Structural study of 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9β-ol

The infrared spectra in several media and the crystal structure of 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]-nonan-9β-ol ( I ) (Scheme I) have been determined, in order to complete the structural study described for the title compound from the ¹H and ¹³C nmr data [1]. The bicyclic system adopts a flattened chair-chair conformation in which the cyclohexane ring is more flattened. The methyl and phenyl groups are in equatorial positions and the OH group in an axial position with respect to the piperidine ring.     

Synthesis and properties of 3-substituted 3-azabicyclo-[3.3.1]nonan-9-amines

Catalytic hydrogenation of 3-benzyl- and 3-tert-butoxycarbonyl-3-azabicyclo[3.3.1]nonan-9-one oximes over Raney nickel gave the corresponding 3-substituted 3-azabicyclo[3.3.1]nonan-9-amines which were converted into amides via reactions with acetyl and chloroacetyl chlorides and maleic and succinic anhydrides, into Schiff bases by condensation with benzaldehyde and 4-chlorobenzaldehyde, and into isothiocyanates by treatment with thiophosgene in the presence of K₂CO₃. 3-Benzyl- and 3-tert-butoxycarbonyl-3-azabicyclo-[3.3.1]nonan-9-yl isothiocyanates readily reacted with methanol, aniline, and sodium azide to produce methyl thiocarbamate, thiourea, and dihydrotetrazole-5-thione derivatives having a 3-azabicyclo[3.3.1]nonane fragment.     

Conformational effect in 2,4-diphenyl-3-aza-6,6-dimethyl-7-oxabicyclo [3.3.1]nonan-9-ol C21H25O2N

Kazakh State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 5, pp. 167–169, September–October, 1991.     

Crystal and molecular structure of 6,6-dimethyl-cis-2,4-diphenyl-3-aza-7-oxabicyclo[3.3.1]nonan-9-one

A method is presented for synthesizing 6,6-dimethyl-2,4-diphenyl-3-aza-7-oxabicyclo[3.3.1]nonan-9-one. The x-ray structure shows that the compound in the crystal exists in the chair-boat conformation with the piperidine ring in the boat form. The two phenyl substituents in the 2- and 4-positions are responsible for such a conformation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1400–1402, October, 1990.     

Molecular modeling, X-ray diffraction analysis, and the study of iNOS inhibitor activity of 3-imino-2,4-diazabicyclo[3.3.1]nonan-1-ol hydrochloride

iNOS-Inhibitor activity of 3-imino-2,4-diazabicyclo[3.3.1]nonan-1-ol hydrochloride was predicted basing on molecular modeling and was confirmed by experiments in vitro. The results of the study by XRD analysis of the molecular and crystal structure of this compound are reported.     

Spectroscopic study of 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-α(β)-ols

3-Methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-α(β)-ols have been synthesized and studied by ir, ¹H and ¹³C nmr spectroscopy. In deuteriochloroform and perdeuteriobenzene solutions, these compounds adopt a flattened chair-chair conformation in which the cyclohexane ring is more flattened. From the ¹H and ¹³C nmr data, several stereoelectronic effects have been deduced. The complete and unambiguous assignment of all protons of the 3-azabicyclo[3.3.1]nonane system, not described up to date, has been carried out.     

Synthesis of N-arylmethyl-3-azabicyclo[3.3.1]nonan-9-ones

Russian Journal of Organic Chemistry -     

Structure, Conformation, and Stereodynamics of N-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes and N-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones(1)

The variable temperature (1)H, (13)C, and (19)F NMR spectra were measured for the title N-nitrosamines. The observed unusually low N-N rotation barriers (12-15 kcal/mol) result from a significant deviation of the nitrosamino system from planarity. A pyramidal character of the amino nitrogen was confirmed by the X-ray crystal structures of two compounds and by bathochromic shifts of the n-pi absorption bands in the UV spectra. The nonplanarity of the nitrosamino moiety is due to the strong pseudoallylic A((1,3)) strain caused by the steric interaction of the NNO group with the neighboring aryl substituents fixed in the equatorial positions of the bicyclic skeleton. In addition, the barriers to the C-C rotation of aryl groups were examined at temperatures lower than required to "freeze" the N-N rotation and different DeltaG() values were observed for the aryls oriented syn and anti to the nitroso oxygen.     

Synthesis, structural and crystallographic study of some carbamates derived from 9-methyl-9-azabicyclo[3.3.1]nonan-3α-ol

A series of benzimidazole, thiazole and benzothiazole carbamates derived from 9-methyl-9-azabicyclo[3.3.1]nonan-3α-ol was synthesized and studied by ¹H, ¹³C, 2D NMR and IR spectroscopy. To assist in the interpretation of the spectroscopic data, the crystal structure of 3 (9-methyl-9-azabicyclo[3.3.1]nonan-3α-yl 2-amino-1H-benzimidazole-1-carboxilate) was determined by X-ray diffraction. It has been found that 1-carbamates and 2-carbamates can be obtained in the case of the benzimidazole derivatives. The benzimidazole-1-carbamates are obtained in higher yields (41, 38%) than the benzimidazole-2-carbamates (3, 9%). The compounds studied displayed in CDCl₃ solution a preferred chair–boat conformation with the substituted ring in a distorted boat form and the N–CH₃ substituent in an axial position with respect to the chair piperidine ring. This conformation is similar to that determined by X-Ray diffraction for compound 3.     

X-ray structural study of 2,3-diphenyl-4-morpholinomethyl-5-ethynyl-2-thio-2-phosphabicyclo[4.4.0]decan-5-ol

Institute of Chemical Sciences, Academy of Sciences of the Kazakh SSR. Institute of Heteroorganic Compounds, Academy of Sceences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 3, pp. 153–156, May–June, 1990.     

New homoleptic metal complexes of Schiff bases derived from 2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-one

New bidentate Schiff-base ligands 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarbothioamide HL¹ and 2-(2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-ylidene)hydrazinecarboxamide HL² were synthesized from the condensation of 2,4-di-p-tolyl-3-azabicyclo[3.3.1]nonan-9-one with thiosemicarbazide and semicarbazide, respectively. Homoleptic complexes of these ligands, of general formula K[Cr(L ⁿ )₂Cl₂], K₂[Mn(L ⁿ )₂Cl₂], K₂[Fe(L¹)₂Cl₂] and [M(L ⁿ )₂] (where M = Co(II), Ni(II) Cu(II), Zn(II), Cd(II), and Hg(II) ions; n = 1 or 2) are reported. The mode of bonding and overall geometry of the complexes were determined through IR, UV-Vis, NMR and mass spectral studies, magnetic moment measurements, elemental analysis, metal content, and conductance. These studies revealed octahedral geometry for Cr(III), Mn(II), and Fe(II) complexes, square planar for Cu(II), Co(II), and Ni(II) complexes and tetrahedral for Zn(II), Cd(II), and Hg(II) complexes.     

Revised stereochemistry of 3-AZA-3-methyl-6-cycloalkylamino-bicyclo[3.3.1]nonan-9-OLS

The re-examination of stereochemistry of the title compounds is reported. The present results suggest a more reasonable configuration assignments than previously described.     

Reactions of 3-substituted 3-azabicyclo[3.3.1]nonan-9-ones with nitrogen-containing nucleophiles

Condensation of 3-substituted 3-azabicyclo[3.3.1]nonan-9-ones with hydroxylamine and hydrazine hydrate gave the corresponding oximes, hydrazones, and azines. Reductive amination of the title compounds in the presence of sodium triacetoxyhydridoborate led to the formation of 3-substituted 3-azabicyclo[3.3.1]nonan-9-amines which were converted into the corresponding dihydrochlorides by treatment with dry hydrogen chloride. Treatment of 3-tert-butoxycarbonyl derivatives with HCl under analogous conditions was accompanied by elimination of the tert-butoxycarbonyl group to produce 3-azabicyclo[3.3.1]nonan-9-amine dihydrochlorides.     

Synthesis and characterisation of 3-aza-7-phosphabicyclo[3.3.1]nonan-9-ones

Novel 3-aza-7-phosphabicyclo[3.3.1]nonan-9-ones have been synthesised via the Mannich reaction of a phosphorinanone, a primary amine and formaldehyde. The new phosphorus-nitrogen (PN) compounds are rigid and adopt a twin-chair conformation both in solution and the solid states. The coordination properties of the PN compounds were explored and a stable platinum complex was synthesised in which the PN ligand was bonded through both donor atoms.