Fluoroalkylating agent
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 R 1 is a C1 to C8 fluoroalkyl group; R 2 and R 3 are each independently a C1 to C12 alkyl group or the like; Y 1 to Y 4 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): R 4 —S—R 1 having an introduced C1 to C8 fluoroalkyl group is easily obtained by reacting a compound of the general formula (2): R 4 —S—Z wherein R 4 is a hydrocarbon group or the like; and Z is a leaving group, with the compound of the general formula (1).
1. 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, 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) 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 Br − ;
(ii) 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 I − ;
(iii) R 1 is a trifluoromethyl group,
R 2 and R 3 are each a methyl group,
Y 1 is a hydrogen atom,
Y 2 is a methyl group,
Y 3 is a methyl group,
Y 4 is a hydrogen atom, and
X − is I − ;
(iv) R 1 is a trifluoromethyl group,
R 2 and R 3 are each a methyl group,
Y 1 is a hydrogen atom,
Y 2 is a chlorine atom,
Y 3 is a hydrogen atom,
Y 4 is a hydrogen atom, and
X − is Br − ;
(v) 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 bromine atom,
X − is Br −
(vi) R 1 is a trifluoromethyl group,
R 2 is a butyl group,
R 3 is a propyl substituted by a SO 3 H group,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is H 2 PO 4 − ;
(vii) R 1 is a trifluoromethyl group,
R 2 is a butyl group,
R 3 is a propyl substituted by a SO 3 H group,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is HSO 4 − ;
(viii) R 1 is a trifluoromethyl group,
R 2 is a butyl group,
R 3 is a propyl substituted by a SO 3 H group,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is p-tosylate;
(ix) R 1 is a trifluoromethyl group,
R 2 is a methyl group,
R 3 is a CH═CH—COCF 3 ,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is triflate, and
(x) R 1 is CH 2 F,
R 2 is a methyl group,
R 3 is an ethyl group,
Y 1 , Y 3 and Y 4 are each a hydrogen atom,
Y 2 is CF 3 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.
2. The agent 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 agent 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 agent 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. A compound represented by the general formula (1A):
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;
provided that the following cases of (i) to (x) are excluded:
(i) 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 Br − ;
(ii) 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 I − ;
(iii) R 1 is a trifluoromethyl group,
R 2 and R 3 are each a methyl group,
Y 1 is a hydrogen atom,
Y 2 is a methyl group,
Y 3 is a methyl group,
Y 4 is a hydrogen atom, and
X − is I − ;
(iv) R 1 is a trifluoromethyl group,
R 2 and R 3 are each a methyl group,
Y 1 is a hydrogen atom,
Y 2 is a chlorine atom,
Y 3 is a hydrogen atom,
Y 4 is a hydrogen atom, and
X − is Br − ;
(v) 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 bromine atom,
X − is Br −
(vi) R 1 is a trifluoromethyl group,
R 2 is a butyl group,
R 3 is a propyl substituted by a SO 3 H group,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is H 2 PO 4 − ;
(vii) R 1 is a trifluoromethyl group,
R 2 is a butyl group,
R 3 is a propyl substituted by a SO 3 H group,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is HSO 4 − ;
(viii) R 1 is a trifluoromethyl group,
R 2 is a butyl group,
R 3 is a propyl substituted by a SO 3 H group,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is p-tosylate;
(ix) R 1 is a trifluoromethyl group,
R 2 is a methyl group,
R 3 is a CH═CH—COCF 3 ,
Y 1 , Y 2 , Y 3 and Y 4 are each a hydrogen atom and
X − is triflate; and
(x) R 1 is CH 2 F,
R 2 is a methyl group,
R 3 is an ethyl group,
Y 1 , Y 3 and Y 4 are each a hydrogen atom,
Y 2 is CF 3 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.
6. The compound according to claim 5 , 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 − .
7. The compound according to claim 5 , 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 − .
8. The compound according to claim 5 , 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 − .