# US 10,308,613 B2 · Fluoroalkylating agent

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- Number: US 10,308,613 B2
- Document ID: US10308613B2
- Status: Granted
- Kind: B2
- Application number: 15/314,999
- Filed: 2015-06-24
- Published: 2017-07-13
- Granted: 2019-06-04
- Earliest claimed: 2014-06-26
- Assignees: Kumiai Chemical Industry Co., Ltd.
- Applicants: Kumiai Chemical Industry Co., Ltd.
- Inventors: Kentaro Kawazoe; Kotaro Yoshioka
- Web page: https://patentgrep.com/patent/US10308613B2

## CPC

- C07D 235/10: Radicals substituted by halogen atoms or nitro radicals
- C07C 29/38: by reaction with aldehydes or ketones
- C07C 31/38: containing only fluorine as halogen
- C07C 67/343: by increase in the number of carbon atoms
- C07C 319/14: of sulfides
- C07C 319/20: by reactions not involving the formation of sulfide groups
- C07C 323/12: the carbon skeleton being acyclic and saturated
- C07D 213/30: Oxygen atoms
- C07D 333/16: by oxygen atoms
- C07B 61/00: Other general methods
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

Problem to be Solved It is intended to provide an industrially preferable fluoroalkylating agent and use thereof. Solution The present invention provides a fluoroalkylating agent represented by the general formula (1) wherein R1 is a C1 to C8 fluoroalkyl group; R2 and R3 are each independently a C1 to C12 alkyl group or the like; Y1 to Y4 are each independently a hydrogen atom, a halogen atom, or the like; and X− is a monovalent anion. 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).

## Claims

### Claim 1

A fluoroalkylating agent represented by the general formula (1):
wherein R1 is a C1 to C8 fluoroalkyl group;
R2 and R3 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;
Y1, Y2, Y3 and Y4 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 Y1 and Y2, Y2 and Y3, or Y3 and Y4, 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, 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,
provided that the following cases of (i) to (x) are excluded:
(i) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom, and
X− is Br−;
(ii) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom, and
X− is I−;
(iii) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1 is a hydrogen atom,
Y2 is a methyl group,
Y3 is a methyl group,
Y4 is a hydrogen atom, and
X− is I−;
(iv) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1 is a hydrogen atom,
Y2 is a chlorine atom,
Y3 is a hydrogen atom,
Y4 is a hydrogen atom, and
X− is Br−;
(v) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1, Y2, Y3 and Y4 are each a bromine atom,
X− is Br−
(vi) R1 is a trifluoromethyl group,
R2 is a butyl group,
R3 is a propyl substituted by a SO3H group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is H2PO4−;
(vii) R1 is a trifluoromethyl group,
R2 is a butyl group,
R3 is a propyl substituted by a SO3H group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is HSO4−;
(viii) R1 is a trifluoromethyl group,
R2 is a butyl group,
R3 is a propyl substituted by a SO3H group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is p-tosylate;
(ix) R1 is a trifluoromethyl group,
R2 is a methyl group,
R3 is a CH═CH—COCF3,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is triflate, and
(x) R1 is CH2F,
R2 is a methyl group,
R3 is an ethyl group,
Y1, Y3 and Y4 are each a hydrogen atom,
Y2 is CF3 and
X− is p-tosylate;
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.

### Claim 2 (depends on 1)

The agent according to claim 1, wherein
R1 is a C1 to C4 perfluoroalkyl group;
R2 and R3 are each independently a C1 to C4 alkyl group or a phenyl group;
Y1, Y2, Y3 and Y4 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−,
BF4−,
CF3SO3−,
HOSO3−, CH3OSO3− or C2H5OSO3−.

### Claim 3 (depends on 1)

The agent according to claim 1, wherein
R1 is a trifluoromethyl group or a pentafluoroethyl group;
R2 and R3 are each independently a methyl group, an ethyl group or a phenyl group;
Y1, Y2, Y3 and Y4 are each independently a hydrogen atom, a chlorine atom or a nitro group; and
X− is Cl−, Br−, I−,
BF4−,
CF3SO3−,
HOSO3−, CH3OSO3− or C2H5OSO3−.

### Claim 4 (depends on 1)

The agent according to claim 1, wherein
R1 is a trifluoromethyl group;
R2 and R3 are each a methyl group;
Y1, Y2, Y3 and Y4 are each a hydrogen atom; and
X− is CH3OSO3−.

### Claim 5

A compound represented by the general formula (1A):
wherein R1 is a C1 to C8 fluoroalkyl group;
R2 and R3 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;
Y1, Y2, Y3 and Y4 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 Y1 and Y2, Y2 and Y3, or Y3 and Y4, 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;
provided that the following cases of (i) to (x) are excluded:
(i) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom, and
X− is Br−;
(ii) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom, and
X− is I−;
(iii) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1 is a hydrogen atom,
Y2 is a methyl group,
Y3 is a methyl group,
Y4 is a hydrogen atom, and
X− is I−;
(iv) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1 is a hydrogen atom,
Y2 is a chlorine atom,
Y3 is a hydrogen atom,
Y4 is a hydrogen atom, and
X− is Br−;
(v) R1 is a trifluoromethyl group,
R2 and R3 are each a methyl group,
Y1, Y2, Y3 and Y4 are each a bromine atom,
X− is Br−
(vi) R1 is a trifluoromethyl group,
R2 is a butyl group,
R3 is a propyl substituted by a SO3H group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is H2PO4−;
(vii) R1 is a trifluoromethyl group,
R2 is a butyl group,
R3 is a propyl substituted by a SO3H group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is HSO4−;
(viii) R1 is a trifluoromethyl group,
R2 is a butyl group,
R3 is a propyl substituted by a SO3H group,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is p-tosylate;
(ix) R1 is a trifluoromethyl group,
R2 is a methyl group,
R3 is a CH═CH—COCF3,
Y1, Y2, Y3 and Y4 are each a hydrogen atom and
X− is triflate; and
(x) R1 is CH2F,
R2 is a methyl group,
R3 is an ethyl group,
Y1, Y3 and Y4 are each a hydrogen atom,
Y2 is CF3 and
X− is p-tosylate;
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.

### Claim 6 (depends on 5)

The compound according to claim 5, wherein
R1 is a C1 to C4 perfluoroalkyl group;
R2 and R3 are each independently a C1 to C4 alkyl group or a phenyl group;
Y1, Y2, Y3 and Y4 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−,
BF4−,
CF3SO3−,
HOSO3−, CH3OSO3− or C2H5OSO3−.

### Claim 7 (depends on 5)

The compound according to claim 5, wherein
R1 is a trifluoromethyl group or a pentafluoroethyl group;
R2 and R3 are each independently a methyl group, an ethyl group or a phenyl group;
Y1, Y2, Y3 and Y4 are each independently a hydrogen atom, a chlorine atom or a nitro group; and
X− is Cl−, Br−, I−,
BF4−,
CF3SO3−,
HOSO3−, CH3OSO3− or C2H5OSO3−.

### Claim 8 (depends on 5)

The compound according to claim 5, wherein
R1 is a trifluoromethyl group;
R2 and R3 are each a methyl group;
Y1, Y2, Y3 and Y4 are each a hydrogen atom; and
X− is CH3OSO3−.