Halides acids, degradation with

Ketones from a-halogenocarboxylic acid halides Curtins degradation with loss of 1 C-atom... 

Silver salts of carboxylic acids react with bromine or chlorine in an inert solvent to give carbon dioxide, a silver halide, and the halide containing one less carbon atom than the acid. The method has been reviewed. " Both low- and high-molecular-weight aliphatic bromides have been prepared. "t i i The degradation of silver salts of aromatic acids is complicated by nuclear halogenation." The procedure is valuable as a step in the synthesis of oi-bromo esters (C, to C,) from dicarboxylic acids. ... 

In the Barbier-Wieland degradation, the alpha-methylene group in an aliphatic carboxylic acid is removed in a sequence of reaction steps, effectively a chainshortening. The inverse procedure is the Amdt-Eistert synthesis, where an acid is converted into acyl halide and reacts with diazomethane to give the highest homolog. 

The Cunius degradation of acyl azides prepared either by treatment of acyl halides with sodium azide or trimethylsilyl azide [47] or by treatment of acyl hydrazides with nitrous acid [f J yields pnmarily alkyl isocyanates, which can be isolated when the reaction is earned out in aptotic solvents If alcohols are used as solvents, urethanes are formed Hydrolysis of the isocyanates and the urethanes yields primary amines. 

Lindblom and Blander (1980) have given a number of examples of relevance in the pharmaceutical industry. These include C-alkylations, 0-alkylations, and A-alkylations. The C-alkylation of phenylacetonitrile, (mono- and di-) alkylation of benzylpenicillin with a-chlorodiethyl carbonate (where the acid part and the halide part in the esterification would have degraded quickly under normal conditions adopted for the reaction), A-alkylation of purines and adenine, etc. are discussed at some length and the supremacy of PTC is clearly shown. 

Recently several pubhcations have examined replacing aqueous solvents with ionic liquids. Since simple and complex sugars are soluble in many imidazolium hahdes, water is not required as a co-solvent and degradation of HMF is minimal. Lansalot-Matras et al. reported on the dehydration of fmctose in imidazolium ionic liquids using acid catalyst (6). Moreau et al. reported that l-H-3-methylimidazolium chloride has sufficient acidity to operate without added acid (7). And we reported that a 0.5 wt% loading (6 mole% compared to substrate) of many metal halides in 1-ethyl-3-methylimidazohum chloride ([EMIM]C1) result in catalytically active materials particularly useful for dehydration reactions (8). 

The formation of hydrated electrons by the photolysis of halide ions in solution may be envisaged in two steps. The first step is the CTTS absorption leading to (X -). The second step is a slow, thermal process releasing the electron in competition with degradation and recapture. In the presence of acid and alcohol, photolysis of halide solutions generates H2 with a yield that increases both with acid and alcohol concentrations (seejortner et al., 1962, 1963, 1964). At 25°, the limiting quantum yields are 0.98 for Cl- at 185 nm, 0.6 and 0.5 for Brat 185 and 229 nm, respectively, and 0.3 and 0.25 for I- at 254 and 229 nm, respectively. Since most of these yields are less than 1, the direct reaction of HsO and (Xaq-) is ruled out. Instead, it is proposed that eh is produced from the... 

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