PART I. RADICAL ANION SUBSTITUTION AT TERTIARY CARBON: REACTIONS EMPLOYING SODIUM NITRITE. PART II. RADICAL ANION SUBSTITUTION AT TERTIARY CARBON: REACTIONS EMPLOYING SODIUM PHENOXIDE. PART III. MISCELLANEOUS REACTIONS INVOLVING THE PARA-NITROCUMYL SYSTEM
Abstract
Part I. Sodium nitrite reacts with p-nitrocumyl chloride in the light in dimethylsulfoxide at room temperature to give high yields of the tertiary nitro compound, (alpha), p-dinitrocumene. In addition, small amounts of p-nitrocumyl alcohol are isolated. Evidence is presented that this reaction proceeds via a radical anion chain mechanism. Support for the mechanism is provided by the fact that electron transfer agents, such as p-dinitrobenzene, and radical traps, such as oxygen, drastically reduce the rate of reaction and, also, diminish the proportion of nitro compound in the product. Furthermore, the reaction is light catalyzed as shown by rate dependence on illumination. Sodium nitrite reacts, albeit rather slowly, with m-nitrocumyl chloride giving 50-60% yields of the tertiary nitro compound, (alpha), m-dinitrocumene. The production of m-nitrocumyl alcohol is also observed. Here, oxygen and p-dinitrobenzene are without effect and, the reaction shows little response to light. The reaction of m-nitrocumyl chloride with sodium nitrite is presumed to arise from a radical anion non-chain (cage) process. Part II. Good yields (50-75%) of the tertiary ether, p-nitrocumylphenyl ether, are obtained on treating p-nitrocumyl chloride or (alpha), p-dinitrocumene with sodium phenoxide in dimethylsulfoxide or dimethylformamide. There are reasons for believing that these reactions are also radical anion processes. Part III. Treatment of p-nitrocumyl-1-methyl-2-naphthyl ether with sodium thiophenoxide at room temperature produces p-nitrocumylphenyl sulfide. This reaction exhibits a dramatic light effect--in the dark it does not occur. Sodium thiophenoxide also reacts with p-trifluoromethylcumyl chloride in dimethylformamide to give 15-20% yields of the tertiary sulfide, p-trifluoromethylcumylphenyl sulfide. While it has not been rigorously established, the production of the tertiary sulfide is taken to be a consequent of the radical anion mechanism.
Degree
Ph.D.
Subject Area
Organic chemistry
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