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Transition metal arene complexes in reactions with nucleophilic reagents. XV. Nucleophilic replacement of the fluorine atom by the methoxy group catalyzed by (eta-benzene)(eta-ethyltetramethylcyclopentadienyl)-rhodium(III) in the reaction of fluoroarenes with methanol

Journal Article · · J. Org. Chem. USSR (Engl. Transl.); (United States)
OSTI ID:7076453
; ;

The replacement of the fluorine atom by a methoxy group in the reaction of fluoroarenes with methanol is efficiently catalyzed by ((eta-C/sub 6/H/sub 6/)Rh(eta-C/sub 5/EtMe/sub 4/))/sup 2 +/(PF/sub 6//sup -/)/sub 2/, which permits the synthesis of alkyl aryl ethers under mild conditions without using alkali. Evidence was obtained indicating that the catalysis is a consequence of activation of the fluoroarenes upon their reversible ..pi..-coordination with the ((eta-C/sub 5/EtMe/sub 4/)Rh)/sup 2 +/ fragment. The yield of the products of the methanolysis of fluorobenzene and its derivatives and also of 1-fluoronaphtalene depends significantly on the structure of the aryl group and increases in the series: 2-FC/sub 6/H/sub 4/F < 2,4,6-Me/sub 3/C/sub 6/H/sub 2/F < 2-ClC/sub 6/H/sub 4/F < 4-HOC/sub 6/H/sub 4/F < 3,4-Me/sub 2/C/sub 6/H/sub 3/F < 1-C/sub 10/H/sub 7/F < 2-, 3- and 4-MeC/sub 6/H/sub 4/F or MeOC/sub 6/H/sub 4/F < C/sub 6/H/sub 5/F. The effect of the concentration of methanol and the catalyst and of temperature on the reaction rate was studied.

Research Organization:
Novosibirsk Institute of Organic Chemistry (USSR)
OSTI ID:
7076453
Journal Information:
J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 23:6; ISSN JOCYA
Country of Publication:
United States
Language:
English

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Arene complexes of transition metals in reactions with nucleophilic reagents. XVII. Nucleophilic substitution of the fluorine atom by alkoxy groups, catalyzed by the (/eta/-benzene)(/eta/-ethyltetramethylcyclopentadienyl)rhodium(III) dication, in the reaction of fluoroarenes with alcohols
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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical &amp; Physicochemical Properties
ACTIVATION ENERGY
ALCOHOLS
AROMATICS
BENZENE
CATALYSIS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
CONDENSED AROMATICS
DEHALOGENATION
ENERGY
FLUORINATED AROMATIC HYDROCARBONS
HALOGENATED AROMATIC HYDROCARBONS
HETEROGENEOUS CATALYSIS
HYDROCARBONS
HYDROXY COMPOUNDS
KINETICS
METHANOL
NAPHTHALENE
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
REACTION KINETICS
RHODIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
TEMPERATURE DEPENDENCE
TRANSITION ELEMENT COMPLEXES
YIELDS