SOLVENT AND CROWN ETHER/CRYPTAND EFFECTS ON THE OXIMATE-PROMOTED 1,2-ELIMINATION FROM BETA-PHENLYMERCAPTOETHYL p-NITROPHENOLATE. FORMATION AND REACTIVITY OF A CROWN ETHER-COMPLEXED POTASSIUM OXIMATE ION PAIR

Authors
  1. Buncel, E.
  2. Kumar, A.
  3. Xie, H-Q.
  4. Moir, R.Y.
Corporate Authors
Defence Research Establishment Suffield, Ralston ALTA (CAN);Queen's Univ, Kingston ONT (CAN) Dept of Chemistry
Abstract
The reactions of Beta-phenlymercaptoethyl p-nitrophenolate (1) with three potassium oximates, viz. potassium 2,3-butanedione monoximate (BDOK), acetophenone oximate (APOK), and acetone oximate (AOK) have been investigated in two nonhydroxylic dipolar aprotic solvents, tetraglyme and dimethyl sulfoxide (DMSO). The reaction products, as determined by H NMR spectroscopy, were p-nitrophenoxide ion and phenyl vinyl sulfide, in accord with an elimination process. A kinetic spectrophotometric study showed that in tetraglyme, the addition of oxime and water in small amounts drastically decreased the rate of reaction of 1 with APOK as a result of hydrogen-bonding interactions with the oximate anion. In tetraglyme as solvent the addition of 2.2.2 crytand greatly enhanced the reactivity of the oximates but the macrocyclic crown ether DC-18-C6 had much smaller effect on rate.
Date of publication
26 Mar 1993
Number of Pages
11
Reprinted from
Can J of Chem., vol 72, 1994, p 437-447
DSTKIM No
94-03751
CANDIS No
143426
Format(s):
Hardcopy;Originator's fiche received by DSIS

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