PART I. A NEW TYPE OF SUBSTITUTION AT A SATURATED CARBON ATOM. PART II. PRELIMINARY STUDIES OF THE ALKYLATION OF THE LITHIUM SALT OF ACETOXIME WITH THE PARA-NITROCUMYL SYSTEM
Abstract
Part I. A new type of substitution which occurs at a saturated carbon atom attached to an anthracene ring is described. Thus, when 9-anthrylmethyltrimethylammonium chloride (I) is treated with the lithium salt of 2-nitropropane (II) only carbon alkylation occurs giving a 91% yield of 2-(9-anthrylmethyl)-2-nitropropane (III). The reaction is shown to take place in two distinct stages; the intermediate, 9-methylene-10-(2-nitropropyl)-9,10-dihydroanthracene, has been isolated and characterized. Anions derived from 2-nitrobutane, nitrocyclohexane and diethylmethylmalonate react similarly and the analogous reaction intermediate has been isolated in each case. The intermediate derived from diethylmethylmalonate when treated with II gives a 91% yield of III, demonstrating the intermolecular character of the second stage. With sodium thiophenoxide, I gives a 62% yield of 9-anthrylmethylphenylsulfide and a 26% yield of 9-methyl-10-thiophenoxyanthracene. Here, too, the reaction is believed to proceed via the multi-step mechanism. With other leaving groups in the 9-anthrylmethyl system carbon alkylation of the 2-nitropropane anion is also observed. Part II. The lithium salt of acetoxime reacts with p-nitrocumyl chloride, (alpha),p-dinitrocumene, and p-nitrocumyl benzoate to give an alkylate of acetoxime in ca 20-40% yields; it is not the carbon alkylate.
Degree
Ph.D.
Subject Area
Organic chemistry
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