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Kinetics and mechanism of Horner–Wadsworth–Emmons reaction of weakly acidic phosphonate in solid–liquid phase-transfer catalysis system

Paper ID Volume ID Publish Year Pages File Format Full-Text
50020 46776 2013 6 PDF Available
Title
Kinetics and mechanism of Horner–Wadsworth–Emmons reaction of weakly acidic phosphonate in solid–liquid phase-transfer catalysis system
Abstract

•HWE reaction of weakly acidic phosphate was developed in SL-PTC system.•The reaction kinetics was investigated under the pseudo-first-order conditions.•The interfacial mechanism for SL-PTC reaction of weakly acidic substrate was proved.•This reaction showed high activity and geometric selectivity at low temperatures.

Homer–Wadsworth–Emmons (HWE) reaction of diethyl benzylphosphonate (DEBP, pKa = 27.55) with aldehyde was performed in a solid–liquid phase-transfer catalysis (SL–PTC) system using sodium hydroxide as the solid phase. Various parameters that influenced the pseudo-first-order rate constant including stirring speed, catalysts, salt, water and temperature were investigated to explore the process of the generation and transfer of the active intermediate. A reasonable interfacial mechanism of the PTC reaction of the weakly acidic substrate was proved for the first time. HWE reactions under SL–PTC conditions showed high activity and geometric selectivity. It is anticipated that this simple and controllable synthesis method should provide a new idea for HWE reaction in chemical industry.

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Keywords
Horner–Wadsworth–Emmons reactions; Solid–liquid phase-transfer catalysis; Interfacial mechanism; The weakly acidic substrate
First Page Preview
Kinetics and mechanism of Horner–Wadsworth–Emmons reaction of weakly acidic phosphonate in solid–liquid phase-transfer catalysis system
Publisher
Database: Elsevier - ScienceDirect
Journal: Catalysis Communications - Volume 36, 5 June 2013, Pages 98–103
Authors
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Subjects
Physical Sciences and Engineering Chemical Engineering Catalysis