PART I. REACTIONS OF 3,5-BIS(TRIFLUOROMETHYL)ALPHA-NITROCUMENE WITH NUCLEOPHILES. PART II. REACTIONS OF 3,5-BIS(TRIFLUOROMETHYL)CUMYL CHLORIDE WITH NUCLEOPHILES. PART III. BIMOLECULAR NUCLEOPHILIC DISPLACEMENT REACTIONS AT THE TERTIARY CARBON ATOM OF VARIOUS CUMYL CHLORIDES. PART IV. MISCELLANEOUS AND PRELIMINARY STUDIES

BARRY NEALE NEWTON, Purdue University

Abstract

Part I. 3,5-bis(Trifluoromethyl)(alpha)-Nitrocumene reacts with the lithium salt of 2-nitropropane to give 90% yields of the carbon alkylate. Light accelerates the reaction, while m-dinitrocumene, di-t-butylnitroxide, and oxygen retard it. A radical anion-free radical chain mechanism is proposed for this reaction. Experiments in which 3,5-bis(trifluoromethyl)(alpha)-nitrocumene is treated with sodium thiophenoxide, sodium azide, and sodium benzenesulfinate are also described. Part II. 3,5-bis(Trifluoromethyl)Cumyl Chloride reacts with the lithium salt of 2-nitropropane to give the carbon alkylate in ca. 30% yield. Carbon alkylation is facilitated by light and retarded by m-dinitrobenzene, di-t-butylnitroxide and oxygen. A radical anion-chain mechanism is proposed for the carbon alkylation process, the first case of a radical anion-chain mechanism in a cumyl system devoid of a nitro group. The reactions of 3,5-bis(trifluoromethyl)cumyl chloride with sodium nitrite, sodium azide, sodium thiophenoxide, sodium benzene sulfinate, piperidine and sodium diethyl malonate are also described Part III. Cumyl chloride, 3,5-bis(trifluoromethyl)cumyl chloride, p-phenylsulfonyl cumyl chloride, and m-nitrocumyl chloride all react with sodium azide in the dark by a bimolecular process, i.e., first order in azide. None of the (alpha)-nitrocumenes react with sodium azide in the dark and this supports the view that the chlorides react with azide ion in the dark by an S(,N)2 displacement process. In two of the four cases there is an unambiguous increase in rate on exposure to light; (m-nitrocumyl chloride and p-phenylsulfonyl cumyl chloride). This suggests that in these cases, in the light, a radical anion process occurs. Part IV. A number of preliminary results are described: (1) a search for chemically induced dynamic nuclear polarization in radical anion reactions, (2) the stability of galvinoxyl free radical in HMPA in the presence of various anions, (3) the reaction of p-trifluoromethyl cumyl chloride with sodium azide and with nitrite, (4) the reaction in HMPA of p-nitrobenzyl chloride and p-nitrobenzyl bromide with the lithium salt of 2-nitropropane, (5) the reaction of 3,5-bis(trifluoromethyl) cumyl azide with sodium thiophenoxide, and (6) the use of 1,3,5-tris-(trifluoromethyl)benzene as a radical anion inhibitor.

Degree

Ph.D.

Subject Area

Organic chemistry

COinS