Part~I.~The reaction of beta-aryl nitro compounds with the sodium salt of methyl mercaptan. Part~II.~The reaction of ring-substituted alpha-nitrocumenes with the sodium salt of methyl mercaptan. Part~III.~The reaction of aliphatic nitro compounds with the sodium salt of methyl mercaptan. Part~IV.~(A)~The reaction of thioethers with the sodium salt of methyl mercaptan; (B)~The reaction of 2,2,4 -trimethyl-4-nitro-3-pentanone with the lithium salt of 2-nitropropane and with sodium thiophenoxide; (C)~The reaction of m-bis-trifluoromethylbenzene with the sodium salt of methyl mercaptan; (D)~A novel displacement of a nitro group from a benzene ring

Stephen Clyde Carlson, Purdue University

Abstract

Part I. Replacement by hydrogen of the nitro group of $\beta$-aryl t-nitro compounds is achieved by the agency of the sodium salt of methyl mercaptan in DMF. Thus, 2,3-dimethyl-2-(p-cyanophenyl)-3-nitrobutane, when treated with the sodium salt of methyl mercaptan, gives an 86% yield of pure 2,3-dimethyl-2-(p-cyanophenyl)butane. When HMPA is the solvent employed, substitution of the nitro group by methyl mercaptide ion competes with replacement of the nitro group by hydrogen. Thus treatment of 2,3-dimethyl-2-(p-cyanophenyl)-3-nitrobutane with the sodium salt of methyl mercaptan gives 2,3-dimethyl-2-(p-cyanophenyl)-butane in 55% yield as well as a 34% yield of pure 2,3-dimethyl-2-(p-cyanophenyl)-3-thiomethoxybutane. A radical anion-free radical chain mechanism is proposed. The possibility of a spirane intermediate is investigated. Part II. Ring substituted $\alpha$-nitrocumenes react rapidly with the sodium salt of methyl mercaptan both in HMPA and in DMSO to give the corresponding $\alpha$-thiomethoxycumenes. Part III. The nitro groups of strictly aliphatic t-nitrocompounds are also replaced by hydrogen on treatment with the sodium salt of methyl mercaptan. For example, treatment of t-nitrooctane with the sodium salt of mercaptan in HMPA results in a 55% yield of pure isooctane. Part IV. (A) The reduction of $\beta$-aryl thioethers and cumyl thio-ethers on treatment with the sodium salt of methyl mercaptan in HMPA is described. (B) 2,2,4-Trimethyl-4-nitro-3-pentanone when treated with the lithium salt of 2-nitropropane gives a 21% yield of the highly branched nitro ketone, 2,2,4,4,5-pentamethyl-5-nitro-3-hexanone, also the pivaloyl ester of acetoxime and pivalic acid. (C) Aryl -CF$\sb3$ groups are slowly transformed into -CH$\sb2$-S-CH$\sb3$ groups by the agency of the sodium salt of methyl mercaptan in HMPA in the light. There is no reaction in the dark. (D) Displacement of the aryl nitro group from 2,3-dimethyl-2-(p-nitrophenyl)-3-nitrobutane accounts for ca 30% of the product observed when the dinitro compound is treated with the sodium salt of methyl mercaptan. (Abstract shortened with permission of author.)

Degree

Ph.D.

Advisors

Kornblum, Purdue University.

Subject Area

Chemistry

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