Methods for producing and purifying organotin compounds, suppressing formation of dialkyl tin compounds and selectively removing tetrakis(dialkylamino) tin compounds

Patent metadata

Field	Value
Publication number	US-2025101051-A1
Application number	US-202418825707-A
Country	US
Kind code	A1
Filing date	Sep 5, 2024
Priority date	Sep 8, 2023
Publication date	Mar 27, 2025
Grant date	—

Abstract

Aspects of the disclosure relate to methods for producing organotin compounds with high purity, which may involve the use of specific additives or reaction conditions. Methods for purifying organotin compounds and suppressing the formation of impurities in organotin compounds are also described.

First claim

We claim:

1 . A method for synthesizing a monoalkyl tin triamide compound having formula (1) by reacting a monoalkyl tin trihalide compound having formula (5) with a metal amide compound having formula (6) or (7), wherein the reaction is performed in the presence of tin a tetrahalide having formula (4):
R 1 Sn(NR 1 ′ 2 ) 3   (1)
SnX 4   (4)
R 1 SnX 3   (5)
M 1 NR 1 ′ 2   (6)
M 2 (NR 1 ′ 2 ) 2   (7)

wherein R 1 is an alkyl group having about 1 to 30 carbon atoms which may be substituted with at least one halogen, oxygen, or nitrogen atom; R 1 ′ is an alkyl group having about 1 to 10 carbon atoms; M 1 is a monovalent metal, M 2 is a divalent metal, and each X is independently F, Cl, Br, or I.

2 . A method of synthesizing a monoalkyl tin triamide compound having formula (1):
R 1 Sn(NR 1 ′ 2 ) 3   (1)

wherein R 1 and R 1 ′ are each independently a primary alkyl group having about 1 to about 10 carbon atoms or a secondary alkyl group having about 3 to about 10 carbon atoms, the method comprising:
(a) preparing a metal dialkylamide solution
(b) preparing a mixture comprising a tin tetrahalide compound having formula (4) and a monoalkyl tin trihalide compound having formula (5); and
(c) adding the mixture to the metal dialkylamide solution:
SnX 4   (4)

R 1 SnX 3   (5)

wherein each X is independently F, Cl, Br, or I.

3 . A method of synthesizing a monoalkyl tin triamide compound having formula (1) and containing no detectable amount of a dialkyl tin diamide compound having formula (2):
R 1 Sn(NR 1 ′ 2 ) 3   (1)
R 1 2 Sn(NR 1 ′ 2 ) 2   (2)

wherein R 1 and R 1 ′ are each independently a primary alkyl group having about 1 to about 10 carbon atoms or a secondary alkyl group having about 3 to about 10 carbon atoms, the method comprising:
(a) lithiating a dialkylamine in a solution containing a first solvent to produce a lithium dialkylamide having a concentration in the solution of up to about 10 wt %;
(b) preparing a premix solution comprising tetrachlorotin and an alkyltrichloro tin compound R 1 SnCl 3 in a second solvent, wherein an amount of the tetrachlorotin in the premix solution is about 0.1 to about 5 mol % relative to the amount of the alkyl trichlorotin compound;
(c) adding the premix solution to the lithium dimethylamide at about −10° C. to about 10° C. to produce a reaction mixture, wherein the amount of lithium dimethylamide in the reaction mixture is at least about 3.09 equivalents relative to the amount of the alkyl trichlorotin compound;
(d) removing the LiCl salt product by filtration; and
(e) removing the first solvent and the second solvent under vacuum to produce a product containing the monoalkyl tin triamide having formula (1) and no detectable amount of the dialkyl tin diamide compound having formula (2).

4 . A method of synthesizing a monoalkyl tin triamide compound having formula (1) and containing no detectable amount of a dialkyl tin diamide compound having formula (2):
R 1 Sn(NR 1 ′ 2 ) 3   (1)
R 12 Sn(NR 1′ 2 ) 2   (2)

wherein R 1 and R 1 ′ are each independently a primary alkyl group having about 1 to about 10 carbon atoms or a secondary alkyl group having about 3 to about 10 carbon atoms, the method comprising:
(a) lithiating a dialkylamine in a solution containing a first solvent to produce a lithium dimethylamide having a concentration in the solution of up to about 10 wt %;
(b) adding a solution of tetrachlorotin in a second solvent to the lithium dialkylamide at about −15° C. to about 0° C. to produce a reaction mixture containing about 0.3% to about 2 mol % tetrakis(dialkylamino) tin relative to an amount of the lithium dialkylamide;
(c) adding a solution of an alkyl trichlorotin compound R 1 SnCl 3 in a third solvent to the reaction mixture at about −15° C. to about 10° C., wherein the amount of lithium dimethylamide in the reaction mixture is at least about 3.09 equivalents relative to the amount of the alkyl trichlorotin compound and wherein the amount of tetrachlorotin in the reaction mixture is about 0.1 mol % to about 5 mol % relative to the amount of the alkyl trichlorotin compound;
(d) removing the LiCl salt product by filtration; and
(e) removing the first solvent, the second solvent, and the third solvent under vacuum to produce a product containing the monoalkyl tin triamide having formula (1) and no detectable amount of the dialkyl tin diamide compound having formula (2).

5 . A method of synthesizing a monoalkyl tin triamide compound having formula (1) and containing no detectable amount of a dialkyl tin diamide compound having formula (2):
R 1 Sn(NR 1 ′ 2 ) 3   (1)
R 12 Sn(NR 1′ 2 ) 2   (2)

wherein R 1 and R 1′ are each independently a primary alkyl group having about 1 to 10 carbon atoms or a secondary alkyl group having about 3 to 10 carbon atoms, the method comprising:
(a) lithiating a dialkylamine in a solution containing a first solvent to produce a lithium dimethylamide having a concentration in the solution of up to about 10 wt %;
(b) adding a solution of tetrakis(dialkylamino) tin in a second solvent to the lithium dimethylamide at about −15° C. to about 0° C. to produce a reaction mixture, wherein an amount of tetrakis(dialkylamino) tin in the reaction mixture is about 0.3 mol % to about 2 mol % relative to the amount of the lithium dialkylamide;
(c) adding a solution of an alkyl trichlorotin compound R 1 SnCl 3 in a third solvent to the reaction mixture at about −15° C. to about 0° C., wherein the amount of lithium dimethylamide in the reaction mixture is at least about 3.09 equivalents relative to the amount of the alkyl trichlorotin compound;
(d) removing the LiCl salt product by filtration; and
(e) removing the first solvent, the second solvent, and the third solvent under vacuum to produce a product containing the monoalkyl tin triamide having formula (1) and no detectable amount of the dialkyl tin diamide compound having formula (2).

6 . The method according to claim 3 , wherein R 1 is an isopropyl group and the compound having formula (1) has formula (3):

7 . The method according to claim 4 , wherein R 1 is an isopropyl group and the compound having formula (1) has formula (3):

8 . The method according to claim 5 , wherein R 1 is an isopropyl group and the compound having formula (1) has formula (3):

9 . The method according to claim 1 , wherein R 1 is an isopropyl group and the compound having formula (1) has formula (3):

10 . The method according to claim 6 , wherein the compound having formula (1) contains no detectable amount of substances having a chemical shift in a 119 Sn NMR spectrum around −84 ppm.

11 . The method according to claim 7 , wherein the compound having formula (1) contains no detectable amount of substances having a chemical shift in a 119 Sn NMR spectrum around −84 ppm.

12 . The method according to claim 8 , wherein the compound having formula (1) contains no detectable amount of substances having a chemical shift in a 119 Sn NMR spectrum around −84 ppm.

13 . A method for producing a tin composition (P1) comprising a monoalkyl tin compound having formula (A1) and a purity of at least about 80 mol %, t

Assignees

• Gelest Inc
• Mitsubishi Chem Corp

Inventors

• Yang Li
• Nguyen Thao
• Ishii Koki
• Hioki Yuta
• MATSUZAKA Koki

Classifications

• C07F7/2224

  Compounds having one or more tin-oxygen linkages · CPC title

• C07F7/2208

  Compounds having tin linked only to carbon, hydrogen and/or halogen · CPC title

• C07F7/2296

  Purification, stabilisation, isolation · CPC title

• C07F7/2284 Primary

  Compounds with one or more Sn-N linkages · CPC title