The salts of chloronium ions R-Cl(+)-R (R = CH3 or CH2Cl): formation, thermal stability, and interaction with chloromethanes.
The interaction of CH3Cl/CD3Cl or CH2Cl2/CD2Cl2 with the carborane acid H(CHB11Cl11) (abbreviated as H{Cl11}) generates the salts of CH3-{Cl11} and CH2Cl-{Cl11} and their deuterio analogs, respectively, which are analogs of the salts of asymmetric chloronium cations. Next, salts of chloronium cations CH3-Cl(+)-CH3, ClCH2-Cl(+)-CH2Cl, and ClCH2-Cl(+)-CH3 and their deuterio analogs were obtained from the above compounds. The asymmetric ClCH2-Cl(+)-CH3 cation was found to be unstable, and at ambient temperature, slowly disproportionated into symmetric cations (CH3)2Cl(+) and (CH2Cl)2Cl(+). At a high temperature (150 °C), disproportionation was completed within 5 minutes, and the resulting cations further decomposed into CH3-{Cl11} and CH2Cl-{Cl11}. The molecular fragment ClCH2-(X) of the compounds (X = {Cl11}, -Cl(+)-CH2Cl, or -Cl(+)-CH3) is involved in exchange reactions with CH2Cl2 and CHCl3, converting into CH3-(X) with the formation of chloroform and CCl4, respectively.
Vorozhtsov Institute of Organic Chemistry, Siberian Branch of Russian Academy of Sciences (SB RAS), Novosibirsk 630090, Russia. evgenii@nioch.nsc.ru.
Evgenii S
ES
Stoyanov