688-73-3

Basic information

• Product Name: Tributyltin
• Synonyms: TIN TRIBUTYL HYDRIDE;TRIBUTYLTIN HYDRIDE;TRIBUTYLSTANNANE;TRI-N-BUTYLTIN HYDRIDE;TRI-N-BUTYLSTANNANE;TRI-N-BUTYLTIN;Tri-n-butyltinhydride,97%;Tri-n-butyltinhydride,98+%
• CAS NO: 688-73-3
• Molecular Formula: C₁₂H₂₈Sn
• Molecular Weight: 291.06
• EINECS: 211-704-4
• Product Categories: Organometallics;Alkyl Metals;Classes of Metal Compounds;Grignard Reagents & Alkyl Metals;Reduction;Sn (Tin) Compounds;Synthetic Organic Chemistry;Typical Metal Compounds;OrganotinsSynthetic Reagents;Tin Hydrides;Organometallic Reagents;Organotin;Metal HydridesChemical Synthesis;New Products for Chemical Synthesis;Synthetic Reagents;organotin compound;Tin Hydrides;Chemical Synthesis;Organometallic Reagents;Organotins;Synthetic Reagents
• Mol File: 688-73-3.mol
• Article Data: 23

Chemical Properties

• Melting Point: <0°C
• Boiling Point: 80 °C0.4 mm Hg(lit.)
• Flash Point: 104 °F
• Appearance: colorless/liquid
• Density: 1.082 g/mL at 25 °C(lit.)
• Vapor Pressure: 5 hPa (20 °C)
• Refractive Index: n20/D 1.473(lit.)
• Storage Temp.: 2-8°C
• Water Solubility: REACTS
• Sensitive: Air & Moisture Sensitive
• BRN: 3587329
• CAS DataBase Reference: Tributyltin(CAS DataBase Reference)
• NIST Chemistry Reference: Tributyltin(688-73-3)
• EPA Substance Registry System: Tributyltin(688-73-3)

Safety Data

• Hazard Codes: T,N,F
• Statements: 10-21-25-36/38-48/23/25-50/53-15-67-65-11
• Safety Statements: 35-36/37/39-45-60-61-62-36/37-33-26-16
• RIDADR: UN 1993 3/PG 3
• WGK Germany: 3
• RTECS: WH8675000
• F: 1-10
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 688-73-3(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 688-73-3 differently. You can refer to the following data:
1. Tributyltin hydride (TBTH) is as a reagent for the reductive ionic 1,5-cyclization of 3-azamuconoates (3-azahexa-2,4-dienedioates). Tributyltin hydride can also mediate cyclisation of unsaturated ethers and amines bearing an aldehyde or α,β-unsaturated ketone group. Tributyltin hydride is also a reducing agent for the reduction of nitroalkenes.
2. A widely used radical reagent used in reductive cleavage,1 radical dehalogenation, and intramolecular radical cyclization.2

Chemical Properties

clear colourless liquid

uses

Different sources of media describe the uses of 688-73-3 differently. You can refer to the following data:
1. Tributyltin hydride the most commonly used tin hydride，it is less toxic than the more volatile trierhyl and trimethyl analogues, and it is therefore the most widely used organostannane.Tributyltin hydride, the reagent of choice for generating alkyl radical, is also widely used in aryl radical cyclization. Other reagents developed for this purpose include samarium diiodide, palladium reagents organosilanes as well as manganese triacetate and transition metals for carbocyclization.
2. Tributyltin hydride is used to effect carbon—carbon bond formation with the displacement of halide from a suitably oriented haloalkyl group.

Application

Has been reviewed. Catalyzes the Si-H reduction of α,β-unsaturated ketones. Useful in the reductive amination of ketones and aldehydes to form 3° amines.

Hazard

Moderately toxic by inhalation.

Safety Profile

Moderately toxic by inhalation. When heated to decomposition it emits acrid smoke and irritating fumes. See also TIN COMPOUNDS.

Purification Methods

Dissolve it in Et2O, add quinol (500mg for 300mL, to stabilize it), dry over Na2SO4, filter, evaporate and distil it under dry N2. It is a clear liquid if dry and decomposes very slowly. In the presence of H2O, traces of tributyl tin hydroxide are formed in a few days. Store it in sealed glass ampoules in small aliquots. It is estimated by reaction with aqueous NaOH when H2 is liberated. CARE: stored samples may be under pressure due to liberated H2. [Van Der Kerk et al. J Appl Chem 7 366 1937, Ono et al. Tetrahedron 41 4013 1985, Neuman Synthesis 665 1987, Curran Synthesis 417 1988, Beilstein 4 IV 4312.]

InChI:InChI=1/3C4H9.Sn/c3*1-3-4-2;/h3*1,3-4H2,2H3;/rC12H27Sn/c1-4-7-10-13(11-8-5-2)12-9-6-3/h4-12H2,1-3H3

Synthetic route

tributyltin methoxide (1067-52-3) + diborane (19287-45-7) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In pentane -78°C; 3 h;	100%
In not given	99.8%
In not given	99.8%

sodium tetrahydroborate (16940-66-2) + tributyltin chloride (1461-22-9) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In 1,2-dimethoxyethane formation at room temperature;;	96%
In 1,2-dimethoxyethane formation at room temperature;;	96%

dichlorobis(acetylacetonato-O,O')titanium(IV) + tri-n-butyltin lithium (4226-01-1) → titanium(III) tris-acetylacetonate + Ti(CH3COCHCOCH3)2(Sn(CH3(CH2)3)3)2 + tri-n-butyl-tin hydride (688-73-3) + bis(tri-n-butyltin) (813-19-4)

Conditions	Yield
In tetrahydrofuran byproducts: LiCl, Ti(Sn(C4H9)3)1.7; addn. of Bu3SnLi to Ti-compound in soln. (-78°C), stirred, mixt. brought to 20°C, soln. became blue; evapn. in vac., residue washed with pentane, sublimation (10**-3 Torr, 90°C); elem. anal., chromy.;	A 90% B 0% C 30% D 96%

tributyltin chloride (1461-22-9) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
	95%
With aluminium amalgame In not given formation on reaction for 6 h at 10°C;;	60%
With aluminium amalgame In not given formation on reaction for 6 h at 10°C;;	60%

borane (13283-31-3) + 1-(tributylstannyl)naphthalene (972-09-8) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In tetrahydrofuran byproducts: 1-naphthylboronic acid; to srirred soln. of Sn-compound in THF was added soln. of BH3 in THF under N2, mixt. was left at room temp. for 1 h, refluxed for 3 h, cooled, Et2O and water was added; dried with MgSO4, solvent was removed under vac., column chromy. on silica gel with hexane and hexane-Et2O, recrystd. from water;	95%
In tetrahydrofuran byproducts: 1-naphthylboronic acid; to srirred soln. of Sn-compound in THF was added soln. of BH3 in THF under N2, mixt. was left at room temp. for 1 h, refluxed for 1 h, cooled, Et2O and water was added; dried with MgSO4, solvent was removed under vac., column chromy. on silica gel with hexane and hexane-Et2O, recrystd. from water;	72%

tributyltin butoxide (3882-70-0) + bis(tri-n-butyltin)oxide (56-35-9) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
With (SiH(CH3)O)(n) exothermic react.;	95%

(N,N-diethylamino)tributyltin (1066-87-1) + diborane (19287-45-7) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In pentane formation at -78°C;;	94.4%
In pentane formation at -78°C;;	94.4%

chloro(methyl)phenylsilane (1631-82-9) + tributyltin ethoxide (682-00-8) → diethoxy-methyl-phenyl-silane (775-56-4) + tributyltin chloride (1461-22-9) + tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
2:1; room temp.;	A 94% B n/a C n/a
2:1; room temp.;	A 94% B n/a C n/a

tributyltin methoxide (1067-52-3) + (+)-methyl-(α-naphthyl)-phenylsilane (1025-08-7, 1025-09-8, 7427-12-5, 17037-10-4) → methoxy(methyl)(1-naphthyl)phenylsilane (3553-88-6, 16544-83-5, 16952-14-0, 18544-02-0) + tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In toluene Kinetics; 100°C; 12 h;;	A 92% B n/a
In toluene Kinetics; 100°C; 12 h;;	A 92% B n/a

tributyltin ethoxide (682-00-8) + (+)-methyl-(α-naphthyl)-phenylsilane (1025-08-7, 1025-09-8, 7427-12-5, 17037-10-4) → CH3(C6H5)(1-C10H7)SiOC2H5 (143731-59-3) + tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
100°C; 12 h;	A 92% B n/a
100°C; 12 h;	A 92% B n/a
100°C; 12 h;	A 92% B n/a

borane (13283-31-3) + (p-methoxyphenyl)tri-n-butylstannane (70744-47-7) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In tetrahydrofuran byproducts: p-anisylboronic acid; to srirred soln. of Sn-compound in THF was added soln. of BH3 in THF under N2, mixt. was left at room temp. for 1 h, refluxed for 1 h, cooled, Et2O and water was added; dried with MgSO4, solvent was removed under vac., column chromy. on silica gel with hexane and hexane-Et2O, recrystd. from water;	91%

dimethylamine borane (74-94-2) + tributylstannyl trifluoromethanesulfonate (68725-14-4) → (μ-dimethylamino)diborane (23273-02-1) + tri-n-butyl-tin hydride (688-73-3) + cyclic(dimethylamino borane) dimer (23884-11-9)

Conditions	Yield
With 2,2,6,6-tetramethylpiperidine In further solvent(s) byproducts: H2; N2 or Ar; 1,2-dichlorobenzene soln. of nBuSnOTf (0.39 mmol) and 2,2,6,6-tetramethylpiperidine (0.4 mmol) added to soln. of B compd. (0.42 mmol), mixt. stirred at 20°c for 2 h; NMR;	A 2% B n/a C 91%

sodium tetrahydroborate (16940-66-2) + bis(tri-n-butyltin)oxide (56-35-9) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In ethanol Sn compd. dissolved in abs. ethanol at 0°C under Ar, then added NaBH4, allowed to warm to room temp., stirred for 1 h; EtOH removed in vac., residue dissolved in hexane, washed with water, dried, evapd. under reduced pressure;	90%

tributyltin methoxide (1067-52-3) + (S)-(-)-α-naphthylphenylmethylsilane (1025-09-8) → methoxy(methyl)(1-naphthyl)phenylsilane (3553-88-6, 16544-83-5, 16952-14-0, 18544-02-0) + tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In toluene Kinetics; 100°C; 12 h;;	A 90% B n/a
In toluene Kinetics; 100°C; 12 h;;	A 90% B n/a

borane (13283-31-3) + 2-tri-n-butylstannylanisole (86487-17-4) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In tetrahydrofuran byproducts: o-anisylboronic acid; to srirred soln. of Sn-compound in THF was added soln. of BH3 in THF under N2, mixt. was left at room temp. for 1 h, refluxed for 1 h, cooled, Et2O and water was added; dried with MgSO4, solvent was removed under vac., column chromy. on silica gel with hexane and hexane-Et2O, recrystd. from water;	90%

tributyltin ethoxide (682-00-8) + (S)-(-)-α-naphthylphenylmethylsilane (1025-09-8) → CH3(C6H5)(1-C10H7)SiOC2H5 (143731-59-3) + tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
100°C; 12 h;	A 89% B n/a
100°C; 12 h;	A 89% B n/a
100°C; 12 h;	A 89% B n/a

tributyltin methoxide (1067-52-3) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
With poly(methylhydrosiloxane) In not given to Bu3SnOMe poly(methylhydrosiloxane) was added and stirred at room temp. for 8 h; distillation under reduced pressure;	89%
Multi-step reaction with 2 steps 2: C6H5(CH3)2SiH View Scheme
Multi-step reaction with 2 steps 2: C6H5(CH3)2SiH View Scheme

Tri-n-butyl-tri-n-butyl-siloxy-zinn (16524-87-1) + poly(methylhydrosiloxane) (43435-60-5) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In not given formation at room temperature;; distillation;;	88%
In not given formation at room temperature;; distillation;;	88%

{(HSiO1.5)(n)((CH3)2SiO)(n)} + Tri-n-butyl-tri-n-butyl-siloxy-zinn (16524-87-1) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
1:2; 150°C;	88%
1:2; 150°C;	88%

lithium aluminium tetrahydride (16853-85-3) + tributyltin chloride (1461-22-9) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In diethyl ether heating on reflux for 2-4 h; decomposition of excess LiAlH4 on addn. of ice-water;; distillation;;	87%
In diethyl ether heating on reflux for 2-4 h; decomposition of excess LiAlH4 on addn. of ice-water;; distillation;;	87%
In diethyl ether heating on reflux for 2-4 h; decomposition of excess LiAlH4 on addn. of ice-water;; distillation;;	74%

borane (13283-31-3) + (2-tolyl)tributyltin (68971-87-9) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In tetrahydrofuran byproducts: o-tolylboronic acid; to srirred soln. of Sn-compound in THF was added soln. of BH3 in THF under N2, mixt. was left at room temp. for 1 h, refluxed for 1 h, cooled, Et2O and water was added; dried with MgSO4, solvent was removed under vac., column chromy. on silica gel with hexane and hexane-Et2O, recrystd. from water;	86%

tributyltin ethoxide (682-00-8) + poly(methylhydrosiloxane) (43435-60-5) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In not given formation at room temperature;; distillation;;	86%
In not given formation at room temperature;; distillation;;	86%

Methyl-phenyl-ethoxy-silan (17198-96-8, 147377-23-9, 147377-34-2) + tributyltin ethoxide (682-00-8) → diethoxy-methyl-phenyl-silane (775-56-4) + tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
1:1; room temp.;	A 86% B n/a
1:1; room temp.;	A 86% B n/a

C40H160O40Si40 + tributyltin ethoxide (682-00-8) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
1:1; 30 min; little contaminated with siloxane fragments;	86%

borane (13283-31-3) + tributylphenylstannane (960-16-7) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In tetrahydrofuran byproducts: phenylboronic acid; to srirred soln. of Sn-compound in THF was added soln. of BH3 in THF under N2, mixt. was left at room temp. for 1 h, refluxed for 1 h, cooled, Et2O and water was added; dried with MgSO4, solvent was removed under vac., column chromy. on silica gel with hexane and hexane-Et2O, recrystd. from water;	85%

borane (13283-31-3) + tributyl(p-tolyl)stannane (31614-66-1) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In tetrahydrofuran byproducts: p-tolylboronic acid; to srirred soln. of Sn-compound in THF was added soln. of BH3 in THF under N2, mixt. was left at room temp. for 1 h, refluxed for 1 h, cooled, Et2O and water was added; dried with MgSO4, solvent was removed under vac., column chromy. on silica gel with hexane and hexane-Et2O, recrystd. from water;	84%

poly(methylhydrosiloxane) (43435-60-5) + bis(tri-n-butyltin)oxide (56-35-9) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In not given formation at room temperature;; distillation;;	79%
In not given formation at room temperature;; distillation;;	79%

Cyclohexyloxy-tributyl-stannan (1749-41-3) + (+)-methyl-(α-naphthyl)-phenylsilane (1025-08-7, 1025-09-8, 7427-12-5, 17037-10-4) → (CH3)(C6H5)(C10H7)SiOC6H11 + tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
for 88 h at 120°C; retention >87%;	A 79% B n/a
for 88 h at 120°C; retention >87%;	A 79% B n/a
for 88 h at 120°C; retention >87%;	A 79% B n/a

tributyltin formate (5847-51-8) → tri-n-butyl-tin hydride (688-73-3) + bis(tri-n-butyltin) (813-19-4) + tetra-n-butyltin(IV) (1461-25-2)

Conditions	Yield
heating 11.5 h at 150 to 185°C;	A 6.9% B 77.5% C 5.2%
heating 11.5 h at 150 to 185°C;	A 6.9% B 77.5% C 5.2%
In neat (no solvent) byproducts: CO2; heating for 11.5 h at 150-185°C under N2;;	A 6.9% B n/a C n/a

tributyl(tris(phenyl)siloxy)tin (16524-88-2) + poly(methylhydrosiloxane) (43435-60-5) → tri-n-butyl-tin hydride (688-73-3)

Conditions	Yield
In not given formation at room temperature;; distillation;;	76%
In not given formation at room temperature;; distillation;;	76%

tri-n-butyl-tin hydride (688-73-3) + Methyl 2-butynoate (23326-27-4) → methyl (2E)-3-(tributylstannyl)but-2-enoate (151568-81-9, 151568-82-0)

Conditions	Yield
Stage #1: tri-n-butyl-tin hydride With n-butyllithium In tetrahydrofuran at -78℃; for 0.166667h; Stage #2: With methanol In tetrahydrofuran at -78℃; for 0.05h; Stage #3: Methyl 2-butynoate In tetrahydrofuran at -78℃; for 1.5h;	100%

tri-n-butyl-tin hydride (688-73-3) + cyclohexa-1,3-diene (1165952-91-9) → tributyl(cyclohex-2-en-1-yl)stannane (112520-99-7, 1177092-71-5)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In benzene at 20℃; for 1h; Inert atmosphere;	100%
With tetrakis(triphenylphosphine) palladium(0) In benzene at 20℃; for 0.166667h; Inert atmosphere;	78%
tetrakis(triphenylphosphine) palladium(0) In benzene at 20℃; for 0.25h;	78.6%

tri-n-butyl-tin hydride (688-73-3) + acetylenedicarboxylic acid diethyl ester (762-21-0) → (CH3CH2CH2CH2)3SnC(COOC2H5)CHCOOC2H5 (3422-68-2, 4276-31-7, 6150-36-3)

Conditions	Yield
0°C;; cis-trans-ratio = 10:1;;	100%
0°C;; cis-trans-ratio = 10:1;;	100%
In not given

oct-1-ene (111-66-0) + tri-n-butyl-tin hydride (688-73-3) → tributyl(octyl)stannane (14775-14-5)

Conditions	Yield
With diisobutylaluminium hydride 75-80°C;;	100%
With (iso-C4H9)2AlH 75-80°C;;	100%
With diisobutylaluminium hydride 75-80°C;;	100%

tri-n-butyl-tin hydride (688-73-3) + phenylacetylene (536-74-3) → (E)-1-phenyl-(2-tributylstannyl)ethene (66680-87-3, 66680-88-4, 79159-76-5)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); oxygen In benzene-d6 at 80℃; for 2h; diastereoselective reaction;	100%
In not given 100-150°C, 48 h;	93%
With C44H72O4Ru2(2-) In tetrahydrofuran at 30℃; for 0.166667h; Solvent; UV-irradiation; Inert atmosphere; stereoselective reaction;	92%

perfluorobenzaldehyde (653-37-2) + tri-n-butyl-tin hydride (688-73-3) → Perfluorphenylmethoxytributylzinn (20749-43-3) + Perfluorphenylmethyl-(perfluorphenyl-tributylstannoxymethyl)-ether (20428-47-1)

Conditions	Yield
In neat (no solvent) 2:3 mole ratio of (C4H9)3SnH and aldehyde, 20. degree.C; 2.6:1 mixt. of (C4H9)3SnOCH2C6F5 and the 1:2 adduct (C4H9)3SnOCH(C6F5)OCH2C5F6;	A 100% B n/a
In neat (no solvent) 2:3 mole ratio of (C4H9)3SnH and aldehyde, 20. degree.C; 2.6:1 mixt. of (C4H9)3SnOCH2C6F5 and the 1:2 adduct (C4H9)3SnOCH(C6F5)OCH2C5F6;	A 100% B n/a
In not given reaction at 20°C;;

chloro-trimethyl-silane (75-77-4) + tri-n-butyl-tin hydride (688-73-3) → trimethylsilyltributyltin (17955-46-3)

Conditions	Yield
In tetrahydrofuran 1) DIPA, THF, -78°C; 2)TMSCl, room temp.;	100%
With n-butyllithium; diisopropylamine In tetrahydrofuran cooling of soln. of diisopropylamine in THF to -78°C for 10 min; addn. of n-BuLi for 5 min; after 5 min heating to room temp.; addn. of SnH(n-Bu)3 for 5 min; stirring at room temp. for 20 min; addn. of Me3SiCl; stirring at room temp. for >10 min; evapn., chromy. on silica gel (hexanes);	99%
In neat (no solvent) deprotonation of (C4H9)3HSn with LDA followed by quench with (CH3)3SiCl;

tri-n-butyl-tin hydride (688-73-3) + benzenesulphonyl isocyanate (2845-62-7) → N-<(Tri-n-butylstannyloxy)-methylen>-benzolsulfonamid (37755-83-2)

Conditions	Yield
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%

tri-n-butyl-tin hydride (688-73-3) + Tosyl isocyanate (4083-64-1) → (C4H9)3SnOCHNSO2C6H4CH3 (37755-84-3)

Conditions	Yield
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%

CH2CHC(CH3)(SO2C6H4CH3)CH2CH2COOCH3 (76425-45-1) + tri-n-butyl-tin hydride (688-73-3) → (CH3(CH2)3)3SnCH2CHC(CH3)CH2CH2COOCH3

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In benzene under N2 a mixture of Sn-compound, sulfone, and AIBN in dry benzene wasrefluxed for 5 h; evapd.;	100%

4-methoxybenzenesulfonyl isocyanate (7018-76-0) + tri-n-butyl-tin hydride (688-73-3) → (C4H9)3SnOCHNSO2C6H4OCH3 (37755-85-4)

Conditions	Yield
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%

tri-n-butyl-tin hydride (688-73-3) + 4-Chlorophenylsulfonyl isocyanate (5769-15-3) → (C4H9)3SnOCHNSO2C6H4Cl (38421-33-9)

Conditions	Yield
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%
In cyclohexane 1:1 mole ratio of educts, at room temp.;	100%

tri-n-butyl-tin hydride (688-73-3) + (+)-(1S,3S,4R)-menthyl pyruvate (93059-38-2) → (C4H9)3SnOCH(CH3)COOC10H19

Conditions	Yield
Irradiation (UV/VIS); accelerated by UV light; two diastereomeric isomers in equal amts.;	100%
Irradiation (UV/VIS); accelerated by UV light; two diastereomeric isomers in equal amts.;	100%

C16H35OSn(1+)*C18HBF15(1-) + tri-n-butyl-tin hydride (688-73-3) + (but-2-yn-1-yloxy)(tert-butyl)dimethylsilane (83591-03-1) → C22H48OSiSn (1403390-08-8, 1403390-34-0, 1416133-99-7)

Conditions	Yield
In tetrahydrofuran; benzene-d6 at 50℃; for 18h;	100%

5-O-benzyl-1,3-O-methyl-2-O-[(methylthio)thiocarbonyl]-α-D-ribo-furanose (1451073-41-8) + tri-n-butyl-tin hydride (688-73-3) → 5-O-benzyl-1,3-O-dimethyl-2-O-tributylstannylmethylthio-α-D-ribo-furanose (1451073-58-7)

Conditions	Yield
Stage #1: 5-O-benzyl-1,3-O-methyl-2-O-[(methylthio)thiocarbonyl]-α-D-ribo-furanose With triethyl borane In benzene at 20℃; for 0.0833333h; Stage #2: tri-n-butyl-tin hydride In benzene for 1.3h;	100%

1-phenyl-1-butyne (622-76-4) + tri-n-butyl-tin hydride (688-73-3) → (Z)-tributyl(1-phenylbut-1-en-2-yl)stannane

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); oxygen In benzene-d6 at 80℃; for 2h; diastereoselective reaction;	100%
With C44H72O4Ru2(2-) at 30℃; for 0.166667h; Reagent/catalyst; Time; UV-irradiation; stereoselective reaction;	99 %Spectr.

tri-n-butyl-tin hydride (688-73-3) + (3,3-difluorocycloprop-1-ene-1,2-diyl)dibenzene → (1SR,3RS)-tributyl(2,2-difluoro-1,3-diphenylcycloprop-1-yl)-stannane

Conditions	Yield
With triethyl borane In tetrahydrofuran; hexane at 80℃; for 4h;	100%
With triethyl borane In tetrahydrofuran; hexane at 80℃; for 4h; Temperature;	100%

(tert-butyldimethylsilyl)acetylene (86318-61-8) + tri-n-butyl-tin hydride (688-73-3) → tert-butyldimethyl[(tributylstannyl)ethynyl]silane

Conditions	Yield
Stage #1: (tert-butyldimethylsilyl)acetylene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: tri-n-butyl-tin hydride In tetrahydrofuran; hexane at -78℃; for 3h;	100%

2,2-dimethyl-3-butyne (917-92-0) + tri-n-butyl-tin hydride (688-73-3) → tributyl(3,3-dimethyl-1-butyn-1-yl)stannane (58064-10-1)

Conditions	Yield
Stage #1: 3,3-Dimethylbut-1-yne With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: tri-n-butyl-tin hydride In tetrahydrofuran; hexane at -78℃; for 1h;	100%
With pyridine; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; zinc trifluoromethanesulfonate at 70℃; for 8h; Schlenk technique; Inert atmosphere; chemoselective reaction;	57%

2-methyl-6-phenylhex-3-yn-2-ol (57443-39-7) + tri-n-butyl-tin hydride (688-73-3) → (Z)-2-methyl-6-phenyl-3-(tributylstannyl)hex-3-en-2-ol

Conditions	Yield
With [RuCl2pentamethylcyclopentadiene]n In dichloromethane for 0.0833333h; Inert atmosphere;	100%
With [RuCl2pentamethylcyclopentadiene]n In dichloromethane for 1.08333h; Schlenk technique; Inert atmosphere;	5.16 g

tri-n-butyl-tin hydride (688-73-3) + (4R,5R,E)-5-hydroxy-4,6-dimethyl-N-(prop-2-yn- 1-yl)hept-2-enamide (180779-80-0) → (4R,5R,E)-5- hydroxy-4,6-dimethyl-N-((E)-3-(tributylstannyl)allyl)hept-2-enamide

Conditions	Yield
Stage #1: tri-n-butyl-tin hydride With n-butyllithium; copper(l) cyanide In tetrahydrofuran; hexane at -78℃; for 0.583333h; Inert atmosphere; Sealed tube; Stage #2: (4R,5R,E)-5-hydroxy-4,6-dimethyl-N-(prop-2-yn- 1-yl)hept-2-enamide In tetrahydrofuran; hexane at -78℃; for 1.25h; Inert atmosphere; Sealed tube;	100%
Stage #1: tri-n-butyl-tin hydride With n-butyllithium; copper(I) cyanide In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: (4R,5R,E)-5-hydroxy-4,6-dimethyl-N-(prop-2-yn- 1-yl)hept-2-enamide In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere;	100%
With n-butyllithium; copper(l) cyanide	100%
Stage #1: tri-n-butyl-tin hydride With n-butyllithium; copper(l) cyanide In tetrahydrofuran; hexane for 0.583333h; Inert atmosphere; Stage #2: (4R,5R,E)-5-hydroxy-4,6-dimethyl-N-(prop-2-yn- 1-yl)hept-2-enamide In tetrahydrofuran; hexane for 1.25h; Inert atmosphere;	100%

tert-butyl (((S,5Z,8Z)-6-methyldeca-5,8-dien-1-yn-4-yl)oxy)-diphenylsilane + tri-n-butyl-tin hydride (688-73-3) → tert-butyl (((S,1E,5Z,8Z)-6-methyl-1-(tributylstannyl)deca-1,5,8-trien-4-yl)oxy)diphenylsilane

Conditions	Yield
With tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine; tricyclohexylphosphine tetrafluoroborate In dichloromethane at 0℃; for 2.5h; Inert atmosphere;	100%

C20H27NO4 + tri-n-butyl-tin hydride (688-73-3) → C32H55NO4Sn

Conditions	Yield
With n-butyllithium; copper(I) cyanide	100%

C20H27NO4 + tri-n-butyl-tin hydride (688-73-3) → C32H55NO4Sn

Conditions	Yield
With n-butyllithium; copper(I) cyanide	100%

tri-n-butyl-tin hydride (688-73-3) + 2,4,6-tri-tert-butyl-1,3,5-triphosphinine (173166-52-4) → C27H55P3Sn

Conditions	Yield
at 20℃; for 24h; Temperature; Inert atmosphere; Schlenk technique; Glovebox;	100%

tri-n-butyl-tin hydride (688-73-3) + C20H27NO4 → C32H55NO4Sn

Conditions	Yield
Stage #1: tri-n-butyl-tin hydride With n-butyllithium; copper(l) cyanide In tetrahydrofuran; hexane for 0.583333h; Inert atmosphere; Stage #2: C20H27NO4 In tetrahydrofuran; hexane for 1.25h; Inert atmosphere;	100%

tri-n-butyl-tin hydride (688-73-3) + C13H21NO2 → C25H49NO2Sn

Conditions	Yield
Stage #1: tri-n-butyl-tin hydride With n-butyllithium; copper(l) cyanide In tetrahydrofuran; hexane for 0.583333h; Inert atmosphere; Stage #2: C13H21NO2 In tetrahydrofuran; hexane for 1.25h; Inert atmosphere;	100%

tri-n-butyl-tin hydride (688-73-3) + C13H21NO2 → C25H49NO2Sn

Conditions	Yield
Stage #1: tri-n-butyl-tin hydride With n-butyllithium; copper(l) cyanide In tetrahydrofuran; hexane for 0.583333h; Inert atmosphere; Stage #2: C13H21NO2 In tetrahydrofuran; hexane for 1.25h; Inert atmosphere;	100%

-butyl vinyl ether (111-34-2) + tri-n-butyl-tin hydride (688-73-3) → <2-Butyloxy-ethyl>-triisobutyl-zinn (51283-48-8)

Conditions	Yield
In neat (no solvent) other Radiation; under Ar; (60)Co-irradiation; 1.5:1 molar ratio (olefine:Sn-compound) ;25°C; GLC;	99%
other Radiation; gamma-radiation;;	99%
other Radiation; gamma-radiation;;	99%
In not given other Radiation; γ-radiation;;

Upstream product

• 27652-13-7 (E)-4-bromo-3-methyl-2-butenoic acid methyl ester 
• 3034-53-5 2-bromo-1,3-thiazole 
• 7440-31-5 stannane 
• 55476-27-2 hypobromous acid ethyl ester 
• 4226-01-1 tri-n-butyltin lithium 
• 7732-18-5 water 
• 994-89-8 tributylethynyltin 
• 1002-53-5 dibutylstannane 
• 56-35-9 bis(tri-n-butyltin)oxide 
• 16940-66-2 sodium tetrahydroborate 
• 1067-52-3 tributyltin methoxide 
• 19287-45-7 diborane 
• 1066-87-1 (N,N-diethylamino)tributyltin 
• 16853-85-3 lithium aluminium tetrahydride 

Downstream Products

• 932-92-3 cyclohexyl ethyl ether 
• 127084-51-9 C₂₀H₄₂OSSn 
• 74-84-0 ethane 
• 110-82-7 cyclohexane 
• 4808-30-4 bis(tributyltin)sulfide 
• 35525-50-9 bis(tri-n-butylstannyl) ethane dithiolate 
• 127084-53-1 C₂₁H₃₉NSSn 
• 142-82-5 n-heptane 
• 10596-55-1 S-Ethyl S'-methyl dithiocarbonate 
• 294-62-2 cyclododecane 
• 17314-32-8 tributyl(methylthio)stannane 
• 139107-54-3 3,5-Dicyano-cyclohex-1-enecarboxylic acid ethyl ester 
• 139107-55-4 3,5-Dicyano-cyclohex-2-enecarboxylic acid ethyl ester 
• 139107-48-5 4-Cyano-2-[1-tributylstannanyl-meth-(Z)-ylidene]-butyric acid ethyl ester 

Relevant articles and documents

Metal hydrides as electron donors. The mechanism of oxidative cleavage with tris(phenanthroline) complexes of iron(III)

The group 4 metal hydrides HMR3 (M = silicon, germanium, tin; R = alkyl, phenyl) react spontaneously with 2 equiv of tris(phenanthroline)iron(III) perchlorate, FeL3(ClO4)3, in acetonitrile solutions. Although the second-order kinetics (first order in each reactant) indicate that the selective cleavage of only the hydrido-metal bond proceeds from a rate-limiting bimolecular process, there is no significant deuterium kinetic isotope effect. The free-energy dependence of the second-order rate constant kH for the silicon and germanium hydrides follows the Marcus relationship with slope α close to the theoretical value of 8.5 for an outer-sphere electron-transfer process. The paramagnetic cation HMR3+, similar to that formed by electron impact or photoionization of HMR3, is postulated to be a metastable intermediate which undergoes spontaneous scission of the hydrogen-metal bond, followed by a further rapid oxidation of the fragment by a second equivalent of FeL33+. The rate-limiting, outer-sphere mechanism for HMR3 accords with that previously established for electron transfer between the related series of peralkylmetals MR4 and the same FeL33+ complexes. The electron-transfer rate constants kH and kR for HMR3 and MR4, respectively, are compared for their sensitivity to changes in the standard reduction potentials E° of FeL33+ and the gas-phase ionization potentials ID of HMR3 and MR4. Polarization and solvation effects appear to be especially important in electron transfer from metal hydrides, especially those of tin.

Aluminumoxyhydride: Improved synthesis and application as a selective reducing agent

Aluminumoxyhydride (HAlO) has been obtained by the reaction of aluminum hydride with the siloxane (Me2HSi)2O or the stannoxane (Bu3Sn)2O as an amorphous colorless insoluble powder. The highest-purity product resulted from the reaction of H3Al· NMe3 with (Me2HSi)2O. However, HAlO suspensions in tetrahydrofuran (THF) of sufficient quality for synthetic applications can be prepared from commercially available reagents with only minor precautions. A LiAlH4 solution in THF was treated successively with Me 3SiCl and (Me2HSi)2O, followed by heating at 60°C for 20 h. The resulting suspensions are 0.4-0.5 M in active hydride content and selectively reduce aldehydes and ketones to the respective alcohols in the presence of any other common nonprotic functional group.

METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND

PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT

Reactions of amine-and phosphane-borane adducts with frustrated Lewis pair combinations of Group 14 triflates and sterically hindered nitrogen bases

The ability of trialkyl Group 14 triflates in combination with amine and pyridine bases to dehydrogenate amine-and phosphane-borane adducts has been investigated. By using multinuclear NMR spectroscopy, it has been shown that Me2NH ·BH3 (11) is efficiently converted to [Me2N-BH2]2 (12) by the so-called "frustrated Lewis pair" (FLP) of nBu3SnOTf (4, -OTf = -OSO2CF3) and 2,2,6,6-tetramethylpiperidine (6). Within the scope of the study, exchange of the Lewis acid effects the rate of dehydrogenation in the order: 4 gt; Me3Si-OTf (2) gt; Et 3SiOTf (3). Exchange of the Lewis base for 2,6-di-tert-butylpyridine (5) has also been shown to reduce the rate of reaction, whereas 1,3-di-tert-butylimidazol-2-ylidene (7) reacted directly with 2 to afford 1,3-bis-tert-butyl-4-(trimethylsilyl)imidazolium triflate (8[OTf]). For FLP combinations for which dehydrogenation reaction times are longer, detectable quantities of [H2B(μ-H)(μ-NMe2)BH2] (14) are observed. Both the dehydrogenation reaction and competitive formation of this product are proposed to proceed by initial hydride abstraction by the Lewis acid, followed by deprotonation by the Lewis base, or combination with further dimethylamine-borane and elimination of [Me2NH2]OTf (18[OTf]), respectively. In contrast to 11, MeNH2·BH 3 (22) was not found to cleanly dehydrogenate to either [MeNH-BH 2]3 or [MeN-BH]3 under the same conditions. An alternative reaction pathway was observed with either 2 or 4 and 6 with Ph 2PH ·BH3 (23), resulting in P-silylation or P-stannylation of the phosphane-borane, respectively.