A. N. Nesmeyanov

Reactivity of diphenylstibine

1. n nThe reaction of diphenylstibine with ethynylbenzene leads to diphenylstyrylstibine. n n n n n2. n nWith carbon tetrachloride diphenylstibine forms chloroform, benzene, chlorodiphenylstibine, and hydrogen chloride, and with benzotrichloride - benzylidene chloride and chlorodiphenylstibine. A reaction scheme is proposed for this process. n n n n n3. n nThe reactions of diphenylstibine with dilute hydrochloric acid, with acetic acid, and with benzoic acid go with liberation of hydrogen and lead, respectively, to chloro-, acetoxy-, and (benzoyloxy)-diphenylstibines.

Bimetallic derivatives of the ethylene series

1. n nThe addition of organometallic hydrides to ethynyl organometallic compounds gave a series of bimetallic derivatives of the ethylene series in a mixture of cis- and trans-isomers: (n-C4H9)3SnCH=CHSb(C4H9-n)2; (n-C4H9)3SnCH=CHP(C4H9-n)2; (n-(C4H9-n)2SbCH=CHAs((C4H9-n)2; (C6H5)3SnCH=CHP(C4H9-n)2; (nC4H9-n)2SbCH=CHP(C4H9-n)2; (C6H5)2SbCH=CHP(C4H9-n)2. n n n n n2. n nA reaction of di-n-butylstibine with ethynyl-di-n-butoxyborate gave: (n-C4H9)2SbCH=CHSn(C4H9-n)2; (n-C4H9-n)2SbB(OC4H9-n)2.

Products of mercuric salt addition to dis ubstituted acetylenes

The syntheses and properties of cls and trans-1-methyl-2-acetoxy -1-propen-1-ylmercury acetate, 1-methyl2-acetoxy-2-propen-1-ylmercury acetate and 1,2-diphenyl-2-acetoxy-1-ylmercury acetate are described.

Reaction of some organometallic monohydrides with ethynylferrocene

1. n nThe addition of triphenylstannane, triphenylgermane and diphenylstibine to ethynylferrocene was accomplished. n n n n n2. n n(1-Ferrocenyl-2-triphenylstannyl)ethylene reacts with mercuric chloride, formingβ-ferrocenylvinylmercury chloride, which in the presence of KI is converted to di-(β-ferrocenylvinyl)mercury. n n n n n3. n nThe reaction ofα-chlorovinylferrocene with lithium triphenylstannane gives (1-ferrocenyl-1-triphenylstannyl)ethylene.

Synthesis of cis-β-chlorovinyl compounds of mercury

1. n nMethods were described for the preparation of the pure cis-isomers of theβ-chlorovinyl compounds of mercury and thallium and some of their new constants were given. n n n n n2. n nThe NMR and IR spectra of the cis- and trans-isomers of theβ-chlorovinyl compounds of mercury, thallium and tin characterize the purity of the described stereoisomers. n n n n n3. n nThe previously expressed rule regarding the retention of configuration of the cis- and trans-β-chlorovinyl groups in electrophilic and homolytic substitution reactions was again corroborated.

Rates of acidolysis of cis- and trans -β-chlorovinylmercury chloride by hydrogen chloride in aqueous dioxane

1. n nThe rate constants and parameters of the Arrhenius equation of the acidolysis of trans-β-chloro-vinylmercury chloride by hydrogen chloride in 99% aqueous dioxane were determined. n n n n n2. n nThe rate of acidolysis of cis-β-chlorovinylmercury chloride in 99% aqueous dioxane is three times lower than the rate of the trans-isomer, with all other conditions equal.

Synthesis of organoantimony compounds by exchange between organomercury compounds and antimony halides

1. n nIn the reactions of bis-cis-2-chlorovinylmercury with antimony penta- and trichlorides, dichlorotris-cis-2-chlorovinylantimony and tris-cis-2-chlorovinylstibine are formed, respectively. The substances described earlier as dichlorotris-cis-2-chlorovinylantimony and tris-cis-2-chlorovinylstibine are the cis-trans-trans isomers. n n n n n2. n nThe reactions of tris-cis-2-chlorovinylstibine with chlorine and bromine lead to the formation of dichloro- and dibromo-tris-cis-2-chlorovinylantimonys. n n n n n3. n nThe trans isomers of the 2-chlorovinyl compounds of antimony react with liberation of acetylene at a lower concentration of alkali and at a lower temperature than the cis isomers. n n n n n4. n nExchange reactions between antimony pentachloride and R2Hg provide a convenient method for the synthesis of aliphatic and aromatic compounds of formula R3SbCl2.

Kinetics of reactions ofβ-elimination of acetylene from cis- and trans-β-chlorovinylmercury chlorides under the action of potassium iodide

1. n ntrans-β-Chlorovinylmercury chloride is more reactive in theβ-elimination of acetylene than the cis-isomer. n n n n n2. n nThe second-order rate constants of the reaction of trans- and cis-β-chlorovinylmercury chlorides with potassium iodide in aqueous 89% ethanol were determined spectrophotometricaily.

Trialkenyldialkyl- and trialkenyldiarylantimonys

1. n nDiphenyltri-cis-propenylantimony, diphenyltri-trans-propenylantimony, and triisopropenyldiphenylantimony were synthesized from the corresponding isomeric trialkenyldibromoantimonys and phenylmagnesium bromide. n n n n n2. n nAn investigation was made of the decomposition by halogens of the trialkyldiethyl- and trialkenyl-diphenylantimonys prepared, and it was shown that, except in the case of diethyltri-trans-propenylantimony, in all the cases investigated alkenyl groups were split off first, not ethyl or phenyl groups. n n n n n3. n nThe infrared absorption spectra were investigated of the geometric isomers isolated.

Kinetics of the decomposition of symmetrical organomercury compounds

A series of organic radicals arranged in order of their rates of removal from symmetrical organomercury compounds with hydrogen chloride in different solvents is given.