1-(2-acyloxyethyl)cyclopropyl sulfonate compound, 3-halomethyl-3-butenyl carboxylate compound, and method for producing 4-alkyl-3-methylenebutyl carboxylate

Patent metadata

Field	Value
Publication number	US-9611211-B2
Application number	US-201514974052-A
Country	US
Kind code	B2
Filing date	Dec 18, 2015
Priority date	Dec 25, 2014
Publication date	Apr 4, 2017
Grant date	Apr 4, 2017

Abstract

Provided is a simple, selective and efficient method for producing 4-alkyl-3-methylenebutyl carboxylates such as 7-methyl-3-methylene-7-octenyl propionate. More specifically, provided is, for example, a method for producing a 4-alkyl-3-methylenebutyl carboxylate compound, comprising an acyloxylation step of subjecting a 1-(2-haloethyl)cyclopropyl sulfonate compound (1) to acyloxylation to obtain a 1-(2-acyloxyethyl)cyclopropyl sulfonate compound (2), a halogenation step of subjecting the compound (2) to halogenation involving cyclopropyl-allyl rearrangement to obtain a 3-halomethyl-3-butenyl carboxylate compound (3), and a coupling step of subjecting the compound (3) to a coupling reaction with an organometallic reagent (4) to obtain the 4-alkyl-3-methylenebutyl carboxylate compound (5).

First claim

The invention claimed is:

1. A method for producing a 4-alkyl-3-methylenebutyl carboxylate compound, the method comprising:
an acyloxylation step of subjecting a 1-(2-haloethyl)cyclopropyl sulfonate compound represented by General Formula (1):

wherein X 1 represents a halogen atom and Z represents a monovalent hydrocarbon group having 1 to 10 carbon atoms and optionally containing one or more unsaturated bonds,

to acyloxylation to obtain a 1-(2-acyloxyethyl)cyclopropyl sulfonate compound represented by General Formula (2):

wherein R 1 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms and optionally containing one or more unsaturated bonds,

a halogenation step of subjecting the 1-(2-acyloxyethyl)cyclopropyl sulfonate compound (2) to halogenation involving cyclopropyl-allyl rearrangement to obtain a 3-halomethyl-3-butenyl carboxylate compound represented by General Formula (3):

wherein X 2 represents a halogen atom, which may be the same as or different from X 1 ,

and
a coupling step of subjecting the 3-halomethyl-3-butenyl carboxylate compound (3) to a coupling reaction with an organometallic reagent represented by General Formula (4):
R 2 M   (4)

wherein R 2 represents a monovalent hydrocarbon group having 1 to 10 carbon atoms and optionally containing one or more unsaturated bonds, which may be the same as or different from R 1 , and
M represents a cationic moiety,

to obtain the 4-alkyl-3-methylenebutyl carboxylate compound represented by Formula (5):

2. The method for producing a 4-alkyl-3-methylenebutyl carboxylate compound according to claim 1 , wherein R 1 is an ethyl group, R 2 is a 3-methyl-3-butenyl group, and the 4-alkyl-3-methylenebutyl carboxylate compound is 7-methyl-3-methylene-7-octenyl propionate represented by Formula (5a):

Assignees

• Shinetsu Chemical Co

Inventors

• Kinsho Takeshi
• Ishibashi Naoki
• Nagae Yusuke

Classifications

• C07C2601/02

  with a three-membered ring · CPC title

• C07C69/65 Primary

  of unsaturated acids · CPC title

• C07C303/30 Primary

  by reactions not involving the formation of esterified sulfo groups · CPC title

• C07C317/04

  of an acyclic saturated carbon skeleton · CPC title

• C07C67/293

  by isomerisation; by change of size of the carbon skeleton · CPC title