N-methylhydrazine

N-Methylhydrazine was purchased from Fluka and was used without any purification. All the operations should be carried out under a well-vented hood since N-methylhydrazine is a carcinogen. 

These building blocks can be obtained either by the Miller cyclization of (5-hydroxy-ct-amino acids or by the Staudinger reaction7 ([2+2] ketene-imine cycloaddition). The procedure reported here follows the second route and has the advantages of being diastereospecific and to proceed in high yield. For a large scale preparation, the harmful and toxic N-methylhydrazine can be replaced by N,N-dlmethyl-1,3-propanediamine. Further transformations of the key intermediate have been reported elsewhere.7 9... 

The formation of malonaldehyde induced by the Fenton reaction (Fe2+ plus H202 in excess) has been studied using the N-methylhydrazine assay (Matsu-fuji and Shibamoto 2004). Under such conditions, the yield of malonaldehyde is much lower (2 x 10"5 mol per mol Fe2+ 1 x 10 4 when Fe2+ is complexed by EDTA) than in the radiolytic system discussed above. The reasons for these differences are not yet known. 

Gyromitrin is a volatile derivative of hydrazine (see Figure 4) with the chemical formula of acetaldehyde methyl formylhydrazone and is readily converted to N-methyl-N-formyl hydrazine and N-methylhydrazine. It is primarily a liver toxin although the red blood cells and central nervous system are also involved. The... 

Ring expansion of homophthalic anhydride 114 on reaction with N-i- r-N-methylhydrazine in acetic acid resulted in the 2,3-benzodiazepinedione derivative 115 in moderate yield. The combination of the less hindered nitrogen (NCH3) and the more reactive carbonyl group in 114 may explain the regioselectivity observed. Functionalisation of C5 by the azido group then led ultimately via the amine 116 and the peptide 117 to the 2,3-benzodiazepine-1,4-diones 118. These final compounds were designed to act as peptidomimetics at the carboxy terminus of hydroxyamides one such compound 118 (R =... 

A second method which is used to analyze volatile o,p-unsaturated aldehydes such as acrolein and 4-hydroxynonenal and dicarbonyls such as malondialdehyde, utilizes N-methylhydrazine derivatization (Figure 1) and GC-NPD analysis (14), This method was originally used to measure flee malondialdehyde during UV irradiation of hexane solutions containing free fatty acids, com oil, or beef fat, but has been used successfully for analysis of malondialdehyde in biological and food systems (15-17). 

Figure 1. Stable derivatives from carbonyl compounds with N-methylhydrazine.

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