Synthesis and study on 2,4,6,8-tetraaryl- 3,7-diazabicyclo[3.3.1]nonanes and their derivatives

1-Carbethoxy-2,4,6,8-tetraaryl-3,7-diazabicyclo[3.3.1] nonan-9-ones (1, 2) were synthesized and their 1H and 13C NMR data are reported. Chemical shifts and spectral assignments for 2,4,6,8-tetrakis(4-chlorophenyl)-3,7-diazabicyclo[3.3.1]nonan-9-one (3), 2,4,6,8-tetraphenyl-3-thia-7-azabicyclo[3.3.1]nonan-9-one (4) and 2,4,6,8-tetraaryl-3,7-diazabicyclo[3.3.1]nonanes (5-7) are also included.     

A facile synthesis of 1,1-bis(silyl)ethenes

Symmetrical 1,1-bis(silyl)ethenes have been easily prepared via ruthenium complex-catalyzed silylative coupling cyclization of 1,2-bis(dimethylvinylsiloxy)ethane to give 2,2,4,4-tetramethyl-3-methylene-1,5-dioxa-2,4-disilacycloheptane with excellent selectivity and good yield, followed by its reaction with Grignard reagents. The cyclic product can also be effectively transformed into cyclic carbosiloxane, 2,2,4,4,6,6,8,8-octamethyl-3,7-dimethylene-1,5-dioxa-2,4,6,8-tetrasilacyclooctane.     

Heterocyclization of hydrazine with acetaldehyde and H2S

Hydrazine is regioselectively condensed with a mixture of acetaldehyde and H₂S at a temperature below −10 °C to form 2,4,6,8-tetramethyl-3,7-dithia-1,5-diazabicyclo[3.3.0]-octane. The reaction at 0 °C with the reverse order of mixing of the starting reagents affords 2,4,6-trimethyl(1,3,5-dithiazinan-5-yl)amine as the major product.     

Synthesis and structure of 2,4,6,8-tetramethyl-3,7-dithia-2,4,6,8-tetraazabicyclo[3.3.0]octane 3,3,7,7-tetraoxide

Condensation of N,N′-dimethylsulfamide with glyoxal gave 2,4,6,8-tetramethyl-3,7-dithia-2,4,6,8-tetraazabicyclo[3.3.0]octane 3,3,7,7-tetraoxide, a sulfur-containing analog of 2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione (Mebicar). The product structure was studied by X-ray analysis.     

Synthesis and separation of stereoisomeric 2,4,6,8-tetrasubstituted 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes

Heterocyclization of hydrazine with aldehydes R-CHO (R = Me, Et, Prⁿ, Buⁿ, n-C₅H₁₁, Ph, 4-MeOC₆H₄, 3-Py) and H₂S leads to stereoisomeric 2,4,6,8-tetrasubstituted 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes, which were separated by column chromatography. The trans-transoid-trans-configuration of tetramethyl(-ethyl,-propyl)-3,7-dithia-1,5-diazabicyclo-[3.3.0]octanes was inferred from the X-ray diffraction and ¹H and ¹³C NMR spectroscopic data.     

Diphosphatetraazacyclooctatetraenes. II. Properties and degradations

1,5-Bis(diphenylphospha)-3,7-bis(perfluoroalkylether)-2,4,6,8- tetraazacyclooctatetraene and 1,3-bis(diphenylphospha)-5,7-bis(perfluoroalkylether) -2,4,6,8-tetraazacyclooctatetraene were found to decompose at 316°C to phospha-s-triazines. The symmetrical arrangement liberated perfluoroalkylether nitrile with concommitant formation of the corresponding diphospha-s-triazine; the unsymmetrical isomer eliminated the (C₆H₅)₂PN unit to give the monophospha-s-triazine. The thermal and oxidative stabilities of the two compounds differed widely, with the unsymmetrical isomer being significantly more stable than the symmetrical arrangement. Spectral data pertinent to these results are discussed. Both materials were found to be effective in arresting perfluoroalkylether fluid degradation in oxidizing atmospheres in the presence of metal alloys.     

Synthesis,crystal and molecular structure of 3,7-ditosyl-1,5-diphenyl-3,7-diazabicyclo[3.3.1]nonane

3,7-Ditosyl-1,5-diphenyl-3,7-diazabicyclo[3.3.1]nonane has been found to adopt a chair–chair conformation in the crystalline state in contrast to 3,7-ditosyl-1,5-diphenyl-3,7-diazabicyclo[3.3.1]nonan-9-one, which had been previously found to exist in a chair-boat conformation.     

Synthesis and transformations of polyhedral compounds. Synthesis of 2-[quinolin-3(2)-yl]-1,3-diazaadamantanes

A number of new 1,3-diazaadamantane derivatives containing quinoline fragments on C² have been synthesized by condensation of 1,5-dialkyl-3,7-diazabicyclo[3.3.1]nonan-9-one, 1,5-dimethyl-3,7-diazabicyclo-[3.3.1]nonan-9-ol, and 1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonane with 2-oxo-1,2-dihydroquinoline-3-carbaldehyde, 2-chloro- and 2-iodoquinoline-3-carbaldehyde, and quinoline-2-carbaldehyde.     

Bromometrische Bestimmung des Thionins und seiner Derivate

Zusammenfassung Es wurde die Möglichkeit einer Bromierung von Thionin, Methylenblau, Methylengrün und Azur A in Äthanol durch Bromwasser studiert. Es wurden die Verbindungen 2,4,6,8-Tetrabrom-3,7-diamino-phenthiazoniumhydroxyd, 2,4,6,8-Tetrabrom-3,7-tetramethyldiamino-phenthiazoniumbromid und 6,8-Dibrom-4-nitro-3,7-tetramethyldiamino-phenthiazoniumhydroxyd isoliert und beschrieben. Der Verlauf der Bromierung wurde potentiometrisch verfolgt und Bedingungen zur quantitativen Bestimmung gefunden.Mit 1 Abbildung     

Synthesis,structural, and biochemical study of a series of methyl 2,6-diaryl-1-methyl-4-oxopiperidine-3,5-dicarboxylates and a series of methyl 2,4-diaryl-3,7-dimethyl-9-oxo-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylates

A series of methyl-2,6-diaryl-1-methyl-4-oxopiperidine-3,5-dicarboxylates Ia-c and 2,4-diaryl-3,7-dimethyl-1,5-dimethoxycarbonyl-9-bispidinones IIa-c have been synthesized and studied by ir, ¹H and ¹³C nmr spectroscopy and the crystal structure of methyl 2,4-diphenyl-3,7-dimethyl-9-oxo-3,7-diazabicyclo[3,3.1]nonane-1,5-dicarboxylate (IIa) has been determined by X-ray diffraction. The enolic form of compound Ia (I'a) was also studied.     

2,4,6,8-Tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione as a mild and convenient reagent for iodination of aromatic compounds

2,4,6,8-Tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione (tetraiodoglycoluril) is a convenient reagent for preparative iodination of benzene, alkylbenzenes, polycyclic hydrocarbons, aromatic amines, and phenol ethers in organic solvents under mild conditions.     

13,17,53,57-Tetraphenyl-13,17,53,57-tetrathio-3,7-dithia-1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane with an unusual conical-like conformation

1³,1⁷,5³,5⁷-tetraphenyl-1³,1⁷,5³,5⁷-tetrathio-3,7-dithia-1,5(1,5)-di(1,5-diaza-3,7-diphosphacyclooctana)-2,4,6,8(1,4)-tetrabenzenacyclooctaphane 2b was obtained by sulfurization of the corresponding macrocyclic tetraphosphine 1b. The structure of the inclusion complex of tetrasulfide 2b with DMF was investigated by the X-ray crystal structure analysis. A novel for this type of cyclophanes and relatively rare conical-like conformation of the macrocycle was found. A methyl group from one of the solvating DMF molecules penetrates the macrocyclic cavity of 2b from the side of the wider rim. According to quantum-chemical simulations, this may be the reason of the unusual conical conformation of 2b because the cavity of the macrocycles of this type is highly flexible. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis of 2-monofunctionalized 2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones

New (1R*,5S*)-2-R-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-diones containing the terminal carboxy or hydroxy group in the substituent R were synthesized by cyclocondensation of 4,5-dihydroxyimidazolidin-2-one with 1-R-ureas. Single-crystal X-ray diffraction analysis showed that 2-carboxyethyl-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione crystallizes as a racemate.     

New Synthesis of 2,4,6,8-Tetramethyl-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione Using Etidronic Acid as a “Green” Catalyst

Russian Journal of Organic Chemistry - A new method has been developed for the synthesis of 2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione in 62% yield using etidronic acid...     

Chiral cage molecules generated by regioselective O-alkylation of a doubly-bridged calix[8]arene

A calix[8]arene doubly-bridged at the 1,5-phenol units and 3,7-phenol units has a cage structure with D_2d symmetry. Regioselective introduction of methyl groups into the residual 2,4,6,8-phenol units affords five different cage compounds: that is, three racemic compounds, one meso compound, and one achiral compound. This paper reports systematic studies on the preparation methods of these new cage compounds and spectroscopic classification of their molecular symmetries. The results indicate that these compounds have a latent potential as a platform for designing chiral cage molecules with an ionophoric inner cavity.     

Preparation and X-ray analyses of siloxane-bridged acyclic and 8-membered cyclic phosphaethenes

Two Mes¹PC (Mes¹ = 2,4,6-tri-t-butylphenyl) parts were successfully combined with one or two disiloxane chain(s) by the reaction of 2-silyl-1-phosphaethenyllithium with dichlorotetramethyldisiloxane, and the structures of bis(1-bromo-2-phosphaethenyl)disiloxane and 3,7-diphosphinidene-2,2,4,4,6,6,8,8-octamethyl-1,5-dioxa-2,4,6,8-tetrasilacyclooctane were characterized by spectroscopic analyses and X-ray crystallography.     

Synthesis of N,N′-di(tert-butyl)bispidin-9-ones

Condensation of 1,3,5-tri(tert-butyl)-1,3,5-triazacyclohexane with acetone gave 3,7-di(tert-butyl)-1,5-bis[(tert-butylamino)methyl]bispidin-9-one. Reactions with ethyl methyl ketone and other ketones of the formula RCH₂COCH₃ yielded 5-R-3,7-di(tert-butyl)-1-[(tert-butylamino)methyl]bispidin-9-ones, while reactions with diethyl ketone and other symmetrical ketones of the formula RCH₂COCH₂R afforded 1,5-R-3,7-di(tert-butyl)bispidin-9-ones.     

Structure of 3,7-Diazabicyclo[3.3.1]nonane Complexes as the Basis of Creating New Metallocyclic Supramolecular Ensembles

The molecular and crystal structure of the complex of cupric bromide with 1,5-diphenyl-3,7-dimethyl-3,7-diazabicyclo[3.3.1]nonan-9-ones was studied. The geometry of the complexes of bispydines with cupric halides was shown to depend on the substituent at the nitrogen atom.     

The configuration and solid state conformation of 3,7-dihydroxy-1,5-bis(p-bromophenyl)octahydro-1,5-diazocine

The crystal structure of 3,7-dihydroxy-1,5-bis(p-brornophenyl)octahydro-1,5-diazocine ( 4 ) has been determined from the three dimensional x-ray diffraction data. This infers a similar structure for 3,7-dihydroxy-1,5-diphenyloetahydro-1,5-diazocine ( 1 ). The molecules are in a twist crown conformation and the configuration of the hydroxyl groups on the 3,7-positions is cis.     

Reaction of 1,3,5-tri-tert-butylbenzene with 2,4,6,8-tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione

Reactions of 1,3,5-tri-tert-butylbenzene with 2,4,6,8-tetraiodo-2,4,6,8-tetraazabicyclo[3.3.0]octane-3,7-dione in acetic and trifluoroacetic acids involve substitution of one or two tert-butyl groups in the aromatic ring with formation of mono-, di-, and triiodo-substituted derivatives. No iodo derivatives are formed in acetonitrile.