US 7,126,021 B2Granted

Method for preparing β-phosphorus nitroxide radicals

AssigneeArkema (formerly ATOFINA)

InventorsOlivier Guerret, Jean-Luc Couturier, Christophe Le Mercier

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Abstract

The present invention relates to a process for the preparation of β-phosphorated nitroxide radicals which consist in preparing, in a first step, an aminophosphonate by reaction of a carbonyl compound, of a primary amine and of a phosphorous compound in the presence of a Lewis acid and then, in a second step, in oxidizing the said crude aminophosphonate using nonhalogenated organic peracids in a water/organic solvent two-phase medium with an aqueous phase buffered at a pH ranging from 5 to 12.

Claims12

Dependent claims

Process for the manufacture of compounds of general formula:

in which R1 and R2, which are identical or different, represent a hydrogen atom, a linear, branched or cyclic alkyl radical having a number of carbon atoms ranging from 1 to 10, an aryl radical, or an aralkyl radical having a number of carbon atoms ranging from 1 to 10, or else R1 and R2 are connected to one another so as to form a ring which includes the carbon atom carrying the said R1 and R2 radicals, the said ring having a number of carbon atoms, including the carbon carrying the R1 and R2 radicals, ranging from 3 to 8;
R3 represents a linear or branched and saturated or unsaturated hydrocarbonaceous radical which can comprise at least one ring, the said radical having a number of carbon atoms ranging from 1 to 30;
and R4 and R5, which are identical or different, represent a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 20 or a cycloalkyl, aryl, alkoxyl, aryloxyl, aralkyloxyl, perfluoroalkyl, aralkyl, dialkyl- or diarylamino, alkylarylamino or thioalkyl radical, or else R4 and R5 are connected to one another so as to form a ring which includes the phosphorus atom, the said heterocycle having a number of carbon atoms ranging from 2 to 4 and being able in addition to comprise one or more oxygen, sulphur or nitrogen atoms;
the said process consisting in oxidizing an aminophosphonate of formula
in a solvent medium using a nonhalogenated organic peracid in a water/solvent two-phase medium with an aqueous phase buffered at a pH ranging from 5 to 12;
the said aminophosphonate being obtained by reaction of a carbonyl compound R1R2C(O), of a primary amine R3NH2 and of a phosphorus compound HP(O)R4R5, R1, R2, R3, R4 and R5 having the meanings given above, by carrying out the following (successive) stages:
a) a carbonyl compound R1R2C(O) is reacted with a primary amine R3NH2 according to an R1R2C(O)/R3NH2 molar ratio of between 0.8 and 1.5 and preferably of between 0.9 and 1.1 at a temperature of between 0° C. and 120° C. and a pressure ranging from 1 to 10 bar;
then the water formed is removed from the reaction medium;
and
b) the compound obtained in a) is reacted with a phosphorus compound HP(O)R4R5;
the said process being characterized in that stage b) is carried out in the presence of a Lewis acid using an HP(O)R4R5/compound obtained in stage a) molar ratio substantially equal to 1 at a temperature at most equal to 100° C. and in that the medium obtained in b) is subjected directly and without purification to an oxidation reaction carried out according to the conditions mentioned above.

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Dependencies are inferred from the claim text.

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Abstract

Process for the manufacture of compounds of general formula:

in which R1 and R2, which are identical or different, represent a hydrogen atom, a linear, branched or cyclic alkyl radical having a number of carbon atoms ranging from 1 to 10, an aryl radical, or an aralkyl radical having a number of carbon atoms ranging from 1 to 10, or else R1 and R2 are connected to one another so as to form a ring which includes the carbon atom carrying the said R1 and R2 radicals, the said ring having a number of carbon atoms, including the carbon carrying the R1 and R2 radicals, ranging from 3 to 8;
R3 represents a linear or branched and saturated or unsaturated hydrocarbonaceous radical which can comprise at least one ring, the said radical having a number of carbon atoms ranging from 1 to 30;
and R4 and R5, which are identical or different, represent a linear or branched alkyl radical having a number of carbon atoms ranging from 1 to 20 or a cycloalkyl, aryl, alkoxyl, aryloxyl, aralkyloxyl, perfluoroalkyl, aralkyl, dialkyl- or diarylamino, alkylarylamino or thioalkyl radical, or else R4 and R5 are connected to one another so as to form a ring which includes the phosphorus atom, the said heterocycle having a number of carbon atoms ranging from 2 to 4 and being able in addition to comprise one or more oxygen, sulphur or nitrogen atoms;
the said process consisting in oxidizing an aminophosphonate of formula
in a solvent medium using a nonhalogenated organic peracid in a water/solvent two-phase medium with an aqueous phase buffered at a pH ranging from 5 to 12;
the said aminophosphonate being obtained by reaction of a carbonyl compound R1R2C(O), of a primary amine R3NH2 and of a phosphorus compound HP(O)R4R5, R1, R2, R3, R4 and R5 having the meanings given above, by carrying out the following (successive) stages:
a) a carbonyl compound R1R2C(O) is reacted with a primary amine R3NH2 according to an R1R2C(O)/R3NH2 molar ratio of between 0.8 and 1.5 and preferably of between 0.9 and 1.1 at a temperature of between 0° C. and 120° C. and a pressure ranging from 1 to 10 bar;
then the water formed is removed from the reaction medium;
and
b) the compound obtained in a) is reacted with a phosphorus compound HP(O)R4R5;
the said process being characterized in that stage b) is carried out in the presence of a Lewis acid using an HP(O)R4R5/compound obtained in stage a) molar ratio substantially equal to 1 at a temperature at most equal to 100° C. and in that the medium obtained in b) is subjected directly and without purification to an oxidation reaction carried out according to the conditions mentioned above.

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