10-Thiaanthracenes. I. Mechanism of the Reaction of 3-Phenylthioxanthylium Salt with Organometallic Reagents

概要

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9-Phenylthioxanthylium perchlorate (I) reacts under an N_2 stream with C_6H_5MgBr and CH_2MgI and gives 9,9-diphenylthioxanthene (II) and 9-methyl-6-phenylthioxanthene (IV), respectively, as main products. In the presence of air, 9-phenylthioxanthyl peroxide (III) is formed as a by-product by the reaction of I with C_6H_5MgBr. The mechanism of these reactions was clarified by the studies by the ESR technique. The spectrum of 9-phenylthioxanthyl radical (VI), which was a reaction intermediate, was analyzed by the McLachlan SCF-MO computation. The electron spin resonance spectrum of VI was alos observed by the formation of 9,10-diphenyl-10-thiaanthracene (V) by the reaction of I with C_6H_5Li. In order to examine the mechanism of formation of thioxanthenes and thiaanthracenes, the chemical reactivity of VI was studied. VI reacted with iodine, air, and the solvents such as ether and THF to give XIII, III, and XII, respectively. It did not react with organometallic reagents such as Grignard reagents and C_6H_5Li but reacted with ether to give XII only. However, it gave IV and V by the reaction with CH_3MgI and C_6H_5Li, respectively, in the presence of CoBr_2. These experimental results show that the radical mechanism considierably contributes to the reactions between I and organometallic reagents.
公益社団法人日本薬学会の論文
1973-08-25