1-halo-6,9-pentadecadiene and method for producing (7Z,10Z)-7,10-hexadecadienal

Patent metadata

Field	Value
Publication number	US-10138191-B2
Application number	US-201815951765-A
Country	US
Kind code	B2
Filing date	Apr 12, 2018
Priority date	Apr 21, 2017
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

Provided are a 1-halo-6,9-pentadecadiene useful as an intermediate having a skipped diene skeleton and a method for producing (7Z,10Z)-7,10-hexadecadienal. More specifically, provided are a method for producing (7Z,10Z)-7,10-hexadecadienal including steps of subjecting a Grignard reagent formed from a (6Z,9Z)-1-halo-6,9-pentadecadiene to a nucleophilic substitution reaction with an orthoformate ester to obtain a (7Z,10Z)-1,1-dialkoxy-7,10-hexadecadiene; and hydrolyzing the (7Z,10Z)-1,1-dialkoxy-7,10-hexadecadiene in the absence of an oxidation reaction to obtain the (7Z,10Z)-7,10-hexadecadienal; and the like.

First claim

The invention claimed is:

1. A method for producing (7Z,10Z)-7,10-hexadecadienal of Formula (9):

comprising steps of:
subjecting a Grignard reagent formed from a (6Z,9Z)-1-halo-6,9-pentadecadiene of Formula (1-6Z9Z):

wherein X stands for a halogen atom,

 to a nucleophilic substitution reaction with an orthoformate ester of Formula (2):

wherein R may be same with or different from each other and stands for an alkyl group having from 1 to 6 carbon atoms,

 to obtain a (7Z,10Z)-1,1-dialkoxy-7,10-hexadecadiene of Formula (3):

wherein R may be same with or different from each other and stands for an alkyl group having from 1 to 6 carbon atoms; and

hydrolyzing the (7Z,10Z)-1,1-dialkoxy-7,10-hexadecadiene (3) to obtain the (7Z,10Z)-7,10-hexadecadienal (9).

2. The method for producing (7Z,10Z)-7,10-hexadecadienal according to claim 1 , further comprising steps of:
subjecting a triarylphosphonium (3Z)-3-nonylide of Formula (4-3Z):

wherein Ar may be same with or different from each other and stands for an aryl group,

 to a Wittig reaction with a 6-halohexanal of Formula (5):
OHC(CH 2 ) 5 X  (5),

wherein X stands for a halogen atom,

 to obtain the (6Z,9Z)-1-halo-6,9-pentadecadiene (1-6Z9Z), and
converting the (6Z,9Z)-1-halo-6,9-pentadecadiene (1-6Z9Z) into the Grignard reagent.

3. The method for producing (7Z,10Z)-7,10-hexadecadienal according to claim 2 , further comprising a step of treating a 3-nonyltriarylphosphonium halide with a metal alkoxide of an alcohol having a pKa of from 12.0 to 16.5 at a temperature of from −20 to 0° C. to obtain the triarylphosphonium (3Z)-3-nonylide (4-3Z).

4. A 1-halo-6,9-pentadecadiene of Formula (1):
CH 3 (CH 2 ) 4 CH═CHCH 2 CH═CH(CH 2 ) 5 X  (1),

wherein X stands for a halogen atom.

5. A method for producing a (6Z,9Z)-1-halo-6,9-pentadecadiene of Formula (1-6Z9Z):

comprising a step of subjecting a triarylphosphonium (3Z)-3-nonylide of Formula (4-3Z):

wherein Ar may be same with or different from each other and stands for an aryl group,

to a Wittig reaction with a 6-halohexanal of Formula (5):
OHC(CH 2 ) 5 X  (5),

wherein X stands for a halogen atom,

to obtain the (6Z,9Z)-1-halo-6,9-pentadecadiene (1-6Z9Z).

6. The method for producing a (6Z,9Z)-1-halo-6,9-pentadecadiene according to claim 5 , further comprising a step of treating a 3-nonyltriarylphosphonium halide with a metal alkoxide of an alcohol having a pKa of from 12.0 to 16.5 at a temperature of from −20 to 0° C. to obtain the triarylphosphonium (3Z)-3-nonylide (4-3Z).

Assignees

• Shinetsu Chemical Co

Inventors

• Miyake Yuki
• Kinsho Takeshi
• Fujii Tatsuya

Classifications

• C07C21/19

  Halogenated dienes · CPC title

• C07C17/2635

  involving a phosphorus compound, e.g. Wittig synthesis · CPC title

• C07C45/42 Primary

  by hydrolysis · CPC title

• C07C41/56

  by condensation of aldehydes, paraformaldehyde, or ketones · CPC title

• C07C41/52 Primary

  by substitution of halogen only · CPC title