Genre
- Journal Article
Laser flash photolysis of para-substituted 3-chloro-3-benzyldiazirines in isooctane produces the corresponding carbenes, which react with pyridine to form ylides or undergo 1,2-H migration to form the (Z)- and (E)-beta-chlorostyrenes. The rate for the 1,2-H migration is determined by plotting the pseudo-first-order rate constants for the growth of the ylide vs [pyridine] and extrapolating to zero pyridine concentration. In the case of (p-chlorobenzyl)chlorocarbene, the carbene decay can be monitored directly at 310 nm, whereas in [p-(trifluoromethyl)benzyl]chlorocarbene, the 285-nm trace may bc analyzed as the sum of the absorption of the carbene and of the product beta-chlorostyrenes. A Hammett plot of the logarithms of the rate constants for 1,2-H migration vs sigma(p) values gave a rho-value of -1.0, consistent with a hydride-like 1,2-H shift to the carbene center. The rate constants for the cyclopropanation of carbenes with tetramethylethylene (TME) were determined. In particular, the cyclopropanation of (p-chlorobenzyl)chlorocarbene with TME gave a negative activation energy of -4.7 kcal mol-1.
UNIV BORDEAUX 1,CHIM PHYS LAB A,CNRS,URA 348,F-33405 TALENCE,FRANCE.; LIU, MTH, UNIV PRINCE EDWARD ISL,DEPT CHEM,CHARLOTTETOWN C1A 4P3,PEI,CANADA.
WASHINGTON; 1155 16TH ST, NW, WASHINGTON, DC 20036
AMER CHEMICAL SOC
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Source type: Electronic(1)
Language
- English
Subjects
- ALKENES
- 1,2-HYDROGEN MIGRATION
- Kinetics
- REARRANGEMENT
- PARAMETERS
- ABSOLUTE RATE
- ALKYLCHLOROCARBENES
- Chemistry, Multidisciplinary
- ADDITIONS