11-halo-3-undecene compound and a process for preparing the same and a process for preparing 9-dodecenal compound

Patent metadata

Field	Value
Publication number	US-12116328-B2
Application number	US-202016922679-A
Country	US
Kind code	B2
Filing date	Jul 7, 2020
Priority date	Jul 9, 2019
Publication date	Oct 15, 2024
Grant date	Oct 15, 2024

Abstract

The present invention provides a process for preparing an 11-halo-3-undecene compound (7) in which X 1 represents a halogen atom, the process comprising a step of subjecting a nucleophilic reagent, 3-hexenyl compound (5): in which M 2 represents Li or MgZ 2 , wherein Z 2 represents a halogen atom or a 3-hexenyl group, to a coupling reaction with a 1-halo-5-halopentane compound (6) in which X 3 and X 4 may be same with or different from each other and represent a halogen atom, to produce the 11-halo-3-undecene compound (7). The present invention also provides a process for preparing a 9-dodecenal compound (4): the process comprising a step of subjecting a nucleophilic reagent, 8-undecenyl compound (1) in which M 1 represents Li or MgZ 1 , wherein Z 1 represents a halogen atom or an 8-undecenyl group, and an orthoformic ester compound (2) in which R may be same with or different from each other and represents an alkyl group having 1 to 6 carbon atoms, to a nucleophilic substitution reaction to produce a 1,1-dialkoxy-9-dodecene compound (3) in which R are as defined above; and hydrolyzing the 1,1-dialkoxy-9-dodecene compound (3) thus obtained to produce the 9-dodecenal compound (4).

First claim

The invention claimed is:

1. A process for preparing a (9Z)- or (9E)-9-dodecenal compound of the following formula (4):
CH 3 CH 2 CH═CH(CH 2 ) 7 CHO  (4)

the process comprising steps of
subjecting a nucleophilic reagent, a (3Z)- or (3E)-3-hexenyl compound, of the following general formula (5):
CH 3 CH 2 CH═CH(CH 2 ) 2 M 2   (5)

in which M 2 represents Li or MgZ 2 , wherein Z 2 represents a halogen atom or a 3-hexenyl group, to a coupling reaction with a 1-halo-5-halopentane compound of the general formula (6):
X 3 (CH 2 ) 5 X 4   (6)

in which X 3 represents a chlorine atom and X 4 represents a bromine atom,
in the presence of a cuprous halide and a trialkyl phosphite compound having 3 to 9 carbon atoms to produce a (3Z)- or (3E)-11-halo-3-undecene compound of the following general formula (7):
CH 3 CH 2 CH═CH(CH 2 ) 7 X 1   (7)

in which X 1 represents a chlorine atom; and
preparing the nucleophilic reagent, (8Z)- or (8E)-8-undecenyl compound of the following general formula (1);
CH 3 CH 2 CH═CH(CH 2 ) 7 M 1   (1)

in which M 1 represents Li or MgZ 1 , wherein Z 1 represents a halogen atom or an 8-undecenyl group,
from the (3Z)- or (3E)-11-chloro-3-undecene compound (7) thus obtained, respectively;
subjecting the nucleophilic reagent, (8Z)- or (8E)-8-undecenyl compound (1) thus obtained to a nucleophilic substitution reaction with an orthoformic ester compound of the following general formula (2):

in which R may be same with or different from each other and represents an alkyl group having 1 to 6 carbon atoms,
to produce a (9Z)- or (9E)-1,1-dialkoxy-9-dodecene compound of the following general formula (3):
CH 3 CH 2 CH═CH(CH 2 ) 7 CH(OR) 2   (3)

in which R is as defined above, respectively; and
hydrolyzing the (9Z)- or (9E)-1,1-dialkoxy-9-dodecene compound (3) thus obtained, in the presence of oxalic acid to produce the (9Z)- or (9E)-9-dodecenal compound (4), respectively.

2. The process according to claim 1 , wherein the nucleophilic reagent (1) is (8E)-8-undecenyl compound, of the following general formula (1-1):

wherein the nucleophilic reagent (5) is (3E)-3-hexenyl compound, of the following general formula (5-1):

and
wherein the 11-halo-3-undecene compound (7) is (3E)-11-halo-3-undecene compound of the following general formula (7-1):

wherein the 9-dodecenal compound of the following formula (4) is (9E)-9-dodecenal of the following formula (4-1):

and
wherein the 1,1-dialkoxy-9-dodecene compound (3) is (9E)-1,1-dialkoxy-9-dodecene compound of the following general formula (3-1):

3. The process according to claim 1 , wherein the nucleophilic reagent (1) is (8Z)-8-undecenyl compound, of the following general formula (1-2):

wherein the nucleophilic reagent (5) is (3Z)-3-hexenyl compound, of the following general formula (5-2):

and
wherein the 11-halo-3-undecene compound (7) is (3Z)-11-halo-3-undecene compound of the following general formula (7-2):

wherein the 9-dodecenal compound of the following formula (4) is (9Z)-9-dodecenal of the following formula (4-2):

and
wherein the 1,1-dialkoxy-9-dodecene compound (3) is (9Z)-1,1-dialkoxy-9-dodecene compound of the following general formula (3-2):

4. A process for preparing a 9-dodecenal compound of the following formula (4):
CH 3 CH 2 CH═CH(CH 2 ) 7 CHO  (4):

the process comprising steps of
preparing a nucleophilic reagent, 8-undecenyl compound, of the following general formula (1)
CH 3 CH 2 CH═CH(CH 2 ) 7 M 1   (1)

in which M 1 represents Li or MgZ 1 , wherein Z 1 represents a halogen atom or an 8-undecenyl group from an 11-halo-3-undecene compound of the following general formula (7):
CH 3 CH 2 CH═CH(CH 2 ) 7 X 1   (7)

in which X 1 represents a halogen atom;
subjecting, the nucleophilic reagent, 8-undecenyl compound (1) thus obtained, to a nucleophilic substitution reaction with an orthoformic ester compound of the following general formula (2):

in which R may be same with or different from each other and represents an alkyl group having 1 to 6 carbon atoms,
to produce a 1,1-dialkoxy-9-dodecene compound of the following general formula (3):
CH 3 CH 2 CH═CH(CH 2 ) 7 CH(OR) 2   (3)

in which R is as defined above; and
hydrolyzing the 1,1-dialkoxy-9-dodecene compound (3) thus obtained, in the presence of oxalic acid to produce the 9-dodecenal compound (4).

Assignees

• Shinetsu Chemical Co

Inventors

• Miyake Yuki
• Kinsho Takeshi
• Komatsu Ryo

Classifications

• C07C21/04 Primary

  Chloro-alkenes · CPC title

• C07C41/50

  by reactions producing [IMAGE cpc-sch-C07C-0958.gif] groups · CPC title

• C07C45/42

  by hydrolysis · CPC title

• C07C21/02

  containing carbon-to-carbon double bonds · CPC title

• C07C17/275

  of hydrocarbons and halogenated hydrocarbons · CPC title