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ETHYLIDENE DIACETATE AS A PRECURSOR TO N-VINYL FORMAMIDE (NVF) OR N-VINYL ACETAMIDE (NVA)

IP.com Disclosure Number: IPCOM000019437D
Publication Date: 2003-Sep-12

Publishing Venue

The IP.com Prior Art Database

Abstract

There are a number of synthetic pathways to NVF monomer, however, all of the commercially attractive routes require the elimination of HX from the precursors CH3CH(X)NHCHO where X = CN, OR, NHCHO. The technology leading to CH3CH(X)NHCHO requires as the first step condensation of acetaldehyde with HX where X = CN or NHCHO.

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RESEARCH DISCLOSURE

ETHYLIDENE DIACETATE AS A PRECURSOR TO N-VINYL FORMAMIDE (NVF) OR N-VINYL ACETAMIDE (NVA)

1. Introduction

There are a number of synthetic pathways to NVF monomer, however, all of the commercially attractive routes require the elimination of HX from the precursors CH3CH(X)NHCHO where X = CN, OR, NHCHO. The technology leading to CH3CH(X)NHCHO requires as the first step condensation of acetaldehyde with HX where X = CN or NHCHO.

An alternative route involves the reaction of ethylidene diacetate (EDA) with formamide. If N-vinyl acetamide is the desired vinylic monomer, EDA can be reacted with acetamide. Ethylidene diacetate is a co-product in the methyl acetate carbonylation to acetic anhydride process. It also can be made from the condensation of acetic anhydride with acetaldehyde.

Ethylidene diacetate has not been previously employed as a precursor to mono-and bis-amide ethanes or to N-substituted monomers. If the leaving group ability of the acetoxy group of EDA, as well as the nucleophilic character of amide derivatives can be exploited then the corresponding mono- and bis-amide ethanes can be prepared.

2. Nucleophilic Substitution Chemistry

2.1 Base Induced Ethylidene Diacetate - Amide Substitution

It has been discovered that the substitution of the acetoxy groups on ethylidene diacetate with various amide derivatives can be performed in a basic slurry. Under these conditions, mono- and bisamide ethanes and N-substituted vinylamides are formed. The reaction can be conducted with equimolar quantities of organic reactants and base, with an excess of EDA, or with an excess of the amide derivative. The substitution chemistry can be conducted in acetonitrile solvent or without solvent. When excess organic reactants are used, the amide derivative or ethylidene diacetate can serve as the solvent. The reaction can be conducted at sub-ambient temperatures up to 80°C (the boiling point of acetonitrile) in acetonitrile solvent or at higher temperatures when acetonitrile is not used. Ideal conditions to maximize formation of bisamide ethanes and vinylamides is discussed below.

When ethylidene diacetate and acetamide are exposed to basic reaction media, such as cesium carbonate or sodium hydroxide, five major products are produced (Equation 1). Substitution of both acetoxy groups for acetamide leads to ethylidene bisacetamide (EBA) (4). N-Vinylacetamide (2) is also formed and probably arises from either the base-induced elimination of formamide from compound 4 under the reaction conditions or it may simply result from the cracking of 4 on the gas chromatograph injection port that is used to analyze these reaction mixtures. The dimer of 2 (compound 3) is found in small amounts, and its presence suggest that NVA is a real component of the reaction mixture. The other two products produced are acetaldehyde and diacetamide (1). Diacetamide is presumably derived from the addition of acetamide to the carbonyl carbon of the acetoxy group. Ac...