Method for the synthesis of alpha-aminoalkylenephosphonic acid

Patent metadata

Field	Value
Publication number	US-10464958-B2
Application number	US-201715848219-A
Country	US
Kind code	B2
Filing date	Dec 20, 2017
Priority date	Jul 17, 2012
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

The present invention is related to a new method for the synthesis of alpha-aminoalkylenephosphonic acid or its phosphonate esters comprising the steps of forming a reaction mixture by mixing a P—O—P anhydride moiety comprising compound, having one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V), an aminoalkanecarboxylic acid and an acid catalyst, wherein said reaction mixture comprises an equivalent ratio of alpha-aminoalkylene carboxylic acid to P—O—P anhydride moieties of at least 0.2, and recovering the resulting alpha-aminoalkylene phosphonic acid compound or an ester thereof from the reaction mixture.

First claim

The invention claimed is:

1. A method for the synthesis of an alpha-aminoalkylenephosphonic acid or an ester thereof, the method comprising the steps of:
a) forming a reaction mixture by mixing an alpha-aminoalkylenecarboxylic acid, an acid catalyst, and a compound comprising one or more P—O—P anhydride moieties, wherein at least one of the P—O—P anhydride moieties comprises one P-atom at the oxidation state (+III) and the other P-atom at the oxidation state (+III) or (+V); and
b) recovering the resulting alpha-aminoalkylenephosphonic acid or an ester thereof from said reaction mixture, wherein at least one carboxylic acid group in the alpha-aminoalkylenecarboxylic acid is replaced by a phosphonic acid group or an ester thereof, and wherein
said alpha-aminoalkylenecarboxylic acid is selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-benzyliminodiacetic acid, N-methyliminodiacetic acid, iminodiacetic acid, N,N-bis(carboxymethyl)-1-glutamic acid, trisodium-N,N-bis(carboxymethyl)-alanine, N-cyanomethyl alanine, N,N-bis(cyanomethyl)-glycine, 4-morpholinoacetic acid, pyroglutamic acid, N-acetyl glycine, N,N-bis(carboxymethyl)-6-aminohexanoic acid, N-phenyl glycine, N-tosyl glycine, trans-1,2-cyclohexyldiaminotetraacetic acid monohydrate, N-phosphonomethyliminodiacetic acid, iminodiacetic acid grafted on resin, 1,4,7,10-tetraazadodecane-1,4,7,10-tetraacetic acid, N-phthaloglycine, and N′N′-dimethylglycine; and
said P—O—P anhydride moiety comprising compound is selected from the group consisting of tetraphosphorus hexaoxide, P 4 O 7 , P 4 O 8 , P 4 O 9 , tetraethylpyrophosphite, and combinations thereof.

2. The method according to claim 1 wherein the reaction mixture is formed by gradually adding the P—O—P anhydride moiety comprising compound to a mixture comprising the alpha-aminoalkylenecarboxylic acid and the acid catalyst.

3. The method according to claim 1 wherein the reaction mixture is formed by gradually adding a mixture comprising the alpha-aminoalkylenecarboxylic acid and the acid catalyst to a mixture comprising the P—O—P anhydride moiety comprising compound.

4. The method according to claim 1 , the method further comprising, after step a) and before step b):
adding water to the reaction mixture after completion of the conversion of the alpha-aminoalkylenecarboxylic acid into the alpha-aminoalkylene phosphonic acid or ester thereof;
bringing the reaction mixture comprising the added water to a temperature of between 20° C. and 100° C.; and
maintaining the reaction mixture comprising the added water at said temperature for at least 10 minutes.

5. The method according to claim 1 , wherein the P—O—P anhydride moiety comprising compound is tetraphosphorus hexaoxide.

6. The method according to claim 5 , wherein the tetraphosphorus hexaoxide has a purity of at least 95%.

7. The method according to claim 5 , wherein the tetraphosphorus hexaoxide contains less than 1000 ppm elemental phosphorus (P 4 ), expressed in relation to P 4 O 6 .

8. The method according to claim 1 , wherein the P—O—P anhydride moiety comprising compound is tetraethylpyrophosphite.

9. The method according to claim 1 , wherein the P—O—P anhydride moiety comprising compound is selected from the group consisting of tetraphosphorus hexaoxide, P 4 O 7 , P 4 O 8 , P 4 O 9 , and combinations thereof.

10. The method according to claim 1 , wherein the alpha-aminoalkylenecarboxylic acid compound is selected from:
iminodiacetic acid, N,N-bis(cyanomethyl)-glycine, and N-phosphonomethyliminodiacetic acid.

11. The method according to claim 1 , wherein the acid catalyst is a homogeneous Brønsted acid catalyst selected from the group consisting of methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, hydrochloric acid, phosphorous acid, phosphoric acid and mixtures thereof.

12. The method according to claim 1 , wherein the acid catalyst is a heterogeneous Brønsted acid catalyst selected from the group consisting of:
(i) solid acidic metal oxides, optionally supported onto a carrier material;
(ii) cation exchange resins selected from the group consisting of copolymers of styrene, ethylvinyl benzene and divinyl benzene, functionalized so as to graft SO 3 H moieties onto the aromatic group and perfluorinated resins carrying carboxylic and/or sulfonic acid groups;
(iii) organic sulfonic, carboxylic and phosphonic Brønsted acids which are substantially immiscible in the reaction mixture at the reaction temperature;
(iv) an acid catalyst derived from:
the interaction of a solid support having a lone pair of electrons onto which is deposited an organic Brønsted acid;
the interaction of a solid support having a lone pair of electrons onto which is deposited a compound having a Lewis acid site; or
heterogeneous solids functionalized by chemical grafting with a Brønsted acid group or a precursor of the Brønsted acid group; and

(v) heterogeneous heteropolyacids containing hydrogen, one of phosphorus and silicon, and one of tungsten and molybdenum.

13. The method according to claim 1 , wherein the acid catalyst is a Lewis acid catalyst selected from the group consisting of LiN(CF 3 SO 2 ) 2 , Mg(OCF 3 SO 2 ) 2 , Al(OCF 3 SO 2 ) 3 , Bi(OCF 3 SO 2 ) 3 , Sc(OCF 3 SO 2 ) 3 , and combinations thereof.

14. The method according to claim 1 , wherein the reaction mixture comprises a diluent selected from the group consisting of 1,4-dioxane, toluene, ethylacetate, sulfolane, acetonitrile, 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, and mixtures thereof.

15. The method according to claim 1 , wherein the P—O—P anhydride moiety comprising compound is mixed with a mixture of the alpha-aminoalkylenecarboxylic acid and the acid catalyst, at a temperature between 20° C. and 120° C.

16. The method according to claim 1 , wherein the reaction mixture, after completion of the mixing in step a), is maintained at a temperature between 20° C. and 100° C. for a period of time comprised between 10 minutes and 72 hours.

17. The method according to claim 1 , wherein the obtained alpha-aminoalkylenephosphonic acid is selected from the group consisting of aminomethylphosphonic acid, (N,N-dimethylamino)methylphosphonic acid, phthalimidomethylphosphonic acid, N-phenyl-aminomethylphosphonic acid, N-tosyl-aminomethylphosphonic acid, N-phosphonomethyl glycine, phosphonomethyliminodiacetic acid, 4-morpholinemethylphosphonic acid, 4-amino-4-phosphonobutyric acid, 5-phosphono-2-pyrrolidone, N,N-bis(phosphonomethyl)-6-amino-hexanoic acid, N,N-bis(phosphonomethyl)-4-amino-4-phosphono-butyric acid, N,N-bis(phosphonomethyl)-4-amino-glutamic acid, N,N-bis(phosphonomethyl)-1-amino-ethyl-phosphonic acid, imino (bismethylenephosphonic acid), N-methyl-imino (bismethylenephosphonic acid), N-benzyl-imino (bismethylenephosphonic acid), aminotrismethylenephosphonic acid, ethylene diamino tetra-(methylene phosphonic acid), trans-1,2-cyclohexyldiaminotetramethylenephosphonic acid, 1,4,7,10-tetraazadodecane-1,4,7, 10-tetramethylenephosphonic acid, and N-methyl-iminodiphosphonic acid.

18. The method according to claim 1 , wherein carbon monoxide produced during the conversion of the alpha-aminoalkanecarboxylic acid is recovered from the reaction mixture.

19. The method according to claim 1 , wherein a yield of alpha-aminoalkylenephosphonic acid or ester thereof, based on the alpha-aminoalkylenecarboxylic acid, of at least about 80% is achieved.

20. The method acc

Assignees

• Monsanto Technology Llc

Inventors

• Notte Patrick
• Cogels Samuel
• Burck Sebastian

Classifications

• C07F9/6524

  having four or more nitrogen atoms as the only ring hetero atoms · CPC title

• C07F9/3813

  N-Phosphonomethylglycine; Salts or complexes thereof · CPC title

• C07F9/5728

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• C07F9/6533 Primary

  Six-membered rings · CPC title

• C07F9/3886

  Acids containing the structure -C(=X)-P(=X)(XH)2 or NC-P(=X)(XH)2, (X = O, S, Se) · CPC title