Competing chlorination of 1,1-dichloroethane and chlorobenzene
The competition between the substitutive chlorination of 1,1-dichloroethane and the additive chlorination of chlorobenzene under photoinitiation conditions with wide variation of the temperature (248-323/degree/K), the chlorine concentration (O-1.23 M), and the ratio of the competitors was investigated. The fraction of the substitutive chlorination of 1,1-dichloroethane increases with increase in the temperature and the (CH/sub 3/CHCl/sub 2/)/(C/sub 6/H/sub 5/Cl) ratio and with decrease in the concentration of molecular chlorine. The results were interpreted by a free-radical mechanism of chlorination involving the formation of /pi/ complexes between the chlorine atoms and the chlorobenzene molecules ArH /yields/ /dot char/Cl and rearrangement of the latter into /sigma/ complexes. On the basis of the proposed mechanism an equation was obtained for the selectivity of the chlorination of the system with parameters reflecting the complexing characteristics of the aromatic solvent. A comparative analysis of these parameters for chlorobenzene and o-dichlorobenzene in terms of the structure of these solvents is given.
- Research Organization:
- D.I. Mendeleev Moscow Chemical Technology Institute (USSR)
- OSTI ID:
- 6007897
- Journal Information:
- J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 23:11; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
AROMATICS
ARRHENIUS EQUATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINATED AROMATIC HYDROCARBONS
CHLORINATION
CHLORINE
COMPLEXOMETRY
ELEMENTS
EQUATIONS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENATED AROMATIC HYDROCARBONS
HALOGENATION
HALOGENS
IODOMETRY
MOLECULAR STRUCTURE
NONMETALS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
QUANTITY RATIO
RADICALS
TEMPERATURE DEPENDENCE
TITRATION
YIELDS