Novel 2H-1,2,3-Triazole Sodium Complex from N-[2-Amino-1,2-dicyanovinyl]alkanamides

Abstract

Diazotization at 0 o C of N-[2-amino-1,2-dicyanovinyl]ethanamide 2aor propanamide 2b prepared from diaminomaleonitrile (DAMN) 1 using aqueous acetic acid and NaNO 2 solution furnished sodium complex 3. The X-ray structure of the complex 3 showed that it is a 1:1 mixture of the neutral 2H-triazole heterocycle 4ii and its anion deprotonated at the central (N) atom of the ring, together with a sodium counter ion and two coordinated water molecules.However, when the diazotization reaction was carried out in the presence of aqueous HCl, the product was 5-cyano-2H-[1,2,3]triazole-4-carboxylic acid amide monohydrate 4ii. Diazotization of DAMN 1 using aqueous HCl furnished 1H-1,2,3-triazole-4,5-dicarbonitrile 5, whereas with acetic acid there was no reaction, and hence no route analogous to that leading to complex 3. The structure of both complex 3 and the triazole monohydrate 4ii were solved using X-ray crystallography, and the compounds under study were fully characterized using spectroscopic techniques.

A long symmetric N...H...N hydrogen bond in bis(4-aminopyridinium)(1+) azide(1−): redetermination from the original data

“…For the search in the Cambridge Structural Database (Groom et al, 2016), the D-H distance was set in the interval 1.30-1.45 Å and the non-bonding distance between the donor and acceptor nitrogen atoms was set in the interval 2.6-3.0 Å . (Marsh & Clemente, 2007); (c) 2,1,3-benzoselenadiazole 2,1,3-benzoselenadiazolium pentaiodide (Gieren et al, 1985) (Heravi et al, 2005); (e) bis[(3,5-dimethylpyrazole)(3,5dimethylpyrazolyl)]platinum(II) (Umakoshi et al, 2008); (f) 4-{2-(pyridin-4-yl)oxy]-1,2bis(2,3,5,6-tetrafluoro-4-iodophenyl)ethoxy}pyridin-1-ium iodide bis(nitrobenzene) (Martí-Rujas et al, 2012); (g) 5,6:14,15-dibenzo-1,4-dioxa-8-azonia-12-azacyclopentadeca-5,14-diene 5,6:14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadeca-5,14-diene perchlorate (Tušek-Božić et al, 2005); (h) dioxidotetrakis(4-methylpyridine)rhenium(V) 4methylpyridinium 4-methylpyridine diodide (Krawczyk et al, 2014); (i) 4-methylpyridinium trans-bis(-picoline)tetrakis(thiocyanato)molybdenum 4-methylpyridine (Kitanovski et al, 2009); (j) bis(4,4 0 -bipyridinium) hexakis( 2 -sulfido)tetragermaniumtetrasulfide 4,4 0 -bipyridine heptahydrate (Wang et al, 2003); (k) 4,4 0bipyridinium 4-(pyrid-4-yl)pyridinium 4,4 0 -bipyridine hexakis(isothiocyanato-N)-iron (Wei et al, 2002); (l) tris(2-benzimidazolylmethyl)ammonium 3,5-dinitrobenzoate 3,5dinitrobenzoic acid clathrate (Ji et al, 2004); (m) (2R,4S,5R)-9-(hydroxyimino)-6 0methoxycinchonan-1-ium (2R,4S,5R)-N-hydroxy-6 0 -methoxycinchonan-9-imine chloride methanol solvate (Zohri et al, 2015); (n) catena-[bis( 2 -aqua)-(5-cyano-2H-1,2,3triazole-4-carboxamide)(4-cyano-1,2,3-triazole-5-carboxamide)sodium] (Al-Azmi et al, 2007); (o) (1,1 0 -hydrogenbis{4-[1 0 -(4-pyridyl)ferrocen-1-yl]pyridine}) 4-[1 0 -(4-pyridyl)ferrocen-1-yl]pyridinium tris(5-carboxy-2-thienylcarboxylate) bis(thiophene-2,5-dicarboxylic acid) (Braga et al, 2008); (p) cytosinium 4-amino-2-hydroxybenzoate cytosine monohydrate (Cherukuvada et al, 2013); (q) cytosinium acetylenedicarboxylate cytosine monohydrate (Perumalla et al, 2013).…”

Synthetic Routes to a Triazole and Tetrazole with Trinitroalkyl Substitution at Nitrogen

“…Since the treatment of 2 with HNO 3 surprisingly yielded triazole 3 , which could be due to nitrosation, control experiments were carried out by using nitrite in HCl and H 2 SO 4 , and indeed, with both systems, the formation of the identical triazole 3 was observed, which is reported for other triazoles . Therefore, we conclude that in the initial HNO 3 approach sufficient amounts of the nitrosonium cation NO + prevail and react with maleonitrile 2 .…”