Process for preparing organotin compounds

• US 4,174,346 A
• Filed: 06/02/1977
• Issued: 11/13/1979
• Est. Priority Date: 01/30/1976
• Status: Expired due to Term

• Current Assignee: Albright & Wilson Limited
• Original Assignee: Albright & Wilson Limited
• Inventors: Collins, John D., Wood, Donald A.
• Primary Examiner(s): Sneed, Helen M. S.
• Application Number:
  US05/802,626
• Time in Patent Office: 894 Days
• Field of Search: 260/429.7
• US Class Current: 556/88
• CPC Class Codes: C07F 7/2208 Compounds having tin linked only to carbon, hydrogen and/or halogen
• CPC Class Codes: C07F 7/2224 Compounds having one or more tin-oxygen linkages

Abstract

Tricycloalkyltin chlorides e.g. tricyclohexyltin chlorides, which may be converted to the fungicide tricyclohexyl hydroxide, are made by reacting an organic tricycloalkyltin, in which the organic is not cycloalkyl and cycloalkyl is optionally substituted cyclohexyl, with organic tin trihalide.

Claims

1. A process for preparing a tricycloalkyltin compound, which comprises reacting at a temperature of between 110°

C. and 180°

C.

an organotricycloalkyltin of formula RSnR₃ ", wherein R" is a cycloalkyl group selected from the group consisting of cyclohexyl and cyclohexyl substituted by at least one inert substituent, and R is a radical selected from the group consisting of alkyl, alkenyl, aralkyl and aryl groups,

with an organotin trichloride of formula R'"'"'SnCl₃, wherein R'"'"' is an organic group,

the molar ratio of said organotricycloalkyltin to said organotin trichloride being between 0.8;

1 and 1;

1.2,

to form a mixture comprising tricycloalkyltin chloride and a diorganotin dichloride.

2. A process according to claim 1 wherein the reaction is performed at between 130°

C. and 150°

C.

3. A process according to claim 1 wherein the reaction is carried out in the absence of a liquid diluent.

4. A process according to claim 1 wherein R is an alkyl group of 1-8 carbon atoms.

5. A process according to claim 1 wherein R'"'"' is an alkyl group of 1-8 carbon atoms.

6. A process according to claim 3 wherein R and R'"'"' are the same alkyl group of 1-8 carbon atoms.

7. A process according to claim 6 wherein R and R'"'"' are butyl groups.

8. A process according to claim 1 wherein the tricycloalkyltin chloride is separated from the diorganotin dichloride by preferential crystallization of the tricycloalkyltin chloride from a solution of the mixture.

9. A process according to claim 8 wherein the tricycloalkyltin chloride is crystallized from isopropanol solution.

10. A process according to claim 1 wherein a mixture of tricycloalkyltin chloride with the diorganotin dichloride in solution in an inert liquid water immiscible organic diluent is treated with an aqueous base to form an organic phase comprising tricycloalkyltin hydroxide, an aqueous phase and a precipitate of diorganotin oxide or hydroxide and then separating the tricycloalkyltin hydroxide from the organic phase.

11. A process according to claim 1 wherein a portion of said tricycloalkyltin chloride in said mixture is removed to form a residue containing the remaining portion of tricycloalkyltin chloride and said diorganotin dichloride, and said residue is treated with an aqueous base to form an organic phase comprising tricycloalkyltin hydroxide, an aqueous phase and a precipitate of diorganotin oxide or hydroxide and then separating the tricycloalkyltin hydroxide from the organic phase.

12. A process according to claim 1 wherein the organotin trichloride has been made by reaction of an organotricycloalkyltin of formula R'"'"'SnR₃ " with stannic chloride.

14. A process according to claim 5, wherein said organotricycloalkyltin is an alkyltricyclohexyltin in which the alkyl group R has 1-8 carbon atoms, wherein R is the same as R'"'"', and wherein said reaction is at a temperature between 120°

C. and 160°

C. and in the absence of a liquid diluent to form a mixture comprising tricyclohexyltin chloride and dialkyltin dichloride.

18. A process according to claim 14 wherein said second mixture in solution in an inert water immiscible organic solvent is treated with an aqueous solution of base to form an organic phase comprising tricyclohexyltin hydroxide, an aqueous phase and a precipitate of dialkyltin oxide or hydroxide and then the tricyclohexyltin hydroxide is separated from said organic phase.

19. A process according to claim 1 wherein R and R'"'"' are the same alkyl group of 1-8 carbon atoms.

20. A process according to claim 3 wherein the tricycloalkyltin chloride is separated from the diorganotin dichloride by preferential crystallization of the tricycloalkyltin chloride from a solution of the mixture.

21. A process according to claim 3 wherein the tricycloalkyltin chloride is separated from the diorganotin dichloride by preferential crystallization of the tricycloalkyltin chloride from an isoproponol solution of the mixture.

22. A process according to claim 3 wherein a mixture of tricycloalkyltin chloride with the diorganotin dichloride in solution in an inert liquid water immiscible organic diluent is treated with an aqueous base to form an organic phase comprising tricycloalkyltin hydroxide, an aqueous phase and a precipitate of diorganotin oxide or hydroxide and then separating the tricycloalkyltin hydroxide from the organic phase.

23. A process according to claim 3 wherein a portion of said tricycloalkyltin chloride in said mixture is removed to form a residue containing the remaining portion of tricycloalkyltin chloride and said diorganotin dichloride, and said residue is treated with an aqueous base to form an organic phase comprising tricycloalkyltin hydroxide, an aqueous phase and a precipitate of diorganotin oxide or hydroxide and then separating the tricycloalkyltin hydroxide from the organic phase.

24. A process according to claim 14 wherein R and R'"'"' are butyl.

25. A process according to claim 14 wherein the tricyclohexyltin chloride is crystallized from isopropanol solution of the said mixture.

26. A process according to claim 1 wherein said organotin trichloride is made by reacting an organotricycloalkyltin with stannic chloride in a molar ratio of between 1.8:

1 and 2.2;

1 at a temperature of less than 100°

C. to form (i) tricycloalkyltin chloride, (ii) said organotin trichloride and (iii) excess organotricycloalkyltin, and (ii) and (iii) are then reacted at said temperature of between 110°

C. and 180°

C. to form additional tricycloalkyltin chloride and diorganotin dichloride.

27. A process according to claim 4 wherein said organotin trichloride is made by reacting an organotricycloalkyltin with stannic chloride in a molar ratio of between 1.8:

1 and 2.2;

1 at a temperature of less than 100°

C. to form (i) tricycloalkyltin chloride, (ii) said organotin trichloride and (iii) excess organotricycloalkyltin, and (ii) and (iii) are then reacted at said temperature of between 110°

C. and 180°

C. to form additional tricycloalkyltin chloride and diorganotin dichloride.

28. A process according to claim 7 wherein said organotin trichloride is made by reacting an organotricycloalkyltin with stannic chloride in a molar ratio of between 1.8:

1 and 2.2;

1 at a temperature of less than 100°

C. to form (i) tricycloalkyltin chloride, (ii) said organotin trichloride and (iii) excess organotricycloalkyltin, and (ii) and (iii) are then reacted at said temperature of between 110°

C. and 180°

C. to form additional tricycloalkyltin chloride and diorganotin dichloride.

29. A process according to claim 3 wherein the reaction is performed at 120°

-160°

C.

30. A process according to claim 29 wherein R is an alkyl group of 3-8 carbon atoms.

31. A process according to claim 30 wherein the tricycloalkyltin chloride is separated from the diorganotin dichloride by preferential crystallization of the tricycloalkyltin chloride from an isopropanol solution of the mixture.

32. A process according to claim 3 wherein the reaction is performed at 130°

-150°

C. for 1-5 hours.

33. A process according to claim 30 wherein R is butyl.

34. A process according to claim 26 wherein the organotricycloalkyltin and stannic chloride are reacted in solution below 100°

C. and the subsequent reaction is carried out at 120°

-160°

C. in the absence of a liquid diluent.

35. A process according to claim 27 wherein the organotricycloalkyltin and stannic chloride are reacted in solution below 100°

C. and the subsequent reaction is carried out at 120°

-160°

C. in the absence of a liquid diluent.

36. A process according to claim 28 wherein the organotricycloalkyltin and stannic chloride are reacted in solution below 100°

C. and the subsequent reaction is carried out at 120°

-160°

C. in the absence of a liquid diluent.

38. A process according to claim 10 wherein said diorganotin dichloride is a dialkyltin dichloride wherein each alkyl group contains 3-8 carbon atoms.

39. A process according to claim 11 wherein said diorganotin dichloride is a dialkyltin dichloride wherein each alkyl group contains 3-8 carbon atoms.

41. A process according to claim 14 wherein said second mixture of tricyclohexyltin chloride and dialkyltin dichloride, in which the alkyl groups contain 3-8 carbon atoms in solution in an inert water immiscible organic solvent, is treated with an aqueous solution of base to form an organic phase containing tricyclohexyltin hydroxide, and an aqueous phase and a precipitate of dialkyl oxide or hydroxide, and then the tricyclohexyltin hydroxide is recovered from said organic phase.

13. A process for preparing a tricycloalkyltin compound wherein an organotricycloalkyltin of formula RSnR₃ ", wherein R is a radical selected from the group consisting of alkyl, alkenyl, aralkyl and aryl groups and R" is a cycloalkyl group selected from the group consisting of cyclohexyl and cyclohexyl substituted by at least one inert substituent, and stannic chloride are mixed in a molar ratio of between 1.8:

1 and 2.2;

1 and the mixture heated at a temperature of 130°

-180°

C. to form a second mixture comprising tricycloalkyltin chloride and diorganotin dichloride.

15. A process according to claim 13 wherein R and R'"'"' are butyl.

16. A process according to claim 13 wherein the tricyclohexyltin chloride is crystallized from isopropanol solution of the said mixture.

17. A process according to claim 13 wherein said second mixture in solution in an inert water immiscible organic solvent is treated with an aqueous solution of base to form an organic phase comprising tricyclohexyltin hydroxide, an aqueous phase and a precipitate of dialkyltin oxide or hydroxide and then the tricyclohexyltin hydroxide is separated from said organic phase.

37. A process according to claim 13 wherein the organotricycloalkyltin and stannic chloride are reacted in solution below 100°

C. and the subsequent reaction is carried out at 120°

-160°

C. in the absence of a liquid diluent.

40. A process according to claim 13 wherein said second mixture of tricyclohexyltin chloride and dialkyltin dichloride, in which the alkyl groups contain 3-8 carbon atoms in solution in an inert water immiscible organic solvent, is treated with an aqueous solution of base to form an organic phase containing tricyclohexyltin hydroxide, and an aqueous phase and a precipitate of dialkyl oxide or hydroxide, and then the tricyclohexyltin hydroxide is recovered from said organic phase.