SUBSTITUTION AT A TERTIARY CARBON ATOM

MELVIN MICHAEL KESTNER, Purdue University

Abstract

Sodium p-toluenesulfinate reacts with 2-iodo-2-nitropropane, and 2-bromo-2-nitropropane, and sodium benzenesulfinate reacts with 2,2-dinitropropane to give the corresponding (alpha)-nitro sulfones in good yields. Evidence is presented which supports the view that these reactions involve a radical anion-free radical chain pathway. Diethyl-2-methyl malonic ester reacts with nitrite, sulfinate, azide, thiophenoxide, methyl malonate and 2-nitropropane anions to give the corresponding substituted methyl malonic ester. Diethyl-2-methyl-2-nitro malonate reacts with the thiophenoxide anion to give primarily the anion of methyl malonic ester, with the 2-nitropropane anion to form the (beta)-nitro malonic ester, and with methyl malonate anion to give the tetraester of butane 1,1,3,3 tetracarboxylic acid. Evidence is presented which supports the view that the latter two reactions involve radical chain pathways. 2,2-Dinitropropane reacts with azide, cyanide, thiophenoxide, and methyl malonate anions forming the corresponding (alpha)-substituted nitro compounds. Methoxide ion also reacts with 2,2-dinitropropane, however, 1-methoxy-2,3-dimethyl-2,3-dinitrobutane is the product. 2-Nitroisobutyronitrile reacts with azide, methyl malonate, and thiophenoxide anions, however, only the latter anion gives a stable (alpha)-substituted nitrile. Likewise, 2-bromoisobutyronitrile reacts with the thiophenoxide anion forming the (alpha)-substituted nitrile. Initiation of reactions of (alpha),p-dinitrocumene and p-nitrocumyl chloride with various nucleophiles using sodium naphthalenide, sodium in HMPA, and sodium superoxide are reported. The results support the view that (alpha),p-dinitrocumene and p-nitrocumyl chloride react via a radical chain pathway. The following results are contained in the final section: (1) the reactions of p-nitrocumyl chloride, and (alpha),p-dinitrocumene, with the salt of 2-nitropropane, (2) the reactions of p-nitrocumyl chloride, and (alpha),p-dinitrocumene, with sodium cyanide, and (3) the retardation of the reaction of (alpha),p-dinitrocumene and the benzenesulfinate anion by galvinoxyl.

Degree

Ph.D.

Subject Area

Organic chemistry

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