I. V. Shakhkel'dyan

Synthesis and Structure of 1,9-Dinitro-5-oxa-11-azatricyclo[6.4.0.04,9]dodecan-2-one

A series of 6,11-disubstituted 1,9-dinitro-5-oxa-11-azatricyclo[6.4.0.04,9 ]dodecan-2-ones were prepared from anionic adducts of 2,4-dinitrophenol with propanone and 2-phenylethanone carbanions by successive selective reduction with sodium borohydride and aminomethylation with formaldehyde and primary amines. By spectral methods and by quantum-chemical calculations following PM3 method the structure of the molecules synthesized was shown to contain all the three rings in a chair form with equatorial substituents in positions 6 and 11.

3-Methyl-1,5-dinitro-3-azabicyclo[3.3.1]non-7-ene

The 3-azabicyclo[3.3.1]non-7-ene skeleton of the title compound, C 9 H 13 N 3 O 4 , has a sofa-chair conformation. There are two molecules in the asymmetric unit with different orientations of their nitro groups.

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.

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.

Aminomethylation by Formaldehyde and Primary Amines of Anionic σσ-Adduct Obtained from 2,4-Dinitrophenol and Acetophenone Carbanion

By condensation of 2,4-bis(aci-nitro)-3-(2-phenyl-2-oxoethyl)cyclohex-5-en-1-one with formaldehyde and primary amines a series of N-substituted 9-(2-phenyl-2-oxoethyl)-1,5-dinitro-3-azabicyclo[3.3.1]non-7-en-6-ones was synthesized. With the use of X-ray analysis the cyclohexenone fragment in the 3-(2-bromoethyl)-1,5-dinitro-9-(2-phenyl-2-oxoethyl)-3-azabicyclo[3.3.1]non-7-en-6-ones was established to exist in sofa conformation, and the nitrogen-containing ring to have the chair conformation with equatorial orientation of substituents in 3 and 9 positions. The regio- and stereoselectivity of the reaction under study was interpreted relying on the quantum-chemical calculations by AM1 and PM3 procedures.

3-Azabicyclo[3.3.1]nonane Derivatives: III. Synthesis of 3-Substituted 9-Acetonyl-1,5-dinitro-3-azabicyclo[3.3.1]-non-6-en-8-ones by Mannich Condensation of the Janovsky σ-Adduct of 2,4-Dinitrophenol with Acetonide Ion

A number of 9-acetonyl-1,5-dinitro-3-azabicyclo[3.3.1]non-6-en-8-one derivatives were synthesized by Mannich condensation of 3-acetonyl-2,4-bis(aci-nitro)cyclohex-5-en-1-one disodium salt with formaldehyde and primary amines.

3-Azabicyclo[3.3.1]nonane Derivatives: V. Synthesis of 7-Polyfluoroalkoxy-1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes

A number of 7-polyfluoroalkoxy-1,5-dinitro-3-azabicyclo[3.3.1]non-6-enes were synthesized by reduction of 3,5-dinitrophenyl polyfluoroalkyl ethers with sodium tetrahydridoborate, followed by the Mannich reaction with formaldehyde and primary amines.

Synthesis and conformation of 6,8,10-trinitro-1,4-dioxaspiro[4.5]decane

Abstractcis, trans-6,8,10-Trinitro-1,4-dioxaspiro[4.5]decane was synthesized by reduction of the corresponding spirocyclic anionic δ-complex with potassium tetrahydroborate. The molecular structure and the conformation of the title compound were established by X-ray diffraction analysis and1H NMR spectroscopy.

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.

Reactions of Aromatic Nitro Compounds: LXXIV. Azo Coupling of Anionic Nitroarene σ-Complexes with Aromatic Diazo Compounds. Effect of Reaction Conditions on the Yield of Nitroazobenzenes

Effect of a number of factors on the yield of nitroazobenzenes in the reaction of 4-nitro- and 4-dimethylaminobenzenediazonium tetrafluoroborates with anionic σ adducts derived from 1,3-dinitrobenzene was studied. Conditions were found which allow nitroazobenzenes to be prepared in 80-90% yield.