Nitrogen chloroacetate

Other interesting regioselective reactions are carried out within the synthesis of nitrofurantoin. Benzaidehyde semicarbazone substitutes chlorine in chloroacetic ester with the most nucleophilic hydrazone nitrogen atom. Transamidation of the ester occurs with the di-protic outer nitrogen atom. Only one nucleophilic nitrogen atom remains in the cyclization product and reacts exclusively with carbonyl compounds. 

In 1880, Liebermann and Voltzkow (40), and then Voltzkow (41), condensing chloroacetic acid with both ethyl N-phenylthiocarbamate and p-tolylisothiocyanate obtained homologous compounds to which they attributed formulas 40 and 41, whereas their structure probably derives from that of 38 by substituting an aryl group on the cyclic nitrogen. 

A dry 500-ml round-bottomed three-necked flask fitted with a stirrer, internal thermometer, and a pressure-equalized dropping funnel is placed under nitrogen and the flask is charged with 0.148 mole of freshly distilled cyclohexanone and 0.148 mole of freshly distilled ethyl chloroacetate. A solution of 6.0 g of potassium and 125 mL of dry terr-butyl alcohol is introduced into the dropping funnel, and the system is exhausted and... 

The aqueous solution of the disodlum salt of Lnitrogen atmosphere in the course of 30 minutes with stirring with a solution of 104 g of chloroacetic acid (1.1 mols) and 4 g of sodium pyrosulfite in 200 ml of water. 

Interaction of 24 with ethyl chloroacetate in methanolic sodium methox-ide afforded the triazin-3,14-dione derivative 27. The alternate structure 28 was excluded on the basis of spectral data [58,59]. Based on the reaction conditions, (sodium methoxide) structure 27 is thought to result from the initial formation of a sodium salt on the less basic imino nitrogen atom, which cyclizes into 27 with elimination of NaCl and EtOH (Scheme 12). The IR spectrum of 27 showed a characteristic C = 0 absorption band at 1650 cm-1,... 

Nitromethane, CH3N02, is a volatile liquid. It may be obtained by direct vapour phase nitration of paraffinic hydrocarbons either with nitric acid vapours (Hass et al. [1-8]) or with nitrogen dioxide (T. Urbanski and Slebodzinski [9]). It may also be prepared by the action of sodium- or potassium nitrite on chloroacetic acid... 

There are numerous examples of quaternizing alkylations of imidazoles using such diverse reagents as alkyl, alkenyl or aralkyl halides, ethyl chloroacetate, phenacyl bromide or dimethyl sulfate. Since water is frequently held very tenaciously by imidazole quaternary salts the compounds are often best prepared in anhydrous conditions (e.g. dry benzene solvent in a dry nitrogen atmosphere) even though the reaction is commonly slower in non-polar solvents. 

The reaction of a free diaminosarcophagine with an excess of chloroacetate under basic conditions led to a mixture of mono- and dicarboxymethylsarcophagines with substitution at the secondary nitrogen atoms these were isolated as complexes with a cobalt(III) ion (Scheme 42) [117]. 

Extending the chain has allowed the five-step synthesis of a tetraamine with tosyl groups on the two center nitrogen atoms (Stetter and Roos, 1954 Stetter and Mayer, 1961 Takada et al., 1988). The procedure used the reaction of Ay,Ay -ditosylethylenediamine with derivatives of chloroacetic acid. 

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