Carbanion photochemistry. 6. Formation of a reactive carbene via photoinduced halide elimination

Journal Article · Wed Jul 28 04:00:00 EDT 1982 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00379a050· OSTI ID:6645218

Tolbert, L M; Siddiqui, S

Solutions of the requisite anion (ca 0.1 M) were produced by 10% excess potassium tert-butoxide treatment of 2-bromo- or 2-chloro-1,3-diphenylindene in dimethyl sulfoxide. A 10-fold excess of olefin was added, and the mixture irradiated. Reactions were monitored by gas chromatography and carried to ca 60 to 90% conversion. The mixtures were quenched with water and extracted with methylene chloride, and the products were separated by column chromatography. The major product was isolated in over 50% yield as a colorless oil and exhibited a molecular ion in the mass spectrum corresponding to the loss of halogen and the addition of the olefin. The case of cyclohexene is used as an example. In addition to aromatic peaks, the NMR showed absorbances in the styryl, olefinic, allylic methine and ring methylene regions. Elemental analysis showed that the compound was a 50:50 mixture of diastereomeric i-(cyclohex-2-enyl)-1,3-diphenylindenes. The reaction kinetics are discussed.

• Research Organization: Univ. of Kentucky, Lexington
• OSTI ID: 6645218
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 104:15; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400500* -- Photochemistry
ALKANES
AROMATICS
BROMINATED AROMATIC HYDROCARBONS
CARBANIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORINATED AROMATIC HYDROCARBONS
CHROMATOGRAPHY
CONDENSED AROMATICS
CYCLOALKANES
DECOMPOSITION
DMSO
GAS CHROMATOGRAPHY
HALOGENATED AROMATIC HYDROCARBONS
HYDROCARBONS
HYDROGEN COMPOUNDS
IONS
KINETICS
MAGNETIC RESONANCE
MASS SPECTRA
METHYLENE CHLORIDE
NUCLEAR MAGNETIC RESONANCE
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
RESONANCE
SEPARATION PROCESSES
SPECTRA
SULFOXIDES
WATER
YIELDS