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US 6,624,322 B1Granted
Method for preparing β-phosphorous nitroxide radicals
AssigneeAtofina
InventorsJean-Philippe Gillet, Olivier Guerret, Paul Tordo
Life of this patent
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Abstract
The invention concerns a method for preparing β-phosphorous nitroxide radicals which comprises preparing in a first step an aminophosphonate by reacting a carbonyl compound, a primary amine and a phosphorous compound, then in a second step in oxidizing said aminophosphonate using on-halogenated organic peracids in a two-phase organic water/solvent medium with a buffered aqueous phase with a pH ranging between 5 and 12.
Claims32
A process for the manufacture of at least one compound of formula I:
- in which R1 and R2, which are identical or different, represent a hydrogen atom, a linear, branched or cyclic alkyl radical having 1 to 10 carbon atoms, an aryl radical, or an aralkyl radical having 1 to 10 carbon atoms or else R1 and R2 are connected to one another so as to form a ring, said ring having 3 to 8 carbon atoms, R3 represents a linear, branched or cyclic, saturated or unsaturated, hydrocarbon radical having 1 to 30 carbon atoms;
- and R4 and R5, which are identical or different, represent a linear or branched alkyl radical having 1 to 20 carbon atoms or a cycloalkyl, aryl, alkoxyl, aryloxyl, aralkyloxyl, perfluoroalkyl, aralkyl, dialkyl- or diarylamino, alkylarylamino or thioalkyl radical, or R4 and R5 are connected to one another so as to form a heterocyclic ring which includes the phosphorus atom, said heterocyclic ring having 2-4 carbon atoms and optionally containing one or more oxygen, sulfur or nitrogen hetero atoms;
- said process comprising forming and oxidizing a β-phosphoroamine of formula II:
- wherein said forming of β-phosphoroamine (II) comprises the following stages:
- a) a carbonyl compound R1R2C(O) is reacted with a primary amine R3NH2 with an R1R2C(O)/R3NH2 molar ratio of between 0.8 and 1.5, at a temperature of between 0° C. and 120° C., and a pressure ranging from 1 to 10 bar;
- the resultant water formed is removed from the reaction medium and an imine of the formula R1R2C═NR3 (III) is obtained;
- b) the imine of formula III is reacted with a phosphorus compound HP(O)R4R5 with an HP(O)R4R5/imine molar ratio of at most equal to 1.5 at a temperature of between 0° C. and 120° C.;
- c) an acidic treatment of the reaction medium obtained in b) is carried out, a water-immiscible organic solvent is subsequently added, a settled out resultant aqueous phase is recovered and then a basic treatment of said aqueous phase is carried out to form said β-phosphoroamine of formula II;
- d) the resultant β-phosphoroamine of formula II is extracted from the aqueous phase with an organic solvent identical to that previously used in c);
- e) said solvent is then completely removed and said β-phosphoroamine (II) is isolated and
- wherein said oxidizing of β-phosphoroamine to β-phosphorated nitroxide is conducted according to the following stages:
- a1) the β-phosphoroamine (II) obtained in e) is dissolved in a water-immiscible organic solvent to form an organic medium;
- b1) subsequently, an amount of non-halogenated organic peracid, according to a peracid/β-phosphoroamine (II) molar ratio ranging from 1.5 to 2.5, and a sufficient amount of a basic aqueous solution of an alkali metal carbonate or hydrogencarbonate or of an alkaline earth metal carbonate or hydrogencarbonate or alternatively of an ammonia solution to produce a pH ranging from 5 to 12 are simultaneously added with vigorous stirring, at a temperature of between −10° C. and +40° C., to the organic medium until the β-phosphoroamine (II) has been converted;
- c1) the organic phase is then separated and the resultant β-phosphorated nitroxide provided,
- or, alternatively, stages d), e), and a1) are omitted and, instead, a stage of adding a water-immiscible organic solvent to the β-phosphoroamine of formula II from stage c) to form an organic medium and then carrying out stages b1) and c1) are conducted.
12 more elements
A process for the manufacture of at least one compound of formula I:
- in which R1 and R2, which are identical or different, represent a hydrogen atom, a linear, branched or cyclic alkyl radical having 1 to 10 carbon atoms, an aryl radical, or an aralkyl radical having 1 to 10 carbon atoms or else R1 and R2 are connected to one another so as to form a ring, said ring having 3 to 8 carbon atoms, R3 represents a linear, branched or cyclic, saturated or unsaturated, hydrocarbon radical having 1 to 30 carbon atoms;
- and R4 and R5, which are identical or different, represent a linear or branched alkyl radical having 1 to 20 carbon atoms or a cycloalkyl, aryl, alkoxyl, aryloxyl, aralkyloxyl, perfluoroalkyl, aralkyl, dialkyl- or diarylamino, alkylarylamino or thioalkyl radical, or R4 and R5 are connected to one another so as to form a heterocyclic ring which includes the phosphorus atom, said heterocyclic ring having 2-4 carbon atoms and optionally containing one or more oxygen, sulfur or nitrogen hetero atoms;
- said process comprising providing a medium comprising an aqueous phase, ethyl acetate, and a β-phosphoroamine of formula II:
- and adding to said medium, an amount of non-halogenated organic peracid, according to a peracid/β-phosphoroamine (II) molar ratio ranging from 1.5 to 2.5, and a sufficient amount of a basic aqueous solution of an alkali metal carbonate or hydrogencarbonate or of an alkaline earth metal carbonate or hydrogencarbonate or alternatively of an ammonia solution to produce a pH ranging from 5 to 12 with vigorous stirring, at a temperature of between −10° C. and +40° C., to convert the β-phosphoroamine (II) to said compound of formula (I).
1 more element
A process for the manufacture of at least one compound of formula I:
- in which R1 and R2, which are identical or different, represent a hydrogen atom, a linear, branched or cyclic alkyl radical having 1 to 10 carbon atoms, an aryl radical, or an aralkyl radical having 1 to 10 carbon atoms or else R1 and R1 are connected to one another so as to form a ring, said ring having 3 to 8 carbon atoms, R3 represents a linear, branched or cyclic, saturated or unsaturated, hydrocarbon radical having 1 to 30 carbon atoms;
- and R4 and R5, which are identical or different, represent a linear or branched alkyl radical having 1 to 20 carbon atoms or a cycloalkyl, aryl, alkoxyl, aryloxyl, aralkyloxyl, perfluoroalkyl, aralkyl, dialkyl- or diarylamino, alkylarylamino or thioalkyl radical, or R4 and R5 are connected to one another so as to form a heterocyclic ring which includes the phosphorus atom, said heterocyclic ring having 2-4 carbon atoms and optionally containing one or more oxygen, sulfur or nitrogen hetero atoms;
- said process comprising providing a β-phosphoroamine of formula II:
- and oxidizing said β-phosphoroamine to β-phosphorated nitroxide according to the following stages:
- a1) dissolving the β-phosphoroamine (II) in a water-immiscible organic solvent to form an organic medium;
- and
- b1) subsequently, simultaneously adding to said organic medium, an amount of non-halogenated organic peracid, according to a peracid/β-phosphoroamine (II) molar ratio ranging from 1.5 to 2.5, and a sufficient amount of a basic aqueous solution of an alkali metal carbonate or hydrogencarbonate or of an alkaline earth metal carbonate or hydrogencarbonate or alternatively of an ammonia solution to produce a pH ranging from 5 to 12, with vigorous stirring, at a temperature of between −10° C. and +40° C., to convert the β-phosphoroamine (II) to said compound of formula I.
4 more elements
Dependencies are inferred from the claim text.