Synthesis,characterization, and antibacterial activities of two new copper(II) glycinate complexes incorporating 2-(4′-thiazolyl)benzimidazole/2-(2-pyridyl)benzimidazole

Two new complexes, [Cu(TBZ)(Gly)(H₂O)]Cl (1) and [Cu(HPB)(Gly)Cl]?·?2H₂O (2) (TBZ?=?2-(4′-thiazolyl)benzimidazole, HPB?=?2-(2-pyridyl)benzimidazole, and Gly?=?glycinate), have been synthesized and characterized by elemental analysis, molar conductivity, UV-Vis, and IR methods. The complexes, structurally characterized by single-crystal X-ray crystallography, show a slightly distorted square-pyramidal coordination geometry in which two nitrogen atoms of TBZ or HPB and the carboxylate oxygen and amino nitrogen of glycinate bind in the plane and a water or chloride coordinated at the axial site. The complexes, free ligands, and copper(II) chloride were tested for their ability to inhibit growth of Bacillus subtilis, Staphylococcus aureus, and Salmonella. The results show that the complexes have good antibacterial activities against the microorganisms compared with their ligands and copper(II) chloride.     

Condensed Imidazo-1,2,4-azines. 31. Synthesis and Chemical Transformations of Substituted 1,2,4-Triazepino[2,3-a]benzimidazoles

By reaction of 1,2-diaminobenzimidazole with 1,3-diketones, acetoacetic ester and its derivatives, we have synthesized substituted 1,2,4-triazepino[2,3-a]benzimidazole and 5H-1,2,4-triazepino[2,3-a]benzimidazol-4-one. By reaction of 5H-2-methyl-1,2,4-triazepino[2,3-a]benzimidazol-4-one with aromatic aldehydes or phenyldiazonium chloride, we have obtained 3-arylidene(phenylazo) derivatives of this compound, and by reaction with P₂S₅ we have obtained 5H-2-methyl-1,2,4-triazepino[2,3-a]benzimidazole-4-thione. We have shown that when reacted with ammonia, primary or secondary amines, the latter forms 4-amino-substituted 2-methyl-1,2,4-triazepino[2,3-a]benzimidazole.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

Condensation of 1-Substituted 1,2,3,9a-Tetrahydro-9H-imidazo[1,2-a]indol-2-one Derivatives with Aromatic Aldehydes

Condensation of 1-alkyl-, 1-allyl-, and 1-benzyl-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-ones with benzaldehydes in acetic acid and subsequent treatment of the reaction mixture with potassium hydroxide afforded 1-substituted 9a-(2-phenylethenyl)-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one derivatives. 1-Methyl- and 1-ethyl-9a-[2-(4-dimethylaminophenyl)ethenyl]-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-ones were synthesized by alkylation of 9a-[2-(4-dimethylaminophenyl)ethenyl]-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one with methyl- and ethyl iodides in DMF in the presence of a strong base.     

4-Oxo-3,4-dihydroquinazolinyl- and Benzimidazolylacetonitriles in Annelation Reactions of a Haloquinoline Ring

The interaction of 4-oxo-3,4-dihydroquinazolinyl- and benzimidazolylacetonitriles with 2,6-dihalobenzaldehydes leads to 3-(2,6-dihalophenyl)-2-(4-oxo-3,4-dihydro-2-quinazolinyl)acrylonitriles and 2-(1H-benzo[d]imidazol-2-yl)-3-(2,6-dihalophenyl)acrylonitriles respectively. As a result of intramolecular cyclization of these nitriles 4-halo-12-oxo-12H-quino[2,1-b]quinazoline-6-carbonitriles and 4-halobenzo[4,5]imidazo[1,2-a]quinoline-6-carbonitriles respectively are formed.     

The investigations in 2,3′-biquinoline series. 25*. Synthesis of 4-(2-quinolinyl)-pyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinolines and 4-(2-quinolyl)-imidazo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinolines

A method has been developed for the synthesis of 4-(2-quinolinyl)-1,2,3,3a-tetrahydropyrrolo-[1,2-a]quinolines based on the 1,3-dipolar cycloaddition reaction of α,β-unsaturated carbonyl compounds to 2,3′-biquinolinium salts. Oxidation in benzene using MnO₂ gave 4-(2-quinolinyl)-pyrrolo[1,2-a]quinolines. It was found that a side product of the 1,3-dipolar cycloaddition is 7,14-di-benzoyl-6,13-di(2-quinolyl)-6a,7,13a,14-tetrahydro-7a,14a-diazadibenzo[a,h]anthracene. Reaction of 1′-phenacyl-2,3′-biquinolinium salts with hydroxylamine in acetic acid gave 4-(2-quinolyl)imidazo-[1,2-a]quinolines. *For Communication 24 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 433–439, March, 2009.     

The Use of 4-(Bromomethylene)-5,5-dimethyl-1,3-dioxolan-2-one as “Masked” α-Bromo-α'-Hydroxy Ketone in the Synthesis of Heterocyclic Systems

4-(Bromomethylene)-5,5-dimethyl-1,3-dioxolan-2-one was obtained on the basis of the readily obtainable 4-methylene-5,5-dimethyl-1,3-dioxolan-2-one. It forms 2-imidazo[1,2-a]pyridin-2-yl-2-propanol with 2-aminopyridine, 11a-hydroxy-1,1-dimethyl-3-oxo-1,5,11,11a-tetrahydro[1,3]oxazolo[3,4-a]pyrido[1,2-d]-10-pyrazinium bromide with 2-(aminomethyl)pyridine, and the corresponding derivative of 4-hydroxyoxazolidin-2-one with 2-(3,4-dimethoxyphenyl)ethylamine. The last product was converted by intramolecular amidoalkylation without isolation into 10b-(bromomethyl)-8,9-dimethoxy-1,1-dimethyl-1,5,6,10b-tetrahydro[1,3]oxazolo[3,4-a]isoquinolin-3-one.     

三元TBZ/HPB-铜(Ⅱ)-L-蛋氨酸配合物的合成、表征、抑菌活性及与DNA的作用

本文合成了2个新的三元铜(Ⅱ)配合物:[Cu(TBZ)(L-Met)(H2O)]ClO4.H2O(1)和[Cu(HPB)(L-Met)]ClO4(2)[TBZ=2-(4′-噻唑基)苯并咪唑,HPB=2-(2-吡啶)苯并咪唑,L-Met=L-蛋氨酸]。通过元素分析、摩尔电导率、IR、UV-Vis及电喷雾质谱对这些配合物进行了表征。用二倍稀释法研究了配合物的抗菌活性,发现配合物对金黄色葡萄球菌(Staphylococcus aureus,G+),枯草杆菌(Bacillussubtilis,G+),沙门氏杆菌(Salmonella,G-)和大肠杆菌(Escherichia coil,G-)具有良好的抑制作用。采用电子吸收光谱、荧光光谱、粘度测定及琼脂凝胶电泳方法研究了配合物与DNA的相互作用,结果表明,配合物以插入方式与DNA作用,在维生素C存在下通过羟自由基.OH,单线态氧1O2或者1O2类似物如Cu-O2,切割pBR322 DNA双螺旋结构。     

Synthesis,structures, and luminescent properties of two cadmium polymers of 4-carboxyl phenoxyacetate and 2-(2-pyridyl)benzimidazole

Two-dimensional complexes of [Cd(cpoa)(o-pbim)] _n (1) and {[Cd₃(cpoa)₃(o-pbim)₂] · 2H₂O} _n (2) (cpoa²⁻ = 4-carboxyphenoxy acetate, o-pbim = 2-(2-pyridyl)benzimidazole) are synthesized under hydrothermal condition. Single crystal X-ray diffraction analysis shows that complex 1 contains a mono-nuclear unit, whereas complex 2 contains a trinuclear unit. The structural difference of 1 and 2 can be attributed to the various coordination modes of asymmetrically semi-flexible cpoa²⁻ ligand. The luminescent properties of these two compounds are also investigated.     

A facile synthesis of pyrrolo[1,2-a]benzimidazoles and pyrazolo[3,4:4′,3′]pyrrolo[1,2-a]benzimidazole derivatives

Reaction of 2-cyanomethylbenzimidazole 1 with hydrazonoyl halides 2 led to formation of pyrrolo[1,2-a]benzimidazole derivatives 7. Similar reaction of 1 with halides 3 afforded 5-amino-4-(benzimidazol-2-yl)pyrazole derivatives 11 or 1-amino-2-arylpyrazolo[3,4:4′,3′]pyrrolo[1,2-a]benzimidazol-4-one 14 depending on the reaction conditions. The mechanisms of the studied reactions are discussed.     

9,9-二甲基-2-(4-甲氧基苯基)-4-苯基-9H-吡啶并[1,2-a]吲哚高氯酸盐的微波合成及晶体结构

利用2,3,3-三甲基-3H-吲哚高氯酸盐、1-苯基-3-(4-甲氧基苯基)-2-丙烯-1-酮与哌啶在微波辐射条件下合成了9,9-二甲基-2-(4-甲氧基苯基)-4-苯基-9H-吡啶并[1,2-a]吲哚高氯酸盐, 在甲醇中培养出单晶, 通过X射线单晶结构分析法测定分子结构和晶体结构, 晶体属于正交晶系, Pca2₁空间群, 晶胞参数为: a＝2.7923(6) nm, b＝0.92126(17) nm, c＝1.8345(4) nm, V＝4.7190(16) nm³, D_c＝1.345 g/cm³, μ＝0.201 mm^－1, F(000)＝2000, Z＝8, R₁＝0.0566, wR₂＝0.1320.     

环丙沙星-铜(Ⅱ)-TBZ/HPB配合物的合成、抗菌活性及与DNA作用

合成并表征了两个新的配合物：[Cu(HCP)(TBZ)](NO₃)₂·(H₂O)₂ (1)和[Cu(HCP)(HPB)](NO₃)₂·(H₂O)_1.5 (2)[HCP=环丙沙星,TBZ=2-(4′-噻唑基)苯并咪唑,HPB=2-(2-吡啶)-苯并咪唑]。配合物1属于三斜晶系,P1 空间群,a=0.909 5(2) nm,b=1.330 1(3) nm,c=1.355 2(3) nm,α=93.518(3)°,β=97.192(3)°,γ=106.361(3)°,V=1.552 6(6) nm³,Z=2,D_c=1.598 g·cm^-3,μ=0.849 mm^-1。用二倍稀释法研究了配合物的抗菌活性,发现配合物对大肠杆菌(Escherichia coli,G-)、沙门氏杆菌(Salmonella,G-)和枯草杆菌(Bacillus subtilis,G+)具有良好的抑制作用。应用电子吸收光谱、荧光光谱、粘度测定及凝胶电泳研究了配合物与DNA的作用,结果表明配合物以插入方式与DNA作用,在维生素C存在下通过·OH切割 pBR322 DNA双螺旋结构。     

Interaction of benzimidazole-2-thione with propargyl bromide and 1,3-dibromopropyne

Interaction of benzimidazole-2-thione with propargyl bromide under found conditions permitted the direct synthesis of 2-(2-propynylsulfanyl)-3H-1,3-benzimidazolium bromide, the base 2-(2-propynylsulfanyl)-1H-1,3-benzimidazole, stable crystalline 2-(1,2-propadienylsulfanyl)-1H-1,3-benzimidazole, and 3-methyl[1,3]thiazolo[3,2-a][1,3]benzimidazole. The reaction of benzimidazole-2-thione with 1,3-dibromopropyne in chloroform or absolute methanol gave 2-(3-bromo-2-propynylsulfanyl)-3H-1,3-benzimidazolium bromide, and in absolute methanole in the presence of a twofold excess of sodium methoxide the reaction proceeded stereo-and regioselectively to give 3-[(Z)-bromomethylidene][1,3]thiazolo[3,2-a][1,3]benzimidazole. Presented to Academician B. A. Trofimov on his 70^th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, 1399–1405, September, 2008.     

Cyclizations of N-(1-Chloro-2,2,2-trihaloethylidene)-O-methylurethanes with 5-Amino-3-methylisoxazole and 3-Amino-5-methylisoxazole

N-(1-Chloro-2,2,2-trihaloethylidene)-O-methylurethanes undergo cyclization with 5-amino-3-methylisoxazole and 3-amino-5-methylisoxazole to give respectively 6-trihalomethylisoxazolo[5,4-d]pyrimidin-4(5H)-ones and 2-trihalomethyl-4H-isoxazolo[2,3-a]-1,3,5-triazin-4-ones.     

Synthesis and X-ray crystal structure of pyrrolo[1,2-a]benzimidazoles

Reaction of nitrilimines 1 with 2-cyanomethylbenzimidazole 2 gave the 3-arylazo-2-methylpyrrolo[1,2-a]benzimidazole 4a rather than the reported 2-arylazo-3-methylpyrrolo[1,2-a]benzimidazole 3a. The correct structure of the product was determined using X-ray crystal structure analysis. The similar reaction of nitrilimines with 2-aminobenzimidazole 5 gave the acyclic nucleophilic addition product 6.     

Cyclocondensation of N-aryl-3-oxobutanethioamides with 5-amino-3-R-4-R1-pyrazoles

The cyclocondensation products of N-aryl-3-oxobutanethioamides with 5-amino-3-R-4-R¹-pyrazoles are 4-(arylamino)-2-methyl-7-R-8-R¹-pyrazolo[1,5-a]pyrimidine and pyrazolo[1,5-a]pyrimidine-4-thione derivatives, the ratio of which depends on the nucleophilicity of the starting 5-amino-3-R-4-R¹-pyrazoles and the presence of a proton donor solvent. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1550-1555, October, 2008.     

Synthese und Reaktionsverhalten von 3-(Bis(alkylthio)methylen)-3H-isobenzofuran-1-on-und 2-(Bis(alkylthio)methylen)-3(2H)-benzofuranon-Derivaten

Summary 3(Bis(alkylthio)methylene)-3H-isobenzofuran-1-ones2a–e and 2-(bis(alkylthio)methylene)-3(2H)-benzofuranone derivatives4a–c are obtained by reaction of phthalides1a–d or 3(2H)-benzofuranone (coumaranone3), respectively, with carbon disulfide under basic conditions followed by alkylation. The reaction behaviour of the new compounds2 and4 is investigated. 2-((2-Dimethylthio-1-oxo)ethyl)benzoic acid N,N-dimethylamide (7a) and 2-((2-dimethylthio-1-oxo)ethyl)-benzoic acid 2-methylpiperidide (7b) are surprisingly formed instead of the methylthio substitution products by treatment of2a with the corresponding amine in the presence of aluminum chloride.

Herrn Professor Dr. Dr. h. c.Waldemar Adam zum 60. Geburtstag gewidmet     

Synthesis and study of new 2-aryl-1-(4-nitrophenyl)-1,1a-dihydroazireno[1,2-a]quinoxaline derivatives

New derivatives of photochromic 2-aryl-1-(4-nitrophenyl)-1,1a-dihydroazireno[1,2-a]quinoxalines were synthesized by condensation of 4-methyl-and 4,5-dimethyl-1,2-phenylenediamine with 1,3-diaryl-2,3-dibromopropan-1-ones. The reactions of 4-methyl-1,2-phenylenediamine produce mixtures of regioisomers. The chemical properties of the reaction products were studied. The structure of one of the latter was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 350–356, February, 2006.     

Synthesis of N-(7-methyl-5-oxo-5H-1M,3,4-thiadiazolo[3,2-a]pyrimidin-2-yl)-N'-phenylhydrazine and its reaction with bromine

Synthesis of the title compound is described and its reaction with bromine is studied. This involves oxidation of the hydrazine moiety and sequential bromination of the benzene and thiadiazolopyrimidine nuclei to give, respectively, 2-(4-bromophenylazo)-7-methyl-5-oxo-5H-1, 3,4-thiadiazolo[3,2-a]pyrimidine and 6-bromo-2-(4-bromophenylazo)-7-methyl-5-oxo-5H-1, 3,4-thiadiazolo[3,2-a]pyrimidine.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 219–220, January, 1993.     

Reactions of 3-[N-chloroacetylamino-N-(4-nitrophenyl)]-2-formylindole with alkylamines

The reactions of 3-[N-chloracetylamino-N-(4-nitrophenyl)]-2-formylindole (1a) with 2-(N, N-dialkylamino)ethylamines afford complex condensation products 7b,c consisting of two similar but not identical diazepinoindole fragments. For the reaction of compound 1a with 3-(N,N-diethylamino)propylamine, the process occurs in a different manner, and the predominant product is 4-ethylaminopropyl-1-(4-nitrophenyl)-2-oxo-1,2,3,4,5,6-hexahydro[1,4]diazepino[6,5-b]indole hydrocloride (14). Two routes of these unexpected transformations were proposed. The structures of the synthesized products were proved by the ¹sH and ¹³C NMR, HMBC, and HSQC (direct proton-carbon correlation) spectra. Dedicated to Academician V. A. Tartakovsky on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1536–1542, August, 2007.