Synthesis and dynamic stereochemistry of 1,5-disubstituted 2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-ones

The 1-isopropyl and 1-benzyl derivatives of 1,5-tetrahydrobenzodiazepin-2-one were synthesized by alkylation under the conditions of phase-transfer catalysis. The inversion of the heterocycle was studied by PMR spectroscopy, and the free energies of activation were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 254–258, February, 1986.     

2-芳基-4-甲基-2,3,4,5-四氢-(1,5)-苯并硫氮杂 的晶体结构研究

本文报道2-p-硝基-4-甲基-2,3,4,5-四氢-(1,5)-苯并硫氮杂 的两顺反式异构体的晶体结构. 顺式异构体属正交晶系, 空间群为反式异构体属单斜晶系, 空阒空间群为 , 晶胞参数:晶体结构由SHELXTL直接法程序解出, 用块矩最小二乘法修正, 最后的偏离因子:顺式异构体结构分析表明: 顺式异构体为类椅式构象, 反式异构体类扭船式构象. 这为进一步归纳这类化合物的结构特征和立体化学规律提了条件.     

Synthesis and spectral properties of n-alkyl-4-methyl-7(8)-nitro-2,3,4,5-tetrahydro-(1h)-1,5-benzodiazepin-2-ones

Alkylation of 4-methyl-7(8)-nitro-2,3,4,5-tetrahydrobenzodiazepin-2-ones under phase transfer catalytic conditions or in dry acetone occurs only at position 1. The 5-alkyl isomers are obtained by reductive alkylation of 4-methyl-7(8)-nitro-2,3-dihydro-1,5-benzodiazepin-2-ones. The UV, IR, PMR, and mass spectra of the isomeric compounds are reported.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 959–963, July, 1992.     

Synthesis of 1h-2,3,4,5-tetrahydro- 1,5 -benzodiazepin-2-ones by reductive cyclization of 3- (o-nitrophenylamino)propionic acids

A new synthesis of 1H-2,3,4,5-tetrahydro-1,5-benzodiazepin-2-ones (I) by the reductive cyclization of o-nitro derivatives of N-phenyl--alanine is described. It is more convenient to use the amide of acrylic acid rather than acrylic acid itself, its nitrile, or ester for the synthesis of I from the appropriate o-phenylenediamines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 987–991, July, 1971.     

Synthesis of nitro-substituted 4-methyl-2,3-dihydro- and 2,3,4,5-tetrahydro-1H-1,5-benzo-2-diazepinones

The nitration of 4-methyl-2,3-dihydro-1H-1,5-benzo-2-diazepinone gives the 7 nitro derivative. The 8-nitro isomer was obtained from 4-nitro-1,2-phenylenediamine. The catalytic hydrogenation of the nitrobenzodiazepinones gives the 7- and 8-amino derivatives. The nitrobenzodiazepinones exist in the enol form in alkaline media.     

Synthesis and rearrangements of 2,3,4,5-tetrahydro-3-benzazocin-6(1H)ones

The preparation of 3-benzenesulfonyl- and 3-benzoyl-2,3,4,5-tetrahydro-3-benzazoein-6(1H)-ones by intramolecular acylation is described. Acid catalyzed rearrangements of these 3-benzazocin-6-ones occurs by 3,4-bond cleavage, which is followed by intramolecular or intermolecular alkylation, to produce indanones (i.e. XIV) or a 3,4-dihydroisoquinoline (II), respectively. In addition to spectral support for these structures, an independent synthesis of II is described from a known 3,4-dihydroisoquinoline. Two rearrangements of 3-benzazocin-6-ones under alkaline conditions are also described, and the products are again evidence for 3,4-bond cleavage to vinylphenones. These beuzazocine rearrangements have been observed only with the 6-keto compounds.     

Azabicyclo chemistry II. Synthesis of 1,5-methano-2,3,4,5-tetrahydro-1H-2-benzazepines. B-norbenzomorphans

The syntheses of the B-norbenzomorphans, 1,5-methano-2,3,4,5-tetrahydro-1H-2-benzazepine (1a) and its N-methyl derivative (Ib) were accomplished. Phenylsuccinic anhydride (III) was cyclized to 3-carboxy-1-indanone (IVa), which was converted by the Arndt-Eistert method to the homologous methyl indanone-3-acetate (V). One experiment in the synthesis of V led to the by-products 3-carboxamido-1-indanone (IVd) and 3-(N-methylcarboxamido)-1-indanone (IVe), identified by physical and chemical means. Methyl 1-aminoindan-3-acetate (VII) was prepared by catalytic reduction of methyl indanone-3-acetate oxime (VI). Hydrolysis of VII afforded 1-aminoindan-3-acetic acid (VIII), which was cyclized with dicyclohexylcarbodiimide to 1,5-methano-2,3,4,5-tetrahydro-1H-2-benzazepin-3-one (IX). Reduction (lithium aluminum hydride) of IX gave amine Ia which was then methylated to Ib. The mass spectral fragmentation patterns of IX and Ia are discussed.     

Synthesis and biological activity of 5-vinyl- and 5-allyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indoles

Russian Chemical Bulletin - A synthetic approach to the vinylation and allylation of tetrahydro-γ-carbolines with alkane dimethyl sulfonates in the presence of sodium hydride was developed....     

A general route to the synthesis of 1,5-methano- and 1,5-ethano- 2,3,4,5-tetrahydro-1H-3-benzazepines

A general approach to preparing 1,5-methano- (1) and 1,5-ethano-2,3,4,5-tetrahydro-1H-3-benzazepine (2) is discussed. This strategy involves converting an indanone or tetralone (4) to a cyanohydrin (3) which is subjected to hydrogenolysis followed by lactamization and reduction to provide bicyclic aryl piperidine (1) and bicyclic aryl homopiperidine (2).     

Electron ionization fragmentation mechanisms of different substituted 2,3-dihydro- and 2,3,4,5-tetrahydro-1,5-benzothiazepines

The electron ionization induced fragmentations of ten biologically significant 2,3-dihydro-1,5-benzothiazepines and the corresponding 2,3,4,5-tetrahydro-1,5-benzothiazepines have been studied by low- and high-resolution mass spectrometry. The fragmentations follow a general pattern, the details of which are discussed with respect to the nature and position of the substituent in the aromatic ring. The dihydro- and tetrahydro-1,5-benzothiazepines both undergo fragmentation through four routes (A-D). However, the most significant fragmentation takes place through route A, leading to the elimination of ring A or ring B of the molecule. The difference between the fragmentation patterns of dihydro- and tetrahydro-1,5-benzothiazepines appears mainly in route E where a phenylallylhydroxybenzene cation appears in all tetrahydro-1,5-benzothiazepines but is not observed in the corresponding dihydro derivatives.     

Quantum chemical estimation of reactivity of 2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones in electrophilic aromatic substitution

DFT B3LYP calculation study was employed to estimate the regioselectivity of an electrophilic aromatic substitution in functionalized 2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones. Charge density, frontier molecular orbital study, energetics of σ-complex intermediates of electrophilic substitution reactions in the 2,3,4,5-tetrahydro-1,5-benzodiazepin-2(1H)-ones yield information on different reactivity of aromatic sites. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:263–270, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20015     

Tautomerism of the Thioamide Group in 4-Methyl-7-nitro-2,3,4,5-tetrahydro-1,5-benzodiazepine-2-thione

When 4-methyl-7-nitro-2,3,4,5-tetrahydro-1H-1,5-benzodiazepin-2-one were reacted with phosphorus pentasulfide, the corresponding benzodiazepine-2-thione and its thiol tautomer were formed, which via the 2-methylmercapto derivative were converted to 4-(2-acetylhydrazino)-2-methyl-8-nitro-2,3-dihydro-1H-1,5-benzodiazepine.     

Oxidative cyclization of amino alcohols catalyzed by a CpIr complex. Synthesis of indoles, 1,2,3,4-tetrahydroquinolines,and 2,3,4,5-tetrahydro-1-benzazepine

[reaction: see text] A new iridium-catalyzed oxidative cyclization of amino alcohols has been revealed. Indole derivatives are synthesized in good to excellent yields from 2-aminophenethyl alcohols by means of a [CpIrCl(2)](2)/K(2)CO(3) catalytic system. The present catalytic system is also effective for syntheses of 1,2,3,4-tetrahydroquinolines from 3-(2-aminophenyl)propanols and 2,3,4,5-tetrahydro-1-benzazepine from 4-(2-aminophenyl)butanol.     

Synthesis of N-acyl-4-methyl-7(8)nitro-2,3,4,5-tetrahydro-1H-1-5-benzodiazepin-2-ones and their spectral properties

The conditions were studied o f mono- and diacylation of 7(8)-nitro-2, 3, 4, 5-tetrahydro-1H-1, 5-benzodiazepin-2ones. It was found that under mild conditions (lower temperatures, weak acylating agents), the 7-nitro isomers are acylated only at the 5 -position; increase in the temperature or treatment with an active acylating agent gives the 1,5-diacyl derivatives. Under mild conditions the 8-nitro isomer is not acylated, while under more rigorous conditions a mixture of mono- and diacylated products is formed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 30, No. 1, pp. 99–105, January, 1994.     

Regio- and stereocontrolled synthesis of novel 3-sulfonamido-2,3,4,5-tetrahydro-1,5-benzothiazepines from 2-(bromomethyl)- or 2-(sulfonyloxymethyl)aziridines

2-(Bromomethyl)-1-sulfonylaziridines were converted into novel 3-sulfonamido-2,3,4,5-tetrahydro-1,5-benzothiazepines upon treatment with 2-aminothiophenol in THF in the presence of K2CO3. Starting from 3-substituted 2-(sulfonyloxymethyl)aziridines, a regio- and stereocontrolled synthesis of trans-2-phenyl- and trans-4-(phenyl or propyl)-3-sulfonamido-2,3,4,5-tetrahydro-1,5-benzothiazepines was developed in good yields via two different reaction pathways, depending on the nature of the sulfonyloxy group.     

Synthesis of 1-aryl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indoles (1,2,3,4-tetrahydro-β-carbolines) under high pressures

The reactions of aromatic aldehydes with tryptamine (1) in solvents of different polarity were studied. The yields of carbolines in the chosen media decrease with an increase in the donating properties of the aryl substituent, but they markedly increase at a high pressure (5 kbar), especially for compounds with electron-donating aryl groups. The phase transition of dioxane at 5 kbar also sharply increases the yields of the target products.