Allyl vinylacetate

Allyl vinylacetate is the main product in the reaction of allyl alcohol with carbon monoxide in the presence of tris-(tri-(p-fluorophenyl)-phosphine)-platinum at 200 °C without addition of another alcohol. At a reaction temperature of 250 °C allyl crotonate is obtained by thermal isomerization [551],... 

Vinylacetic acid. Place 134 g. (161 ml.) of allyl cyanide (3) and 200 ml. of concentrated hydrochloric acid in a 1-htre round-bottomed flask attached to a reflux condenser. Warm the mixture cautiously with a small flame and shake from time to time. After 7-10 minutes, a vigorous reaction sets in and the mixture refluxes remove the flame and cool the flask, if necessary, in cold water. Ammonium chloride crystallises out. When the reaction subsides, reflux the mixture for 15 minutes. Then add 200 ml. of water, cool and separate the upper layer of acid. Extract the aqueous layer with three 100 ml. portions of ether. Combine the acid and the ether extracts, and remove the ether under atmospheric pressure in a 250 ml. Claisen flask with fractionating side arm (compare Fig. II, 13, 4) continue the heating on a water bath until the temperature of the vapour reaches 70°. Allow the apparatus to cool and distil under diminished pressure (compare Fig. II, 20, 1) , collect the fraction (a) distilling up to 71°/14 mm. and (6) at 72-74°/14 mm. (chiefly at 72 5°/ 14 mm.). A dark residue (about 10 ml.) and some white sohd ( crotonio acid) remains in the flask. Fraction (6) weighs 100 g. and is analytically pure vinylacetic acid. Fraction (a) weighs about 50 g. and separates into two layers remove the water layer, dry with anhydrous sodium sulphate and distil from a 50 ml. Claisen flask with fractionating side arm a further 15 g. of reasonably pure acid, b.p. 69-70°/12 mm., is obtained. 

The only practical methods for the preparation of vinylacet.ic acid involve hydrolysis of allyl cyanide 6 carbonation of allylmag-nesium bromide 8 or the malonic acid synthesis.9... 

When aqueous NaOH is given as a base, isomerization of the product butenoic acids can be extensive depending on the nature and concentration of base. In dilute aqueous solutions alcohols do not react to form the respective esters, however, the reactions are strongly accelerated due to the increased solubility of the substrates in the catalyst-containing aqueous-alcoholic phase. For example, with 23-33 % (v/v) ethanol in water the [PdCl2(TPPTS)2]-catalyzed hydroxycarbonylation of allyl chloride proceeded with TOF-s of 1850-2400 h and with a vinylacetic/crotonic acid ratio of 21 [16]. Addition of [CuCb] increased the overall conversion rate (by a factor of 2 at [Cu]/[Pd] = 8) but at the same time the side reactions... 

The reaction of 1 with an allylic bromide is interesting because a /(//-carboxylic acid ester or an a-substituted vinylacetic acid ester can be obtained (equation II). 

The best materials are produced by curing unsaturated polyester during copolymerization with different types of unsaturated monomers and oligomers, such as styrene and its derivatives, methyl methacrylate, vinylacetate, sulfone-type compounds, allyl esters, and oligo(ester acrylates).5... 

Acid hydrolysis of the simpler olefinic nitriles to olejinic acids occurs without appreciable migration of the double bond. Acrylic acid is made by hydrolysis of acrylonitrile with sulfuric acid (78%). Concentrated hydrochloric acid is used to convert allyl cyanide to vinylacetic acid (75-82%). Similarly, 3"pentenonitrile furnishes a 70% yield of 3-pen-tenoic acid, but the isomeric 2-methyl-3-butenonitrile is not hydrolyzed under the same conditions. The alkaline hydrolysis of higher-molecular-weight branched a, -olefinic nitriles gives mixtures of isomeric and /S,7-olefinic acids. ... 

Dicyclohexylborane is comparable to disiamylborane (1, 57-59,2,29) in effecting selective hydroboration of dienes1 and of olefins containing reactive functional groups near the double bond (e.g., ethyl vinylacetate and allyl benzoate ). 

The intermolecular carbon-carbon bond forming reaction involving allylic sulfones has also been considered without mediators. The successful addition of 2-functionalized allyl sulfones to vinylacetate, taking advantage of favorable polar effects, has been performed by Whitham and co-workers (equation (70))... 

The carbonylation of nitrobenzene to phenyl isocyanate is catalysed by [RhCl(CO)2]2 + L (L=MoCl6 or py.H+Cl- >), [RhH(CO)(PPh3)3], = and PdCl2-pyMe+ Carbonylation of allylic substrates has also been studied in detail rhodium phosphine complexes [e.g., RhCl(PPh3)s] are particularly useful for the synthesis of AT-alkyl-2-pyrrolidones [reactions (6)], whereas the carbonylations of allylic alcohols to vinylacetate esters [reaction (7)] are best carried out with [PdCl2(PAr3)a]10MCl2 (M=Sn or Ge). ... 

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