Selenium heterocycles. XXXII . Synthesis of [1]benzoxepino[3,4-d]-thiazole, [1]benzothiepino[3,4-d]thiazole, [1]benzoxepino[3,4-d]selenazole,and [1]benzothiepino[3,4-d]selenazole. four novel heterocycles

Starting from the readily available ethyl 2-phenyl-4-methyl-thiazole-5-carboxylate (III), 2-phenyl-4-chloromethyl-thiazole (VIII) and 2-aryl-4-chloromethylselenazole (XIV), 2-phenyl-4,10-dihydro-10-oxo-[1]benzoxepino[3,4-d]thiazole (Ia), 2-phenyl-4,10-dihydro-10-oxo[1]benzothiepino[3,4-d]thiazole (Ib), 2-aryl-4,10-dihydro-10-oxo[1]benzoxepino[3,4-d]selenazoles (IIa-IIe) and 2-aryl-4,10-dihydro-10-oxo[1]benzothiepino[3,4-d]selenazoles (IIf-IIj) were prepared.     

The synthesis of [1]benzothieno[2,3-c]quinolines, [1]benzothieno[2,3-c][1,2,4]triazolo[4,3-a]quinoline,and [1]benzothieno[2,3-c]tetrazolo[1,5-a]quinoline

Photocyclization of 3-chloro-N-phenylbenzo[b]thiophene-2-carboxamide 10 afforded [1]benzothieno[2,3-c]-quinolin-6(5H)-one 11 which was chlorinated to 6-chloro[1]benzothieno[2,3-c]quinoline 12 followed by dechlorination to give [1]benzothieno[2,3-c]quinoline 5 . A series of 6-substituted alkoxy and thioalkoxy[1]benzothieno[2,3-c]quinoline derivatives were prepared along with the N-methyl quaternary salt 13 of 5 . 6-Chloro[1]-benzothieno[2,3-c]quinoline 12 was converted into 6-hydrazino[1]benzothieno[2,3-c]quinoline 23 which upon treatment with formic acid yielded [1]benzothieno[2,3-c][1,2,4]triazolo[4,3-a]quinoline 6 . Treatment of 23 with nitrous acid resulted in [1]benzothieno[2,3-c]tetrazolo[1,5-a]quinoline 7 . Compounds 6 and 7 are novel heterocyclic ring systems.     

Chemistry of 1,2,3-thiadiazole. IV. Synthesis of [1]benzoxepino-[3,4-d][1,2,3]thiadiazole, [1]benzothiepino-[3,4-d][1,2,3]thiadiazole, [1]benzoxepino[4,3-d][1,2,3]thiadiazole, [1]benzoxepino[4,3-d]oxazole and [1]benzoxepino[4,3-d]oxazole. Four novel heterocycles

Starting from the readily available 4-bromomethy-5-carbethoxy 1,2,3-thiadiazole (V), 5-bromomethy-4-carbethoxy-1,2,3-thiadiazole (IX) and ethyl 2-aryl-5-bromomethyloxazole-4-carboxylate (XIV), 4,10-dihydro-10-oxo[1]benzoxepino[3,4-d][1,2,3]thiadiazole (Ia), 4,10-dihydro-10-oxo[1]benzothiepino[3,4-d][1,2,3]thiadiazole (Ib), 4,10-dihydro-4-oxo[1]benzothiepino[4,3-d] [1,2,3]thiazole (II), 2-aryl-4,10-dihydro-4-oxo[1]benzoxepino[4,3-d]oxazoles (XIXa-XIXc) and 2-aryl-4,10-dihydro-4-oxo[1]benzothiepino[4,3-d]oxazoles (XIXd-XIXf) were prepared.     

1, 1-Difluoro-1H-cyclopropa[a]naphthalene

1, 1-Difluorocyclopropa[a]naphthalene ( 1b ) is prepared in three steps from 4-bromo-1,2-dihydronaphthalene ( 7 ) via carbene addition, benzylic bromination and bidehydrohalogenation. Structural evidence for formation of 1b is based on ¹H- and ¹⁹F-NMR spectroscopy. Compound 1b is stable in solution at ?30°. Upon reaction with MeOH/H⁺ it is converted to a 1:2 mixture of 1- and 2-methylnaphthoate ( 10 and 11 , respectively).     

Helic[6]arene-Based Chiral Pseudo[1]rotaxanes and [1]Rotaxanes

Chiral pseudo[1]rotaxanes and [1]rotaxanes constructed from macrocyclic arenes still remain a big challenge mainly owing to the lack of such chiral macrocycles. In this work, a new system of chiral pseudo[1]rotaxanes formed by self-inclusion of helic[6]arene containing amide linked with the terminal tertiary amines was first discovered. Based on an atom-economic stopping strategy, a pair of chiral [1]rotaxanes were conveniently obtained in almost quantitative yields by blocking the pseudo[1]rotaxanes with monobenzyl bromide of tetraphenylethene. The structures of pseudo[1]rotaxanes and [1]rotaxanes were characterized by 2D NMR spectra in solution, combined with DFT calculations. The photophysical properties further revealed the efficient chirality transfer of helic[6]arene to the tetraphenylethene moiety, compared to their unthreaded chiral isomers. The discovery of the chiral pseudo[1]rotaxanes allows for a wide and available synthesis of chiral [1]rotaxanes, and also opening a new avenue to the design of chiral supramolecular materials.     

Arene imine derivatives of nitrogen heterocycles: 1a,9b-dihydrobenz[h]-azirino[f]quinoline, 1a,9b-dihydrobenz[f]azirino[h]quinoline and 1a,9b-dihydroazirino[f][1,10]phenanthroline

The syntheses of the K-imine derivatives of benzo[h]quinoline ( 1 ), benzo[f]quinoline ( 2 ) and 1,10-phenanthroline ( 3 ) are described. The parent nitrogen heterocycles were oxidized with sodium hypochlorite to the corresponding K-oxides, 4, 6 and 8 , which in turn were reacted with sodium azide. The resulting azido alcohols were then cyclized with triethyl phosphite to the title compounds 5, 7 and 9 . The oxirane ring cleavage in benzo[h]quinoline 5,6-oxide ( 4 ) and in benzo[f]quinoline 5,6-oxide ( 6 ) by sodium azide proceeded by the predicted regioselectivity: 4 gave trans-5-azido-5,6-dihydro-6-benzo[h]quinolinol ( 11 ) and trans-6-azido-5,6-dihydro-5-benzo[h]quinolinol ( 10 ) as the major and minor products respectively, and 6 yielded solely trans-6-azido-5,6-dihydro-5-benzo[f]quinolinol ( 12 ). The latter compound proved by X-ray analysis to crystallize as a hydrogen bonded dimer.     

Zur Kenntnis von Li2[CuO2] [1, 2]

On Li₂[CuO₂] At the first time single crystals of Li₂[CuO₂] are prepared by exchange reaction. The crystal structure (I mmm) with a = 365.4(0), b = 285.9(0), c = 937.4(0) pm, Z = 2, d_x = 3.73 g/cm³, d_pyk = 3.67 g/cm³ was refined (four-circle-diffractometer data PW 1100, 343 I_o(hkl), MoKα, R = 0.046, R_w = 0.041). The characteristic structure element is the planar chain \documentclass{article}\pagestyle{empty}\begin{document}$ {}_\infty ^1 \left[{{\rm CuO}_{4/2}} \right]^{2 -} $\end{document}. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated.     

1, 4-Diazabicyclo [2.2.2] octanes

1,4-Diazabicyclo[2.2.2]octane hydrochloride methylchloride was obtained from N-benzoylpiperazine through 1-(2-hydroxyethyl)-4-benzoylpiperazine, 1-(2-acetoxyethyl)-4-benzoylpiperazine methyltosylate, 1-(2-hydroxyethyl)piperazine methylchloride, and 1-(2-chloroethyl)piperazine methylchloride.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 845–847, June, 1976.     

Pyrazolo[1, 2-a]pyrazoliumolates as novel structure elements in liquid crystals [1]

A series of pyrazolo[1, 2-a]pyrazoliumolates of type 3, 4, and 5 was prepared. Compound 4(R³ = CH₃) shows liquid crystalline properties (C 158.5 N 162 I).     

Synthesis of 1, 2-diazabicyclo [2.2.2] octane, 1, 2-diazabicyclo [3.2.1]-octane,and their derivatives

1, 2-Diazabicyclo [2.2.2] octane, its 6-methyl homolog, and 1, 2-diazabicyclo [3.2.1] octane are synthesized by a general method involving nitrosation of piperidine carboxylic acids, subsequent reduction to 1-aminopiperidine carboxylic acids, cyclization to 3-keto-1, 2-diazabicycloalkanes, reduction of the latter to 1, 2-diazabicycloalkanes. A number of 2-substituted 1, 2-diazabicyclo [2.2.2] octanes are synthesized.     

Enantioselective sensing of amines based on [1 + 1]-, [2 + 2]-, and [1 + 2]-condensation with fluxional arylacetylene-derived dialdehydes

Four induced circular dichroism (ICD) probes exhibiting a stereodynamic arylacetylene framework and terminal aldehyde units have been prepared. The CD silent sensors generate a strong chiroptical response to substrate-controlled induction of axial chirality upon selective [1 + 1]-, [2 + 2]-, and [1 + 2]-condensation. The intense Cotton effects can be exploited for in situ ICD analysis of the absolute configuration and ee of a wide range of amines.     

Synthesis of 1H-thieno[3,4-c]pyrazoles,thieno[3,4-b]furans,selenolo[3,4-b]furans and pyrrolo[3,4-d]thiazoles

Starting from the readily available aryl 2-methyl-5-phenyl-3-furyl ketones, 5-methyl-1H-1-phenylpyrazole-4-yl ketones and 4-methyl-2-phenyl-5-thiazolylcarboxaldehyde, a series of 2-phenyl-4-arylthieno[3,4-b]-furan, 2-phenyl-4-(p-methoxyphenyl)selenolo[3,4-b]furan, 4-aryl-1H-1-phenylthieno[3,4-c]pyrazole and 5-benzyl-2-phenylpyrrolo[3,4-d]thiazole were prepared in high yield.     

Synthesis of 1-azacycl[3.2.2]azine and 1-azabenzo[h]cycl[3.2.2]azine

1-Azacycl[3.2.2]azines were synthesized from 2-methylthioimidazo[1,2-a]pyridines, 2a and 2b , by using [2 + 8] cycloaddition reaction with dimethyl acetylenedicarboxylate as the key step. Synthesis of 1-azabenzo-[h]cycl[3.2.2]azine was also described.     

Synthesis and total 1H-NMR assignment of [1]benzothieno-[2,3-c] [1,10]phenanthroline

The synthesis of [1]benzothieno[2,3-c][1,10]phenanthroline ( 5 ) is described. It was obtained in four steps from known starting materials. The basic skeleton of the molecule and of the phenanthroline ring were formed via photocyclization. The total assignment of ¹H-nmr spectra was accomplished with the aid of two-dimensional nmr methods.     

Synthesis of 5,6-dihydro-4H-pyrrolo[1, 2-a] [1,4]benzodiazepines

The title compounds are. Prepared by the reaction of carbonyl compounds with 1-(2′-amino-methylphenyl)pyrrole hydrochloride.     

A comparative study on the synthesis of the 1H[1]benzothieno[2,3-d]-imidazole and 1H[1]benzothieno[2,3-d]-v-triazole

Alternate routes for the synthesis of the new title compounds are described. The experimental procedure for the isolation of the unstable 2,3-diaminobenzo[b]thiophene as the dichloride salt is presented.