Method for the synthesis of N-phosphonomethyliminodiacetic acid

Patent metadata

Field	Value
Publication number	US-10364262-B2
Application number	US-201314415684-A
Country	US
Kind code	B2
Filing date	Jul 17, 2013
Priority date	Jul 17, 2012
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

Abstract

A method for synthesis of N-phosphonoalkyliminodiacetic acid or derivatives thereof by forming a reaction mixture having an acid catalyst, a compound of the following general formula R1—CH2—NX—CH2—R2 and a compound having one or more P—O—P anhydride moieties to form a compound having a formula R1—CH2—N(—CH2PO3R32)(—CH2—R2) wherein in R1—CH2—NX—CH2—R2: X is —CH2—OH or —CH2—COOH; R1 and R2 are independently selected from the group consisting of nitrile, C1-C4 alkyl carboxylate, and carboxylic acid for when X is —CH2—OH, or R1 and R2 are both carbonyl groups linked by a hydrogen substituted nitrogen atom or a C1-C4-alkyl substituted nitrogen atom; and R3 is H, an alkyl group, or an aryl group; the anhydride moieties in the P—O—P anhydride compound have one P atom at the oxidation state (+III) and one P atom at the oxidation state (+III) or (+V); and 2) hydrolyzing the mixture to form N-phosphonomethyliminodiacetic acid or one of its derivatives.

First claim

The invention claimed is:

1. A method for synthesis of N-phosphonomethyliminodiacetic acid or derivatives thereof selected from the group consisting of phosphonate esters of N-phosphonomethyliminodiacetic acid, carboxylate esters of N-phosphonomethyliminodiacetic acid, phosphonate and carboxylate esters of N-phosphonomethyliminodiacetic acid, N-phosphonomethyliminodiacetic acid salts, phosphonate esters of N-phosphonomethyliminodiacetic acid salts, carboxylate esters of N-phosphonomethyliminodiacetic acid salts and phosphonate-carboxylate esters of N-phosphonomethyliminodiacetic acid salts, wherein a cation of the salt is selected from the group consisting of ammonium, isopropylammonium, ethanolammonium, dimethylammonium, trimethylsulfonium, sodium and potassium,
comprising the steps of:
a) forming an anhydrous reaction mixture comprising an acid catalyst, a compound of the following general formula R 1 —CH 2 —NX—CH 2 —R 2 and a compound having one or more P—O—P anhydride moieties, to form a compound having the general formula R 1 —CH 2 —N(—CH 2 PO 3 R 3 2 )(—CH 2 —R 2 ), wherein in the compound of the formula R 1 —CH 2 —NX—CH 2 —R 2 :
X is —CH 2 —COOH and R 1 and R 2 are each independently nitrile or C 1 -C 4 alkyl carboxylate, or R 1 and R 2 are both carbonyl groups linked by means of a hydrogen substituted nitrogen atom or a C 1 -C 4 -alkyl substituted nitrogen atom; or
X is —CH 2 —OH and R 1 and R 2 are each independently nitrile, C 1 -C 4 carboxylate, or carboxylic acid, or R 1 and R 2 are both carbonyl groups linked by means of a hydrogen substituted nitrogen atom or a C 1 -C 4 -alkyl substituted nitrogen atom;
and wherein in the compound having the general formula R 1 —CH 2 —N(—CH 2 PO 3 R 3 2 )(—CH 2 —R 2 ), R 3 is H, an alkyl group; and
the P—O—P anhydride moieties comprising compound is a compound wherein at least one of the one or more P—O—P anhydride moieties comprises one P atom at the oxidation state (+III) and one P atom at the oxidation state (+III) or (+V) and is selected from the group consisting of tetraphosphorus hexaoxide, P 4 O 7 , P 4 O 8 , P 4 O 9 , pyrophosphites of general formula (RO) 2 P—O—P(OR) 2 wherein R is an alkyl or aryl group, and combinations thereof, and
b) hydrolyzing the compound having the general formula R 1 —CH 2 —N(—CH 2 PO 3 R 3 2 )(—CH 2 —R 2 ) to form N-phosphonomethyliminodiacetic acid or one of its derivatives.

2. The method of claim 1 wherein the R 1 —CH 2 —NX—CH 2 —R 2 compound is a 4-X-piperazine-2,6-dione or a 4-X-1-(C 1 -C 4 alkyl)piperazine-2,6-dione.

3. The method of claim 1 , wherein ratio of N—X moieties to P—O—P anhydride moieties is between 0.3 and 2.0.

4. The method of claim 1 , wherein the compound of the general formula R 1 —CH 2 —NX—CH 2 —R 2 is selected from the group consisting of N-hydroxymethyliminodiacetonitrile, N-hydroxymethyliminodiacetic acid, N-hydroxymethyliminodiacetic acid dimethylester, N-hydroxymethyliminodiacetic acid diethylester, N-carboxymethyliminodiacetonitrile, N-carboxymethyliminodiacetic acid dimethylester and N-carboxymethyliminodiacetic acid diethylester.

5. The method of claim 1 , wherein the compound comprising the P—O—P anhydride moieties 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.

6. The method of claim 1 , wherein the compound comprising the P—O—P anhydride moieties is tetraphosphorus hexaoxide.

7. The method of 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.

8. The method of claim 1 , wherein the acid catalyst is a heterogeneous Brønsted acid selected from the group consisting of:
(i) supported or unsupported solid acidic metal oxides;
(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 an aromatic group and perfluorinated resins carrying carboxylic and/or sulfonic acid groups;
(iii) organic sulfonic, carboxylic and phosphonic Brønsted acids, wherein the Brønsted acids are substantially immiscible in the reaction mixture at a reaction temperature;
(iv) an acid catalyst derived from:
interaction of a solid support having a lone pair of electrons onto which is deposited an organic Brønsted acid;
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 thereof; and
(v) heterogeneous heteropolyacids of the general formula H x PM y O z wherein P is selected from phosphorus and silicon and M is selected from tungsten and molybdenum and combinations thereof.

9. The method of claim 1 , wherein the acid catalyst is a homogeneous Lewis acid 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 , and Sc(OCF 3 SO 2 ) 3 .

10. The method of claim 1 , wherein the acid catalyst is a heterogeneous Lewis acid obtained from interaction of a homogeneous Lewis acid catalyst and an organic or inorganic polymer compound.

11. The method of claim 1 , wherein step a) is carried out in the presence of a solvent selected from the group consisting of 1,4-dioxane, toluene, ethyl acetate, acetonitrile, sulfolane, 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl) imide, and mixtures thereof.

12. The method of claim 1 , wherein the P—O—P anhydride moiety comprising compound is gradually added to the compound with general formula R 1 —CH 2 —NX—CH 2 —R 2 while maintaining a temperature of step a) below 100° C.

13. The method of claim 1 , wherein the P—O—P anhydride moiety comprising compound is gradually added in step a) and wherein after completion of addition of the P—O—P anhydride moiety comprising compound, step a) is heated to a temperature between 20° C. and 100° C. and maintained at the temperature for a period of time between 1 hour and 24 hours.

14. The method of claim 1 , wherein the hydrolysis of step b) is performed at a temperature between 20° C. and 120° C., for a period between 10 minutes and 24 hours.

15. The method of claim 1 , wherein the hydrolysis of step b) is performed under alkali conditions.

16. The method of 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.

17. The method of claim 1 , further comprising converting the N-phosphonomethyliminodiacetic acid or a derivative thereof to N-(phosphonomethyl)glycine.

18. The method of claim 1 , wherein the compound of the following general formula R 1 —CH 2 —NX—CH 2 —R 2 is N-hydroxymethyliminodiacetic acid.

19. The method of claim 18 , 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.

20. The method of claim 19 , wherein the P—O—P anhydride moiety comprising compound is tetraphosphorus hexaoxide.

21. The method of claim 18 , further comprising converting the N-phosphonomethyliminodiacetic acid or a derivative thereof to N-(phosphonomethyl)glycine.

Assignees

• Monsanto Technology Llc

Inventors

• Devaux Albert
• Burck Sebastian
• Notte Patrick

Classifications

• C07F9/3808 Primary

  Acyclic saturated acids which can have further substituents on alkyl · CPC title

• C07F9/3813

  N-Phosphonomethylglycine; Salts or complexes thereof · CPC title