Synthesis,Crystal Structure and Luminescent Property of Cadmium Complex Based on 2-（2-（1Hbenzo[d]imidazol-2-yl）benzyl）-1H-benzo[d]-imidazole

The complex [Cd(bbb)Cl2]·DMF·H2O, where bbb is 2-(2-(1H-benzo[d]imidazol-2-yl)benzyl)-1H-benzo[d]imidazole, was synthesized and characterized by X-ray single-crystal structure analyses. For the complex: C24H25Cl2CdN5O2, Mr = 598.77, crystal system, triclinic, space group P1, a = 9.9878(12), b = 10.0008(12), c = 13.2217(15) , α = 80.674(2), β = 72.158(2), γ = 86.776(2)°, V = 1240.5(3) 3, Z = 2, Dc = 1.598 g/cm3, λ = 0.71073, μ(MoKα) = 1.127 mm–1, F(000) = 600, S = 1.04, R = 0.0905 and wR = 0.3088 for 4805 observed reflections with I 2σ(I). It is a neutral complex. The distorted tetrahedral geometry of cadmium ion is coordinated by two nitrogen atoms of ligand and two chloride ions. The complex emits blue green luminescence with emission peaks at 480 nm in DMF solution.     

Synthesis,Crystal Structure and Luminescent Property of a Dinuclear Cadmium Complex Based on 2-(2-(1H-Benzo[d]imidazol-2-yl)-phenyl)-1-phenyl-1H-benzo[d]imidazole

A dinuclear cadmium complex [Cd_2(bppb)Cl_4×2DMF](1), where bppb is 2-(2-(1 Hbenzo[d]imidazol-2-yl)phenyl)-1-phenyl-~1 H-benzo[d]imidazole, was synthesized and characterized by X-ray single-crystal structure analyses. For 1: C_(58) H_(50) Cd_2 Cl_4 N_(10) O_2, M_r = 1285.68, monoclinic system, space group P2_1/n, a = 16.136(3), b = 10.612(2), c = 16.270(3) ?, β = 96.209(2)°, V = 2769.7(9) ?~3, Z = 2, D_c = 1.542 g/cm~3, λ = 0.71073 ?, μ(Mo Kα) = 1.013 mm~(–1), F(000) = 1296, S = 1.055, R = 0.0393 and wR = 0.1185 for 4876 observed reflections with I 2σ(I). One 9 mium ion which is five-coordinated by three chloride ions and two nitrogen atoms from bppb. Two cadmium ions are bridged by two chloride ions. The Cd_2(bppb)_2 Cl_2(μ-Cl_2) decomposes at 350 ℃ which is much lower by 70 ℃ than [Cd_2(bpbb)_2 Cl_2(μ-Cl_2)](420 ℃). The complex emits blue luminescence in both DMF solution and solid powder. Phenyl ring substituting NH hydrogen atom of benzimidazole group in ligand can not obviously change the UV-vis and luminescence spectra peaks location of the benzimidazole cadmium complex.     

Parallel Solid-Phase Synthesis of disubstituted 3-(1H-benzo[d]imidazol-2-yl)imidazolidine-2,4-diones and 3-(1H-benzo[d]imidazol-2-yl)-2-thioxoimidazolidin-4-ones

A multistep approach to construct novel 3-(1H-benzo[d]imidazol-2-yl)imidazolidine-2,4-diones and 3-(1H-benzo[d]imidazol-2-yl)-2-thioxoimidazolidin-4-ones from commercially available amino acids, amines, and carboxylic acids is described. Coupling of Fmoc-amino acid to resin-bound aminobenzimidazole provided following Fmoc elimination free amine. Treatment of the free amine with 1,1′-carbonyldiimidazole or 1,1′-thiocarbonyldiimidazole furnished the corresponding hydantoins and thiohydantoins via intramolecular cyclization. The desired aminobenzimidazole tethered hydantoins or thiohydantoins were isolated in good yields.     

2a,4a-Diazacyclopenta[c,d]Azulenes

A method of preparing 5-aryl-1,2-pentaniethyleneimidazoles from O-methylcaprolactim and -aminoacetophenone hydrochlorides is described. It is shown that 1, 2-tri-, -tetra-, and -pentamethyleneirrüdazoles and phenacyl bromide give the corresponding quaternary imidazolium salts, cyclization of which in the presence of base gives the previously unknown 5,6, 78-tetrahydro-2a, 4a-diazacyclopenta(c,dJazulenes (IVa-i).T. G. Shevchenko National Unkiversity, Kiev 254017. T. G. Shevchenko Educational Institute, Chernigov 250037. Translated from Khimiya Geterotskilicheskikh Soedinenii, No. 8, pp. 1072–1077, August, 1996. Original article submitted February 27, 1996; revision submitted June 27, 1996.     

Rearrangement of 2,2′-dipropionylazoxybenzenes to 3-[1-alkoxy-1-(2-propionylarylamino)ethyl]benzo[c]isoxazoles

2,2-Dipropionylazoxybenzenes undergo rearrangement to the corresponding 3-[1-alkoxy-1-(2-propionylarylamino)ethyl]benzo[c]isoxazoles in the case of base catalysis; this transformation is realized only in the case of ortho,ortho' orientation of the propionyl groups in the substrate molecule and with the participation of the solvent as a reagent. A mechanism for the rearrangement that assumed the participation of one of the propionyl groups in intramolecular reduction of the azoxy group to an azo group is proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 743–748, June, 1983.     

Research on benz[c,d]indolin-2-one derivatives. Bromination of benz[c,d]indolin-2-onecarboxylic acids

It was experimentally observed that electrophilic substitution in, respectively, the 6 and 8 positions or the 8 position occurs when a carboxy group is present in the peri positions (in the 5 or 6 position) of benz[c,d]indolin-2-one. When two carboxy groups are simultaneously present in the 5 and 6 positions or when there is one carboxy group in the 6 position and a bromo substituent in the 5 position, the carboxy group is readily replaced by bromine. The electronic structures and reactivities of benz[c,d]indolin-2-one derivatives were investigated by spectroscopy and quantum chemistry.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1363–1367, October, 1985.     

基于2-(2′-吡啶基)苯并咪唑的Zn2+比例计量型荧光识别

本文以荧光分子2-(2'-吡啶基)苯并咪唑(2-PBI)作为1,1'-联(2-芳杂环)类化合物模型.研究利用其2,2'-N原子螯合Zn2 导芳环共面化和荧光发射红移实现Zn2 比例计量检测的可行性.2-PBI在不同体系中的Zn2 荧光响应行为表明Zn2 结合将导致最大发射波长明显红移(乙腈36 nm;HEPES缓冲液39 nm).具有比例计量型Zn2 荧光探针的基本特点.2-PBI还具有显著的Zn2 荧光响应选择性,可以同时作为构建比例计量型探针的信号团和受体的基本骨架.通过对2-BPI的荧光机制和Zn2 识别行为的分析,提出了以2-PBI为基本骨架构建实用化比例计量型探针的途径.     

Synthesis,spectral and electrochemical properties of halogenated 6-alkyl-5-aryl-1-(benzo[d]thiazol-2-yl)-3-phenylverdazyls and 5-aryl-1-(benzo[d]thiazol-2-yl)-3-phenyl-6-vinylverdazyls

Chemistry of Heterocyclic Compounds - A sequence of alkylation, cyclization, and oxidation reactions was used to convert 5-aryl-1-(benzo[d]thiazol-2-yl)-3-phenylformazans into...     

Benzo[c,d]indole carbocyanines

A symmetrical and some asymmetrical carbocyanines (benzo[c,d]indole derivatives) were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 340–341, March, 1973.     

达比加群酯中间体3-【【【2-{[(4-氰基苯基)氨基]甲基}-1-甲基-1H-苯并咪唑-5-基】羰基】(吡啶-2-基)氨基】丙酸乙酯的合成

以对氨基苯腈为起始原料,经胺化反应制得N-(4-氰基苯基)甘氨酸(4);4与N-[3-氨基-4-(甲基氨基)苯甲酰基]-N-2-吡啶-β-丙氨酸乙酯(5)经酰胺化后经闭环反应,合成了达比加群酯的关键中间体——3-【【【2-{[(4-氰基苯基)氨基]甲基}-1-甲基-1H-苯并咪唑-5-基】羰基】(吡啶-2-基)氨基】丙酸乙酯,总收率79.6%,其结构经~1H NMR和ESI-MS确证。     

Synthesis,characterization and antioxidant,antibacterial activity Zn2+, Cu2+, Ni2+ and Co2+, complexes of ligand [2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole]

New metal complexes of (Zn(II), Co(II), Ni(II) and Cu(II)) based on the ligand 2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole] were synthesized, whose structures were determined with the different spectroscopic techniques ¹H NMR,¹³C NMR, FT-IR, UV–Visible and by mass spectrometry. The thermal analysis was performed by TG-DTA. The antioxidant activity of the ligand and its complexes was evaluated by DPPH (2,2-diphenyl-1-picrylhydrazyl) method, in comparison with the synthetic antioxidant, ascorbic acid. The results obtained showed that the antioxidant activity of the ligand and its complexes is moderate and that the copper complex has a high activity that exceeds that of ascorbic acid. Antimicrobial activity of the ligand and its metal complexes was studied against two Gram-positive bacteria: Bacillus subtilis ILP1428B, Staphylococcus aureus CIP543154 and two Gram-negative bacteria: Pseudomonas aeruginosa ATCC27653, Escherichia coli CIP5412 (American Type Culture Collection)the activity data show that the metal complexes are more potent than the free ligand.     

Synthesis of (Z)-4-hydroxytamoxifen and (Z)-2-[4-[1-(p-hydroxyphenyl)-2-phenyl]-1butenyl]phenoxyacetic acid

The synthesis of (Z)-4-hydroxytamoxifen and (Z)-2-[4-[1-(p-hydroxyphenyl)-2-phenyl]-1-butenyl]phenoxyacetic acid was accomplished using a McMurry reaction as the key step. The perfluorotolyl derivatives of the McMurry products enabled the separation of the minor undesirable geometrical isomer. The methodology proceeds without E,Z isomerization, employs a very mild final debenzylation step compatible with a large array of functional groups, and can be applied to the generation of a variety of 4-hydroxytamoxifen analogues.     

COPPER(II) COMPLEXES OF 1-[O-ALLYLPHENOXY]-3-[ISOPROPYLAMINO]-2-PROPANOL (ALPRENOLOL)

Abstract

Complexation of Cu(II) with the antihypertension drug Alprenolol (HAlp) under different conditions (metal/ligand ratios and solvents) results in the formation of two complexes - a binuclear green one, Cu₂Alp₂Cl₂ (1), and a mononuclear violet species CuAlp₂·2H₂O (2). Single crystals of (1) were isolated and its structure determined by X-ray diffraction. In the complex Alprenolol molecules are bidentately coordinated and each Cu atom is bound with NH, and bridged by the deprotonated OH group of the ligand to the second Cu centre. The chloride ions are coordinated to copper as terminal ligands. The mononuclear complex (2) was characterized using electronic and IR spectra, EPR, magnetochemical, calorimetric, thermogravimetric methods and elemental analysis. Copper is coordinated through O^? and N of OH and NH groups of the ligands in a distorted tetrahedral structure. The structure includes also two solvent molecules per CuAlp₂ unit.     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

配合物[1-(4′-bromo-2′-fluorobenzyl)pyridinium]2[Ni(mnt)2]和[1-(4′-bromo-2′-fluorobenzyl)pyrazinium]2[Ni(mnt)2](mnt2-=maleonitriledithiolate dianion)的合成及晶体结构

本文报道两个含双(马来二氰基二硫烯)镍(Ⅱ)配合物阴离子的离子对化合物。对阳离子为1-(4′-溴-2′-氟苄基)吡啶 盐时,生成配合物1。晶体数据:三斜晶系,空间P1群,a=0.7086(2)nm,b=1.0968(3)nm,c=1.1775(3)nm,α=69.914(5)°,β=89.495(5)°,γ=74.765(5)°,V=0.8259(4)nm³,Z=1。对阳离子为1-(4′-溴-2′-氟苄基)吡嗪鎓盐时,生成配合物2。晶体数据:单斜晶系,空间群P2₁/n,a=0.71554(17)nm,b=1.4262(3)nm,c=1.6725(4)nm,β=100.396(4)°,V=1.6788(7)nm³,Z=4。两个配合物中,阴离子为拟平面结构,镍原子均位于对称中心。变换对阳离子上的芳环种类对晶体的堆积结构产生影响。