Process for preparation of thiophosphoryl chloride and acephate

Patent metadata

Field	Value
Publication number	US-12281131-B2
Application number	US-202017770083-A
Country	US
Kind code	B2
Filing date	Oct 13, 2020
Priority date	Oct 19, 2019
Publication date	Apr 22, 2025
Grant date	Apr 22, 2025

Abstract

The present invention discloses an improved process for preparation of acephate and intermediates thereof. More particularly, the present invention relates to a process for preparation of thiophosphoryl chloride useful for commercial production of pesticides and pharmaceutically active compounds.

First claim

The invention claimed is:

1. A process for preparing of thiophosphoryl chloride comprising reacting phosphorus trichloride with sulfur, in thiophosphoryl chloride, in the presence a base, wherein said reacting is carried out within a period of less than 60 minutes and said process is recycled for 5 to 7 cycles.

2. The process as claimed in claim 1 wherein said base is a trialkylamine.

3. The process as claimed in claim 2 wherein said trialkylamine base is tributylamine.

4. The process as claimed in claim 2 wherein said base is in an amount in the range of 0.01-0.08 per mole fraction of phosphorus trichloride.

5. The process as claimed in claim 1 wherein a molar ratio of phosphorus trichloride and sulfur is about 1:1.

6. The process as claimed in claim 1 wherein said reaction is carried out at a temperature in range of 100-150° C.

7. The process as claimed in claim 1 wherein said reaction is carried out at normal atmospheric pressure.

8. The process as claimed in claim 1 further comprising distilling pure thiophosphoryl chloride from the reaction mixture leaving behind a distillation heel.

9. The process as claimed in claim 8 further comprising recycling the distillation heel to a subsequent reaction stage of the phosphorous trichloride and sulfur to produce the thiophosphoryl chloride.

10. The process as claimed in claim 9 wherein said recycling after a first stage is operated for more than 50 cycles to produce pure thiophosphoryl chloride.

11. The process as claimed in claim 10 wherein said reacting is carried out at a temperature in range of 100-150° C.

12. A process for preparing acephate comprising
a) preparing thiophosphoryl chloride, and
b) converting the thiophosphoryl chloride to acephate,
wherein said step a) comprises treating phosphorus trichloride, thiophosphoryl chloride and sulfur in the presence of a tributyl amine catalyst to obtain the thiophosphoryl chloride for a period of less than 60 minutes.

13. The process as claimed in claim 11 wherein the base is.

14. The process as claimed in claim 12 further comprising distilling pure thiophosphoryl chloride from the reaction mixture leaving behind a distillation heel.

15. The process as claimed in claim 14 further comprising recycling the distillation heel to a subsequent reaction stage of the phosphorous trichloride and sulfur to produce the thiophosphoryl chloride.

16. The process as claimed in claim 12 , wherein said conversion in step b) comprises at least one step selected from
(i) treating thiophosphoryl chloride with methanol to obtain O-methyl phosphorodichloridothioate,
(ii) treating O-methyl phosphorodichloridothioate with methanol to obtain O,O-dimethyl phosphorochloridothioate; or
(iii) treating O,O-dimethyl phosphorochloridothioate with base to obtain O,O-dimethyl phosphoramidothioate.

17. The process as claimed in claim 16 further comprises acetylating O,O-dimethyl phosphoramidothioate in presence of acetic anhydride to obtain acephate.

18. The process as claimed in claim 12 , wherein reacting proceeds by isolating each step product, without isolating each step product, or as continuous process.

19. The process as claimed in claim 1 wherein thiophosphoryl chloride is obtained with a purity of at least 95%.

Assignees

• Upl Ltd

Inventors

• Shroff Rajju Devidas
• Prasad Vic
• Desai Amul Manubhai
• Wankhade Gopalrao Atul
• Kataria Lilaram Kamal
• Tiwari Raj Kumar
• ARORA Raj Kumar

Classifications

• C01P2006/80

  Compositional purity · CPC title

• C01B25/14 Primary

  Sulfur, selenium, or tellurium compounds of phosphorus · CPC title

• C07F9/2487 Primary

  containing the structure P(=X)n-N-C(=X) (X = O, S, Se; n = 0, 1) · CPC title

• A01N57/28

  containing acyclic or cycloaliphatic radicals · CPC title

• C07F9/2479

  Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) · CPC title