A-Nitrocarboxylic acids

Treating the dianion of a carboxylic acid with an alkyl nitrate leads to an a-nitrocarboxylic acid which readily undergoes decarboxylation to the corresponding nitroalkane. This method is particularly useful for the synthesis of arylnitromethanes containing electron-donating groups. ... 

Other stabilized anions that were successfully C-arylated include the anions of nitroalkanes, a-methyl-a-nitrocarboxylic acid derivatives, esters, triphenylmethane, indole and scatole. Nitroalkanes gave high yields of the a-C-aryl derivatives. Ita the presence of BTMG, 2-nitropropane reacts with triphenylbismuth dichloride or tetraphenylbismuthonium p-toluenesulfonate to lead to a-nitrocumene (86 or 77% respectively). The reaction using triphenylbismuth dichloride and TMG was applied to the synthesis of a-methyl-a-phenylglycine via arylation of a-nitropropionic acid esters. ... 

Reactions of carbonyl compounds with nitroalkanes like nitromethane (Henry reaction) are described in Volume 2, Chapter 1.10. The doubly activated ethyl nitroacetate readily reacts with aliphatic, aromatic and heteroaromatic aldehydes to give a,p-unsaturated-a-nitrocarboxylic acid esters in the presence of TiCU/V-methylmorpholine as mixtures of cis and trans isomers. ... 

Reaction of levoglucosenone with amides of a-nitrocarboxylic acids resulted in the formation of the tetrahydropyridones 77 and with acetoacetic acid amides, mixtures of the keto and enol tautomers were obtained [137]. 

N-Carbalkoxy-a-amino-carboxylic acids Dicarboxylic acid imides, N-carbaryloxy-a,3-Ethylene-a-nitrocarboxylic acid esters... 

Nitration of active methylene groups—a-Nitrocarboxylic acid esters s. 11, 547... 

Synthesis of a-nitrocarboxylic acid esters from tert-amines s. 4, 753 with ethyl a-nitropropionate s. R. V. Heinzelman et al., J. Org. Ghem. 25, 1548 (1960)... 

Pedersen KJ (1932) The decomposition of a-nitrocarboxylic acids with some remarks on the decomposition of )5-ketocarboxylic acids. J Phys Chem 38 559-571 Pedersen KJ (1949) The effect of metal ions on the rate of decomposition of nitroacetic acid. Acta Chem Scand 3 676-696... 

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