Nitroacetic acid, decarboxylation

E) Decarboxylation of Nitroacetic Acid. The stability of the carboxyl group (which, if attached to a —CH2 group, Is quite stable) depends on the other groups which are adjacent to it. The effect of the nitro group is illustrated as follows ... 

Although the chelate magnesium salt (1) of the aci-form of nitroacetic acid had not been characterized, its existence in solution had been suggested from the striking effect of magnesium ions on the rate of decarboxylation of nitroacetic acid. 

Table 59 presents activation parameters for the decarboxylation of trichloroacetic acid in various basic solvents. Presumably the acid is in the form of its anion in these solvents. The activation parameters fall into a fairly narrow range and the differences presumably represent specific solvation effects. In an acidic solvent, decanoic acid, the activation parameters for the decomposition of potassium trichloroacetate are increased considerably. The values are A/f = 41.4 kcal.mole" and A5 = 27.7 eu . The activation parameters presumably reflect a composite of a prior equilibrium between decanoic acid and the trichloroacetate anion along with decarboxylation of the latter anion. The rate of decarboxylation of sodium nitroacetate is about five times faster in methanol than in water . This effect was attributed to dispersion of the negative charge at the transition state , a process which is more favorable in the less polar methanol solvent. Similarly, the decar-... 

The general approach can be enlarged and conditions for condensation made milder by the use of further-activated esters, thus condensation with methyl nitroacetate produces 3-nitro-coumarins, condensations with Wittig ylides " allow orffto-hydroxyaryl ketones to be used ° and the use of diethyl malonate (or malonic acid ) (a 3-ester can be removed by hydrolysis and decarboxylation ), malononitrile, ethyl trifluo-roacetoacetate, or substituted acetonitriles in a Knoevenagel condensation, produces coumarins with a 3-ester, 3-trifluoroacetyl, " 3-cyano, or 3-alkyl or -aryl substituent. Condensation with IV-acetylglycine generates 3-acetylamino-coumarins. ... 

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