776-76-1

Basic information

• Product Name: DIPHENYLMETHYLSILANE
• Synonyms: LS 4880;NSC 111638;SID 4555.0;methyldiphenyl-silan;DIPHENYLMETHYLSILANE;METHYLDIPHENYLSILANE;DIPHENYLMETHYLSILANE, 97+%;Diphenylmethylsilane(Methyldiphenylsilane)
• CAS NO: 776-76-1
• Molecular Formula: C₁₃H₁₄Si
• Molecular Weight: 198.34
• EINECS: 212-281-9
• Product Categories: Reduction;Si (Classes of Silicon Compounds);Si-H Compounds;Silicon Compounds (for Synthesis);Synthetic Organic Chemistry
• Mol File: 776-76-1.mol
• Article Data: 35

Chemical Properties

• Melting Point: 20 °C
• Boiling Point: 93-94 °C1 mm Hg(lit.)
• Flash Point: >230 °F
• Appearance: colourless liquid
• Density: 0.995 g/mL at 25 °C(lit.)
• Refractive Index: n20/D 1.571(lit.)
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• BRN: 1867183
• CAS DataBase Reference: DIPHENYLMETHYLSILANE(CAS DataBase Reference)
• NIST Chemistry Reference: DIPHENYLMETHYLSILANE(776-76-1)
• EPA Substance Registry System: DIPHENYLMETHYLSILANE(776-76-1)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 1
• F: 10
• TSCA: Yes
• Hazardous Substances Data: 776-76-1(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless liquid

Application

Used to reduce α-alkoxy ketones to diols and α-amino ketones to aminoethanols with high stereoselectivity.

InChI:InChI=1/C13H13Si/c1-14(12-8-4-2-5-9-12)13-10-6-3-7-11-13/h2-11H,1H3

Synthetic route

1-aminomorpholine (4319-49-7) + 1,2-dimethyl-1,1,2,2-tetraphenyldisilane (1172-76-5) → methyldiphenylsilane (776-76-1) + 1-morpholine (121667-15-0)

Conditions	Yield
With potassium hydride In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide for 72h; Ambient temperature;	A 96% B 93%

methoxy(methyl)diphenylsilane (18407-48-2) → methyldiphenylsilane (776-76-1)

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide; sodium tetrahydroborate; ethyl bromide; tetraoctyl ammonium bromide In benzene-d6 at 20℃; for 24h; Reagent/catalyst; Solvent;	92%

chloromethyldiphenylsilane (144-79-6) → methyldiphenylsilane (776-76-1) + 1,2-dimethyl-1,1,2,2-tetraphenyldisilane (1172-76-5)

Conditions	Yield
Stage #1: chloromethyldiphenylsilane In tetrahydrofuran at 30℃; for 10h; Stage #2: With hydrogenchloride In 1,4-dioxane	A 91% B 5%
With aluminium trichloride 1) electrolysis; Yield given. Multistep reaction. Yields of byproduct given;

4-{[(E)-(Methyl-diphenyl-silanyl)-imino]-methyl}-phenol → methyldiphenylsilane (776-76-1) + 4-cyanophenol (767-00-0)

Conditions	Yield
With 1,3-dimethyl-2-imidazolidinone; sodium hexamethyldisilazane In tetrahydrofuran at 185℃;	A n/a B 91%

1,2-dimethyl-1,1,2,2-tetraphenyldisilane (1172-76-5) + 1,1-dimethylhydrazine (57-14-7) → methyldiphenylsilane (776-76-1) + 1,1-bis(diphenylmethylsilyl)-2,2-dimethylhydrazine (121667-17-2)

Conditions	Yield
With potassium hydride In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide for 72h; Ambient temperature;	A 89% B 83%

chloromethyldiphenylsilane (144-79-6) → methyldiphenylsilane (776-76-1)

Conditions	Yield
With sodium tetrahydroborate In acetonitrile at 20℃; for 0.25h; Solvent; Reagent/catalyst; Schlenk technique; Inert atmosphere;	84%
Stage #1: chloromethyldiphenylsilane With N,N,N,N,N,N-hexamethylphosphoric triamide; magnesium at 90℃; for 20h; Inert atmosphere; Stage #2: Acidic conditions;	77.9%
Stage #1: chloromethyldiphenylsilane With sodium iodide In tetrahydrofuran; benzene-d6 at 20℃; for 2h; Inert atmosphere; Schlenk technique; Stage #2: With [N-[4-(dimethylamino)phenyl]-2-pyridinecarboxamidato](pentamethylcyclopentadienyl)iridium trifluorometanesulfonate; hydrogen; N-ethyl-N,N-diisopropylamine In tetrahydrofuran; benzene-d6 at -196 - 60℃; under 3040.2 Torr; for 48h; Schlenk technique;	42%
With lithium aluminium tetrahydride
With water; N,N,N,N-tetraethylammonium tetrafluoroborate 1) DME, HMPA, -6 deg C, electrolysis; Yield given. Multistep reaction;

1,2-dimethyl-1,1,2,2-tetraphenyldisilane (1172-76-5) → methyldiphenylsilane (776-76-1)

Conditions	Yield
With [Ni2(1,3-diisopropyl-imidazolin-2-ylidene)4(μ-1,5-cyclooctadiene)]; hydrogen In toluene at 20℃; under 1350.14 Torr; for 48h; Catalytic behavior; Inert atmosphere; Schlenk technique;	83%

Dichloromethylsilane (75-54-7) + bromobenzene (108-86-1) → methyldiphenylsilane (776-76-1)

Conditions	Yield
With magnesium In tetrahydrofuran at 0 - 20℃; Inert atmosphere; Schlenk technique;	82%
With magnesium 2) ether; Multistep reaction;

lithium aluminium tetrahydride (16853-85-3) + chloromethyldiphenylsilane (144-79-6) → methyldiphenylsilane (776-76-1)

Conditions	Yield
In not given	78%

Benzyldimethyl<(methyldiphenylsilyl)methyl>ammonium bromide (72443-54-0) → N,N'-dimethylbenzylamine (103-83-3) + methyldiphenylsilane (776-76-1) + 1-(Diphenylmethylsilyl)-trimethylamin (54926-32-8) + N,N-dimethyl(2-methylbenzyl)amine (4525-48-8)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran for 10h; Heating; Further byproducts given;	A 3% B 77% C 14% D 25%

iodobenzene (591-50-4) + methylphenylsilane (766-08-5) → methyldiphenylsilane (776-76-1)

Conditions	Yield
With bis(tri-t-butylphosphine)palladium(0); triethylamine In tetrahydrofuran at 20℃; for 48h; Inert atmosphere;	77%
With ytterbium 1.) THF, 0 deg C, 30 min, 2.) THF, r.t., 2 h; Yield given; Multistep reaction;

Dichloromethylsilane (75-54-7) + phenylmagnesium chloride → methyldiphenylsilane (776-76-1)

Conditions	Yield
In tetrahydrofuran at 100℃; for 1h;	A 66% B 13.4%
In tetrahydrofuran at 100℃; for 1h;	A 66% B 13.4%

+ sodium bis(1,2-benzenediolato)methylsilicate → methyldiphenylsilane (776-76-1)

Conditions	Yield
In diethyl ether at 35℃; for 2h;	60%

methylphenylsilane (766-08-5) + phenylmagnesium bromide (100-58-3) → methyldiphenylsilane (776-76-1)

Conditions	Yield
With lithium chloride In tetrahydrofuran at 50℃; for 2h; Inert atmosphere;	57%

(CO)5WC(OEt)SiPh3 + ethyl vinyl ether (109-92-2) → tungsten hexacarbonyl (14040-11-0) + (CH2)C(SiPh3)(EtO) + methyldiphenylsilane (776-76-1)

Conditions	Yield
With carbon monoxide In neat (no solvent) High Pressure; under dried N2; addn. of N-methylbenzimine at 25°C to a soln. of W-complex (CO-pressure: 50 atm); stirring for 2 d at room temp., then for 1-2 h at 80-100°C; vac.-evapn. until dryness; residue dissolved in petroleum ether/ether; chromy. (silica gel/petroleum ether/ether); recrystn. from petroleum ether; elem. anal.;	A n/a B 45% C n/a

methylphenylsilane (766-08-5)

Conditions	Yield
With potassium hydride In 1,2-dimethoxyethane for 64h; Ambient temperature;	41%

→ methyldiphenylsilane + 1,2,3-Trimethyl-1,2,3-triphenyl-trisilan (42083-74-9) + C28H34Si4 (84098-82-8)

Conditions	Yield
With nickel; triphenylphosphine In tetrahydrofuran at 80℃; Product distribution; Irradiation;	A n/a B 20% C 40% D 25%

(CO)5WC(OEt)SiPh2Me + ethyl vinyl ether (109-92-2) → tungsten hexacarbonyl (14040-11-0) + (CH2)C(SiPh2Me)(EtO) + methyldiphenylsilane (776-76-1)

Conditions	Yield
With carbon monoxide In diethyl ether High Pressure; under dried N2; addn. of N-methylbenzimine at 25°C to a soln. of W-complex (CO-pressure: 50 atm); stirring for 2 d at room temp., then for 1-2 h at 80-100°C; vac.-evapn. until dryness; residue dissolved in petroleum ether/ether; chromy. (silica gel/petroleum ether/ether); recrystn. from petroleum ether; elem. anal.;	A n/a B 38% C n/a

Dimethylphenylsilane (766-77-8) → methyldiphenylsilane (776-76-1) + 1,2-diphenyltetramethyldisilane (1145-98-8)

Conditions	Yield
With ferrocenium hexafluorophosphate; [Ir(Me)2Cp*PMe3] In dichloromethane at 80℃; for 24h; Product distribution; Further Variations:; Catalysts; Temperatures; dehydrogenative coupling;	A 3.4% B 37%
With silver tetrafluoroborate; [Ir(Me)2Cp*PPh3] In dichloromethane at 80℃; for 48h; dehydrogenative coupling;	A 17.5% B 25%

(CO)5WC(OEt)SiPhMe2 + ethyl vinyl ether (109-92-2) → tungsten hexacarbonyl (14040-11-0) + (CH2)C(SiPhMe2)(EtO) + methyldiphenylsilane (776-76-1)

Conditions	Yield
under dried N2; soln. of W-complex in ethyl vinyl ether; stirred at 25° C for 6h; vacuum-evapn.; residue was solved in petrol ether/ether (20/1); eluation of all products at -30° C; vacuum evapn.; crystn. from petrol ether/ ether (10/1) at -30° C; elem. anal.;	A n/a B 34% C n/a
With carbon monoxide In neat (no solvent) High Pressure; under dried N2; addn. of N-methylbenzimine at 25°C to a soln. of W-complex (CO-pressure: 50 atm); stirring for 2 d at room temp., then for 1-2 h at 80-100°C; vac.-evapn. until dryness; residue dissolved in petroleum ether/ether; chromy. (silica gel/petroleum ether/ether); recrystn. from petroleum ether; elem. anal.;	A n/a B 34% C n/a

Upstream product

• 75-54-7 Dichloromethylsilane 
• 4319-49-7 1-aminomorpholine 
• 1172-76-5 1,2-dimethyl-1,1,2,2-tetraphenyldisilane 
• 87938-58-7 bis(o-chlorophenyl)methylsilane 
• 75302-84-0 bis(o-bromophenyl)methylsilane 
• 694-80-4 2-bromo-1-chlorobenzene 
• 75-77-4 chloro-trimethyl-silane 
• 60-29-7 diethyl ether 
• 100-59-4 phenylmagnesium chloride 
• 16853-85-3 lithium aluminium tetrahydride 
• 144-79-6 chloromethyldiphenylsilane 
• 109-92-2 ethyl vinyl ether 
• 766-77-8 Dimethylphenylsilane 
• 72443-54-0 Benzyldimethyl<(methyldiphenylsilyl)methyl>ammonium bromide 

Downstream Products

• 791-29-7 methyltriphenylsilane 
• 807-28-3 1,3-Dimethyl-1,1,3,3-tetraphenyldisiloxan 
• 18848-68-5 Methylphosphonsaeure-bis-(methyl-diphenyl-silylester) 
• 64035-67-2 3-(Methyldiphenylsilanyl)propan-1-ol 
• 7126-86-5 N,N'-Bis-trimethylsilyl-N-(methyl-diphenyl-silyl)-aethylendiamin 
• 7036-91-1 N,N'-bis-trimethylsilanyl-N-triphenylsilanyl-ethane-1,2-diamine 
• 20466-56-2 (cyclohexyloxy)diphenylmethylsilane 
• 18407-48-2 methoxy(methyl)diphenylsilane 
• 79628-22-1 heptylmethyldiphenylsilane 
• 70737-24-5 Diethyl-{2-[2-(methyl-diphenyl-silanyl)-ethoxy]-ethyl}-amine 
• 68323-02-4 Methyl-diphenyl-tridecyl-silane 
• 65179-17-1 Cyclohexylidenemethoxy-methyl-diphenyl-silane 
• 22767-77-7 1-[(1E)-prop-1-en-1-yl]naphthalene 
• 78431-70-6 Methyl-(3-naphthalen-1-yl-propyl)-diphenyl-silane 

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