Highly reactive metallic nickel: reductive homocoupling reagent for benzylaic mono- and polyhalides

Journal Article · Fri Jun 15 04:00:00 EDT 1984 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00186a003· OSTI ID:6877152

Inaba, S; Matsumoto, H; Rieke, R D

Metallic nickel, prepared by the reduction of nickel halides with lithium in glyme using naphthalene as an electron carrier, was found to be a useful reagent for the homocoupling of benzylic mono- and polyhalides. Benzyl halides reacted with metallic nickel at room temperature to give the corresponding 1,2-diarylethanes in good to high yields and functional groups on the aromatic ring such as methoxy, chloro, bromo, nitro, cyano, and alkoxycarbonyl groups were not affected under the conditions employed. Benzylic monohalides (1-chloromethyl)- or 2-(bromomethyl)naphthalene, chlorodiphylmethane, and 9-bromofluorene) also underwent coupling reactions with metallic nickel at room temperature to give the corresponding ethane derivatives. On the other hand, benzylic di- and trihalides such as ..cap alpha..,..cap alpha..-dibromotoluene and ..cap alpha..,..cap alpha..,..cap alpha..-trichlorotoluene yielded mixtures of cis and trans isomers of substituted ethenes. The intermediate of the reaction, benzylnickel complex, was trapped with electron deficient olefins such as methyl acrylate and acrylonitrile. 52 references, 2 tables.

• Research Organization: Univ. of Nebraska, Lincoln
• DOE Contract Number: AC02-80ER10603
• OSTI ID: 6877152
• Journal Information: J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 49:12; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
AROMATICS
BROMINATED ALIPHATIC HYDROCARBONS
BROMINATED AROMATIC HYDROCARBONS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINATED AROMATIC HYDROCARBONS
COMPARATIVE EVALUATIONS
CONDENSED AROMATICS
CYANIDES
DATA
DEHALOGENATION
DIMERIZATION
ELEMENTS
ESTERS
ETHERS
EXPERIMENTAL DATA
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENATED AROMATIC HYDROCARBONS
INFORMATION
ISOMERIZATION
KINETICS
METALS
NICKEL
NICKEL COMPOUNDS
NITRO COMPOUNDS
NMR SPECTRA
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
POLYMERIZATION
REACTION INTERMEDIATES
REACTION KINETICS
REAGENTS
REDUCTION
SAMPLE PREPARATION
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS