Degradation carboxylic acids, oxidative

This procedure, coupled with the procedure described on p. 41, illustrates the Barbier-Wieland method for systematically degrading carboxylic acids. foxwor-Desoxycholic acid may be prepared from wor-desoxycholic acid by repetition of this procedure. If the chromic acid oxidation product is not sufficiently solid to filter after dilution with water, the mixture must be extracted with ether and washed with dilute hydrochloric acid before the alkaline extraction. Wxwor-Desoxycholic acid may be crystallized from ethyl alcohol. It melts at 239-241°. 

A15.1.1.1 Carboxylic Acids. Carboxylic acids (R—CO—OH) are an acidic class of compounds that contain only carbon, hydrogen, and oxygen having pAia values in the range of 2 to 5.5. They are much stronger acids than water and alcohols. Carboxylic acids are weak acids. They tend to act as nucleophiles in the anionic form (R—COO ) and more electrophilic when protonated (R—CO—OH). They are not prone to oxidative degradation. Carboxylic acids can be reduced to a primary alcohol (R—CO2—H RCH2OH). 

Free-radical reactions. Silver nitrate, sodium persulfate, and iron(III) nitrate constitute an oxidizing system that degrades carboxylic acids to radicals. Adding these reactive intermediates to radical acceptors such as methyl vinyl ketone, acrylic esters, and acrylonitrile initiates synthetically useful processes. Monoamides of oxalic acid undergo oxidative degradation by (NH )2SjOg in the presence of AgNOj-Cu(OAc)2 to afford isocyanates in a biphasic system (11 examples, 45-87%). ... 

Potassium/tert-butanol Oxidative degradation Carboxylic acid esters from ketones... 

Selective oxidative degradation Carboxylic acids from hydroxymethyl ketones... 

Internal alkynes are oxidized to acytoins by thalliuin(III) in acidic solution (A. McKil-lop, 1973 G.W. Rotermund, 1975) or to 1,2-diketones by permanganate or by in situ generated ruthenium tetroxide (D.G. Lee, 1969, 1973 H. Gopal, 1971). Terminal alkynes undergo oxidative degradation to carboxylic acids with loss of the terminal carbon atom with these oxidants. 

Isoxanthopterin-6-carboxylic acid chlorination, 3, 296 synthesis, 3, 304 Isoxanthopterins catabolism, 3, 322 chlorination, 3, 296 degradation, 3, 308 occurence, 3, 323 oxidation, 3, 287 8-riboside synthesis, 3, 319 silylation, 3, 297 structure, 3, 264, 273 synthesis, 3, 298 Isoxazole, 3-acetohydroximoyl-synthesis, 6, 409 Isoxazole, 5-acetyl-3-chloro-oxidation, 6, 53... 

The nature of the base, CmHijN, varies. When produced from pure Mupinine, m.p. 68-9°, it furnishes on oxidation only 3-methylpyridine-2-carboxylic acid (XV) and pyridine-2 3-dicarboxylic acid. If, however, lupinine, m.p. 63-3°, is used, the resulting pyridine base on oxidation furnishes in addition 2-n-butylpyridine-6-carboxylic acid (XVI) and 6-methylpyridine-2-carboxylic acid (XVII). The conclusion is drawn that lupinine, m.p. 63-3°, is a mixture of 1-lupinine (XI) with aZlolupinine (XII), each of these components furnishing its own lupinane (XIII and XIV), and that these two lupinanes contribute to the final degradation product, the tertiary pyridine base, CioHuN, the two isomerides 2-w-Ijutyl-3-inethylpyridine (XVIII) and 2-w-butyl-6-raethylpyridine (XIX) respectively. These interrelationships are shown by the following scheme —... 

Early attempts to prepare 5-amino- and 5-acylaminobenzofuroxans by hypochlorite oxidation of the corresponding o-nitroanilines met with failure. Pyrolysis of the appropriate azide, however, gives 5-dimetliylamino- and 5-acetamidobenzofuroxan, whereas urethans of type (33) are produced by Curtius degradation of the 5-carboxylic acid. Controlled hydrolysis of the acetamido compound and the... 

Pnre cnltnres of organisms that can oxidize propionate either in the presence of a methanogen or nsing snlfate as electron acceptor have been obtained. These include both Syntrophobacter wolinii and Syntrophobacter pfenigii (Wallrabenstein et al. 1995). The interaction of two organisms, therefore, is clearly not obligatory for the ability to degrade these carboxylic acids under anaerobic conditions. 

Hydrolysis to the diol followed by dehydration to the aldehyde and oxidation to the carboxylic acid is used by a propene-utilizing species of Nocardia (de Bont et al. 1982). Although an ethene-utilizing strain of Mycobacterium sp. strain E44 degrades ethane-l,2-diol by this route, the diol is not an intermediate in the metabolism of the epoxide (Wiegant and de Bont 1980). 

Elder DJE, P Morgan, DJ Kelly (1992) Anaerobic degradation of tra -cinnamate and u-phenylalkane carboxylic acids by the photosynthetic bacterium Rhodopseudomonas palustris evidence for a beta-oxidation mechanism. Arch Microbiol 157 148-154. 

Oxidation of the alkyl group to a carboxylic acid before ring fission. For xylenes, it appears that there are signihcant differences in the degradability of the isomers, o-xylene being apparently more recalcitrant... 

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