PART I. THE ALKYLATION OF THE SODIUM SALT OF ETHYL ACETOACETATE, AN AMBIDENT ANION, WITH TRIETHYLOXONIUM FLUOROBORATE. PART II. RADICAL ANIONS AS INTERMEDIATES IN THE SUBSTITUTION REACTIONS OF A BETA-KETO ESTER SALT. PART III. A NEW AND FACILE SUBSTITUTION REACTION AT A TERTIARY CARBON; THE DISPLACEMENT OF A NITRO GROUP FROM A SATURATED CARBON ATOM

GEORGE SEARS GREENE, Purdue University

Abstract

Part I. The sodium salt of ethyl acetoacetate reacts at 0(DEGREES) with triethyloxonium fluoroborate in ethanol to give a product distribution of 70% carbon alkylate and 30% oxygen alkylate. Part II. In the light, the reaction of the sodium salt of the ethyl ester of (beta)-hydroxycoumarilic acid (I), a (beta)-keto ester, and p-nitrobenzyl chloride (II) in DMF gives almost exclusively carbon alkylation (100% carbon alkylate (C) with no oxygen akylate (0) at 0(DEGREES); 99% C, 1% O at room temperature). In contrast, in the dark, the product distributions are quite variable. In all cases, however, substantial amounts of O-alkylate are formed (54-84% C, 16-46% 0 at 0(DEGREES); 67-91% C, 9-33% O at room temperature). The rate is also affected by light; whereas the light reaction at 0(DEGREES) is 96% complete in 8 hours, the dark reaction at 0(DEGREES) is only 13% complete in 17 hours. The reaction of I and II is not significantly influenced by the presence of catalytic amounts of cupric chloride (contrary to an earlier report). In the light with cupric chloride present (molar ratio to II, 1/140), the product distributions are 100% C with a trace of O at 0(DEGREES), and 97-99% C, 1-3% O at room temperature. Thus, in these reactions, when compared to the identical reactions without cupric chloride, there is but a slight (if any) increase in oxygen alkylation. In the dark, at room temperature, simultaneous reactions give more oxygen alkylation without cupric chloride (67% C, 33% O) than with cupric chloride (84% C, 16% O), a result directly opposite to the reported effect. I reacts with II in the presence of oxygen in the light to give 54% C, 46% O. However, the result is clouded by the simultaneous oxidative destruction of I. I reacts with II in the presence of p-dinitrobenzene (equimolar to II) in the light to give 65% C, 35% O. I reacts with p-nitrobenzyl pentachlorobenzoate in DMF in the light to give a 48% yield of C, a 20% yield of pentachlorobenzene, but no oxygen alkylate. I reacts in DMF with m-nitrobenzyl chloride and p-nitrobenzyl bromide in the light to give respectively 52% C, 48% O and 73% C, 27% O. Part III. In the light I reacts with (alpha),p-dinitrocumene (III) in DMSO to give a 75% yield of carbon alkylate. Such a displacement of a nitro group from a saturated carbon atom is unprecedented. Minor amounts of two dimers derived, respectively, from I and III are isolated. . . . (Author's abstract exceeds stipulated maximum length. Discontinued here with permission of school.) UMI

Degree

Ph.D.

Subject Area

Organic chemistry

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