Process for the preparation of alkylthioalkanoate salts

• US 4,777,289 A
• Filed: 05/08/1986
• Issued: 10/11/1988
• Est. Priority Date: 05/08/1986
• Status: Expired due to Term

• Current Assignee: Novus International, Inc. (Nippon Soda Company Limited)
• Original Assignee: Monsanto Company (Bayer AG)
• Inventors: Ruest, Dennis A.
• Primary Examiner(s): Shaver, Paul F.
• Assistant Examiner(s): Gray, Bruce D.
• Application Number:
  US06/860,949
• Time in Patent Office: 887 Days
• Field of Search: 562/581, 562/556, 562/559, 562/557, 562/606, 562/426, 562/427, 562/428, 568/69, 568/716
• US Class Current: 562/581
• CPC Class Codes: C07C 323/00 Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups

Abstract

A process for the preparation of alkylthioalkanoate salts by reaction of an alkali metal alkylmercaptide with a lactone in the presence of an aprotic polar organic solvent. Preferably, the alkali metal mercaptide is prepared by reaction of an alkylmercaptan and an alkali metal phenate.

Claims

1. A process for the preparation of a compound corresponding to the formula:

space="preserve" listing-type="equation">R.sup.1 --S--(CH.sub.2).sub.n --CH(R.sup.2)--C(O)--OM

where R¹ comprises a lower alkyl group, M is alkali metal, n is an integer between 2 and 4, inclusive and R² is selected from the group consisting of hydrogen, hydroxyl, amino,

space="preserve" listing-type="equation">--OR.sup.3, and

space="preserve" listing-type="equation">--NH--R.sup.4

where R³ is selected from the group consisting of alkyl and aryl, and R⁴ is selected from the group consisting of alkyl, aryl, and acyl, the process comprising;

reacting a lower alkyl mercaptan corresponding to the formula;

space="preserve" listing-type="equation">R.sup.1 --SH,

where R¹ is as defined above, with an alkali metal phenate to produce an alkali metal mercaptide corresponding to the formula;

space="preserve" listing-type="equation">R.sup.1 --S--M

where R¹ and M are as defined above; and

reacting said alkali metal mercaptide, in the presence of an aprotic polar organic solvent, with a lactone corresponding to the formula ##STR4## where R² and n are as defined above.

2. A process as set forth in claim 1 wherein said solvent has a dipole moment greater than 1 and a dielectric constant of greater than about 10.

3. A process as set forth in claim 2 wherein said solvent is selected from the group consisting of dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfoxide, tetramethylurea, pyridine, and ring substituted alkyl pyridines.

4. A process as set forth in claim 3 wherein said solvent comprises pyridine or a ring substituted alkyl pyridine.

5. A process as set forth in claim 1 wherein said alkali metal mercaptide is reacted with said lactone at a temperature of between about 80°

and about 150°

C.

6. A process as set forth in claim 1 wherein between about 1 and about 3 moles of said alkali metal mercaptide are charged per mole of said lactone.

7. A process as set forth in claim 1 wherein R¹ is methyl and R² is hydroxyl.

8. A process for the preparation of an alkythioalkanoate compound corresponding to the formula

View Dependent Claims (9, 10, 11, 12, 13)

9. A process as set forth in claim 8 wherein said solvent has a dipole moment greater than 1 and a dielectric constant greater than about 10.

10. A process as set forth in claim 9 wherein said solvent is selected from the group consisting of dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfoxide, tetramethylurea, pyridine, and ring substituted alkyl pyridines.

11. A process as set forth in claim 10 wherein said solvent is selected from the group consisting of pyridine and ring substituted alkyl pyridines.

12. A process as set forth in claim 8 wherein the reaction is carried out in a system to which said lower alkyl mercaptan and said lactone are charged in a ratio of between about 1 and about 3 moles of said lower alkyl mercaptan per mole of said lactone.

13. A process as set forth in claim 8 wherein R¹ is methyl and R² is hydroxyl.

14. A process for the preparation of a compound corresponding to the formula:

space="preserve" listing-type="equation">R.sup.1 --S--(CH.sub.2).sub.n --CH(R.sup.2)--C(O)--OM

where R¹ comprises a lower alkyl group, M is alkali metal, n is an integer between 2 and 4 inclusive, and R² is selected from the group consisting of hydrogen, hydroxyl, amino,

space="preserve" listing-type="equation">--OR.sup.3 and

space="preserve" listing-type="equation">--NH--R.sup.4

where R³ is selected from the group consisting of alkyl and aryl, and R⁴ is selected from the group consisting of alkyl, aryl, and acyl, the process comprising the steps of;

reacting a substituted or unsubstituted phenol with an alkali metal hydroxide in a crude base reaction system comprising a solvent selected from the group consisting of pyridine and aprotic ring substituted pyridines that form low boiling azeotropes with water;

removing water from said crude base reaction system by azeotropic distillation, thereby forming a substantially anhydrous base reagent mixture containing an alkali metal phenate;

reacting a lower alkyl mercaptan corresponding to the formula;

space="preserve" listing-type="equation">R.sup.1 --S--H

where R¹ is defined above, with said alkali metal phenate, thereby producing an alkali metal mercaptide corresponding to the formula;

space="preserve" listing-type="equation">R.sup.1 --S--M

where R¹ and M are as defined above; and

reacting said alkali metal mercaptide, in the presence of an aprotic polar organic solvent, with a lactone corresponding to the formula;

##STR6## where R² and n are as defined above.

15. A process as set forth in claim 14 wherein said alkali metal mercaptide is formed by reacting said alkylmercaptan with said alkali metal phenate in said anhydrous base reagent system.

16. A process as set forth in claim 15 wherein said lactone is reacted with said alkali metal mercaptide in the presence of a solvent selected from a group consisting of pyridine and ring substituted alkyl pyridines.

17. A process as set forth in claim 16 wherein said process is carried out in a system to which said mercaptan and said lactone are charged in a ratio of between about 1 and about 3 moles of said mercaptan per mole of said lactone.

18. A process as set forth in claim 14 wherein R¹ is methyl and R² is hydroxyl.

19. A process for the preparation of an alkylthioalkanoate compound corresponding to the formula:

space="preserve" listing-type="equation">R.sup.1 --S--(CH.sub.2).sub.n --CH(R.sup.2)--C(O)--OM

where R¹ comprises a lower alkyl group, M is alkali metal, n is an integer between 2 and 4, inclusive, and R² is selected from the group consisting of hydrogen, hydroxyl, amino,

space="preserve" listing-type="equation">--OR.sup.3 and

space="preserve" listing-type="equation">--NH--R.sup.4

where R³ is selected from the group consisting of alkyl and aryl, and R⁴ is selected, from the group consisting of alkyl, aryl, and acyl, the process comprising the steps of;

reacting a substituted or unsubstituted phenol with an alkali metal hydroxide in a crude base reaction system comprising a solvent selected from the group consisting of pyridine and aprotic ring substituted pyridines that form low boiling azeotropes with water;

removing water from said crude base reaction system by azeotropic distillation, thereby forming a substantially anhydrous base reagent mixture;

preparing a final reaction mixture by admixing with said anhydrous base reagent mixture a lower alkylmercaptan corresponding to the formula;

space="preserve" listing-type="equation">R.sup.1 --S--H

where R¹ is as defined above, and a lactone corresponding to the formula;

##STR7## where R² and n are as defined above; and

maintaining the final reaction mixture at a temperature of at least 80°

C. for a time sufficient to form said alkylthioalkanoate compound.

20. A process as set forth in claim 19 wherein said solvent has a dipole moment of at least 1 and a dielectric constant of least about 10.

21. A process as set forth in claim 20 wherein said solvent is selected from the group consisting of dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfoxide, tetramethylurea, pyridine, and ring substituted alkyl pyridines.

22. A process as set forth in claim 21 wherein said solvent comprises pyridine or a ring substituted alkyl pyridine.

23. A process for the preparation of a compound corresponding to the formula:

space="preserve" listing-type="equation">CH.sub.3 --S--(CH.sub.2).sub.2 --CH(R.sup.2)--C(O)--OM

where M is alkali metal and R² is selected from the group consisting of hydrogen, hydroxyl, amino,

space="preserve" listing-type="equation">--OR.sup.3 and

space="preserve" listing-type="equation">--N--R.sup.4

where R³ is selected from the group consisting of alkyl and aryl, and R⁴ is selected from the group consisting of alkyl, aryl, and acyl, the process comprising reacting methylmercaptan with an alkali metal phenate to produce a alkali metal methylmercaptide corresponding to the forumla;

space="preserve" listing-type="equation">CH.sub.3 --S--M,

where M is as defined above; and

reacting said alkali metal methylmercaptide, in the presence of an aprotic polar organic solvent, with a lactone corresponding to the formula;

##STR8## where R² is as defined above.

24. A process for the preparation of a methylthiobutyrate compound corresponding to the formula:

space="preserve" listing-type="equation">CH.sub.3 --S--(CH.sub.2).sub.2 --CH(R.sup.2)--C(O)--OM

where M is alkali metal and R² is selected from the group consisting of hydrogen, hydroxyl, amino,

space="preserve" listing-type="equation">--OR.sup.3 and

space="preserve" listing-type="equation">--NH--R.sup.4

where R³ is selected from the group consisting of alkyl and aryl, and R⁴ is selected from the group consisting of alkyl, aryl, and acyl, the process comprising admixing and reacting, in the presence of an aprotic polar organic solvent, methylmercaptan, an alkali metal phenate and a lactone corresponding to the formula;

##STR9## where R² is as defined above; and

maintaining the resulting mixture at a temperature of at least 80°

C. for a time sufficient to form said methylthiobutyrate compound.

25. A process for the preparation of a compound corresponding to the formula:

space="preserve" listing-type="equation">CH.sub.3 --S--(CH.sub.2).sub.2 --CH(R.sup.2)--C(O)--OM

where M is alkali metal and R² is selected from the group consisting of hydrogen, hydroxyl, amino,

space="preserve" listing-type="equation">--OR.sub.3 and

space="preserve" listing-type="equation">--NH--R.sup.4

where R³ is selected from the group consisting of alkyl and aryl, and R⁴ is selected from the group consisting of alkyl, aryl, and acyl, the process comprising the steps of;

reacting a substituted or unsubstituted phenol with an alkali metal hydroxide in a crude base reaction system comprising a solvent selected from the group consisting of pyridine and aprotic ring substituted pyridines that form low boiling azeotropes with water;

removing water from said crude base reaction system by azeotropic distillation, thereby forming a substantially anhydrous base reagent mixture containing an alkali metal phenate;

reacting methylmercaptan with said alkali metal phenate, thereby producing an alkali metal mercaptide corresponding to the formula;

space="preserve" listing-type="equation">CH.sub.3 --S--M

where M is as defined above; and

reacting said alkali metal mercaptide, in the presence of an aprotic polar organic solvent, with a lactone corresponding to the formula;

##STR10## where R² is as defined above.

26. A process for the preparation of a methylthiobutyrate compound corresponding to the formula:

space="preserve" listing-type="equation">CH.sub.3 --S--(CH.sub.2).sub.2 --CH(R.sup.2)--C(O)--OM

where M is alkali metal and R² is selected from the group consisting of hydrogen, hydroxyl, amino,

space="preserve" listing-type="equation">--OR.sup.3 and

space="preserve" listing-type="equation">--NH--R.sup.4

where R³ is selected from the group consisting of alkyl and aryl, and R⁴ is selected from the group consisting of alky, aryl, and acyl, the process comprising the steps of;

reacting a substituted or unsubstituted phenol with an alkali metal hydroxide in a crude base reaction system comprising a solvent selected from the group consisting of pyridine and aprotic ring substituted pyridines that form low boiling azeotropes with water;

removing water from said crude base reaction system by azeotropic distillation, thereby forming a substantially anhydrous base reagent mixture;

preparing a final reaction mixture by admixing with said anhydrous base reagent mixture methylmercaptan and a lactone corresponding to the formula;

##STR11## where R² is as defined above; and

maintaining the final reaction mixture at a temperature of at least about 80°

C. for a time sufficient to form said methylthiobutyrate compound.