Vinyl compounds esters

Acrylates Acrylonitriles Allyl Esters Cellulose esters Epoxies Ethylenic (unsaturated) hydrocarbons Poly-hydroxy esters(eg Pentaerythritol tetramethacrylate,Ethylene Glycol diacrylate) Polyolefins Vinyl compound esters, acids)... 

Vinyl compounds 23, 40. 6H Vinyl compounds, esters 70, 136 Vinyl compounds, ethers 70 Vinylenes 23, 68, 257 Vinylidene compounds 23, 68... 

Phosphate groups can also be removed by dissolving-metal reduction. Reductive removal of vinyl phosphate groups is one method for conversion of a carbonyl compound to an alkene.224 (See Section 5.7.2 for other methods.) The required vinyl phosphate esters are obtained by phosphorylation of the enolate with diethyl phospho-rochloridate or /V A /V -tetramethyldiamidophosphorochloridate.225... 

Salicylate Esters. The methyl esters of three isomeric vinylsalicylic acids (the 3-, 4- and 5-vinyl compounds) have been prepared, using the synthetic routes outlined above. 

Two reports are available on the rearrangement of mixed vinyl phosphite esters to produce phosphonate diesters in moderate yield.94 95 In both instances, the vinyl phosphite esters were prepared by reaction of the dialkyl phosphorous chloride with highly enolized carbonyl compounds. The mixed ester products undergo thermal rearrangement to the phosphonate diesters (Figure 6.25). 

Since PTFE was first synthesized more than 50 years ago, fluoropolymers have been produced by radical polymerization and copolymerizaton processes, but without any functional groups, for several reasons. First, the synthesis of functional vinyl compounds suitable for radical polymerization is much more complicated and expensive in comparison with common fluoroolefins. In radical polymerization of one of the simplest possible candidates—perfluorovinyl sulfonic acid (or sulfonyl fluoride—there was not enough reactivity to provide high-molecular-weight polymers or even perfluorinated copolymers with considerable functional comonomer content. Several methods for the synthesis of the other simplest monomer—trifluoroacrylic acid or its esters—were reported,1 but convenient improved synthesis of these compounds as well as radical copolymerization with TFE induced by y-irradiation were not described until 1980.2... 

For electron-poor alkynes (Scheme 2) such as acetylene carboxylic acid ethyl ester 4, the activated Au(III) catalysts lead to about 60% of the product 5 as a 3.6 1 Z/E mixture. In contrast, Au(I) complexes of phosphines activated by AgSbF6 or Lewis acids are much better suited, delivering nearly quantitative yields of 5 with complete Z-selectivity (Scheme 4) [2], Only traces of the doubly vinylated compound 6 are observed as a side product. A particularly effective Lewis acid is BF3 OEt2, which also makes the catalytic system cheaper than those using AgSbF6 as the activating agent. 

After separation of the desired major diastereoisomer 154, the removal of the chiral auxiliary furnished vinyl compound 151 in enantiomerically pure form. The latter was directly converted to the 9-membered lactam 144 in 58% yield via a palladium-catalyzed carbonylation (10 atm CO, HCOOH, DME, 150°C). Removal of the methyl ester as previously described furnished (-)-rhazinilam. This elegant work constitutes the first asymmetric total synthesis of the natural product. 

To survey as completely as possible the grafting behavior of EVA copolymers toward various vinyl compounds, our investigations covered the grafting of vinyl acetate, vinylidene chloride, and acrylic and meth-acrylic esters. As polymerization processes, at first we preferred suspension polymerization to exclude the influence of solvents by terminating or transfer reactions during polymerization. Grafting by emulsion polymerization, in which the EVA copolymer was dissolved in the monomer before polymerization, was difficult because coagulate was formed as polymerization proceeded. 

C=CHCH2NAtN=CR has been reported. " Propargylic vinylic compounds give allenic aldehydes, ketones, esters, or amides ... 

A transformation of an ester group into a vinylic group may be accomplished by reacting the ester with / -tolylsulfonylmethylmagnesium iodide followed by NaBH4 reduction to the j6-hydroxysulfones cathodic reduction in DMF at a lead cathode produces the vinylic compound in good yield [84],... 

Functionally substituted benzylic, allylic, and vinylic compounds containing alkoxides, esters, ethers, nitriles, or amides can be reacted with halosilanes under Barbier conditions using HMPT to yield C- and O-silylated products, 1,2- or 1,4-addition products, as well as reductive dimers. Radical and anionic intermediates are postulated, based on SET reactions from the metal, and multiple silated species can be obtained. The use of the TMSCl-Mg-HMPT system has been extensively investigated by Galas group [85] at the University of Bordeaux, and their work has greatly advanced the science of the Barbier reaction with silanes. 

The vinyl group can also be transferred to alcohols to form vinyl ethers starting from vinyl chloride [66], vinyl esters [76], and vinyl ethers [77]. The transfer to water corresponds to a hydrolysis which readily takes place with all vinylic compounds in the presence of palladium salts to form acetaldehyde [78]. 

Vinyl acetic acid, as well as its methyl and 1-butyl esters, was examined by the discovery chemists as dipolarophiles in the [3 + 2] cycloaddition to form analogues of 9. The yields of the isoxazolines were variable, presumably due to the propensity of these vinylic compounds to polymerize. A better alternative was isobutyl ester (8) that is a stable compound and commercially available in large quantities. When this reactant was tested in our group, it regiospecifically produced 9 in consistent 90-95% yields. The accessibility of the two precursors 7 and 8, and the efficiency of the cycloaddition fulfilled our goals of a practical preparation of (R/S)-9. 

The NMR data of vinyl compounds are shown in Tables 12 and 13. A change in the chemical shift of the olefinic proton in the trans position relative to the ester group has been observed, whereas the chemical shift of the cis olefinic proton is scarcely influenced. The change in the chemical shift of the trans olefinic proton in the monomer increases in the following order ... 

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