Vinyl chloroacetate

Ethyl vinyl ether was the first to be prepared, in 1878, by treatment of diethyl chloroacetal with sodium (216). Methyl vinyl ether was first Hsted in Reppe patents on vinylation in 1929 and 1930 (210,211). 

Vinyl chloroacetate, Cp 2Sm(THF)2, toluene, rt, 99% yield. With Sml2 catalyst, the yield is 19%. ... 

Acetic acid is a versatile reagent. It is an important esterifying agent for the manufacture of cellulose acetate (for acetate fibers and lacquers), vinyl acetate monomer, and ethyl and butyl acetates. Acetic acid is used to produce pharmaceuticals, insecticides, and dyes. It is also a precursor for chloroacetic acid and acetic anhydride. The 1994 U.S. production of acetic acid was approximately 4 billion pounds. 

B. Reactions.—(/) Halides. Whereas ylides are alkylated in the normal way on treatment with a-bromo- or a-iodo-esters, quite different reactions occur with a-fluoro- and a-chloro-acetates. When salt-free ylides were refluxed in benzene with ethyl fluoroacetate or trifluoroacetate normal Wittig olefin synthesis took place with the carbonyls of the ester groups to give vinyl ethers, e.g. (14). On the other hand, methyl chloroacetate with... 

Widespread chlorine-containing polymers would include, 1) stable molding material for practical use such as polyvinyl chloride (PVC), polyvinylidene chloride and poly(epichlorohydrin)(PECH) and, 2) reactive polymers capable to introduce additional functional groups via their active chlorines such as chloromethyl polystyrene, poly (3-chloroethyl vinyl-ether) and poly (vinyl chloroacetate). While the latter, especially the chloromethyl polystyrene, has been widely used recently for the synthesis of variety of functional polymers, we should like to talk in this article about the chemical modification of the former, mainly of PVC and PECH, which was developed in our laboratory. 

The formation of cyclopropanes from 7C-deficient alkenes via an initial Michael-type reaction followed by nucleophilic ring closure of the intermediate anion (Scheme 6.26, see also Section 7.3), is catalysed by the addition of quaternary ammonium phase-transfer catalysts [46,47] which affect the stereochemistry of the ring closure (see Chapter 12). For example, equal amounts of (4) and (5) (X1, X2 = CN) are produced in the presence of benzyltriethylammonium chloride, whereas compound (4) predominates in the absence of the catalyst. In contrast, a,p-unsatu-rated ketones or esters and a-chloroacetic esters [e.g. 48] produce the cyclopropanes (6) (Scheme 6.27) stereoselectively under phase-transfer catalysed conditions and in the absence of the catalyst. Phenyl vinyl sulphone reacts with a-chloroacetonitriles to give the non-cyclized Michael adducts (80%) to the almost complete exclusion of the cyclopropanes. 

Uses Manufacture of acetate rayon, acetic anhydride, acetone, acetyl compounds, cellulose acetates, chloroacetic acid, ethyl alcohol, ketene, methyl ethyl ketone, vinyl acetate, plastics and rubbers in tanning laundry sour acidulate and preservative in foods printing calico and dyeing silk solvent for gums, resins, volatile oils and other substances manufacture of nylon and fiber, vitamins, antibiotics and hormones production of insecticides, dyes, photographic chemicals, stain removers latex coagulant textile printing. 

Biological. Vinyl chloride was reported to be a biodegradation product from an anaerobic digester at a wastewater treatment facility (Howard, 1990). Under aerobic conditions. Pseudomonas putida oxidized 1,1,2-trichloroethane to chloroacetic and glyoxylic acids. Simultaneously, 1,1,2-trichloroethane is reduced to vinyl chloride exclusively (Castro and Belser,... 

Chemical/Physical. In a laboratory experiment, it was observed that the leaching of a vinyl chloride monomer from a polyvinyl chloride pipe into water reacted with chlorine to form chloroacetaldehyde, chloroacetic acid, and other unidentified compounds (Ando and Sayato, 1984). 

In fact, the first description of a polymeric vinyl ester dates back to 1912 when Klatte [1] managed to polymerise vinyl chloroacetate to obtain a solid resin. However, the potential of these materials was not seen at that time [2]. Additionally the polymerisation reaction faced severe practical problems leading to products... 

Various halogenated polymers are used as the polymeric initiator for ATRP, for example, vinyl chloride-vinyl chloroacetate and styrene-p-chloromethylstyrene copolymers, bromi-nated butyl rubber, and chlorosulfonated polyethylene [Bomer and Matyjaszewski, 2002 Coskun and Temuz, 2003], (The vinyl chloride units have much lower reactivity for ATRP compared to the vinyl chloroacetate units because of steric reasons.) The density of grafting is adjusted by varying the copolymer composition. 

The grafting-through method has also been studied for ATRP. Vinyl chloroacetate is used as the initiator in ATRP of a monomer such as styrene to produce a macromonomer. Vinyl chloroacetate does not significantly copolymerize with styrene, and the result is a polystyrene vinyl macromonomer, which is then polymerized to a brush polymer [Davis and Matyjaszewski, 2002],... 

Using the grafting-from method with NMP requires the synthesis and (co)polymerization of monomers that contain the nitroxide group [Hawker et al., 2001]. A halogen-containing monomer such as vinyl chloroacetate or p-chloromethylstyrene is reacted with an HO-containing alkoxyamine to yield a vinyl alkoxyamine, which is used as a NMP initiator to... 

Fig. 5.1. Example of graphical determination of wt% conversion lower line) and mol% conversion (upper line) from chlorine content in the esterification of poly(vinyl alcohol) with chloroacetic acid to give (C4H5C102) at 100% conversion (29.5 wt% of chlorine). Dashed lines indicate values corresponding to an observed composition of 14.75 wt% of chlorine...

In 1838 Regnault [15] reported that vinylidene chloride could be polymerized. In 1839 Simon [16] and then Blyth and Hofmann (1845) [17] reported the preparation of polystyrene. These were followed by the polymerization of vinyl chloride (1872) [18], isoprene (1879) [19], methacrylic acid (1880) [20], methylacrylate (1880) [21], butadiene (1911) [22], vinyl acetate (1917) [23], vinyl chloroacetate [23], and ethylene (1933) [24]. Klatte and Rollett [23] reported that benzoyl peroxide is a catalyst for the polymerization of vinyl acetate and vinyl chloroacetate. 

In a closely related investigation, designed to generate vinyl alcohol in solution, divinyl hemiorthoformate [68] was detected as an intermediate in the hydrolyses of divinyloxymethyl dichloro- and trichloro-acetate [67] (Capon et al., 1981b). It is interesting that methyl vinyl hemiorthoformate could not be detected in the hydrolysis of methoxyvinyloxymethyl acetate and chloroacetate under similar conditions. So dimethyl and divinyl hemiorthoformate appear to be more stable than methyl vinyl hemiorthoformate. 

Heating a mixture of 6,7,8,9-tetrahydro-ll//-pyrido[2,l-b]quinazolin-ll-one (7) and acetyl and benzoyl chlorides, acetic anhydride, and vinyl acetate under reflux gave 6-condensation products (123), whereas reactions with ethyl chloroacetate, ethyl dichloroacetate, and chloral hydrate afforded 6-substituted products (124) (86MI7). 6,7,8,9-Tetrahydro-ll//-pyrido[2,l-b]quinazolin-l 1-one (7) and acetic anhydride, heated under reflux for 36 h, gave compound 123 (X = OAc, R = Me or X = Me, R = OAc, 18%) and its 6-acetyl derivative (124, R = COMe) in 31% yield (87JHC175 91JHC2071). 

The acetal was likewise prepared from chloroacetal and [Rh(OEP)]-, the aldehyde from [Rh(OEP)]2 and ethyl vinyl ether [326]. 

Acetic acid Acetic anhydride, chloroacetic acid, ethyl acetate, peracetic acid, vinyl acetate, cellulose acetate, terephthalic acid Food additives, solvent, monomers, resin Cheryan etal., 1997 Ravinder etal., 2000 Patel etal., 2006... 

A number of other unsaturated electrophilic compounds were used by Milkovich 18 as deactivators for living polystyrene or living polydienes. A characterization of the macromonomers obtained showed that the reaction of the living polymer with compounds such as maleic anhydride, vinyl chloroacetate, or 2-chloroethylvinyl ether yields the following unsaturated chain ends (in some cases the addition of 1,1-diphenylethylene is necessary) ... 

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