Fluoroalkylating agent

Patent metadata

Field	Value
Publication number	US-10696640-B2
Application number	US-201916378142-A
Country	US
Kind code	B2
Filing date	Apr 8, 2019
Priority date	Jun 26, 2014
Publication date	Jun 30, 2020
Grant date	Jun 30, 2020

Abstract

A compound of the general formula (3): R4—S—R1 having an introduced C1 to C8 fluoroalkyl group is easily obtained by reacting a compound of the general formula (2): R4—S—Z wherein R4 is a hydrocarbon group or the like; and Z is a leaving group, with the compound of the general formula (1).

First claim

The invention claimed is:

1. A method for the production of a target compound having R 1 , wherein R 1 is as defined below, which comprises reacting a starting compound with a fluoroalkylating agent represented by the general formula (1):

wherein R 1 is a C1 to C8 fluoroalkyl group;
R 2 and R 3 are each independently
a C1 to C12 alkyl group which may have one or more substituents,
a C2 to C6 alkenyl group which may have one or more substituents,
a C2 to C6 alkynyl group which may have one or more substituents,
a C3 to C8 cycloalkyl group which may have one or more substituents, or
a C6 to C10 aryl group which may have one or more substituents;
Y 1 , Y 2 , Y 3 and Y 4 are each independently
a hydrogen atom, a halogen atom, a nitro group, a cyano group,
a C1 to C12 alkyl group which may have one or more substituents,
a C2 to C6 alkenyl group which may have one or more substituents,
a C2 to C6 alkynyl group which may have one or more substituents,
a C3 to C8 cycloalkyl group which may have one or more substituents,
a hydroxy group,
a C1 to C6 alkoxy group,
a C1 to C6 alkylthio group, a C1 to C6 alkylsulfinyl group, a C1 to C6 alkylsulfonyl group,
an amino group, a mono (C1 to C6 alkyl) amino group, a di (C1 to C6 alkyl) amino group,
a C1 to C6 acylamino group,
a formyl group, a C2 to C6 acyl group,
a C1 to C6 alkoxycarbonyl group,
a C6 to C10 aryl group which may have one or more substituents, or
a heterocyclic group which may have one or more substituents, wherein the said heterocyclic group is a 5- to 10-membered heterocyclic group having 1 to 9 carbon atoms and 1 to 4 heteroatoms selected independently from a nitrogen atom, an oxygen atom and a sulfur atom, or two adjacent substituents of Y 1 and Y 2 , Y 2 and Y 3 , or Y 3 and Y 4 , together with carbon atoms to which these substituents are attached, form a 4- to 8-membered carbocyclic ring or a 4- to 8-membered heterocyclic ring having 1 to 4 heteroatoms selected independently from an oxygen atom, a sulfur atom and a nitrogen atom, wherein the said formed ring may have one or more substituents; and
X − is a monovalent anion,
wherein
a) the target compound is a compound represented by the general formula (3):

the starting compound is a compound represented by the general formula (2):

wherein R 1 is a C1 to C4 perfluoroalkyl group,
R 4 is a straight chain or branched chain hydrocarbon group which may have one or more substituents,
a cyclic hydrocarbon group which may have one or more substituents, or
a heterocyclic group which may have one or more substituents,
Z is a leaving group;
or
b) the target compound is a compound represented by the general formula (5):

the starting compound is a compound represented by the general formula (4):

wherein R 1 is a C1 to C4 perfluoroalkyl group,
R 5 is
a straight chain or branched chain hydrocarbon group which may have one or more substituents,
a cyclic hydrocarbon group which may have one or more substituents, or
a heterocyclic group which may have one or more substituents; and
R 6 is
a hydrogen atom,
a straight chain or branched chain hydrocarbon group which may have one or more substituents,
a cyclic hydrocarbon group which may have one or more substituents, or
a heterocyclic group which may have one or more substituents;
wherein, the one or more substituents in each case is independently selected from the group consisting of a halogen atom, a nitro group, a cyano group,
a C1 to C6 alkyl group,
a C2 to C6 alkenyl group,
a C2 to C6 alkynyl group,
a C3 to C8 cycloalkyl group,
a C1 to C6 haloalkyl group,
a hydroxy group,
a C1 to C6 alkoxy group,
a C1 to C6 haloalkoxy group,
a C1 to C6 alkylthio group, a C1 to C6 alkylsulfinyl group, a C1 to C6 alkylsulfonyl group,
a C1 to C6 haloalkylthio group, a C1 to C6 haloalkylsulfinyl group, a C1 to C6 haloalkylsulfonyl group,
an amino group, a mono (C1 to C6 alkyl) amino group, a di (C1 to C6 alkyl) amino group,
a C1 to C6 acylamino group,
a formyl group, a C2 to C6 acyl group,
a C1 to C6 alkoxycarbonyl group,
a mono (C1 to C6 alkyl) aminocarbonyl group, a di (C1 to C6 alkyl) aminocarbonyl group,
a C6 to C10 aryl group,
a C6 to C10 aryloxy group,
a C6 to C10 aryl C1 to C4 alkyl group, and
a heterocyclic group, wherein the heterocyclic group is a 5- to 10-membered heterocyclic group having 1 to 9 carbon atoms and 1 to 4 heteroatoms selected independently from a nitrogen atom,
an oxygen atom and a sulfur atom,
in the presence of a base.

2. The method according to claim 1 , wherein
R 1 is a C1 to C4 perfluoroalkyl group;
R 2 and R 3 are each independently a C1 to C4 alkyl group or a phenyl group;
Y 1 , Y 2 , Y 3 and Y 4 are each independently
a hydrogen atom, a halogen atom, a nitro group, a cyano group,
a C1 to C4 alkyl group or a C1 to C4 haloalkyl group; and
X − is Cl − , Br − , I − ,
BF 4 − ,
CF 3 SO 3 − ,
HOSO 3 − , CH 3 OSO 3 − or C 2 H 5 OSO 3 − .

3. The method according to claim 1 , wherein
R 1 is a trifluoromethyl group or a pentafluoroethyl group;
R 2 and R 3 are each independently a methyl group, an ethyl group or a phenyl group;
Y 1 , Y 2 , Y 3 and Y 4 are each independently a hydrogen atom, a chlorine atom or a nitro group; and
X − is Cl − , Br − , I − ,
BF 4 − ,
CF 3 SO 3 − ,
HOSO 3 − , CH 3 OSO 3 − or C 2 H 5 OSO 3 − .

4. The method according to claim 1 , wherein
R 1 is a trifluoromethyl group;
R 2 and R 3 are each a methyl group;
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom; and
X is CH 3 OSO 3 − .

5. The method according to claim 1 , wherein the reaction is carried out in the presence of a zeolite.

6. The method according to claim 5 , wherein the zeolite is a molecular sieve 3A, a molecular sieve 4A or a molecular sieve 5A.

Assignees

• Kumiai Chemical Industry Co

Inventors

• Kawazoe Kentaro
• Yoshioka Kotaro

Classifications

• C07D235/10 Primary

  Radicals substituted by halogen atoms or nitro radicals · CPC title

• C07C29/38 Primary

  by reaction with aldehydes or ketones · CPC title

• C07D333/16

  by oxygen atoms · CPC title

• C07C31/38

  containing only fluorine as halogen · CPC title

• C07B61/00

  Other general methods · CPC title