US 10,308,613 B2 · Fluoroalkylating agent

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).

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.

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Fluoroalkylating agent

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Fluoroalkylating agent

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Abstract

Claims8