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Synthesis, X-ray and spectroscopic analysis of 2-hydrazino-6-methyl-4-(methoxymethyl)-5-nitropyridine-3-carbonitrile

✍ Scribed by Marina Tranfić; Jasna Halambek; Mario Cetina; Marijana Jukić


Publisher
Elsevier Science
Year
2011
Tongue
English
Weight
913 KB
Volume
1001
Category
Article
ISSN
0022-2860

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✦ Synopsis


Pyridine derivative 2-hydrazino-6-methyl-4-(methoxymethyl)-5-nitropyridine-3-carbonitrile (2) has been obtained from 2-chloro-4-(methoxymethyl)-6-methyl-5-nitropyridine-3-carbonitrile (1) by novel protocol and its structure was determined by X-ray diffraction method. An analysis revealed some structural differences in 2 compared to corresponding 3-cyano-5-nitro-pyridines and 2-hydrazinopyridines. Supramolecular structure contains one NAHÁ Á ÁN and two NAHÁ Á ÁO hydrogen bonds, as well as one CAHÁ Á ÁO hydrogen bond. Structural features have been also studied by FT-IR, FT-R and NMR spectroscopy. FT-IR dilution experiments showed that the character of intermolecular NHÁ Á ÁO and NHÁ Á ÁN interactions in solution depends on concentration. The spectral properties were investigated by UV-vis absorption and fluorescence spectroscopy techniques. Absorption spectra of compounds have been recorded in protic and aprotic solvents in the range 200-550 nm and solvent effects on the absorption spectra of this compound are interpreted. Absorption spectra of aqueous solution of compound 2 were also recorded at different temperatures and pH values and protonation constant was calculated. Unlike previously studied structurally similar compound 1, the title compound 2 does not emit fluorescence.


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## Abstract 2‐Amino‐6‐(3‐methyl‐5‐oxo‐1‐phenyl‐2‐pyrazolin‐4‐yl)‐4‐phenylpyridine‐3‐carbonitrile (1) obtained by the reaction of 4‐(1‐iminoethyl)‐3‐methyl‐1‐phenyl‐2‐pyrazolin‐5‐one with benzylidenemalononitrile, was reacted with triethyl orthoformate followed by hydrazine hydrate, acetic anhydride