11-halo-1,1-dialkoxy-7-undecene compound and processes for preparing a 11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound, a trienal compound, and a dienal compound

Patent metadata

Field	Value
Publication number	US-12479786-B2
Application number	US-202217698022-A
Country	US
Kind code	B2
Filing date	Mar 18, 2022
Priority date	Mar 23, 2021
Publication date	Nov 25, 2025
Grant date	Nov 25, 2025

Abstract

The present invention relates to a process for preparing a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound of the following general formula (3-Z): wherein Y represents a halogen atom, Ar represents, independently of each other, an aryl group, and R 1 and R 2 represent, independently of each other, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may form together a divalent hydrocarbon group, R 1 -R 2 , having 2 to 10 carbon atoms, the process comprising: subjecting a (7Z)-11-halo-1,1-dialkoxy-7-undecene compound of the following general formula (1-Z): wherein X 1 represents a halogen atom, and R 1 and R 2 are as defined above to a phosphonium salt formation reaction with a phosphine compound of the following general formula (2): wherein Ar is as defined above to form the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z).

First claim

The invention claimed is:

1 . A process for preparing a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound of the following general formula (3-Z):

wherein Y represents a halogen atom, Ar represents, independently of each other, an aryl group, and R 1 and R 2 represent, independently of each other, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may form together a divalent hydrocarbon group, R 1 -R 2 , having 2 to 10 carbon atoms,
the process comprising:
subjecting a (7Z)-11-halo-1,1-dialkoxy-7-undecene compound of the following general formula (1-Z):

wherein X 1 represents a halogen atom, and R 1 and R 2 are as defined above,
to a phosphonium salt formation reaction with a phosphine compound of the following general formula (2):
PAr 3   (2)

wherein Ar is as defined above
to form the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z).

2 . A process for preparing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound of the following general formula (6):

wherein R 1 and R 2 represent, independently of each other, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may form together a divalent hydrocarbon group, R 1 -R 2 , having 2 to 10 carbon atoms,
the process comprising:
the process according to claim 1 for preparing the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z),
deprotonating the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) in the presence of a base to form a reaction product mixture, and
subjecting the reaction product mixture to a Wittig reaction with (2E)-2-pentenal of the following formula (5):

to form the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6).

3 . A process for preparing a (7Z,11Z,13E)-7,11,13-hexadecatrienal of the following formula (7):

the process comprising:
the process according to claim 2 for preparing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6), and
hydrolyzing the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) to form (7Z,11Z,13E)-7,11,13-hexadecatrienal (7).

4 . A process for preparing a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound of the following general formula (9):

wherein R 1 and R 2 represent, independently of each other, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may form together a divalent hydrocarbon group, R 1 -R 2 , having 2 to 10 carbon atoms,
the process comprising:
the process according to claim 1 for preparing the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z),
deprotonating the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) in the presence of a base to form a reaction product mixture, and
subjecting the reaction product mixture to a Wittig reaction with pentanal of the following formula (8):
CH 3 (CH 2 ) 3 CHO  (8)

to form the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

5 . A process for preparing (7Z,11Z)-7,11-hexadecadienal of the following formula (10):

the process comprising:
the process according to claim 4 for preparing the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), and
hydrolyzing the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) to form (7Z,11Z)-7,11-hexadecadienal (10).

6 . A process for preparing a mixture comprising a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound of the following general formula (6):

wherein R 1 and R 2 represent, independently of each other, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may form together a divalent hydrocarbon group, R 1 -R 2 , having 2 to 10 carbon atoms,
and a (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound of the following general formula (9):

wherein R 1 and R 2 are as defined above,
the process comprising:
the process according to claim 1 for preparing the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z),
deprotonating the (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) in the presence of a base to form a reaction product mixture, and
subjecting the reaction product mixture to a Wittig reaction with (2E)-2-pentenal of the following formula (5):

and with pentanal of the following formula (8):
CH 3 (CH 2 ) 3 CHO  (8)

to form the mixture comprising the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9).

7 . A process for preparing a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecatrienal of the following formula (7):

and (7Z,11Z)-7,11-hexadecadienal of the following formula (10):

the process comprising:
the process according to claim 6 for preparing the mixture comprising the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9), and
subjecting the mixture comprising the (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound (6) and the (5Z,9Z)-16,16-dialkoxy-5,9-hexadecadiene compound (9) to a hydrolysis reaction condition to form a mixture comprising (7Z,11Z,13E)-7,11,13-hexadecatrienal (7) and (7Z,11Z)-7,11-hexadecadienal (10).

8 . A process for preparing a (3E,5Z,9Z)-16,16-dialkoxy-3,5,9-hexadecatriene compound of the following general formula (6):

wherein R 1 and R 2 represent, independently of each other, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or R 1 and R 2 may form together a divalent hydrocarbon group, R 1 -R 2 , having 2 to 10 carbon atoms,
the process comprising:
deprotonating a (4Z)-11,11-dialkoxy-4-undecenyltriarylphosphonium halide compound (3-Z) of the following general formula (3-Z):

wherein Y represents a halogen atom, Ar represents, independently of each other, an aryl group, and R 1 and R 2 are as defined above,
in the presence of a base to form a reaction product mixture, and
subjecting the reaction product mixture to a Wittig reaction with (2E)-2-pentenal of the following formula (5):

Assignees

• Shinetsu Chemical Co

Inventors

• Miyake Yuki
• Kinsho Takeshi
• Nagae Yusuke

Classifications

• C07F9/5428

  Acyclic unsaturated phosphonium compounds · CPC title

• C07C43/313

  containing halogen · CPC title

• C07C43/303

  having acetal carbon atoms bound to acyclic carbon atoms · CPC title

• C07C41/09

  by dehydration of compounds containing hydroxy groups · CPC title

• C07C47/21

  with only carbon-to-carbon double bonds as unsaturation · CPC title