Chlorotrimethylsilane chloride

A. l-THmethyleilyloxyayalopentsne. A 1-L, two-necked, round-bottomed flask is equipped with a mechanical stirrer and a reflux condenser having a drying tube (calcium chloride). The flask is charged with 200 mL of dimethylformamide (Note 1), 45 g (0.54 mol) of cyclopentanone (Note 2), 65.5 g (0.6 mol) of chlorotrimethylsilane (Note 2) and 185 mL (1.33 mol) of triethylamine (Note 1), and the mixture is refluxed for 17 hr (Note 3). The mixture is cooled, diluted with 350 mL of pentane, and washed four times with 200-mL portions of cold saturated aqueous sodium hydrogen carbonate. The... 

Under the most favourable reaction conditions when methyl chloride is used the crude product from the reaction tube will be composed of about 73.5% dimethyldichlorosilane, 9% trichloromethysilane and 6% chlorotrimethylsilane together with small amounts of other silanes, silicon tetrachloride and high boiling residues. 

Chemical Designations - Synonyms Chlorotrimethylsilane Trimethylsilyl chloride Chemical Formula (CHjjjSiCl. 

THF THP TIPS TIPSOTf TMEDA TMS TMSC1 TMSCN TMS I TMSOTf Ts tetrahydrofuran tetrahydropyranyl tri-isopropylsilyl tri-isopropylsilyl trifluoromethanesulphonate AVV,N N -tetramethylethylenediamine trimethylsilyl trimethylsilyl chloride (chlorotrimethylsilane) trimethylsilyl cyanide (cyanotrimethylsilane) trimethylsilyl iodide (iodotrimethylsilane) trimethylsilyl trifluoromethanesulphonate tosyl (p-tolucnesulphonyl)... 

Chlorotrimethylsilane can be added to alkenes to give alkyl chlorides. 1-Hexene reacts with MesSiCl in water to give 2-chlorohexane. Treatment of an alkene with KHF2 and Sip4 leads to the alkyl fluoride. ... 

A. 1-Trimethylsilyloxycyclohexene. In a 500-ml. three-necked, round-bottomed flask fitted with a mechanical stirrer, a reflux condenser protected with a calcium chloride tube, and a rubber septum are placed 100 ml. of N,Af-dimethylformamide (Note 1) and 60.6 g. (0.60 mole) of triethylamine (Note 2). The solution is stirred while 32.6 g. (0.30 mole) of chlorotrimethylsilane (Note 3) and 24.5 g. (0.25 mole) of cyclohexanone are injected in succession through the septum into the flask. The resulting mixture is stirred and heated under reflux for 6 hours, cooled to room temperature,... 

The diol function of 130 was protected as its acetonide 131 (88 %). Next, the enone function was installed by a-selenation of the enoxysilane, followed by peroxide oxidation and elimination (57 % over two steps). Finally, the unsaturated ketone 132 was homologated by 1,4-addition of trimethylsilylmethyl magnesium chloride, trapping with chlorotrimethylsilane, and reoxidation, to afford the target 117 (88 %). 

Trimethylsilyl chloride (Aldrich Chlorotrimethylsilane) Silane, chlorotrlmethyl- (8,9) (75-77-4)... 

The a-arylamino nitriles 251, obtained from primary aromatic amines, trimethylsilyl cyanide and acetone in the presence of zinc chloride, react with methyllithium to give A-t-butylarylamines 252287. Af,Af-Bis(trimethylsilyl)amines 253 (R = allyl, benzyl, 3-phenylpropyl etc.) are formed in 50-88% yields by the action of chlorotrimethylsilane on primary amines in the presence of a catalytic amount of titanium(IV) chloride288. 

The most convenient synthesis of halogenopyrazines and -quinoxalines is by halogenation of pyrazinones and quinoxalinones with phosphoryl or other acid halides for example, 5-hydroxy-2-pyrazinecarboxylic acid, rather than 5(477)-pyrazinone-2-carboxylic acid, is chlorinated with phosphorus pentachloride/phosphoryl chloride to afford a 63% yield of 5-chloro-2-pyrazinecarbonyl chloride <1994SL814>. Sato and Narita provided an improved synthesis of various halogenopyrazines in which 2(l//)-pyrazinones were activated with chlorotrimethylsilane to give silyl ethers (Section 8.03.7.3). This procedure is most effective for synthesis of bromopyrazines whose overall yields are 62-81% <1999JHC783>. Bromopyrazine is directly prepared by treatment of 2-(l//)-pyrazinone with phosphoryl... 

In the cyclic series several examples, as summarized above, have been provided. The diastereoselectivity, l or u, essentially can be controlled by the choice of the halide in the Grignard reagent and the additive, i.e., employing either organomagnesium bromide with copper(I) bromide and a phosphine, or organomagnesium chloride with copper(I) bromide and chlorotrimethylsilane (see also syn/anti selectivity in Section 1.1.1.2.). 

Substituted cyclohexanones, bearing a methyl, isopropyl, tert-butyl or phenyl group, give, on deprotonation with various chiral lithium amides in the presence of chlorotrimethylsilane (internal quench), the corresponding chiral enol ethers with moderate to apparently high enantioselec-tivity and in good yield (see Table 2)13,14,24> 29 36,37,55. Similar enantioselectivities are obtained with the external quench " technique when deprotonation is carried out in the presence of added lithium chloride (see Table 2, entries 5, 10, and 30)593. 

Synonym Gamma-Chloropropylene Oxide 3-Chloro-1,2-Propylene Oxide Chlorosulfonic Acid Chlorothene Chiorotoluene, Alpha Alpha-Chlorotoluene Omega-Chlorotoluene Chlorotrifluoroethylene Chlorotrimethylsilane Chlorsulfonic Acid Clilorylen Clip Chromic Acid Chromic Anhydride Chromic Oxide Chromium (VI) Dioxychloride Chromium Oxychloride Chromium Trioxide Chromyl Chloride Cianurina Citric Acid Citric Acid, Diammonium Salt Clarified Oil Clorox Cc Ral Coal Tar Oil Cobalt Acetate Cobalt Acetate Tetrahydrate Cobalt (II) Acetate Cobalt Chloride Cobalt (II) Chloride Cobaltous Acetate Cobaltous Chloride Cobaltous Chloride Dihydrate Cobaltous Chloride Hexahydrate Cobaltous Nitrate Cobaltous Nitrate Hexahydrate Cobaltous Sulfate Heptahydrate Cobalt Nitrate Cobalt (II) Nitrate Cobalt Sulfate Compound Name Epichlorohydrin Epichlorohydrin Chlorosulfonic Acid Trichloroethane Benzyl Chloride Benzyl Chloride Benzyl Chloride Trifluorochloroethylene Trimethylchlorosilane Chlorosulfonic Acid Trichloroethylene Cumene Hydroperoxide Chromic Anhydride Chromic Anhydride Chromic Anhydride Chromyl Chloride Chromyl Chloride Chromic Anhydride Chromyl Chloride Mercuric Cyanide Citric Acid Ammonium Citrate Oil Clarified Sodium Hypochlorite Coumaphos Oil Coal Tar Cobalt Acetate Cobalt Acetate Cobalt Acetate Cobalt Chloride Cobalt Chloride Cobalt Acetate Cobalt Chloride Cobalt Chloride Cobalt Chloride Cobalt Nitrate Cobalt Nitrate Cobalt Sulfate Cobalt Nitrate Cobalt Nitrate Cobalt Sulfate... 

An exothermic reaction between cyclopropane 1 and TiCl in methylene chloride produces a wine-red solution of a mixture of titanium homoenolate 2 and chlorotrimethylsilane [10, 19]. When the reaction is performed in hexane, the titanium species precipitates in the form of fine violet needles (approx 90% isolated yield, Eq. (9)). 

Several attempts to prepare palladium(II)-olefin complexes have failed. Thus, organosilicon groups from /3-trimethylsilylstyrene were cleaved (as chlorotrimethylsilane) by palladium(II) chloride (164) with formation of trans,tran.s-1,4-diphenyl-1,3-butadiene. 

B. 2,4-Bis(trimethylsilyloxy)-5-methylpyriniidine. In an oven-dried, 1-L, round-bottomed flask Is placed thymine (12.6 g, 0.1 mol) (Note 1) and chlorotrimethylsilane (Note 7) in 300 mL of benzene (Note 8) under an argon atmosphere. To the stirred suspension is added triethylamine (20.2 g, 0.2 mol) (Note 9) dropwise via a dropping funnel over 1 hr. After the addition is complete, the reaction is stirred overnight. The precipitated triethylammonium chloride and unreacted thymine are removed by suction filtration (Note 10) and the solid is washed with dry benzene (2 x 30 mL). The solvent is then removed with a rotary evaporator. The resulting viscous oil is distilled... 

Reductive coupling of carbonyls to alkenes Titanium(IV) chloride-Zinc, 310 of carbonyls to pinacols Titanium(III) chloride, 302 Titanium(IV) chloride-Zinc, 310 of other substrates Samarium(II) iodide, 270 Reductive cyclization 2-(Phenylseleno)acrylonitrile, 244 Tributylgermane, 313 Tributyltin hydride, 316 Triphenyltin hydride, 335 Trityl perchlorate, 339 Reductive hydrolysis (see Hydrolysis) Reductive silylation Chlorotrimethylsilane-Zinc, 82... 

Triphenylphosphine-Diethyl azodicar-boxylate, 332 Other substitutions Allyltrimethylsilane, 11 Benzylamine, 79 Bromodimethylborane, 47 Chlorotrimethylsilane-Lithium, 81 Crotyltrimethylsilane, 86 Diethylzinc-Titanium(IV) chloride, 21 Lithium bis(dimethylphenylsily 1)-cuprate, 161... 

Metal-containing compounds, Zinc Compounds (Continued) (Carboethoxyalkyl)zinc iodide, 220 (Carboethoxyethyl)zinc iodide, 220 (Carboethoxypropyl)zinc iodide, 220 Chlorotrimethylsilane-Zinc, 82 (Cyanomethyl)zinc bromide, 221 Dibromomethane-Zinc-Copper(I) chloride, 93... 

Reactive metal anodes are quite effective in reactions of aryl chlorides in the presence of a large excess of chlorotrimethylsilane in an undivided cell using a sacrificial aluminum anode in THF/HMPA (4 1) which provide the corresponding aryltrimethylsilanes (equations 76 and 77)101402> p is metPod does not require any diaphragms since oxidation of the aluminum anode takes place predominantly as the anodic reaction (equation 76). When excess amount of electricity is passed, traw.s-tris(lriruclhylsilyl)chlorohcxa-1,3-dienes are formed predominantly (equation 78). 

Hydroxysilatrane (66) can undergo nucleophilic displacement at silicon. For example, it reacts with acetyl chloride (in the presence of Et3N) or with acetic acid/acetic anhydride to yield unstable 1-acetoxysilatrane 67 (equation 95)69. 1-Trimethylsiloxysilatrane (68) was obtained by treatment of 66 with chlorotrimethylsilane (equation 96)69. The reaction of 66 with diphenylchlorophosphine in THF led to the substitution product 69 in 37% yield. When treated with sulfur the latter compound was converted to the corresponding thio derivative 70 (equation 97)325. 

A number of a,/J-unsaUiraled acyl silanes have been prepared from silyl enol ethers of acyl silanes (Scheme 41)129. Addition of phenyl sulphenyl chloride to the silyl enol ether with subsequent elimination of chlorotrimethylsilane gives the a-(phenylthio)acyl silane. Oxidation to the sulphoxide followed by in situ elimination of benzenesulphenic... 

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