Genre
- Journal Article
Laser flash photolysis studies on alpha-methylbenzylchlorodiazirine, n-propylchlorodiazirine, and isopropylchlorodiazirine have been carried out at low temperatures, ranging from 170 to 230 K. The present results, together with those previously obtained with benzylchlorodiazirine and methylchlorodiazirine, provide a direct measurement of the ''by-stander effect'' of alkyl substituents on the C atom in the alpha position of the carbene center. Intermolecular reactions of alpha-methylbenzylchlorocarbene and tetramelhylethylene in isooctane and methylcyclohexane have been measured but this reaction is shown to be too slow to measure by LFP in highly viscous decalin solvent.
UNIV BORDEAUX 1,LAB CHIM PHYS A,URA 348,F-33405 TALENCE,FRANCE.; Liu, MTH, UNIV PRINCE EDWARD ISL,DEPT CHEM,CHARLOTTETOWN,PE C1A 4P3,CANADA.
WASHINGTON; 1155 16TH ST, NW, WASHINGTON, DC 20036
AMER CHEMICAL SOC
PT: J; CR: BONNEAU R, 1989, J AM CHEM SOC, V111, P5973 BONNEAU R, 1996, J AM CHEM SOC, V118, P3829 DIX EJ, 1993, J AM CHEM SOC, V115, P10424 FREY HM, 1970, J CHEM SOC A, P1916 GRAHAM WH, 1965, J AM CHEM SOC, V87, P4396 HOUK KN, 1984, J AM CHEM SOC, V106, P4293 JACKSON JE, 1989, TETRAHEDRON LETT, V30, P1335 JACKSON JE, 1994, ADV CARBENE CHEM, V1 LAVILLA JA, 1989, J AM CHEM SOC, V111, P6877 LIU MTH, 1989, J AM CHEM SOC, V111, P6873 LIU MTH, 1990, J AM CHEM SOC, V112, P3915 LIU MTH, 1992, J AM CHEM SOC, V114, P3604 LIU MTH, 1994, ACCOUNTS CHEM RES, V27, P287 LIU MTH, 1994, J PHOTOCH PHOTOBIO A, V84, P133 MOSS RA, 1994, ADV CARBENE CHEM, V1 MOSS RA, 1995, PURE APPL CHEM, V67, P741 MUROV SL, 1973, HDB PHOTOCHEMISTRY NICKON A, 1993, ACCOUNTS CHEM RES, V26, P84 RIDDICK JA, 1970, TECH CHEM, V2, P95 SCHAEFER HF, 1979, ACCOUNTS CHEM RES, V12, P288 STORER JW, 1993, J AM CHEM SOC, V115, P10426 TOMIOKA H, 1984, J AM CHEM SOC, V106, P454 TURRO NJ, 1982, J AM CHEM SOC, V104, P1754 VONSALIS GA, 1968, J PHYS CHEM-US, V72, P752 WHITE WR, 1992, J ORG CHEM, V57, P2841; NR: 25; TC: 16; J9: J AMER CHEM SOC; PG: 4; GA: VE266
Source type: Electronic(1)
Language
- English
Subjects
- CARBENE
- ALKENES
- 1,2-H MIGRATION
- 1,2-HYDROGEN MIGRATION
- PARAMETERS
- NEGATIVE ACTIVATION-ENERGIES
- ALKYLCHLOROCARBENES
- METHYLCHLOROCARBENE
- rearrangements
- Chemistry, Multidisciplinary
- BENZYLCHLOROCARBENE