Process for producing phosphinates

Patent metadata

Field	Value
Publication number	US-10501485-B2
Application number	US-201615763398-A
Country	US
Kind code	B2
Filing date	Sep 26, 2016
Priority date	Sep 29, 2015
Publication date	Dec 10, 2019
Grant date	Dec 10, 2019

Abstract

The present invention relates primarily to a process for producing particular phosphinates (phosphonous acid monoesters) and use thereof for producing biologically active substances which may be used in the pharmaceutical or agrochemical sector, preferably for producing phosphorus-containing amino acids.

First claim

The invention claimed is:

1. A process for producing a compound of formula (I)

comprising reacting a compound of formula (II)

with a compound of formula (III)
R 2 —OH  (III)

wherein in each case:
R 1 represents (C 1 -C 12 )-alkyl, (C 1 -C 12 )-haloalkyl, (C 6 -C 10 )-aryl, (C 6 -C 10 )-haloaryl, (C 7 -C 10 )-aralkyl, (C 7 -C 10 )-haloaralkyl, (C 4 -C 10 )-cycloalkyl or (C 4 -C 10 )-halocycloalkyl,
R 2 represents (C 3 -C 12 )-alkyl, (C 3 -C 12 )-haloalkyl, (C 6 -C 10 )-aryl, (C 6 -C 10 )-haloaryl, (C 7 -C 10 )-aralkyl, (C 7 -C 10 )-haloaralkyl, (C 4 -C 10 )-cycloalkyl or (C 4 -C 10 )-halocycloalkyl,
R 3 and R 4 each independently of one another represent methyl or ethyl,
in the presence of an acidic catalyst and in the presence of water.

2. The process according to claim 1 , wherein the total amount of water used is at least 0.8 molar equivalents, based on the total amount of compounds of formula (II) used.

3. The process according to claim 1 , wherein the total amount of water used is 1 to 5 molar equivalents, based on the total amount of compounds of formula(II) used.

4. The process according to claim 1 , wherein the total amount of water used is 1 to 3 molar equivalents, based on the total amount of compounds of formula (II) used.

5. The process according to claim 1 , wherein the total amount of water used is 1 to 2 molar equivalents, based on the total amount of compounds of formula (II) used.

6. The process according to claim 1 , wherein the total amount of compounds of formula (III) used is 1 to 25 molar equivalents, based on the total amount of compounds of formula (II) used.

7. The process according to claim 1 , wherein the total amount of compounds of formula (III) used is 3 to 15 molar equivalents, based in each case on the total amount of compounds of formula (II) used.

8. The process according to claim 1 , wherein the pKa of the acidic catalyst under standard conditions is less than 3.

9. The process according to claim 1 , wherein the acidic catalyst is selected from the group consisting of H 3 PO 3 , H 2 SO 4 , HCl, HBr, HClO 4 , dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, methanesulphonic acid, trifluoromethanesulphonic acid, benzenesulphonic acid, p-toluenesulphonic acid, acidic ion exchangers, acidic polysiloxanes and acidic zeolites.

10. The process according to claim 1 , wherein the reaction is carried out as a one-pot reaction.

11. The process according to claim 1 , wherein the reaction is carried out at a temperature in a range from 30 to 140° C.

12. The process according to claim 1 , wherein the reaction is carried out in an inert diluent or diluent-free.

13. The process according to claim 1 , wherein
R 1 represents (C 1 -C 6 -alkyl, (C 1 -C 6 )-haloalkyl, (C 6 -C 8 -aryl, (C 6 -C 8 -haloaryl, (C 7 -C 10 )-aralkyl, (C 7 -C 10 )-haloaralkyl, (C 5 -C 8 -cycloalkyl or (C 5 -C 8 -halocycloalkyl,
and
R 2 represents (C 3 -C 8 )-alkyl, (C 3 -C 8 )-haloalkyl, (C 6 -C 8 -aryl, (C 6 -C 8 -haloaryl, (C 7 -C 10 )-aralkyl, (C 7 -C 10 )-haloaralkyl, (C 5 -C 8 -cycloalkyl or (C 5 -C 8 -halocycloalkyl.

14. The process according to claim 1 , wherein
R 1 represents (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl or (C 6 -C 8 -aryl
R 2 represents (C 3 -C 6 -alkyl or (C 3 -C 6 )-haloalkyl.

15. The process according to claim 1 , wherein
R 1 represents methyl or ethyl,
R 2 represents C 4 -alkyl or C 5 -alkyl.

16. The process according to claim 1 , wherein the total amount of water used is at least 0.95 molar equivalents, based on the total amount of compounds of formula (II) used.

17. The process according to claim 1 , wherein the total amount of compounds of formula (III) used is 5 to 10 molar equivalents, based on the total amount of compounds of formula (II) used.

18. The process according to claim 1 , wherein the pKa of the acidic catalyst under standard conditions is less than 2.

19. The process according to claim 1 , wherein the reaction is carried out at a temperature in a range from 50 to 120° C.

Assignees

• Basf Se

Inventors

• Ressel Hans-Joachim

Classifications

• C07F9/4075

  Esters with hydroxyalkyl compounds · CPC title

• C07F9/3223

  Esters of cycloaliphatic acids · CPC title

• C07F9/3211 Primary

  Esters of acyclic saturated acids which can have further substituents on alkyl · CPC title

• A61K31/662

  Phosphorus acids or esters thereof having P—C bonds, e.g. foscarnet, trichlorfon · CPC title

• A01N57/02

  having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34 · CPC title