Method for producing fluorovinyl ether compound

Patent metadata

Field	Value
Publication number	US-11560347-B2
Application number	US-201917255689-A
Country	US
Kind code	B2
Filing date	Jun 26, 2019
Priority date	Jun 26, 2018
Publication date	Jan 24, 2023
Grant date	Jan 24, 2023

Abstract

A method for synthesizing a fluorovinyl ether compound from a fluorine-containing vinyl compound. Specifically, a method for producing a compound represented by formula (1), comprising step A of reacting a compound represented by formula (2) with a compound represented by formula (3) in the presence of a transition metal catalyst:

wherein the substituents are defined in the disclosure.

First claim

The invention claimed is:

1. A method for producing a compound represented by formula (1):

wherein
R a1 is a hydrogen atom, a halogeno group, an alkyl group, a fluoroalkyl group, or an aromatic group optionally having one or more substituents,
Rf is a fluoro group or a perfluoroalkyl group,
R a2 is a hydrogen atom, a halogeno group, an alkyl group, a fluoroalkyl group, or an aromatic group optionally having one or more substituents, or
R a1 and R a2 may be linked to each other,
R b1 is R S ,
R b2 is a hydrogen atom or R S ,
R b3 is a hydrogen atom or R S , or
two or three of R b1 , R b2 , and R b3 , taken together with the adjacent carbon atom, may form a ring optionally having one or more substituents, and
R S , in each occurrence, is the same or different and represents a hydrocarbon group optionally having one or more substituents,
the method comprising
step A of reacting a compound represented by formula (2):

wherein
R x is a leaving group and is selected from the group consisting of a halogeno group, a sulfonic acid ester group, a fluorosulfonyl group, a nitro group, or a cyano group, and
other symbols are as defined above,
with a compound represented by formula (3):

wherein the symbols in the formula are as defined above,
in the presence of a transition metal catalyst.

2. The production method according to claim 1 , wherein R a1 is a hydrogen atom.

3. The production method according to claim 1 , wherein R a2 is a hydrogen atom or an aryl group.

4. The production method according to claim 1 , wherein R b1 is a C 1-11 fluoroalkyl group, R b2 is a hydrogen atom, and R b3 is a hydrogen atom.

5. The production method according to claim 1 , wherein R b1 is a C 1-11 perfluoroalkyl group, R b2 is a hydrogen atom, and R b3 is a hydrogen atom.

6. The production method according to claim 1 , wherein R x is a halogeno group or a sulfonic acid ester group.

7. The production method according to claim 1 , wherein the transition metal catalyst is at least one member selected from the group consisting of palladium catalysts, copper catalysts, nickel catalysts, platinum catalysts, and iron catalysts.

8. The production method according to claim 1 , wherein the transition metal catalyst is a palladium complex.

9. The production method according to claim 1 , wherein the reaction of step A is performed in the presence of a coordination compound.

10. The production method according to claim 1 , wherein the reaction of step A is performed in the presence of a coordination compound and the coordination compound is a biphenyl compound represented by formula (4-1):

wherein
A 4a is a benzene ring,
A 4b is a benzene ring,
R 4a1 is a phosphino group substituted with two C 1-20 hydrocarbon groups,
R 4a2 is an alkyl group or an alkoxy group,
R 4a3 , in each occurrence, is the same or different and represents a substituent,
R 4b , in each occurrence, is the same or different and represents a substituent,
n4a is a number of 0 to 3, and
n4b is a number of 0 to 5.

11. The production method according to claim 1 , wherein the reaction of step A is performed in the presence of a coordination compound and the coordination compound is a biphenyl compound represented by formula (4-1):

wherein
A 4a is a benzene ring,
A 4b is a benzene ring,
R 4a1 is a phosphino group substituted with two substituents selected from the group consisting of cyclohexyl, tert-butyl, and adamantyl groups,
R 4a2 is a methyl group or a methoxy group,
R 4a3 , in each occurrence, is the same or different and represents a substituent,
R 4b , in each occurrence, is the same or different and represents a substituent,
n4a is a number of 0 to 3, and
n4b is a number of 0 to 5.

12. The production method according to claim 1 , wherein the reaction of step A is performed in the presence of a base.

13. The production method according to claim 1 , wherein the reaction of step A is performed in the presence of a base and the base has a pKa of 36 to 3.6.

14. The production method according to claim 1 , wherein the reaction of step A is performed in the presence of a base and the base is at least one member selected from the group consisting of
(1) acetates, carbonates, hydrogen carbonates, phosphates, hydrogen phosphates, alkoxide salts, hydroxide salts, hydride salts, ammonium salts, or amide salts of alkaline or alkaline earth metals,
(2) polymer-supported bases,
(3) alkali metals, and
(4) amines.

Assignees

• Daikin Ind Ltd

Inventors

• Hoshiya Naoyuki
• Gotou Akihiro
• Kishikawa Yosuke

Classifications

• C07C43/17

  containing halogen · CPC title

• C07C41/16 Primary

  by reaction of esters of mineral or organic acids with hydroxy or O-metal groups · CPC title

• C07C43/176

  having unsaturation outside the aromatic rings · CPC title

• C07F7/1804

  Compounds having Si-O-C linkages (Si-O-acyl linkages C07F7/1896) · CPC title

• C07D333/16

  by oxygen atoms · CPC title