3-Azabicyclo[3.3.1]nonane Derivatives: VIII. Synthesis and Properties of 6(7)-R-3,3-Dimethyl-1,5- dinitro-3-azoniabicyclo[3.3.1]non-6-ene Iodides

N-Alkylation of 6(7)-R-1,5-dinitro-3-methyl-3-azabicyclo[3.3.1]non-6-enes with methyl iodide afforded a series of quaternary ammonium salts whose yield depended on the solvent polarity and character of substituents located in positions 6 or 7 of substrate. The presence of electron-withdrawing groups reduced the yield of the target products compared to unsubstituted compound, whereas the electron-donor substituents increased the yield. As shown by the X-ray diffractionstudy the congormation of the substances was not changed in the course of quaternization. The DTA-TG analysis revealed that in the first stage of thermolysis the 6(7)-R-3,3-dimethyl-1,5-dinitro-3-azoniabicyclo[3.3.1]non-6-ene iodides suffer dealkylation. Two fragmentation paths of compounds synthesized under electron impact were observed: elimination either of methyl iodide or aziridinium cation.     

3-Azabicyclo[3.3.1]nonane Derivatives: IX. Synthesis and Molecular Structure of 3-Azabicyclo[3.3.1]nonane-1,5-diamines in Solution and in Solid State

During catalytic reduction with hydrogen on nickel of a series of 3-substituted 1,5-dinitro-3-azabicyclo-[3.3.1]non-6-enes alongside nitro groups reduction occurred also hydrogenation of the double bond. New diamines of the 3-azabicyclo[3.3.1]nonane series were synthesized, and their structure was established by means of IR, ¹H and ¹³C NMR spectroscopy and X-ray diffraction study.     

Study of the bromination of 1,5-dinitro-3-azabicyclo-[3.3.1]non-6-enes

The electrophilic addition of bromine to 3-substituted 1,5-dinitro-3-azabicyclo[3.3.1]non-6-ene in carbon tetrachloride is accompanied by intramolecular 3,7-cyclization with the formation of 6-bromo-3-R-1,5-dinitro-3-azonia-tricyclo[3.3.10^3,7]nonane tribromides. In the bromination of 1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes containing substituents at the double bond, molecular complexes of halogen with the substrate were obtained. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 862–873, June, 2008.     

Unusual Result of the Reaction of 5,7-Dinitroquinolin-8-ol with Hydrazine Hydrate

Russian Journal of Organic Chemistry - The reaction of 5,7-dinitroquinolin-8-ol with hydrazine hydrate afforded 5-aminopyrido[2,3-d]pyridazin-8(7H)-one in 50% yield instead of expected product of...     

Synthesis and Structure of Derivatives of 9-(2-Oxopropyl)-1,5-dinitro-7,8-benzo-3-azabicylo[3.3.1]non-7-en-6-ones

A number of 3-R-9-(2-oxopropyl)-1,5-dinitro-7,8-benzo-3-azsbicyclo[3.3.1]non-7-en-6-ones was synthesized by Mannich reaction involving Yanovsky adduct of 2,4-dinitronaphthol. It was established by molecular spectroscopy and X-ray diffraction analysis that the piperidine ring in these compounds was in the chairconformation with a diequatorial position of the substituent attached to the heteroatom and 2-oxo-propyl group, and the cyclohexenone fragment was in sofaform. By an example of 3-methyl-9-(2-oxopropyl)-1,5-dinitro-7,8-benzo-3-azsbicyclo[3.3.1]non-7-en-6-one the dissociative ionization of bicyclononanes under the electron impact was investigated.