Method for the synthesis of aminoalkylenephosphonic acid

Patent metadata

Field	Value
Publication number	US-10280189-B2
Application number	US-201314415686-A
Country	US
Kind code	B2
Filing date	Jul 17, 2013
Priority date	Jul 17, 2012
Publication date	May 7, 2019
Grant date	May 7, 2019

Abstract

A method for the synthesis of an aminoalkylenephosphonic acid or its phosphonate esters including the following steps: a) forming, in the presence of an aldehyde or ketone and an acid catalyst, a reaction mixture by mixing a compound having at least one HNR 1 R 2 moiety or a salt thereof, with a compound having one or more P—O—P anhydride moieties, the moieties having one P atom at the oxidation state (+III) and one P atom at the oxidation state (+III) or (+V), wherein the ratio of moles of aldehyde or ketone to N—H moieties is 1 or more and wherein the ratio of N—H moieties to P—O—P anhydride moieties is 0.3 or more, and b) recovering the resulting aminoalkylenephosphonic acid having compound or its phosphonate esters.

First claim

The invention claimed is:

1. A method for the synthesis of an aminoalkylenephosphonic acid or its phosphonate esters, comprising the following steps:
a) forming, in the presence of an aldehyde or ketone and an acid catalyst, a reaction mixture by mixing a compound (a.1.) comprising at least one HNR 1 R 2 moiety or a salt thereof, with a compound (a.2.) having one or more P—O—P anhydride moieties, said moieties comprising one P atom at the oxidation state (+III) and one P atom at the oxidation state (+III) or (+V), wherein the ratio of moles of aldehyde or ketone to N—H moieties is 1 or more and wherein the ratio of N—H moieties to P—O—P anhydride moieties is 0.3 or more,
and wherein:
the HNR 1 R 2 moiety comprising compound (a.1.) is characterized in that:
R 1 and R 2 are independently selected from the group consisting of hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 acyl, optionally comprising one or more heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur and optionally comprising one or more carbonyl moieties, wherein R 1 and R 2 may combine to form a 5-6 membered substituted or unsubstituted ring wherein N—H is incorporated in said ring,
and wherein:
the compound (a.2.) comprising one or more P—O—P anhydride moieties, with said moieties comprising one P atom at the oxidation state (+III) and one P atom at the oxidation state (+III) or (+V), 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;
and
b) recovering the resulting compound comprising aminoalkylene phosphonic acid or one of its phosponate esters.

2. The method according to claim 1 , wherein the ratio of N—H moieties to P—O—P moieties is comprised between 0.3 and 2.0.

3. The method according to claim 1 , wherein the reaction of step a) is performed at a temperature comprised between 20° C. and 120° C., for a period of time comprised between 30 minutes and 24 hours.

4. The method according to claim 1 comprising the additional steps of:
adding water to the reaction mixture after completion of the conversion of the HNR 1 R 2 moiety comprising compound into the aminoalkylenephosphonic acid comprising compound;
bringing the reaction mixture comprising the added water, to a temperature comprised between 20° C. and 150° 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 compound (a.2.) comprising the P—O—P anhydride moiety is selected from the group consisting of tetraphosphorus hexaoxide, and tetraethylpyrophosphite.

6. The method according to claim 1 , wherein the compound (a.2.) comprising the P—O—P anhydride moieties is tetraphosphorus hexaoxide.

7. The method according to claim 1 , wherein the aldehyde has the general formula R—CO—H and R is selected from the group consisting of hydrogen, aliphatic moiety, araliphatic moiety, aromatic moiety and heterocyclic moiety wherein the total number of carbon and hetero atoms is comprised between 1 and 11.

8. The method according to claim 1 , wherein the ketone has the general formula R′—CO—R″ and R′ and R″ are independently selected from the group consisting of aliphatic moiety, araliphatic moiety and aromatic hydrocarbon moiety wherein the total number of carbon atoms is comprised between 1 and 12.

9. The method according to claim 1 , wherein the aldehyde is formaldehyde.

10. 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, trifluoroacetic acid, p-toluenesulfonic acid, hydrochloric acid, phosphorous acid, phosphoric acid and mixtures thereof.

11. The method according to claim 1 , wherein the acid catalyst is a heterogeneous Brønsted acid selected from the group consisting of:
(i) solid acidic metal oxide combinations as such or supported by a carrier material;
(ii) cation exchange resins selected from the group comprising 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 medium 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 therefore; 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.

12. The method according to 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 .

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

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

15. The method according to claim 1 , which comprises the steps of:
a) forming a reaction mixture by mixing a compound (a.1.) comprising at least one HNR 1 R 2 moiety with an aldehyde or a ketone and an acid catalyst optionally in the presence of a solvent, to form a compound comprising at least one aminoalkylol moiety;
b) adding a compound (a.2.) comprising at least one P—O—P anhydride moiety, having one P atom at the oxidation state (+III) and one P atom at the oxidation state (+III) or (+V) to the reaction mixture of step a) comprising at least one aminoalkylol moiety, to form a compound comprising aminoalkylenephosphonic acid;
c) adding water to the reaction mixture of step b); and
d) recovering the resulting compound comprising aminoalkylenephosphonic acid or one of its phosphonate esters.

16. The method according to claim 1 , wherein the hydrolysis, after completion of the formation of the compound comprising aminoalkylenephosphonic acid, is performed at a pH comprised between 4.0 and 7.0.

17. The method according to claim 1 , wherein the hydrolysis, after completion of the formation of the compound comprising aminoalkylenephosphonic acid, is performed at a temperature comprised between 20° C. and 150° C. for a period comprised between 10 minutes and 72 hours.

18. The method according to claim 1 , wherein the ratio of N—H moieties to P—O—P moieties is comprised between 0.5 and 1.5.

19. The method according to claim 3 , wherein the reaction of step a) is performed for a period of time comprised between 1 hour and 20 hours.

20. The method according to claim 1 , wherein the reaction of step a) is performed at a temperature comprised between 40° C. and 100° C., for a period of time comprised between 30 minutes and 24 hours.

Assignees

• Monsanto Technology Llc

Inventors

• Burck Sebastian
• Leclercq Cedric Nicolas
• Notte Patrick

Classifications

• C07F9/653

  Five-membered rings · CPC title

• C07F9/3808 Primary

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

• C07F9/5728

  condensed with carbocyclic rings or carbocyclic ring systems · CPC title

• C07F9/6506

  having the nitrogen atoms in positions 1 and 3 · CPC title

• C07F9/572

  Five-membered rings · CPC title