High purity monoorgano tin compounds and methods for preparation thereof

A method of synthesizing a monoorgano tin compound having formula (1) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorgano tin compound having formula (2):

• R′SnX3 (1)
• R′2SnX2 (2)
• wherein R′ has formula [I] or [II], and X is selected from NR2 and OR, wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms which is optionally substituted with one or more halogen atoms, the method comprising reacting a compound containing an R′ group with a compound having formula SnX4;
• [I] CRaRbRc, wherein Ra is an aromatic ring having about 3 to about 10 carbon atoms which is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms, Rb and Rc are each independently hydrogen or a hydrocarbyl substituent having about 1 to about 10 carbon atoms, wherein each hydrocarbyl substituent is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms;
• [II] CRARBRC, wherein RA is (CH2)nORE, n is 0, 1, or 2, RE is a saturated hydrocarbon group having 1 to about 10 carbon atoms, RB and RC are each independently hydrogen or a saturated hydrocarbon group having about 1 to about 10 carbon atoms, wherein R′ contains about 2 to about 20 carbon atoms, wherein RA and one of RB and RC optionally form a 3 to 8-membered ring containing an ether linkage.

A method of synthesizing a monoorgano tin compound having formula (1) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorgano tin compound having formula (2):

• R′SnX3 (1)
• R′2SnX2 (2)
• wherein R′ has formula [I] or [II], and X is selected from NR2 and OR, wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms which is optionally substituted with one or more halogen atoms, the method comprising reacting a compound containing an OR or NR2 group with a compound having formula R′SnY3, where Y is a reactive ligand;
• [I] CRaRbRc, wherein Ra is an aromatic ring having about 3 to about 10 carbon atoms which is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms, Rb and Rc are each independently hydrogen or a hydrocarbyl substituent having about 1 to about 10 carbon atoms, wherein each hydrocarbyl substituent is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms;
• [II] CRARBRC, wherein RA is (CH2)nORE, n is 0, 1, or 2, RE is a saturated hydrocarbon group having 1 to about 10 carbon atoms, RB and RC are each independently hydrogen or a saturated hydrocarbon group having about I to about 10 carbon atoms, wherein R′ contains about 2 to about 20 carbon atoms, wherein RA and one of RB and RC optionally form a 3 to 8-membered ring containing an ether linkage.

A method of synthesizing a monoorgano tin compound having formula (1) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorgano tin compound having formula (2):

• R′SnX3 (1)
• R′2SnX2 (2)
• wherein R′ has formula [I] or [II], and X is selected from NR2 and OR, wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms which is optionally substituted with one or more halogen atoms, the method comprising reacting a compound containing an OR or NR2 group with a compound having formula R′SnY3, where Y is a reactive ligand, the method comprising:
• (a) reacting a metal compound comprising an alkali metal M and a ligand X with a compound having formula SnY2 to form a compound having formula MSnX3;
• and (b) reacting the compound having formula MSnX3 with a compound R′Z, wherein Z is a halogen atom and Y is a reactive ligand;
• [I] CRaRbRc, wherein Ra is an aromatic ring having about 3 to about 10 carbon atoms which is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms, Rb and Rc are each independently hydrogen or a hydrocarbyl substituent having about 1 to about 10 carbon atoms, wherein each hydrocarbyl substituent is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms;
• [II] CRARBRC, wherein RA is (CH2)nORE, n is 0, 1, or 2, RE is a saturated hydrocarbon group having 1 to about 10 carbon atoms, RB and RC are each independently hydrogen or a saturated hydrocarbon group having about 1 to about 10 carbon atoms, wherein R′ contains about 2 to about 20 carbon atoms, wherein RA and one of RB and RC optionally form a 3 to 8-membered ring containing an ether linkage.

A monoorgano tin compound having formula (1′) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorgano tin compound having formula (2′) and less than about 5 mol % of a compound having formula (5′):

• R″SnX3 (1′)
• R″2SnX2 (2′)
• SnX4 (5′)
• wherein R″ has formula [III], and X is selected from NR2 and OR, wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms which is optionally substituted with one or more halogen atoms;
• [III] a 3 to 5-membered optionally substituted cyclic hydrocarbon or an optionally substituted 3 to 5-membered heterocyclic hydrocarbon ring containing at least one Sulfur, oxygen, or nitrogen atom, wherein a total number of carbon atoms in R″ is about 2 to about 20.

A method of synthesizing a monoorgano tin compound having formula (1′) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorgano tin compound having formula (2′) and less than about 5 mol % of a compound having formula (5′):

• R″SnX3 (1′)
• R″2SnX2 (2′)
• SnX4 (5′)
• wherein R″ has formula [III], and X is selected from NR2 and OR, wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms which is optionally substituted with one or more halogen atoms, the method comprising reacting a compound containing an R″ group with a compound having formula SnX4;
• [III] a 3 to 5-membered optionally substituted cyclic hydrocarbon or an optionally substituted 3 to 5-membered heterocyclic hydrocarbon ring containing at least one Sulfur, oxygen, or nitrogen atom, wherein a total number of carbon atoms in R″ is about 2 to about 20.

A method of synthesizing a monoorgano tin compound having formula (1′) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorgano tin compound having formula (2′) and less than about 5 mol % of a compound having formula (5′):

• R″SnX3 (1′)
• R″2SnX2 (2′)
• SnX4 (5′)
• wherein R″ has formula [III], and X is selected from NR2 and OR, wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms which is optionally substituted with one or more halogen atoms, the method comprising reacting a compound containing an OR or NR2 group with a compound having formula R″SnY3, where Y is a reactive ligand;
• [III] a 3 to 5-membered optionally substituted cyclic hydrocarbon or an optionally substituted 3 to 5-membered heterocyclic hydrocarbon ring containing at least one Sulfur, oxygen, or nitrogen atom, wherein a total number of carbon atoms in R″ is about 2 to about 20.

A method of synthesizing a monoorgano tin compound having formula (1′) having a purity of at least about 95 mol % and containing less than about 5 mol % of a diorgano tin compound having formula (2′) and less than about 5 mol % of a compound having formula (5′):

• R″SnX3 (1′)
• R″2SnX2 (2′)
• SnX4 (5′)
• wherein R″ has formula [III], and X is selected from NR2 and OR, wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms which is optionally substituted with one or more halogen atoms, the method comprising:
• (a) reacting a metal compound comprising an alkali metal M and a ligand X with a compound having formula SnY2 to form a compound having formula MSnX3;
• and (b) reacting the compound having formula MSnX3 with a compound R″Z, wherein Z is a halogen atom and Y is a reactive ligand;
• [III] a 3 to 5-membered optionally substituted cyclic hydrocarbon or an optionally substituted 3 to 5-membered heterocyclic hydrocarbon ring containing at least one Sulfur, oxygen, or nitrogen atom, wherein a total number of carbon atoms in R″ is about 2 to about 20.

An organotin compound having formula (6):

• R′″SnO(3/2-x/2)(OH)x (6)
• wherein 0<x≤3 and R′″ has formula [I], [II], or [III],
• [I] CRaRbRc, wherein Ra is an aromatic ring having about 3 to about 10 carbon atoms which is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms, Rb and Rc are each independently hydrogen or a hydrocarbyl substituent having about 1 to about 10 carbon atoms, wherein each hydrocarbyl substituent is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms;
• [II] CRARBRC, wherein RA is (CH2)nORE, n is 0, 1, or 2, RE is a saturated hydrocarbon group having 1 to about 10 carbon atoms, RB and RC are each independently hydrogen or a saturated hydrocarbon group having about I to about 10 carbon atoms, wherein R′ contains about 2 to about 20 carbon atoms, wherein RA and one of RB and RC optionally form a 3 to 8-membered ring containing an ether linkage;
• [III] a 3 to 5-membered optionally substituted cyclic hydrocarbon or an optionally substituted 3 to 5-membered heterocyclic hydrocarbon ring containing at least one Sulfur, oxygen, or nitrogen atom, wherein a total number of carbon atoms in R′″ is about 2 to about 20.

A composition comprising an organotin compound having formula (6) and an organotin compound having formula (7):

• R′″SnO(3/2-x/2)(OH)x (6)
• RivSnO(3/2-y/2)(OH)y (7)
• wherein 0<x≤3, 0<y≤3, wherein R′″ has formula [I], [II], or [III] and Riv is an optionally substituted hydrocarbon group having about 2 to 20 carbon atoms which is different from R′″;
• [I] CRaRbRc, wherein Ra is an aromatic ring having about 3 to about 10 carbon atoms which is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms, Rb and Rc are each independently hydrogen or a hydrocarbyl substituent having about 1 to about 10 carbon atoms, wherein each hydrocarbyl substituent is optionally substituted with one or more oxygen, nitrogen, and/or halogen atoms;
• [II] CRARBRC, wherein RA is (CH2)nORE, n is 0, 1, or 2, RE is a saturated hydrocarbon group having 1 to about 10 carbon atoms, RB and RC are each independently hydrogen or a saturated hydrocarbon group having about 1 to about 10 carbon atoms, wherein R′ contains about 2 to about 20 carbon atoms, wherein RA and one of RB and RC optionally form a 3 to 8-membered ring containing an ether linkage;
• [III] a 3 to 5-membered optionally substituted cyclic hydrocarbon or an optionally substituted 3 to 5-membered heterocyclic hydrocarbon ring containing at least one Sulfur, oxygen, or nitrogen atom, wherein a total number of carbon atoms in R′″ is about 2 to about 20.

A method for producing a monoalkyltin triamide having formula (11) by reacting an alkylmagnesium reagent having formula (8) or (9) with a tin tetraamide having formula (10) in the presence of a first solvent containing an ether solvent having a boiling point of at least 40° C., comprising a step of distilling off the ether solvent in the presence of a second solvent having an octanol/water partition coefficient greater than the ether solvent and greater than 1.0;

• RvMgX′ (8)
• Rv2Mg (9)
• Sn(NR2)4 (10)
• RvSn(NR2)3 (11)
• wherein Rv is a linear, branched, or cyclic hydrocarbyl group having 1 to 30 carbon atoms which may contain oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms, each R is an alkyl group having 1 to 10 carbon atoms which may contain halogen atoms and multiple R groups may be bonded to each other to form a cyclic structure, and X′ is chlorine, bromine, or iodine.

A method for a producing monoorgano tin trialkoxide compound having formula (1′″), comprising:

• i) reacting a tetraalkynyl tin compound having formula (14) with a magnesium reagent having formula (8′);
• and
• ii) reacting the product of step i) with an alcohol having formula (15):
• R″″Sn(OR)3 (1′″)
• Sn(C≡CRVI)4 (14)
• R″″MgX′ (8′)
• ROH (15)
• wherein each R is each independently a linear or branched alkyl group having about 1 to about 10 carbon atoms and each RVI is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms, or an aryl group having about 6 to 10 carbon atoms, X′ is chlorine, bromine, or iodine, and R″″ is a hydrocarbon group having about 1 to 30 carbon atoms which may contain one or more, oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms.

A method for producing a monoorgano tin trialkoxide compound having formula (1′″), comprising:

• i) reacting a bis[bis(trialkylsilylamino)]tin(II) compound having formula (17) with a hydrocarbyl halide compound having formula (18);
• and
• ii) reacting the product of step i) with an alkali metal alkoxide having formula (15′) and an alcohol having formula (15):
• R″″Sn(OR)3 (1′″)
• Sn[N(SiR3)2]2 (17)
• R″″X′ (18)
• MOR (15′)
• ROH (15)
• wherein each R is independently a linear or branched alkyl group having about 1 to about 10 carbon atoms, X′ is chlorine, bromine, or iodine, M is an alkali metal, and R″″ is a hydrocarbon group having about 1 to 30 carbon atoms which may contain one or more oxygen atoms, nitrogen atoms, silicon atoms, or sulfur atoms.