Crystal and molecular structure of 1,5-diphenyl-3,7-diallyl-3,7-diazabicyclo[3.3.1]nonane-9-one

S. M. Kirov Kazakh State University. Chemical Institute for Oil and Natural Salts, Academy of Sciences of the Kazakh SSR. M. V. Lomonosov State University, Moscow. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 1, pp. 189–192, January–February, 1990.     

Synthesis and structure of new 3,7-diazabicyclo[3.3.1]nonane derivatives

Aminomethylation of triethylammonium 4-aryl-3,5-dicyano-6-oxo-1,4,5,6-tetrahydropyridin-2-olates and their sulfur and selenium analogs, as well as the structure of formed products, were studied in details. The reaction is of general character and leads to the formation of 7-substituted 9-aryl-2,4-dioxo-, 9-aryl-4-oxo-2-thioxo-, 9-aryl-4-oxo-2-selenoxo-3,7-diazabicyclo[3.3.1]nonane derivatives or their salts. The structures of ethyl 9-(2-chlorophenyl)-5-cyano-7-(4-methylphenyl)-2-oxo-4-thioxo-3,7-diazabicyclo[3.3.1]nonane-1-carboxylate (as a complex with N-methylmorpholine) and triethylammonium salt of 7-benzyl-4-oxo-2-selenoxo-9-(2-thienyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarbonitrile were studied by X-ray crystallography.     

Synthesis of 3,7-diacyl-1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonane derivatives as promising lipid bilayer modifiers

Novel 3,7-bis(dialkylaminoacetyl)-1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonanes were synthesized, which can undergo conformational reorganization under the change of solvent polarity, protonation (the change of pH) or complexation with LaCl₃. These compounds are capable of being embedded into the liposomal membranes and can serve as molecular switches for the development of stimulus-sensitive liposomal containers.     

The gas-phase conformation of 3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonane

The gas-phase conformation of the title compound (1) is discussed in reference to its photoelectron spectrum. The experimental lone-pair/lone-pair splitting (0.51 eV), when compared with that of similar diamines and with the results of three sets of MO calculations (MINDO/3, MNDO and STO-3G), leads to the conclusion that 1 exists in the chair-chair conformation. A remarkable sensitivity of the calculations to slight changes in the geometry is noted, and it is suggested that calculations of this type must include geometry-optimization. The question of through-space vs through-bond inteaction of the nitrogen lone pairs was explored by performing MNDO calculations in which the N-N resonance integrals were set to zero. These calculations indicate that in the chair-chair conformation the N-N interaction is mainly through-space. The ¹³CNMR and Ni(acac)₂-induced ¹³C shifts of 1 are discussed.     

pH-Sensitive liposomes with embedded 3,7-diazabicyclo[3.3.1]nonane derivative

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The crystal and molecular structure of 3,7-dicyano-3,5,7-triaza-1-phosphabicyclo[3.3.1]nonane

The crystal and molecular structure of the title compound has been determined by a single crystal x-ray diffraction study using counter-data. The compound crystallizes in the monoclinic space group, P2₁/c, with a = 8.657 ± .001Å, b = 10.513 ± .001Å, c = 10.378 ± .001Å, β = 99.68 ± .01° for Z = 4. The structure was solved by the symbolic addition procedure and refined by block-diagonal least-squares to R = 0.052 for 1479 statistically significant reflections. The geometry of the bicyclic ring system is discussed.     

Cyclopalladate complex of 3-benzyl-7-methyl-3,7-diazabicyclo[3.3.1]nonane

Russian Chemical Bulletin - A new (C,N,N)-pincer cyclopalladate unsymmetrical complex of 3-benzyl-7-methyl-3,7-diazabicyclo[3.3.1]nonane (3-benzyl-7-methylbispidine) was synthesized and...     

Molecular and crystal structure of 3,7-di(2-propenyl)-1,5-diphenyl-3,7-diazabicyclo[3.3.1]-nonan-9-one complexed with copper(II) chloride

We have investigated the molecular and crystal structure of 3, 7-di(2-propenyl)-1, 5-diphenyl-3, 7-diazabicyclo[3.3.1]nonan-9-one complexed with copper(II) chloride. We have shown for the first time that the reason for the distortion of the coordination polyhedron of the metal is the interaction of the substituents at the nitrogen atoms with the halogen atoms.Communication 2 in the series Complexing properties of 3,7-diazabicyclo[3.3.1]nonanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 770–774, June, 1996. Original article submitted April 13, 1996.Deceased.     

Synthesis of novel piperazine based building blocks: 3,7,9-triazabicyclo[3.3.1]nonane, 3,6,8-triazabicyclo[3.2.2]nonane, 3-oxa-7,9-diazabicyclo[3.3.1]nonane and 3-oxa-6,8-diazabicyclo[3.2.2]nonane

The preparation of four novel bridged piperazine building blocks is described: 3,7,9-triazabicyclo[3.3.1]nonane 1, 3-oxa-7,9-diazabicyclo[3.3.1]nonane 2, 3,6,8-triazabicyclo[3.2.2]nonane 3 and 3-oxa-6,8-diazabicyclo[3.2.2]nonane 4. The scaffold of 1 was synthesized from N,N′-dibromobenzenesulfonamide and ethyl acrylate. Compound 2 may be prepared from identical starting materials or alternatively from α,α′-diglycerol. Compounds 3 and 4 were identified as side products from possible aziridinium intermediates.     

Heteroadamantanes and their derivatives. 9. Synthesis of 1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane and derived 2,2-disubstituted 5,7-dinitro-1,3-diazaadamantanes

Heating 1,5-dinitro-3,7-di(tert-butyl)-3,7-diazabicyclo[3.3.1]-nonane with concentrated hydrobromic acid gives 1,5-dinitro-3,7-diazabicyclo[3.3.1]nonane. Cyclization of the latter with various aldehydes and ketones gave a series of 2,2-disubstituted 5,7-dinitro-1,3-diazaadamantanes. The behavior of the synthesized compounds under electron impact has been studied.For Communication 8 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 538–542, April, 1990.