Carboxylic acids, unsaturated hydroxylation

The unsaturated retro-Michael product easily isomerizes to a dicarbonyl when the Cy also carries a hydroxyl group (X = OH in Fig. 2.3). Such components are notoriously unstable. They undergo decarbonylation to a shorter aldehyde and CO. The retro-Michael product can also be converted into a carboxylic acid via hydration of the aldehyde function (Fig. 2.3). Notably, the formation of the carboxylic acid is accompanied by the saturation of the Cp it in fact represents an exchange reaction between the OH, and the aldehydic H. 

YS-822A had nine degrees of unsaturation, all of which have already been assigned to four double bonds, two carbonyls (a lactone and a carboxylic acid) and three rings. Consequently, all the oxygen functional groups at C should be hydroxyls. Thus, the planar structure of YS-822A was determined as 65. 

A very simple synthesis of the pheromone exo-brevicomin (4i) proceeds via an electrochemical Kolbe condensation between the unsaturated carboxylic acid 39 and the ketoacid 40, followed by hydroxylation of the double bond with OSO4, as... 

Composition. Shellac is primarily a mixture of aliphatic polyhydroxy acids in the form of lactones and esters. It has an acid number of ca 70, a saponification number of ca 230, a hydroxyl number of ca 260, and an iodine number of ca 15. Its average molecular weight is ca 1000. Shellac is a complex mixture, but some of its constituents have been identified. Aleuritic acid, an optically inactive 9,10,16-trihydroxypalmitic acid, has been isolated by saponification. Related carboxylic acids such as 16-hydroxy- and 9,10-dihydroxypalmitic acids, also have been identified after saponification. These acids may not be primary products of hydrolysis, but may have been produced by the treatment. Studies show that shellac contains carboxylic acids with long methylene chains, unsaturated esters, probably an aliphatic aldehyde, a saturated aliphatic ester, a primary alcohol, and isolated or unconjugated double bonds. 

Of particular importance in describing the difference between these two families of resins are the locations of die reactive unsaturation. In the polyester resin, these groups are located along the backbone of die polymer with terminal hydroxyl or carboxylic acid groups. The vinyl ester resins contain no significant acidity but terminate in reactive vinyl ester groups. Because of the location of these reactive sites, the vinyl ester resins will homopolymerize as well as coreact with various vinyl monomers. 

To overcome these drawbacks, in recent years much attention has been paid to the development of resins which cem be f2d ricated with the same processes as those for conventional polyester resins, but having superior properties. Vinyl ester resins are the result of such development efforts (4-6). Vinyl ester resins are addition products of Vcurious epoxide resins and ethylenically unsaturated mono-carboxylic acids ( ). It condsines the excellent mechcuiical, chemical cuid solvent resistemce of epoxy resins with the properties found in the unsaturated polyester resins. In general, the cured vinyl ester resin has physical properties superior to the cured conventional ester resin, particulcurly corrosion resistcuice. This arises from the differences in the number and arremgement of polar groups such as ester and hydroxyl groups eind ccurbon-to-ccirbon double bonds present in the polymer chains. 

Enol acetates and corresponding derivatives constitute another class of unsaturated compounds that can advantageously be hydrogenated with high enantiomeric excess. This reaction is related to the enantioselective reduction of ketones. Acylated enol carboxy-lates (as an equivalent of a-keto carboxylic acid) can likewise be successfully reduced with rhodium(I) catalysts based on (5,5)-ethyl-DuPHOS (eq 8). Subsequent deprotection of the hydroxyl group or reduction of the carboxylic acid derivatives so obtained deliver chiral a-hydroxy carboxylates and 1,2-diols, respectively. 

In malic acid the hydroxyl group is in the ie/a-position in relation to one of the carboxyl groups and the formation of an unsaturated acid by the loss of water would be expected. 

Hydroxylation at double bonds of unsaturated carboxylic acids is accomplished stereoselectively by the same reagents as those used to hy-droxylate alkenes. syn Hydroxylation is carried out with potassium permanganate [101] or osmium tetroxide with hydrogen peroxide [130], sodium chlorate [310, 715], potassium chlorate [715], or silver chlorate [310] as reoxidant, anti Hydroxylation is achieved with peroxyacids, such as peroxybenzoic acid [310] or peroxyformic acid, prepared in situ from hydrogen peroxide and formic acid [101] (equation 472). 

Unsaturated polyesters having hydroxyl groups can be prepared by the reaction of glycols, maleic anhydride and dicarboxylic acids in more than the stoichiometric amount of glycols/carboxylic acids (13, 34). Edwards discussed the application of isophthalic unsaturated polyester urethane hybrids in conventional molding techniques (13). He also applied the hybrids to foamed products (21). Vinyl esters can be prepared by the reaction of bisphenol A with glycidyl methacrylate (21). 

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