Method for producing dihalo acetoacetic alkyl esters
View Patent ↗The invention relates to a process for preparing alkyl dihaloacetoacetates of the formula (I) by reacting α,α-dihaloamines of the formula (III) with acetic esters of the formula (II) in the presence of bases.
1. A process for preparing an alkyl dihaloacetoacetate of formula (I)
in which
X is fluorine, chlorine or CF 3 ,
X′ is fluorine, chlorine or bromine,
R 1 is selected from H, C 1-12 -alkyl radicals, C 5-18 -aryl, Cl, bromine and fluorine and
R 3 , independently of R 1 , is selected from C 1-12 -alkyl, C 5-18 -aryl or C 7-19 -arylalkyl radicals, by reacting α,α-dihaloamines of the formula (III)
in which
R 4 is selected from C 1-12 -alkyl radicals, C 5-18 -aryl radicals or C 7-19 -arylalkyl radicals,
R 5 , independently of R 4 , is selected from C 1-12 -alkyl radicals, C 5-18 -aryl radicals or C 7-19 -arylalkyl radicals,
with a carboxylic ester of the formula (II)
in which
R 2 is selected from H, C 1-12 -alkyl radicals, C 5-18 -aryl, Cl, bromine and fluorine.
2. A process according to claim 1 , wherein
X is selected from fluorine, chlorine or CF 3 ;
X′ is selected from fluorine or Cl;
R 1 is selected from C 1-4 -alkyl radicals;
R 2 , independently of R 1 , is selected from C 1-4 -alkyl radicals;
R 3 , independently of R 1 , is selected from C 1-4 -alkyl;
R 4 is selected from C 1-4 -alkyl radicals and
R 5 , independently of R 4 , is selected from C 1-4 -alkyl radicals.
3. A process according to claim 1 , wherein
X is selected from fluorine or chlorine;
X′ is fluorine;
R 1 is selected from hydrogen or fluorine;
R 2 is hydrogen;
R 3 is selected from methyl or ethyl;
R 4 is selected from methyl or ethyl;
R 5 is selected from methyl or ethyl.
4. A process according to claim 1 , wherein said process is effected in the presence of a base.
5. A process according to claim 1 , wherein the α,α-dihaloamine is selected from the group consisting of 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine, 1,1,2,2-tetrafluoroethyl-N,N-diethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-dimethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N -diethylamine, 1,1,2-trifluoro-2-chloroethyl-N,N-dimethylamine and 1,1,2-trifluoro-2-chloroethyl-N,N-diethylamine.
6. A process according to claim, wherein the base is at least the selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, hydrides, alkyllithium reagents and Grignard reagents.
7. A process according to claim 1 , wherein the carboxylic ester is selected from methyl acetate, ethyl acetate, ethyl fluoroacetate, ethyl bromoacetate, ethyl propionate, ethyl phenylacetate and ethyl benzoate.
8. A process according to claim 2 , wherein
X is selected from fluorine or chlorine;
X′ is fluorine;
R 1 is selected from hydrogen or fluorine;
R 2 is hydrogen;
R 3 is selected from methyl or ethyl;
R 4 is selected from methyl or ethyl;
R 5 is selected from methyl or ethyl.
9. A process according to claim 2 , wherein said process is effected in the presence of a base.
10. A process according to claim 3 , wherein said process is effected in the presence of a base.
11. A process according to claim 2 , wherein the α,α-dihaloamine is selected from the group consisting of 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine, 1,1,2,2-tetrafluoroethyl-N,N -diethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-dimethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-diethylamine, 1,1,2-trifluoro-2-chloroethyl-N,N-dimethylamine and 1,1,2-trifluoro-2-chloroethyl-N,N-diethylamine.
12. A process according to claim 3 , wherein the α,α-dihaloamine is selected from the group consisting of 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine, 1,1,2,2-tetrafluoroethyl-N,N -diethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-dimethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-diethylamine, 1,1,2-trifluoro-2-chloroethyl-N,N-dimethylamine and 1,1,2-trifluoro-2-chloroethyl-N,N-diethylamine.
13. A process according to claim 4 , wherein the α,α-dihaloamine is selected from the group consisting of 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine, 1,1,2,2-tetrafluoroethyl-N,N -diethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-dimethylamine, 1,1,2-trifluoro-2-(trifluoromethyl)ethyl-N,N-diethylamine, 1,1,2-trifluoro-2-chloroethyl-N,N-dimethylamine and 1,1,2-trifluoro-2-chloroethyl-N,N-diethylamine.
14. A process according to claim 2 , wherein the carboxylic ester is selected from methyl acetate, ethyl acetate, ethyl fluoroacetate, ethyl bromoacetate, ethyl propionate, ethyl phenylacetate and ethyl benzoate.
15. A process according to claim 3 , wherein the carboxylic ester is selected from methyl acetate, ethyl acetate, ethyl fluoroacetate, ethyl bromoacetate, ethyl propionate, ethyl phenylacetate and ethyl benzoate.
16. A process according to claim 4 , wherein the carboxylic ester is selected from methyl acetate, ethyl acetate, ethyl fluoroacetate, ethyl bromoacetate, ethyl propionate, ethyl phenylacetate and ethyl benzoate.
17. A process according to claim 5 , wherein the carboxylic ester is selected from methyl acetate, ethyl acetate, ethyl fluoroacetate, ethyl bromoacetate, ethyl propionate, ethyl phenylacetate and ethyl benzoate.
18. A process according to claim 6 , wherein the carboxylic ester is selected from methyl acetate, ethyl acetate, ethyl fluoroacetate, ethyl bromoacetate, ethyl propionate, ethyl phenylacetate and ethyl benzoate.