3141-45-5Relevant articles and documents
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Hostettler,H.U.
, p. 2417 - 2426 (1966)
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Kinetics and mechanism of CCU photoreductive degradation on TiOi: The role of trichloromethyl radical and dichlorocarbene
Choi, Wonyong,Hoffmann, Michael R.
, p. 2161 - 2169 (1996)
The mechanism of photoreduction of CCU on illuminated TiO2 surfaces was investigated by selectively trapping transient free radical intermediates. Dichlorocarbene and trichloromethyl radical were trapped with 2,3dimethyl-2-butene during the photocatalytic degradation of CCLt. The rate of formation of trapped :CCl2 and 'CCla was found to be a function of [H22O], pH, [CCLt], the nature of the dissolved gas, and light intensity. Dissolved oxygen was not essential for the degradation of CCLt. The production rate of trapped dichlorocarbene showed light intensity dependencies of second, first, and half order with progressively increasing light intensity. A two-electron photoreductive pathway (via dichlorocarbene formation) was found to be the dominant mechanism leading to the full degradation of CCLt. Since dichlorocarbene is hydrolyzed under basic conditions, the pH and water concentration were found to be integral parameters controlling the complete degradation of CCU to CO, CU2, and HC1. Kinetic equations describing the formation of trapped dichlorocarbene were derived from a proposed mechanism. The comparison of the predicted rate expression to the observed data suggested that the observed two-electron transfer occurred consecutively.
Nugent,Kochi
, p. 371,385 (1977)
Enthalpy versus entropy in chlorocarbene/alkene addition reactions
Moss, Robert A.,Wang, Lei,Zhang, Min,Skalit, Christopher,Krogh-Jespersen, Karsten
, p. 5634 - 5635 (2008/12/20)
We report the first measured activation parameters for the additions of CCl2 and CClF to simple alkenes and demonstrate the existence of enthalpic barriers for CCl2 additions to cyclohexene and 1-hexene. With these two alkenes, addit
Is a phase transfer catalyst really needed for gem-dihalocyclopropanation of alkenes with haloforms in the presence of alkali metal hydroxide?
Karwowska,Jonczyk
, p. 45 - 49 (2008/02/11)
Chloroform, bromoform and dibromochloromethane react with alkenes in the presence of cone. aq. sodium hydroxide, without phase-transfer catalyst, giving gem-dihalocyclopropanes. The process is particularly useful for preparation of gem-bromochlorocyclopropanes which are formed in good yields and in high selectivity.