Diethyl nitromalonate

The hydroxyimino (oxime) group can also be oxidized to a nitro group. For example, diethyl nitrosomalonate gives diethyl nitromalonate in 88% yield on treatment with manganese dioxide in glacial acetic acid for 24 hours at 30°.196... 

When gramine reacts with diethyl nitromalonate, the primary product obtained is diethyl -(3-indolylmethyl)-a-nitromalonate (96.5%), which is converted into tryptophan by partial hydrolysis and decarboxylation, followed by reduction and further hydrolysis.812... 

Nitration of Active Methylene Carbons. Active methylene carbons are nitrated by a number of reagents.With nitric acid the nitration of /S-diketones can be achieved (eq 7). Nitration of diethyl malonate provides diethyl nitromalonate in 92% yield. a-Nitro ketones are obtained by nitration of ketones or enol acetates with the reagent derived from nitric acid and acetic anhydride in moderate to good yields (eq 8). ... 

A. Direct Nitration of Active Methylene Compounds with Nitric Acid 16-1. Preparation of Diethyl Nitromalonate... 

Carbon-Carbon Bond Formation. Direct coupling of an alcohol with a carbon acid by the use of DEAD/TPP has been limited to only a few examples because of the lack of carbon acids with pAa < 13. If enolizable carbonyl compounds are used, alkylation generally takes place on oxygen. Thus the reaction of 1,3-cyclohexanedione with isopropanol, DEAD, and TPP affords exclusively the O-alkylated product (eq 47). Cyanoacetate reacts at the carbon atom, while diethyl malonate is unreactive. However, the reaction of diethyl malonate with alcohols in the presence of ADDP and BU3P affords C-alkylated products in 3-56% yields (eq 48). Ethyl nitroacetate and nitromalonate oxidize the alcohol via an aci-nitro ester (eq 49). o-Nitroarylacetonitriles of general formula (50) undergo alkylation on carbon (eq 50). ... 

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