Genre
- Journal Article
Photolysis of 3-chloro-3-benzyldiazirine in tetramethylethylene gives E- and Z-beta-chlorostyrenes and cyclopropane. Relative rate studies show that the styrenes to cyclopropane ratio increases with increasing diazirine concentration. This permits the determination of the ratio k(D)/k(i) = 8 where k(D) is the rate constant for the reaction of carbene with diazirine and k(i) is the rate constant for the 1,2-hydrogen atom shift of carbene. Laser flash photolysis yields the first absolute rate constant for the reaction of a chlorocarbene with diazirine and a value of 7.7 for k(D)/k(i).
UNIV BORDEAUX 1,CHIM PHYS LAB,CNRS,UA 348,F-33405 TALENCE,FRANCE.; LIU, MTH, UNIV PRINCE EDWARD ISL,DEPT CHEM,CHARLOTTETOWN C1A 4P3,PEI,CANADA.
LAUSANNE 1; PO BOX 564, 1001 LAUSANNE 1, SWITZERLAND
ELSEVIER SCIENCE SA LAUSANNE
PT: J; CR: BONNEAU R, 1989, J AM CHEM SOC, V111, P1973 JACKSON JE, 1988, J AM CHEM SOC, V110, P5595 JACKSON JE, 1989, J AM CHEM SOC, V111, P6874 LIU MTH, 1985, J CHEM SOC CHEM COMM, P982 LIU MTH, 1989, J AM CHEM SOC, V111, P6873 LIU MTH, 1990, J AM CHEM SOC, V112, P3915 MORGAN S, 1991, J AM CHEM SOC, V113, P2782 MOSS RA, 1990, J AM CHEM SOC, V112, P1638 MOSS RA, 1990, J AM CHEM SOC, V112, P5642 MOSS RA, 1990, TETRAHEDRON LETT, V31, P1225 WARNER PM, 1984, TETRAHEDRON LETT, V25, P4211; NR: 11; TC: 11; J9: J PHOTOCHEM PHOTOBIOL A-CHEM; PG: 4; GA: HD116
Source type: Electronic(1)
Language
- English
Subjects
- ALKENES
- TERT-BUTYLCHLOROCARBENE
- 1,2-HYDROGEN MIGRATION
- Chemistry, Physical
- PARAMETERS