Ethylene derivatives silanes

Acetyl peroxide Silanes from ethylene derivatives s. 3, 534 (CHsCOO)s... 

Synthesis of ethylene derivs. from silanes and oxo compds. 

Relatively non-toxic tris(trimethylsilyl)silane performs the same function as Bu3SnH in standard radical-chain reactions, such as hydrocarbon synthesis from ethylene derivs. and iodides. E A mixture of cyclohexyl iodide, acrylonitrile, and 1.2 eqs. tris(trimethylsilyl)silane in toluene heated at 70-90° for 4-5 h in the presence of a little AIBN product. Y 90%. Regioselectivity may also be enhanced, and reaction times... 

Reactions with iron carbonyl Synthesis of silanes and ethylenesilanes from ethylene derivatives... 

Oxidative allq lation. The work of Murai and Kakiuchi on the ruthenium-catalysed ortho-C-H alleviation of aromatic ketones with olefins using [RuH2(CO)(PPh3)3] as precursor has been studied extensively. However, it is limited to certain olefins, such as vinyl silanes, styrene derivatives and ethylene. 

Cuprous chloride Silanes from ethylene derivatives 685. G1... 

The six-position may be functionalized by electrophilic aromatic substitution. Either bromination (Br2/CH2Cl2/-5°) acetylation (acetyl chloride, aluminum chloride, nitrobenzene) " or chloromethylation (chloromethyl methyl ether, stannic chloride, -60°) " affords the 6,6 -disubstituted product. It should also be noted that treatment of the acetyl derivative with KOBr in THF affords the carboxylic acid in 84% yield. The brominated crown may then be metallated (n-BuLi) and treated with an electrophile to form a chain-extender. To this end, Cram has utilized both ethylene oxide " and dichlorodimethyl-silane in the conversion of bis-binaphthyl crowns into polymer-bound resolving agents. The acetylation/oxidation sequence is illustrated in Eq. (3.54). 

Alternatively, some conclusions can be derived from the relative reactivities of car-banions. For example, DePuy and colleagues13 made use of a clever method involving reactions of silanes with hydroxide ion to deduce acidities of such weak acids as alkanes and ethylene. The silane reacts with hydroxide ion to form a pentacoordinate anion that ejects a carbanion held as a complex with the hydroxysilane rapid proton transfer gives the stable silanoxide ion and the carbon acid (equation 5). 

The determination of fluoride in water and inorganic phosphates is described after its conversion to triethylfluorsilane by reaction with triethylchlorsilane in a hydrochloric acid medium The silane derivative is extracted into tetrachloro-ethylene. 

When the ketone contains a bulky group, such as t-butyl, a TMS containing alcohol is obtained instead of a disubstituted hydrocarbon. If the solvent is changed from HMPT to tetramethylurea (TMU), the aryl ring is silylated and a ketone is isolated [88]. When less than 2 Eq of TMSCl are employed, the reaction products contain no silane species. The cyclopropyl and ethylenic benzene derivatives are postulated to arise from a carbene insertion into the f-Bu group and a Me group rearrangement [88]. 

All these complexes are catalytically active for hydrosilylation and dehyd-rogenative silylation of ethylene. High turnovers and high selectivity for vinyl derivatives may be obtained using both mono- and bis-silanes as reagents. " ... 

A nucleotide base-imprinted polymer membrane has been reported in which methacrylic acid was used as a functional monomer for the imprinting of an adenine derivative, 9-ethyladenine [41], A free-standing film was prepared by polymerizing a DMF solution containing methacrylic acid and ethylene glycol dimethacrylate on a silanized glass slide at 65-70 °C under nitrogen atmosphere. 

The possibility of synthesizing alkyl and alkenyl silanes from olefins and acetylenes with silane, SiH, has been investigated by White and Rochow (128). With ethylene various ethyl derivatives of silane and disilane were obtained under conditions suggestive of a free-radical mechanism ... 

---