A. E. Borisov

Reactivity of diphenylstibine

1. The reaction of diphenylstibine with ethynylbenzene leads to diphenylstyrylstibine. 2. With 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. 3. The 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. The 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. 2. A 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. The addition of triphenylstannane, triphenylgermane and diphenylstibine to ethynylferrocene was accomplished. 2. (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. 3. The reaction ofα-chlorovinylferrocene with lithium triphenylstannane gives (1-ferrocenyl-1-triphenylstannyl)ethylene.

Synthesis of cis-β-chlorovinyl compounds of mercury

1. Methods 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. 2. The 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. 3. The 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. The 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. 2. The 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. In 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. 2. The reactions of tris-cis-2-chlorovinylstibine with chlorine and bromine lead to the formation of dichloro- and dibromo-tris-cis-2-chlorovinylantimonys. 3. The 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. 4. Exchange 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. trans-β-Chlorovinylmercury chloride is more reactive in theβ-elimination of acetylene than the cis-isomer. 2. The 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. Diphenyltri-cis-propenylantimony, diphenyltri-trans-propenylantimony, and triisopropenyldiphenylantimony were synthesized from the corresponding isomeric trialkenyldibromoantimonys and phenylmagnesium bromide. 2. An 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. 3. The 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.