PART I. THE REPLACEMENT OF AN ALIPHATIC NITRO GROUP BY HYDROGEN. PART II. A NEW SYNTHESIS OF OLEFINS. PART III. REACTIONS OF PARA-PHENYLSULFONYLCUMYL CHLORIDE AND PARA- PHENYLSULFONYL -ALPHA- NITROCUMENE WITH NUCLEOPHILES

RONALD GENE SMITH, Purdue University

Abstract

Part I. Replacement by hydrogen of the nitro group of t-nitroparaffins is achieved by the agency of sodium thiophenoxide in the presence of triethylamine. Thus, 2,2,3-trimethyl-3-nitrobutyronitrile, when treated with sodium thiophenoxide in 1:1 DMF-triethylamine, gives an 88% yield of pure 2,2,3-trimethylbutyronitrile. A radical anion-free radical mechanism is proposed which postulates hydrogen atom abstraction from triethylamine. This is consistent with the fact that triethylamine is needed for efficient replacement of the nitro group by hydrogen. Part II. A new reaction, the transformation of vicinal dinitro compounds into olefins by the agency of sodium thiophenoxide or sodium sulfide nonahydrate, has been developed. Olefin formation takes place readily at room temperature and gives very pure products in excellent yields. Part III. p-Phenylsulfonylcumyl chloride and p-phenylsulfonyl-(alpha)-nitrocumene react with lithium 2-propanenitronate to give 50-64% yields of the carbon alkylate. A radical anion-free radical chain mechanism is proposed for these reactions. p-Phenylsulfonylcumyl chloride reacts with sodium azide to give a 60% yield of the substitution product while the reaction of sodium azide with p-phenylsulfonyl-(alpha)-nitrocumene gives a 62% yield of the cumyl dimer. The mechanisms of these reactions are discussed.

Degree

Ph.D.

Subject Area

Organic chemistry

COinS