1450-14-2

Basic information

• Product Name: Hexamethyldisilane
• Synonyms: HEXAMETHYLDISILANE;HMD;DISILANE M6;(CH3)6Si2;1,1,1,2,2,2-Hexamethyldisilane;CH7280;disilane,hexamethyl-;Hecamethyldisilane
• CAS NO: 1450-14-2
• Molecular Formula: C₆H₁₈Si₂
• Molecular Weight: 146.38
• EINECS: 215-911-0
• Product Categories: Standards for NMR;Analytical Chemistry;NMR Spectrometry;Si (Classes of Silicon Compounds);Silicon Compounds (for Synthesis);Si-Si Compounds;Synthetic Organic Chemistry;Blocking Agents;Protective Agents;Silylating Agents;Special Silanes;Disilanes;DisilanesVapor Deposition Precursors;Organometallic Reagents;Organosilicon;Precursors by Metal;organosilicon compounds;Chemical Synthesis;Organometallic Reagents;Pharmaceutical Intermediates
• Mol File: 1450-14-2.mol
• Article Data: 75

Chemical Properties

• Melting Point: 9-12 °C(lit.)
• Boiling Point: 112-114 °C(lit.)
• Flash Point: 29 °F
• Appearance: colorless/liquid
• Density: 0.715 g/mL at 25 °C(lit.)
• Vapor Pressure: 24.5mmHg at 25°C
• Refractive Index: n20/D 1.422(lit.)
• Storage Temp.: Flammables area
• Solubility: sol common organic solvents; insol H2O.
• Water Solubility: Insoluble in water. Soluble in alcohol, ether and acetone.
• Stability: Volatile
• BRN: 1633463
• CAS DataBase Reference: Hexamethyldisilane(CAS DataBase Reference)
• NIST Chemistry Reference: Hexamethyldisilane(1450-14-2)
• EPA Substance Registry System: Hexamethyldisilane(1450-14-2)

Safety Data

• Hazard Codes: F,Xi
• Statements: 11-36/37-43-36/37/38
• Safety Statements: 16-23-45-9-33-26-7/9
• RIDADR: UN 1993 3/PG 2
• WGK Germany: 2
• RTECS: JM9170000
• TSCA: Yes
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 1450-14-2(Hazardous Substances Data)

Usage

Chemical Properties

Colorless clear liquid

Uses

Hexamethyldisilane acts as a silylating reagent for allylic acetates, aryl halides and diketones. It is a source material for vapor deposition during silicon carbide growth. It is also used in electronic and semiconducter industries.

Application

Hexamethyldisilane is an important silane protective agent, which can synthesize sodium trimethylsilane, potassium trimethylsilane and lithium trimethylsilane.Preparation of iodotrimethylsilane.Used as trimethylsilane anion reagent.silylating or reducing reagent in combination with a Pd catalyst or a nucleophile.Replaces aromatic nitriles with TMS groups in presence of [RhCl(cod)]2.Precursor for CVD of silicon carbide.Brings about the homocoupling of arenesulfonyl chlorides in the presence of Pd2(dba)3.Used as a solvent for the direct borylation of fluoroaromatics.Reacts with alkynes to form siloles.Undergoes the silylation of acid chlorides to give acylsilanes.

Preparation

Hexamethyldisilane is produced by the reaction of methyl Grignard reagent with methylchlorodisilanes. This reaction is normally conducted in the presence of an ether such as diethyl ether, ethyl propyl ether, THF and the like.

Fire Hazard

Hexamethyldisilazane (HMDZ) is a highly flammable liquid and vapour. HMDZ liquid is lighter than water and may float on water, spreading material during fire fighting. Leaking material or fire runoff to sewer may create fire or explosion hazard. HMDZ vapours are heavier than air and can accumulate to form explosive concentrations. The vapours may also spread a considerable distance to a source of ignition, and flash back towards the source. HMDZ reacts with water to form ammonia. HMDZ is a non-conductor and, therefore, can accumulate static electrical charges when processed, handled or dispensed. HMDZ's flash point is 52 to 53°F, closed cup, for "pure" material.

Purification Methods

The most likely impurity is trimethylchlorosilane (cf boiling point). Wash it with H2O, cold conc H2SO4, H2O again, then aqueous NaHCO3, dry over CaSO4 and fractionate at atmospheric pressure. [Brown & Fowles J Chem Soc 2811 1958.] A grossly impure sample (25% impurities) was purified by repeated spinning band distillation. This lowered the impurity level to 500ppm. The main impurity was identified as 1-hydroxypentamethyldisilane. [Beilstein 4 IV 4277.]

InChI:InChI=1/C6H18Si2/c1-7(2,3)8(4,5)6/h1-6H3

Synthetic route

chloro-trimethyl-silane (75-77-4) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2)

Conditions	Yield
With sodium; lithium In tetrahydrofuran at 25 - 28℃; for 4h; Heating; Irradiation; ultrasound irrad. var. time, var. temperatures, var. metal purity;	100%
With sodium; lithium In tetrahydrofuran at 25 - 28℃; for 4h; Irradiation;	100%
With potassium fluoride; phosphorus; potassium In 5,5-dimethyl-1,3-cyclohexadiene at 90℃; for 12h; Reagent/catalyst; Temperature;	97.3%

chloro-trimethyl-silane (75-77-4) + C39H67FPSi2(1-)*Na(1+) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + C42H76FPSi3

Conditions	Yield
In diethyl ether Heating;	A 68% B 100%

benzophenone (119-61-9) + (trimethylsilyl)potassium (56859-17-7) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + tetraphenylethane-1,2-diol (464-72-2)

Conditions	Yield
In 1,2-dimethoxyethane for 12h; Ambient temperature;	A 85% B 80%

chloro-trimethyl-silane (75-77-4) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + Hexamethyldisiloxane (107-46-0)

Conditions	Yield
With sodium at 130 - 140℃; for 10h;	A 84% B n/a

1,1,3,3-tetramethylindan-2-thione (74768-58-4) + 2,2-dimesitylhexamethyltrisilane (79184-72-8) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + C31H38SSi (110354-69-3)

Conditions	Yield
In cyclohexane for 15h; Ambient temperature; Irradiation; low pressure mercury lamp;	A n/a B 82%

vanadocene monochloride + trimethylsilyl isothiocyanate (2290-65-5) → chloro-trimethyl-silane (75-77-4) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + bis(η5-cyclopentadienyl)vanadium diisothiocyanate

Conditions	Yield
In toluene Heating at 120-150°C for 10 h.;	A 73% B 32% C 76%
In toluene molar ratio V-complex/Me3SiNCS=1:2, evacuated sealed ampul (120-150°C, 10 h);	A 73% B 32% C 76%

Benzylidenemalononitrile (2700-22-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + Benzylmalononitrile (1867-37-4)

Conditions	Yield
With phenanthrene In acetonitrile for 43h; Irradiation; 300 W high pressure mercury lamp, λ>280 nm;	A 75% B 10%

hexachlorodisilane (13465-77-5) + dimethyl zinc(II) (544-97-8) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2)

Conditions	Yield
In diethyl ether Si2Cl6 and 31% excess of Zn(CH3)2 in ether at 85°C in a closed tube;;	74%

vanadocene + trimethylsilyl 2-iodobenzoate (59147-01-2) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + bis(η5-cyclopentadiene)vanadium o-iodobenzoate

Conditions	Yield
In toluene at 20℃; for 60h; Sealed tube;	A n/a B 69%

bis(trimethylsilyl)diphenylgermane (111655-78-8) + 2,3-dimethyl-buta-1,3-diene (513-81-5) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + trimethylphenylsilane (768-32-1) + 1,1-diphenyl-3,4-dimethyl-1-germacyclopent-3-ene (5764-69-2)

Conditions	Yield
In pentane Irradiation (UV/VIS); (N2), 1 h irradiated; gas chromatography; elem. anal., NMR, mass. spectra;	A 68% B 27% C 61%

chloro-trimethyl-silane (75-77-4) + trimethylsilyl cyanide (7677-24-9) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 2-(Bis-trimethylsilanyl-methyl)-1,1,1,3,3,3-hexamethyl-disilazane (72223-62-2) + 2-(Bis-trimethylsilanyl-methyl)-1,1,3,3,3-pentamethyl-1-trimethylsilanylmethyl-disilazane (138482-32-3)

Conditions	Yield
With lithium In tetrahydrofuran at 0℃; Yields of byproduct given;	A 65% B n/a C n/a

methyl(phenyl)bis(trimethylsilyl)germane (134847-65-7) + 2,3-dimethyl-buta-1,3-diene (513-81-5) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 1,3,4-trimethyl-1-(trimethylsilyl)-1-germacyclopent-3-ene (134847-66-8) + (2,3-dimethyl-3-butenyl)methyl(trimethylsilyl){o-(trimethylsilyl)phenyl}germane (134847-67-9) + trimethylphenylsilane (768-32-1) + 1,3,4-trimethyl-1-phenyl-1-germacyclopent-3-ene (51533-82-5)

Conditions	Yield
In pentane Irradiation (UV/VIS); (N2), 1.5 h irradiated; column chromatography; elem. anal., NMR, mass. spectra;	A 60% B 28% C 5% D 35% E 55%

vanadocene + trimethylsilyl 2-iodobenzoate (59147-01-2) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + η5-cyclopentadienevanadium bis-o-iodobenzoate (1428262-40-1) + cyclopenta-1,3-diene (542-92-7)

Conditions	Yield
In toluene at 100℃; for 100h; Time; Sealed tube;	A n/a B 59% C n/a

trimethylphenylsilane (768-32-1) + lithium trimethylstannyl (17946-71-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + trimethyl(phenyl)stannane (934-56-5) + hexamethyldistannane (661-69-8) + trimethyl(trimethylstannyl)silane (16393-88-7) + benzene (71-43-2)

Conditions	Yield
In tetrahydrofuran LiSnMe3 added to PhSiMe3 in THF, stirred at 24°C for 1 h or 50°C for 30 min, hydrolysis with water; org. layer extd. with ether, dried over Na2SO4; products determined by GLC;	A 0% B 0% C 50% D 0% E 0%

1,1,1,4,4,4-hexakis(trimethylsilyl)butin-2 (20932-80-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 1,2-bis(trimethylsilyl)ethane (6231-76-1) + 1,1,4,4-tetrakis(trimethylsilyl) 1,2,3-butatriene (70641-35-9) + Bis(trimethylsilyl)ethyne (14630-40-1)

Conditions	Yield
at 650℃; under 0.001 Torr; Further byproducts given;	A 7% B 5% C 41% D 16%

bis(trimethylsilyl)methane (2117-28-4) + bis-trifluoromethyl-aminooxyl (2154-71-4) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + trimethylsilyl fluoride (420-56-4) + N,N-bis(trifluoromethyl)hydroxylamine (359-63-7) + Perfluoro-2-azapropen (371-71-1)

Conditions	Yield
With bis(trimethylsilyl)methane for 4h; Ambient temperature; Further byproducts given;	A 15% B 40% C 33% D 31%

bis(trimethylsilyl)methane (2117-28-4) + bis-trifluoromethyl-aminooxyl (2154-71-4) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + trimethylsilyl fluoride (420-56-4) + N,N-bis(trifluoromethyl)hydroxylamine (359-63-7) + O-Trimethylsilyl-bis-(trifluormethyl)-hydroxylamin (20485-84-1)

Conditions	Yield
for 4h; Ambient temperature; Further byproducts given;	A 15% B 40% C 33% D 21%

(dimethylphenylgermyl)trimethylsilane (37899-63-1) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + trimethylsilan (993-07-7) + trimethylphenylsilane (768-32-1) + dimethylphenylgermane (7366-21-4) + 1,1,2,2-tetramethyl-1,2-diphenyldigermane (22702-72-3)

Conditions	Yield
With methanol In benzene Irradiation (UV/VIS); irradiation of catenate in benzene containing an excess of methanol with a 110 W low pressure Hg arc lamp at room temp. under Ar for 1-4 h; identification by GC and GC-MS;	A <1 B n/a C 37% D <1 E <1
In cyclohexane Irradiation (UV/VIS); irradiation of catenate in cyclohexane with a 110 W low pressure Hg arc lamp at room temp. under Ar for 1-4 h; identification by GC and GC-MS;	A <1 B 4% C 24% D <1 E <1

tris(trimethylsilyl)silyllithium (4110-02-5) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + tetrakis(trimethylsilyl)silane (4098-98-0) + 2,2,3,3-tetrakis(trimethylsilyl)hexamethyltetrasilane (5181-43-1) + C6H18Li2Si3 (130377-71-8)

Conditions	Yield
at 140 - 150℃;	A n/a B 10% C 27% D 35%

triethylsilane (617-86-7) + 1-<(N,N-dimethylamino)methyl>-2-benzene (155570-15-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 2-(o-tolyl)-1,1,1-triethyl-3,3,3-trimethyltrisilane + o-tolyltris(trimethylsilyl)silane + 2-<2-(N,N-dimethylamino)methylphenyl>-1,1,1-triethyl-3,3,3-trimethyltrisilane

Conditions	Yield
In cyclohexane for 1.66667h; Irradiation;	A n/a B 20% C 33% D 24%

2,3-dimethyl-buta-1,3-diene (513-81-5) + 1-<(N,N-dimethylamino)methyl>-2-benzene (155570-15-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + o-tolyltris(trimethylsilyl)silane + 1-<2-(N,N-dimethylaminomethyl)phenyl>-trimethylsilyl-3,4-dimethylsilacyclopent-3-ene

Conditions	Yield
for 4.5h; Irradiation;	A 33% B 9% C 16%

1-<(N,N-dimethylamino)methyl>-2-benzene (155570-15-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 2-(o-tolyl)-1,1,1-triethyl-3,3,3-trimethyltrisilane + o-tolyltris(trimethylsilyl)silane + 2-<2-(N,N-dimethylamino)methylphenyl>-1,1,1-triethyl-3,3,3-trimethyltrisilane

Conditions	Yield
With triethylsilane In cyclohexane for 1.66667h; Irradiation;	A n/a B 20% C 33% D 24%

ethanol (64-17-5) + bis[2,4,6-tris((dimethylamino)methyl)phenoxy]bis(trimethylsilyl)silane (394739-08-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + [2,4,6-tris((dimethylamino)methyl)phenoxy]trimethylsilane (161787-77-5) + C20H41N3O2Si2 + C32H58N6O3Si

Conditions	Yield
at 120℃; for 48h;	A 2% B 33% C 32% D 31%
In cyclohexane for 4h; Product distribution; Irradiation;	A 7% B 23% C 20% D 6%

chloro-trimethyl-silane (75-77-4) + phenyldi-n-butylchlorosilane (114953-59-2) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 1-phenyl-1,1-di-n-butyltrimethyldisilane (114953-60-5)

Conditions	Yield
With potassium alloy; sodium In benzene for 144h; Heating;	A n/a B 32%

2,3-dimethyl-buta-1,3-diene (513-81-5) + bis[2,4,6-tris((dimethylamino)methyl)phenoxy]bis(trimethylsilyl)silane (394739-08-3) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + [2,4,6-tris((dimethylamino)methyl)phenoxy]trimethylsilane (161787-77-5) + [3,5-bis-dimethylaminomethyl-2-(3,4-dimethyl-1-trimethylsilanyl-2,5-dihydro-1H-silol-1-yloxy)-benzyl]-dimethyl-amine + {3,5-bis-dimethylaminomethyl-2-[3,4-dimethyl-1-(2,4,6-tris-dimethylaminomethyl-phenoxy)-2,5-dihydro-1H-silol-1-yloxy]-benzyl}-dimethyl-amine

Conditions	Yield
at 120℃; for 168h; Product distribution;	A 3% B 32% C 29% D 2%

chloro-trimethyl-silane (75-77-4) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + tris(trimethylsilyl)amine (1586-73-8)

Conditions	Yield
With potassium graphite; Co2(2,2,2-tri(diisopropylphosphinomethylamino)triphenylamine(-3H)); nitrogen In tetrahydrofuran at 25.84℃; under 760.051 Torr; for 12h; Catalytic behavior; Kinetics; Reagent/catalyst; Inert atmosphere;	A n/a B 30%
With trans-[Mo[N2]2(depf)2]; nitrogen; lithium In tetrahydrofuran at 22 - 24℃; under 760.051 Torr; for 100h;	A 16.53 mmol B 0.55 mmol
With trans-[Mo[N2]2(depf)2]; nitrogen; sodium In TETRAHYDROPYRANE at 22 - 24℃; under 760.051 Torr; for 100h;	A 0.29 mmol B 1.08 mmol

adamantane-2-thione (23695-65-0) + 2,2-dimesitylhexamethyltrisilane (79184-72-8) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + C28H36SSi

Conditions	Yield
In cyclohexane for 15h; Ambient temperature; Irradiation; low pressure mercury lamp;	A n/a B 29%

ferrocenium hexafluorophosphate + (C5H5)2Nb(Si(CH3)3)Cl → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + {(C5H5)2Nb(CH2Si(CH3)3)Cl}(1+)*PF6(1-)={(C5H5)2Nb(CH2Si(CH3)3)Cl}PF6 (106420-40-0)

Conditions

Yield

With CH2Cl2 In dichloromethane addn. of cold (-78°C) CH2Cl2 to mixt. of Cp2Nb(SiMe3)Cl and (Cp2Fe)PF6 in 1:1 molar ratio cooled to -78°C under inert atm., allowed to warm to room temp.; further products; evapd., extd. (Et2O), evapn. gave Cp2Fe (NMR, IR); residue extd. (CH2Cl2), soln. filtered, concd., cooling to -45°C gave cryst. target product (elem.anal.); crystn. (MeCN) of residue gave (Cp2NbCl2)PF6 (IR); others products analyzed by GC;

A <1 B 28%

(dimethylphenylgermyl)trimethylsilane (37899-63-1) + 2,3-dimethyl-buta-1,3-diene (513-81-5) → 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + trimethylphenylsilane (768-32-1)

Conditions	Yield
In cyclohexane Irradiation (UV/VIS); irradiation of catenate in cyclohexane containing an excess of 2,3-dimethylbutadiene with a 110 W low pressure Hg arc lamp at room temp. under Ar for 1-4 h; identification by GC and GC-MS;	A <1 B 23%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + Allyl acetate (591-87-7) → propene (187737-37-7) + trimethylsilyl acetate (2754-27-0) + allyl-trimethyl-silane (762-72-1) + (E)-trimethyl(prop-1-en-1-yl)silane (4964-03-8)

Conditions	Yield
tetrakis(triphenylphosphine) palladium(0) at 180℃; for 2h; high pressure, under nitrogen;	A 2 % Chromat. B 100% C 48% D 48%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + (α,α-dichlorobenzyl)trimethylsilane (25115-43-9) → (E)-α,β-bis(trimethylsilyl)stilbene (24894-87-9)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In 1,3,5-trimethyl-benzene at 130℃; for 18h;	100%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + α,β,4-trichlorobenzyltrimethylsilane (53119-90-7) → (E)-α,β-bis(trimethylsilyl)-4,4'-dichlorostilbene

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0) In 1,3,5-trimethyl-benzene at 130℃; for 24h;	100%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → Hexamethyldisiloxane (107-46-0)

Conditions	Yield
With hydrogenchloride; diethyl ether at 120℃; for 70h; Sealed tube;	100%
With carbon monoxide; hydrogen; nickel at 200℃; under 750.06 Torr; for 2h;	59%
With bromobenzene; calcium In water for 1h; Ambient temperature;	5%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 1,3-diphenyl-propen-3-one (614-47-1) → (E)-1,3-diphenyl-3-trimethylsilyl-2-propene (30262-98-7)

Conditions	Yield
With copper(I) trifluoromethanesulfonate benzene In various solvent(s) at 100℃; for 19h;	100%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 3',4'-dimethoxy-1,1'-biphenyl-4-ol (17190-05-5) → 4-(3',4'-methoxyphenyl)phenol trimethylsilyl ether

Conditions	Yield
In pyridine at 115℃; for 3h;	100%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 3'-nitro-[1,1'-biphenyl]-4-ol (53059-30-6) → 4-(3'-nitrophenyl)phenol trimethylsilyl ether (923294-79-5)

Conditions	Yield
In pyridine at 115℃; for 3h;	100%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 2-bromo-4-phenylphenol (92-03-5) → (2-bromo-4-phenyl)phenol trimethylsilyl ether

Conditions	Yield
In pyridine at 115℃; for 3h;	100%

p-cresol (106-44-5) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → trimethyl(4-methylphenoxy)silane (17902-32-8)

Conditions	Yield
In pyridine at 115℃; for 3h;	100%
With lanthanum(III) nitrate hexahydrate In acetonitrile at 20℃;	90%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 4-Phenylphenol (92-69-3) → 4-phenylphenol trimethylsilyl ether (1023-13-8)

Conditions	Yield
In pyridine at 115℃; for 3h;	100%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 2'-fluoro-[1,1'-biphenyl]-4-ol (321-62-0) → 4-(2'-fluorophenyl)phenol trimethylsilyl ether (923294-77-3)

Conditions	Yield
In pyridine at 115℃; for 3h;	100%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + (E)-1,3-diphenyl-2-propen-1-ol (62668-02-4) → (R)-(E)-1,3-diphenyl-3-trimethylsilylpropene (106137-98-8)

Conditions	Yield
With tetrakis(acetonitrile)palladium(II) bis(tetrafluoroborate); allyl alcohol In methanol; dimethyl sulfoxide at 60℃; Inert atmosphere;	100%
With Pd(BF4)2(MeCN)4 In methanol; dimethyl sulfoxide at 50℃; for 15h; Air; regioselective reaction;	69%

iodobenzene (591-50-4) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → trimethylphenylsilane (768-32-1)

Conditions	Yield
With sodium methylate In N,N,N,N,N,N-hexamethylphosphoric triamide	99%
With sodium hydroxide; (o-hydroxyphenyl)diphenylphosphine; PdCl(ϖ-C3H5)2 In tetrahydrofuran at 100℃; for 10h; Substitution; Silylation;	83%
With sodium acetate In N,N-dimethyl acetamide at 120℃; for 24h; Catalytic behavior; Solvent; Reagent/catalyst; Inert atmosphere;	70%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + (1R*,2R*)-(Z)-4-chloro-2-methyl-1-phenyl-3-buten-1-ol (114716-44-8) → (1R*,2R*,3Z)-4-chloro-2-methyl-1-phenyl-1-trimethylsilyloxy-3-butene

Conditions	Yield
for 96h; Ambient temperature;	99%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 1,1-dimethylhydrazine (57-14-7) → N,N-dimethyl-N',N'-bis(trimethylsilyl)hydrazine (684-26-4)

Conditions	Yield
With potassium hydride In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide for 24h; Ambient temperature;	99%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + (2R,3S)-3-Isopropyl-N-(2,4,6-trimethylphenylsulfonyl)-2-vinylaziridine (187532-11-2) → (E,4S)-5-methyl-1-trimethylsilyl-4-[N-(2,4,6-trimethylbenzene)sulfonyl]amino-2-hexene

Conditions

Yield

Stage #1: 1,1,1,2,2,2-hexamethyldisilane With n-butyllithium In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -78℃; for 1h; Metallation; Stage #2: In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -78 - -30℃; transmetallation; Stage #3: (2R,3S)-3-Isopropyl-N-(2,4,6-trimethylphenylsulfonyl)-2-vinylaziridine In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -78℃; Ring cleavage;

99%

pyridine (110-86-1) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → 4-trimethylsilylpryridine (18301-46-7)

Conditions	Yield
Stage #1: pyridine; 1,1,1,2,2,2-hexamethyldisilane With sodium methylate In N,N,N,N,N,N-hexamethylphosphoric triamide for 2h; Stage #2: With water Further stages.;	99%

pyridine (110-86-1) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → 4-trimethylsilyl-1,4-dihydropyridine

Conditions	Yield
Stage #1: pyridine; 1,1,1,2,2,2-hexamethyldisilane With sodium methylate In N,N,N,N,N,N-hexamethylphosphoric triamide for 0.25h; Stage #2: With water Further stages.;	99%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + (E)-benzalacetone (1896-62-4) → ((Z)-1-Trimethylsilanyl-3-trimethylsilanyloxy-but-2-enyl)-benzene

Conditions	Yield
With allyl(cyclopentadiene)palladium(II); trimethylsilyl trifluoromethanesulfonate In benzene at 20℃; for 1h;	99%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + 1-Iodonaphthalene (90-14-2) + 9-(toluene-4-sulfonyl)-1,4-dihydro-1,4-epiazano-naphthalene → 9-Tosyl-2-(trimethylsilyl)-3-(2 (trimethylsilyl)naphthalen-1-yl)-1,2,3,4-tetrahydro-1,4-epiminonaphthalene

Conditions	Yield
With palladium diacetate; caesium carbonate; triphenylphosphine In N,N-dimethyl-formamide at 60℃; for 12h; Schlenk technique; Inert atmosphere;	99%

1,3 dithiane (505-23-7) + ethyl bromide (74-96-4) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → 2-ethyl-2-(trimethylsilyl)-1,3-dithiane (72658-48-1)

Conditions	Yield
Mechanism; multistep reaction; other electrophiles, influence of temperature and reaction time;	98%
Yield given. Multistep reaction;

pyridine-4-carboxylic acid (55-22-1) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → trimethylsilyl 4-pyridinecarboxylate (25436-39-9)

Conditions	Yield
RT, then warmed slowly until violent gas evolution occured;	98%

5-fluorouracil (51-21-8) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → 5-fluoro-2,4-bis(trimethylsilyloxy)pyrimidine (17242-85-2)

Conditions	Yield
With ammonium sulfate for 14h; Heating;	98%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + benzyl alcohol (100-51-6) → benzyloxy-trimethylsilane (14642-79-6)

Conditions	Yield
With lanthanum(III) nitrate hexahydrate In acetonitrile at 20℃;	98%
With 1% Au/TiO2 In ethyl acetate at 25℃; for 1h; Inert atmosphere;	96%
With natural kaolinitic clay In tetrachloromethane for 2h; Ambient temperature;	90%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + (2R,3S)-3-methyl-N-(4-methylbenzenesulfonyl)-2-vinylaziridine (187531-92-6) → (E,4S)-1-trimethylsilyl-4-[N-(4-methylbenzene)sulfonyl]amino-2-pentene

Conditions

Yield

Stage #1: 1,1,1,2,2,2-hexamethyldisilane With n-butyllithium In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -78℃; for 1h; Metallation; Stage #2: In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -78 - -30℃; transmetallation; Stage #3: (2R,3S)-3-methyl-N-(4-methylbenzenesulfonyl)-2-vinylaziridine In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; hexane at -78℃; for 0.5h; Ring cleavage;

98%

4-nitrobenzyl chloride (619-73-8) + 1,1,1,2,2,2-hexamethyldisilane (1450-14-2) → 4-nitrobenzyl trimethylsilyl ether (14856-73-6)

Conditions	Yield
With lanthanum(III) nitrate hexahydrate In acetonitrile at 20℃;	98%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + octanol (111-87-5) → trimethyl(oct-1-yloxy)silane (14246-16-3)

Conditions	Yield
With lanthanum(III) nitrate hexahydrate In acetonitrile at 20℃;	98%
With 1% Au/TiO2 In ethyl acetate at 25℃; for 1.5h; Inert atmosphere;	97%

1,1,1,2,2,2-hexamethyldisilane (1450-14-2) + rac-octan-2-ol (4128-31-8) → trimethyl-(1-methyl-heptyloxy)-silane (18023-52-4)

Conditions	Yield
With lanthanum(III) nitrate hexahydrate In acetonitrile at 20℃;	98%

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 3439-38-1 trimethylsilylethane 
• 16029-98-4 trimethylsilyl iodide 
• 768-32-1 trimethylphenylsilane 
• 544-97-8 dimethyl zinc(II) 
• 75-16-1 methylmagnesium bromide 
• 75-21-8 oxirane 
• 79184-72-8 2,2-dimesitylhexamethyltrisilane 
• 109-99-9 tetrahydrofuran 
• 106-88-7 ethyloxirane 
• 96-09-3 styrene oxide 
• 67-56-1 methanol 
• 993-07-7 trimethylsilan 
• 110-05-4 di-tert-butyl peroxide 

Downstream Products

• 64957-72-8 2-(3-methoxy-2-trimethylsilanyl-phenyl)-4,4-dimethyl-4,5-dihydro-oxazole 
• 3844-94-8 1-(trimethylsilyl)-1-hexyne 
• 71491-61-7 3-(2-trimethylsilyl-1,3-dithian-2-yl)cyclohexanone 
• 119340-78-2 2-benzyl-2-trimethylsilyl-1,3-dithiane 
• 31593-52-9 2-benzyl-1,3-dithiane 
• 110-86-1 pyridine 
• 107-46-0 Hexamethyldisiloxane 
• 17379-37-2 (pyridin-3-yl)trimethylsilane 
• 131216-48-3 1-iodo-1-(trimethylsilyl)-3-phenylpropane 
• 17921-68-5 (4-cyanophenyl)trimethylsilane 
• 25436-37-7 trimethylsilyl 3-pyridinecarboxylate 
• 17881-49-1 (pyridine-2-carbonyloxy)trimethylsilane 
• 1825-61-2 Trimethylmethoxysilane 
• 4112-23-6 1-sila-1,1-dimethylethylene 

Relevant articles and documents

Disproportionation of Trimethylsilyl at 25 deg C. Mercury Photosensitization of Trimethylsilane

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Thermal SiSi/SiSi redistribution of hexaorganodisilane. A new thermally 'forbidden' molecular reaction

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Some Aspects of Chemistry of the N->Si Chelated Aryloxydihydrosilanes R(ArO)SiH2(R = Ph, ArO) and of the 2,2-Diaryloxytrisilane (Me3Si)2Si(OAr)2{ArO = 2,4,6-[(CH3)2NCH2]3C6H2O}

Reactions of the pentacoordinate aryldioxydihydrosilane Ph(Ar)SiH2 (1) with hydroxyl groups, carbonyl derivatives and PCl5 resulted in formation of new alcoxylated, phenoxylated and halogenated hydrosilanes Ph(ArO)(H)X (X = Cl, OR, OAr, OC(O)R), respectively. Treatment of the hexacoordinated (4+2) diaryloxydihydrosilane (ArO)2SiH2 (2) with N-chloro- or N-bromosuccinimide, trimethylsilyltriflate or iodine yielded the novel stable silicenium ion [(ArO)2(H)Si](1+)X(1-). Reactions of 2 with sulfur S8 and the transition metal complex Fe(CO)5 have resulted in the isolation of the new complexes (ArO)2Si = E [E = S, Fe(CO)4]. Decomposition modes of the tetracoordinate 2,2-diaryloxytrisilane (Me3Si)2Si(OAr)2 (3) on thermolysis and photolysis have also been studied; two pathways involving formation of the two silylenes (ArO)(Me3Si): and (ArO)2Si: have been identified by trapping experiments

L'electrosynthese, une voie simple d'acces aux di- et polysilanes

Electrochemical reduction of chlorosilanes, at constant current intensity, in a single compartment cell fitted with a sacrificial aluminium anode, is a practical and convenient route to di-, tri-, and poly-silanes.

Intriguing tetrasodium dication cluster Na4/2+ stabilized between two silyl(fluorosilyl)phosphanide shells [8]

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1: 2-Adducts from Silylenes and 1,3-butadiene

Photochemical generation of dimethylsilylene, methyl(phenyl)silylene and diphenylsilylene in the presence of high concentrations of 1,3-butadiene leads to the formation of 1-sila-3,4-divinylcyclopentanes as major products in addition to the anticipated 1-silacyclopent-3- enes.Also obtained are the ene-reaction products from the silenes, formed by formal 1,3-silyl shifts in the bis(trimethylsilyl)arylsilanes that are employed as the photochemical precursors of MePhSi: and Ph2Si:.Evidence is presented that both the divinylsilacyclopentanes and the silacyclopent-3-enes arise from vinylsilirane intermediates that can be trapped by acetone, yielding stable 3,3-dimethyl-4-vinyl-1- sila-2-oxolanes.Keywords: Silicon; Silylene

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Attenuation of Ni(0) Decomposition: Mechanistic Insights into AgF-Assisted Nickel-Mediated Silylation

In nickel-mediated Kumada cross-coupling reactions, low valent active nickel complexes are often generated in situ and the ligands usually govern the reactivity or stability of these complexes. However, the decomposition of active nickel complexes is inev

Synthesis method of hexamethyl disilane

The invention discloses a synthesis method of hexamethyl disilane and relates to a chemical process. The synthesis method includes: at the absence of oxygen, heating and stirring the inside of a reaction kettle added with xylene, crown ether and metal sodium, and dropwise adding trimethyl chlorosilane into the reaction kettle; after finishing, controlling temperature in the reaction kettle, holding the temperature, dropwise adding water into the reaction kettle when the temperature in the reaction kettle is lowered to 50+/-5 DEG C, and standing for layering; distilling for dehydration throughan oil-water separator to obtain a crude product-hexamethyl disilane. With the participation of the crown ether, metal sodium is used to react with trimethyl chlorosilane, so that electric potential of metal sodium is changed, activity of metal sodium is improved, and yield of the crude product can reach 73.17%. The synthesis method is simple and easy to control and convenient for industrial production.