Nitroacetic acid esters

Nitroacetic acid esters and anudes are potential precursors of amino acids. They are good substrates in Pd(0)-catalyzed allylation with carbonates (Scheme 18) the same as the structurally related open-chain and cyclic a-nitroketones. An intramolecular version is aimed at the preparation of precursors of alkaloid ergoline. 3,4-Dimethylenecyclopentane nitroacetate is prepared in one synthetic step from allyl carbonate (R = Br, R = H) including a C—C bond formation by Pd-catalyzed reductive coupling.f There are more examples of Pd(0)-catalyzed allylation of nitroderiva-tives including nitromethane.f ... 

Reactions of nitroacetic acid ester with aldehydes ... 

Addition of nitroacetic acid esters to carbon-carbon double bonds s. 11, 861 G G->GHGR... 

Substitutedisoxazole-3,5-dicarboxylic acids have been prepared from ethyl nitroacetate and an aldehyde (63BCJii50). A related reaction leads to diethyl 4-hydroxyisoxazole-3,5-dicarboxylate (334) and involves the reaction of acetonedicarboxylic acid ester (333) with nitrosyl chloride (78JHC1519). 

The carboxylation of nitroalkanes with magnesium methyl carbonate followed by esterification gives a-nitro esters in 40-58% yield.14 Magnesium methyl carbonate is prepared by the saturation of a magnesium methoxide suspension in DMF with C02. More elegantly, sodium salt of nitroalkanes can he carboxylated by means of 1 -ethoxycarbonylbenzotriazole to give a-nitro esters in 55-80% yield (Eq. 5.7).15 Nitroacetic acids and its esters can serve as useful... 

M. T. Shipchandler, The Utility of Nitroacetic Acid and its Esters in Organic Synthesis, Synthesis 1979, 666. A.G. Agababyan, G.A. Gevorgyan u. O. L. Mndzhoyan, Amino Acids as the Amine Component in a Mannich Reaction, Usp. Khim. 51, 678 (1982). 

Reichert and Linckens [83] have reviewed gas chromatographic methods for the determination of nitriloacetic acid in potable waters. They point out that esterification of the nitriloacetic acid is required to enable it to be volatilised in the gas-liquid chromatographic column, and they compared a range of esterification reagents and conditions for simplicity and speed of operation. The method chosen involved treatment of a concentrated sample with a mixture of -propanol-acctyl chloride (10 1) and the resulting nitroacetic acid-propyl ester injected into a column, which was fitted with a nitrogen-sensitive detector. The detection limit for nitriloacetic acid in potable water is about lpgL-1. 

Nitriloacetic acid 2% poly(ethanediol) on Chromosorb W Nitroacetic acid converted to trimethyl ester prior to GLC 25pgL [335]... 

Nitrenes as intermediates in synthesis of N-heterocycles 82MI14. Nitroacetic acid and its esters in synthesis of N-heterocycles 79S666. Nitro compounds of aliphatic series, synthesis of N-heterocycles from ... 

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. ... 

Nitroacetic esters. Esterification of nitroacetic acid is not easy to achieve by conventional methods, but it can be performed with the aid of DCC. This procedure serves to anchor nitroacetyl groups to hydroxylated Merrifield resin. 

The utility of nitroacetic acid and its esters in organic synthesis has been reviewed. ... 

M. T. Shipchandler, The Utility of Nitroacetic Acid and its Esters in Organic Synthesis , Synthesis, 1979, 666. 

Hydroxy-o-nitrocarboxylic acid esters from cyclic o-nitroacetals via 2-hydroxy-o-nitrosocarboxylic acid esters Partially protected carbohydrate derivs. 

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