Process for producing phosphinates

Patent metadata

Field	Value
Publication number	US-10968241-B2
Application number	US-201916682348-A
Country	US
Kind code	B2
Filing date	Nov 13, 2019
Priority date	Sep 29, 2015
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

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 method for producing

glufosinate, or a salt thereof, wherein a phosphonous acid monoester of formula (I)

is employed as an intermediate, the method comprising:
(a) reacting a compound of formula (II)

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

to produce a compound of formula (I); and
(b) further reacting the compound of formula (I) with at least one further reactant to produce glufosinate or a salt thereof,
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, and
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 method according to claim 1 , wherein the total amount of water used in process step (a) is at least 0.8 molar equivalents, based on the total amount of compounds of formula (II) used.

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

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

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

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

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

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

9. The method 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 method according to claim 1 , wherein the reaction in process step (a) is carried out as a one-pot reaction.

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

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

13. The method 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 5 )-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 method 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 method according to claim 1 , wherein the compound of formula (I) is further reacted in process step (b) to produce a salt selected from the group consisting of ammonium salts, phosphonium salts, sulfonium salts, alkali metal salts and alkaline earth metal salts of glufosinate.

16. The method according to claim 1 , wherein the compound of formula (I) is further reacted in process step (b) to produce is glufosinate sodium or glufosinate ammonium.

Assignees

• Basf Se

Inventors

• Ressel Hans-Joachim

Classifications

• C07F9/4866 Primary

  the ester moiety containing a substituent or structure which is considered as characteristic · CPC title

• B01J27/16

  containing oxygen {, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr} · 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

• C07F9/4075

  Esters with hydroxyalkyl compounds · CPC title