Anti-Markovnikov selectivity in the addition of thermal chlorine to CH{sub 2}=CHBr and CF{sub 2}=CFBr

Conference · Fri Dec 31 00:00:00 EST 1993

OSTI ID:141482

Bredt, P R; Iyer, R S; Rowland, F S ^[1]

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1. Univ. of California, Irvine, CA (United States)

The addition of thermal chlorine atoms to CH{sub 2}=CHBr and CF{sub 2}=CFBr has been studied at 23{degrees}C from 500 to 3000 torr using {sup 38}Cl from the neutron irradiation of CF{sub 3}Cl as well as thermal {sup 35,37}Cl from the photolysis of COCl{sub 2}. For CH{sub 2}=CHBr, only a slight {open_quotes}anti-Markovnikov{close_quotes} preference for addition to CH{sub 2} vs. CHBr of 1,4 was found, along with a 1,2-bromine migration in the stabilized CH{sub 2}CHBrCl radical. For CF{sub 2}=CFBr, the {open_quotes}anti-Markovnikov{close_quotes} preferences for addition to CF{sub 2} vs. CFBr was found to be 3.0. Mass spectroscopy after radical termination with D{sub 2}S was used with the stable isotopes and CH{sub 2}=CHBr, while radio gas chromatography was applied for {sup 38}Cl analysis. An {open_quotes}anti-Markovnikov{close_quotes} preference is often accompanied by appreciable initial yields of the less-favored radical.

• OSTI ID: 141482
• Report Number(s): CONF-930304--
• Resource Type: Conference proceedings
• Conference Information: 205. American Chemical Society national meeting, Denver, CO (United States), 28 Mar - 2 Apr 1993; Is Part Of 205th ACS national meeting; PB: 1951 p.
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL REACTION KINETICS
CHLORINATION
NEUTRONS
ORGANIC BROMINE COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
PRESSURE DEPENDENCE