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Paper | Regular issue | Vol 31, No. 12, 1990, pp.2209-2218
Published online, 1st January, 1970
DOI: 10.3987/COM-90-5591
Synthesis and Reaction of 7-Bromo-2-(trifluoromethyl)-10-methylphenothiazine with Nitriles and Amines under Aryne-forming Conditions

Edward R. Biehl,* Susan DePaul, Subhash P. Khanapure, Jennifer L. Self, Upali Siriwardane, Stephen Taylor, Long D. Tran, and Matt A. Tschantz

*Department of Chemistry, Southern Methodist University, P.O. Box 750314, Dallas, TX 75275-0314, U.S.A.

Abstract

The titled compound (3) was prepared by treating commercially available 3-(trifluoromethyl)phenothiazine successively with sodium hydride, methyl iodide, and N-bromosuccinimide, and its structure was ascertained by X-ray analysis. The reaction of 3 with certain aliphatic nitriles and LDA gave typical 7- and 6-addition products via aryne (4) in ratios of ca. 85:15, 5:6, respectively. However, treatment of 3 with certain primary and secondary amines and the corresponding lithiated amide afforded a single 7-aminated product (7) in good yields in each case. The reaction of 3 with various phenylacetonitriles and LDA gave mixtures containing an 7-addition product (10) and a 6-arylmethyl-7-cyano rearranged nitrile (11) in similar ratio of 85:15, respectively. The structure of 11 was assigned on the basis of the greater tendency for the repuisite adduct (12), obtained from anion addition to the less favored 4-position of 4, to participate in the TARA pathway than that for the adduct (13), formed from anion addition to the more favored 3-position. The greater regioselectively of amine additions to 4 as compared to those of nitriel anion additions is explained on the basis of the relative reactivities of the amine and nitrile anion nucleophiles.