11Z)-9,11-Hexadecadienal (4)

[0117] [NMR spectrum] 1 H-NMR (500MHz, CDCl 3 ):δ0.90(3H,t,J=6.9Hz),1.29-1.41(12H,m),1.62(2H,tt,J=7.3,7.3Hz),2.08(2H,dt,J=6.9,6.9 Hz), 2.15(2H, dt, J=7.3, 7.3Hz...

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Abstract

The object of the invention is to provide an efficient process for preparing (9E,11Z)-9,11-hexadecadienal. The present invention provides a process for preparing (9E,11Z)-9,11-hexadecadienal (4), saidprocess comprising at least steps: conducting a nucleophilic substitution reaction between an (8E,10Z)-8,10-pentadecadienyl magnesium halide derived from an (8E,10Z)-1-halo-8,10-pentadecadiene (1) and an orthoformate ester (2) to thereby prepare a (9E,11Z)-1,1-dialkoxy-9,11-hexadecadiene (3); and hydrolyzing the (9E,11Z)-1,1-dialkoxy-9,11-hexadecadiene (3) to obtain (9E,11Z)-9,11-hexadecadienal (4).

Description

technical field [0001] The present invention relates to a method for preparing (9E,11Z)-9,11-hexadecadienal. Background technique [0002] The hickory nut borer (Acrobasis nuxvorella) is a serious pest of hickory nuts that can punch holes into the hickory nut and feed within the nut. Pest control of the hickory nut borer with insecticides can lead to outbreaks of secondary pests such as aphids, mites, and leafminers because the insecticides also kill the natural enemies of these secondary pests. Therefore, much hope is placed on mating disruption using sex pheromones. [0003] (9E,11Z)-9,11-Hexadecadienal and (9E,11Z)-9,11-Hexadecadienyl Acetate Identified as Components of the Natural Sex Pheromones of the Hickory Nut Moth (Non-Patent Documents 1 and 2). [0004] Millar et al. describe a method for the preparation of (9E,11Z)-9,11-hexadecadienal in which vinyl iodide derived from 9-decyn-1-ol is substituted with 1-hexyne ( Sonogashira) coupling, followed by alcohol prote...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/51C07C47/21C07C41/50C07C43/303
CPCC07C45/513C07C41/50C07C47/21C07C43/303C07B2200/09C07C45/515C07C29/58
Inventor 渡部友博三宅裕树金生刚长江祐辅
Owner SHIN ETSU CHEM IND CO LTD
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