PART I: A NEW REACTION OF ALPHA-NITRO ESTERS AND NITRILES AND ALPHA, ALPHA-DINITRO COMPOUNDS. PART II: CONCERNING THE MECHANISM OF DISPLACEMENT OF A NITRO GROUP FROM ALPHA-NITRO ESTERS, KETONES, NITRILES AND ALPHA, ALPHA-DINITRO COMPOUNDS BY NITROPARAFFIN SALTS. PART III: (A) PRELIMINARY STUDIES ON THE PREPARATION AND PROPERTIES OF 2-NITROISOPROPYL ARYL SULFONES, (B) PRELIMINARY STUDIES ON THE REACTIONS OF ETHYL-2-NITROISOBUTYRATE AND ETHYL-2-BROMOISOBUTYRATE WITH

STEVEN DOUGLAS BOYD, Purdue University

Abstract

Part I. Salts of nitroparaffins cleanly displace a nitro group of (alpha)-nitro esters, (alpha)-nitro nitriles and (alpha),(alpha)-dinitro compounds to give the corresponding (beta)-nitro compounds. These reactions take place readily at room temperature and give excellent yields of pure products. They are noteworthy for providing very highly branched compounds which, at best, would be exceedingly difficult to prepare by any other means. Part II. The reactions of (alpha)-nitro esters, ketones, and nitriles and (alpha),(alpha)-dinitro compounds with nitroparafin salts are inhibited, or retarded, by free radical scavengers; ie galvinoxyl, di-t-butylnitroxide and p-benzoquinone. p-Dinitrobenzene, an agent which is effective in preventing electron transfer processes, also inhibits these reactions. Furthermore, light speeds up the reactions of (alpha)-nitro esters, (alpha)-nitro nitriles and (alpha),(alpha)-dinitro compounds with nitroparaffin salts. This, and other evidence, strongly supports the radical anion-free radical chain mechanism proposed for these reactions. Part IIIa. Two pure 2-nitroisopropyl aryl sulfones were prepared in 80-85% yields by treating 2-bromo-2-nitropropane with sodium salts of aryl sulfinic acids. A novel displacement of a sulfone group is observed on treating 2-nitroisopropyl phenyl sulfone with the lithium salt of 2-nitropropane; an 81% yield of pure 2,3-dimethyl-2,3-dinitrobutane is isolated. Part IIIb. Piperidine, sodium azide, sodium benzene sulfinate, sodium thiophenoxide and sodium diethyl malonate cleanly displace the bromine of ethyl-2-bromoisobutyrate to give the corresponding tertiary alkylates. In contrast, quinuclidine eliminates hydrogen bromide from the (alpha)-bromo ester. Ethyl-2-nitroisobutyrate fails to react with quinuclidine, piperidine, sodium azide and sodium benzene sulfinate. Sodium thiophenoxide and sodium diethyl malonate react with the (alpha)-nitro ester, however, the expected tertiary alkylates are not formed in significant yields.

Degree

Ph.D.

Subject Area

Organic chemistry

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