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1. A method for the manufacture of an aminohydroxy diphosphonic acid by combining a reaction mixture consisting essentially of the corresponding aminocarboxylic acid, P4O6 and a sulfonic acid and performing the steps as follows:
a: adding the P4O6 to the solution of the aminocarboxylic acid in the sulfonic acid; or b: adding the P4O6 to the sulfonic acid followed by the addition of the amino carboxylic acid; wherein the sulfonic acid is selected from homogeneous and heterogeneous sulfonic and polysulfonic acids; and the amino carboxylic acid and the P4O6 are used in molar ratios of from 4:1 to 1:1 and the sulfonic acid is used in a level of from 1 to 30 equivalents per mol of amino carboxylic acid; and wherein the aminocarboxylic acid is selected from the group of:
(A)(B)N—X1—COOH i wherein X1 is such that there are at least two carbon units between COOH and N; X1 can be represented by a hydrocarbon group selected from linear, branched, cyclic and aromatic species having from 2 to 20 carbon atoms, optionally substituted by one or more groups selected from CF3, F, Cl, SR, NR′2, SO2R and OR; A and B are independently selected from H, hydrocarbon groups having from 1 to 20 carbon atoms in branched, linear, cyclic, aromatic, heterocyclic or hetero aromatic configuration which can be substituted by OR, SR, CF3, F, Cl, NR′2, SO2R and/or R wherein R represents an alkyl group having from 1 to 12 carbon atoms in linear, branched, cyclic, aromatic, heterocyclic or heteroaromatic configuration which can be substituted by OR″, SR″, CF3, F, Cl, NR″′2 and/or SO2R″ wherein R′ is selected from R and hydrogen and can be selected independently; R″ represents a hydrocarbon group having from 1 to 12 carbon atoms in linear, branched, cyclic, aromatic, heterocyclic or heteroaromatic configuration; R″′ is selected from R″ and hydrogen and R″′ groups can be chosen independently; wherein the heterocyclic and heteroaromatic groups can contain from 1 to 4 heteroatoms independently selected from nitrogen, sulphur and oxygen; such that the difference between the number of member atoms in the individual cycles of these heterocyclic or heteroaromatic rings minus the number of heteroatoms in the individual cycles of these heterocyclic or heteroaromatic rings is at least 2; provided that the carbon atom next to the carboxylic acid group is solely connected to hydrogen and, at least, one carbon atom which carries the N(A)(B) group; when A is H, B can also be a COOT group whereby T is a C1-C10 alkyl group or a C6-C10 aromatic moiety;
D-X2—COOH ii wherein X2 is at least one carbon atom between COOH and N; X2 is a hydrocarbon group in linear, branched, cyclic or aromatic configuration having from 1 to 20 carbon atoms in said group, optionally substituted by CF3, F, Cl, NR′2, SR, SO2R and/or OR; with the proviso that when there is only one carbon atom between COOH and N then D represents a heteromonoaromatic group, in all other cases D represents a heteromonocyclic or heteromonoaromatic group containing at least one nitrogen atom directly attached to X2, said heteromono cycle or heteromonoaromatic cycle being represented by a 4 to 8 member ring and containing from 1 to 3 additional hetero atoms chosen from nitrogen, oxygen and sulphur which cycle can be optionally substituted by one or more groups selected from CF3, F, Cl, NR′2, SR, SO2R and OR, which heteromonocycle or heteromonoaromatic cycle can be further substituted by one or more C1-C10 linear, branched, cyclic, aromatic, heterocyclic or heteroaromatic moieties, which can be substituted by one or more groups selected from CF3, F, Cl, NR″′2, SR″, SO2R″ and OR″, wherein R, R′, R″ and R″′ have the meaning recited above; which cyclic, heterocyclic, aromatic or heteroaromatic moieties, containing from 1 to 4 heteroatoms chosen from nitrogen, oxygen and sulphur can be fused onto the D group or attached to the D group by a single bond whereby in the cyclic structure fused onto the D group not more than four individual cycles are present; whereby the heterocyclic and heteroaromatic moieties, fused onto or attached to the D group by a single bond, and the D group itself are such that the difference between the number of member atoms in the individual cycles of these heterocyclic or heteroaromatic rings minus the number of heteroatoms in the individual cycles of these heterocyclic or heteroaromatic rings is at least 2; whereby the D group can also be represented by an imide derived from the NH2 group attached to the X2 moiety, formed by reaction with a cyclic anhydride; provided that the carbon atom next to the carboxylic acid group in ii is solely connected to hydrogen and, at least, one carbon atom which carries the D group and when in ii, X2 is solely a one carbon unit between COOH and N in D, then that carbon atom can be solely substituted by hydrogen and carbon atoms; and
E-X3—COOH iii wherein X3 is a direct link or a C1-C20 linear, branched, cyclic or aromatic hydrocarbon group, optionally substituted by CF3, F, Cl, NR′2, SR, SO2R and/or OR; with the proviso that when X3 is a direct link or when X3 is a one carbon atom unit, there are at least two carbon atoms between the COOH group and the nitrogen atom of E; whereby E is directly attached to X3 via a carbon atom and is represented by a heterocyclic or a heteroaromatic 4 to 14 member ring, containing a nitrogen atom, which hetero cyclic or hetero aromatic group can be optionally substituted by one or more groups selected from CF3, F, Cl, NR′2, SR, SO2R and OR; such heterocyclic and/or heteroaromatic rings can contain from 1 to 3 additional hetero atoms chosen from oxygen, nitrogen and sulphur; such heterocyclic and/or heteroaromatic groups can be further substituted by one or more groups selected from C1-C10 linear, branched cyclic, aromatic, heterocyclic or heteroaromatic hydrocarbon groups which groups can be optionally substituted by CF3, F, Cl, NR″′2, SR″, SO2R″ and/or OR″, wherein R, R′, R″ and R″′ have the meaning recited above; such that the difference between the number of member atoms in the individual cycles of these heterocyclic or heteroaromatic rings minus the number of heteroatoms in the individual cycles of these heterocyclic or heteroaromatic rings is at least 2; provided that when X3 is not a direct link, the carbon atom next to the carboxlic acid group is solely connected to hydrogen and, at least, one carbon atom which carries the E group and when in iii, X3 is only a one carbon unit between COOH and the E group then that carbon atom can be solely substituted by hydrogen and carbon atoms; and c: heating the reaction mixture at a temperature in the range of from 40° C. to 180° C. for a period of from 10 minutes to 30 hours, wherein the reaction contains less than 400 ppm of chlorine expressed in relation to aminohydroxy diphosphonic acid (100%). |
