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2-Bromobenzyl chloride 8a and 2-iodobenzyl chloride 8b are commercially available, from Lancaster Co. and Aldrich, respectively.
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In fact, triarylnitriles 14 have been also prepared by addition of sodium cyanide to halogenated benzyl halides in the presence of base. These results will be published elsewhere.
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1H NMR tecniques showed complete decomposition of methoxylated halobenzyl chlorides 8c,d in the presence of NaH at temperatures above -10°C. Attempts to carry out the alkylation reaction at lower temperatures afforded enamines 15c,d with moderate yields (40-55%). Although no decomposition product was isolated, the autoalkylation of benzyl chlorides under basic conditions has been reported. See: Hauser; C. R.; Brasen, W. R.; Skell, P. S.; Kantor, S. W.; Brodhay, A. E. J. Am. Chem. Soc. 1956, 78, 1653-1658.
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See Experimental Section for more details. An alternative mechanism based on the hydrolysis of 18 to the aldehyde followed by oxidation to the corresponding keto-acid and subsequent decarboxylation was discarded as it could not explain the formation of DMF.
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