Sodium hydride-Dimethylformamide

The method illustrates the ability of the sodium hydride-dimethylformamide system to effect the alkylation of aromatic sulfonamides under mild conditions and in good yield. The method appears to be fairly general. The submitters have prepared N,N-diethyl- and N,N-di- -butyl- >-toluenesulfonamide as well as 2-(/ -tolyIsuIfonyl)benz[/]isoindoline from 2,3-bis-(bromomethyl)naphthalene, and 1 %-tolylsulfony])pyrrolidine from 1,4-dichIorobutane the yield of purified product exceeded 75% in each case. 

Tetraphosphorus decaoxide Organic liquids Sodium hydride Dimethylformamide Sodium tetrahydroborate Dimethylformamide Sodium Dimethylformamide Sulfinyl chloride Dimethylformamide Triethylaluminium Dimethylformamide... 

Nitrobenzenesulfonic acid, 2261 Sodium hydride, Dimethylformamide, 4438 Succinodinitrile, 1429... 

The alkaloids papaverine (23), armepavine (24), and 0-methyl-dauricine (25) have been synthesized by making use of the reaction of the anion of 6,7-dimethoxy-2-benzoyl-l,2-dihydroisoquinaldo-nitrile (26) with the appropriate alkyl halide as the key step. It might be noted that this route to the alkaloids was not as useful as the one noted below involving the reaction of aldehydes with the anion of 26, however, with the advent of the sodium hydride-dimethylformamide room-temperature method it may be that the alkyl halide route could become the method of choice. 

Reaction of 20 with )8-bromopropiophenone using the sodium hydride-dimethylformamide method afforded an intermediate believed to be 27 which was hydrolyzed to the expected 28. ... 

DARZENS CONDENSATION Chloroacetonitrile. Dibenzo-18-crowns-6. Sodium hydride-Dimethylformamide. 

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