Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: X. Synthesis of 4-(1-benzotriazolyl)-5-(1(2)-naphthyloxy)-phthalodinitriles and related phthalocyanines

4-(1-Benzotriazolyl)-5-[1(2)-naphthyloxy]phthalodinitriles were obtained by nucleophilic substitution of bromine and nitro group in 4-bromo-5-nitrophthalodinitrile. These compounds were used for the synthesis of the corresponding octa-substituted phthalocyanines. Spectral data of the compounds obtained were examined.     

Nucleophilic substitution in 4-bromo-5-nitrophthalonitrile: XIV. Synthesis and properties of 4,5-bis[4-(1-methyl-1-phenylethyl)phenoxy]phthalonitrile and phthalocyanines therefrom

4,5-Bis[4-(1-methyl-1-phenylethyl)phenoxy]phthalonitrile was prepared by the nucleophilic substitution of the nitro group and bromine in 4-bromo-5-nitrophathalonitrile. The product was used to synthesize the corresponding octasubstituted phthalocyanine, as well as its magnesium, copper, zinc, cobalt, and nickel complexes. The spectral properties of the synthesized phthalocyanines were studied.     

Synthesis and selected transformations of 1-(5-methyl-1-aryl-1H-1,2,3-triazol-4-yl)ethanones and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl]ethanones

By cycloaddition of arylazides to acetylacetone are obtained derivatives of 1,2,3-triazole. In the reaction of 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] ethanones (VIIa-VIIe) with isatin are obtained 2-[1-(R-phenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-4-quinolinecarboxylic acids (IIIa–IIIe) and 2-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] -4-quinolinecarboxylic acids (IXa, IXb), respectively. We found that 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) readily transform into [5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] acetic acids (IVa–IVc) by the method of Wilgerodt-Kindler. The (5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)acetic acid reacts with 5-phenyl-4-amino-4H-1,2,4-triazol-3-thiol affording 6-[(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl) methyl]-3-phenyl[1,2,4] triazolo[3,4-b] [1,3,4] thiadiazole (VI). Original Russian Text ? N.T. Pokhodylo, R.D. Savka, V.S. Matiichuk, N.D. Obushak, 2009, published in Zhurnal Obshchei Khimii, 2009, vol. 79, no. 2, pp. 320–325.     

1-(Pyrimidin-4-yl)pyrazol-5(4<Emphasis Type="Italic">H</Emphasis>)-one derivatives: II. Electrophilic substitution in 5-hydroxy-3-methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-1<Emphasis Type="Italic">H</Emphasis>-pyrazole

Electrophilic substitution of hydrogen in bicyclic 5-hydroxy-3-methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-1H-pyrazole occurs exclusively at the C⁴ atom of the five-membered heteroring. Unstable electrophilic substitution products are stabilized via addition of the second substrate molecule with formation of bridged adducts.     

Synthesis and tuberculocidic activity of some 4-arylaminomethylene-3-methyl-1-(pyrimidin-2-yl)pyrazol-5(4H)-ones

4-Arylaminomethylene-3-methyl-1-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)pyrazol-5(4H)-ones were synthesized by a three-component reaction between the 6-methyl-2-(3-methyl-5-oxo-2,5-dihydropyrazol-1-yl)pyrimidin-4(1H)-one, triethoxymethane, and an aromatic amine. These compounds were found to exist as aminomethyleneketones regardless of the electronic effects of substituents in the aromatic fragments. The resulting compounds showed pronounced tuberculocidic activity.     

Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: IV. 5-Nitro-4-(phenylthio)phthalodinitrile and Octa-substituted Metal Phthalocyanines Based Thereon

5-Nitro-4-(phenylthio)phthalodinitrile was obtained by nucleophilic substitution of the bromine atom in 4-bromo-5-nitrophthalodinitrile. The product was used to prepare copper(II) and cobalt tetra(5-nitro-4-phenylthio)phthalocyanines, and their spectral properties were studied.     

Synthesis of 5-Amino-1-aryl-4-(4-aryl-1,3-thiazol-2-yl)- 2,3-dihydro-1H-pyrrol-3-ones*

Reactions of 2-(4-aryl-1,3-thiazol-2-yl)-3-oxo-4-chlorobutyronitriles with primary aromatic amines result in nucleophilic substitution of the chlorine atom by amino group, followed by intramolecular addition of the secondary amino group to the cyano group. The products are 5-amino-1-aryl-4-(4-aryl-1,3-thiazol-2-yl)- 2,3-dihydro-1H-pyrrol-3-ones which are structurally related to the known antiischemic drugs.     

1-(Pyrimidin-4-yl)pyrazol-5(4H)-one derivatives: I. Synthesis of 3-methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-pyrazol-5-ol and specificity of its Knoevenagel reaction

3-Methyl-1-(6-methyl-2-methylsulfanylpyrimidin-4-yl)-1H-pyrazol-5-ol available via cyclocondensation of 6-methyl-2-methylsulfanylpyrimidin-4-ylhydrazine with ethyl acetoacetate reacted with aromatic aldehydes to give two kinds of products, 4-arylmethylidene-5-oxo-4,5-dihydropyrazole and arylbis(5-hydroxypyrazol-4-yl)methane derivatives, depending on the substituent in the aromatic aldehyde.     

超声辐射下合成1-[(未)取代苯酰基-3-[5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑-2-基]-硫脲

1-苯基-3-甲基-5-氯吡唑-4-甲酸与氨基硫脲在三氯氧磷中反应得到2-氨基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑(1), 然后分别采用超声辐射法和常规加热法与(未)取代苯甲酰基异硫氰酸酯(2)反应合成了一系列未见报到的1-[(未)取代苯酰基-3-[5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑-2-基]-硫脲(3a～3j). 化合物的结构经元素分析, IR, ¹H NMR确证.     

Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: IX. Synthesis of 4-(morpholin-4-yl)-5-aryloxyphthalodinitriles and copper phthalocyanines based thereon

Nucleophilic aromatic substitution of bromine in 4-bromo-5-nitrophthalodinitrile with the morpholine residue and the subsequent substitution of nitro group with the aryloxy one yielded 4-morpholyl-5-aryloxyphthalodinitriles. From these substances octasubstituted copper phthalocyanines were synthesized, and their physicochemical properties were studied.

     

微波辐射下合成2-(未)取代苯甲酰胺基-5-(1-苯基-3-甲基-5-氯吡唑- 4-基)-1,3,4-噻二唑衍生物

分别在微波辐射和常规加热条件下, 通过2-氨基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑(1)与(未)取代苯甲酰氯(2a～2j)反应, 合成了一系列未见文献报道的2-(未)取代苯甲酰胺基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑衍生物(3a～3j). 标题化合物的结构经元素分析, IR, 1H NMR确证.     

Synthesis and spectral analysis of (±)-cis-N-[1-(2-hydroxy-2-phenyl-ethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide and (±)-cis-N-[1-(2-hydroxy-1-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide

Treatment of (±)-cis-N-(3-methyl-4-piperidyl)-N-phenylpropanamide (2) with styrene oxide (1) yielded a mixture of (±)-cis-N-[1-(2-hydroxy-2-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide (3) and (±)-cis-N-[1-(2-hydroxy-1-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide (4) . The structure of compound 3 was confirmed by an unambiguous synthesis via (±)-cis-N-[1-(2-oxo-2-phenylethyl)-3-methyl-4-piperidyl]-N-phenylpropanamide (6) . The proton and carbon-13 resonances of compounds 3 and 4 were assigned with the aid of two-dimensional heteronuclear correlation experiments.     

Nitroimidazoles. VI. Syntheses of 1-methyl-2-(1,3,4-thiadiazol-2-yl)-5-nitroimidazole and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-5-nitroimidazole

Starting from readily available 1-methyl-5-nitroimidazole-2-carboxylic acid hydrazide (1), 1-methyl-2-(1,3,4-thiadiazol-2-yl)-5-nitroimidazole (4) and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-5-nitroimidazole (10) were prepared. The reaction of 1 with formic acid gave 1-(1-methyl-5-nitroimidazole-2-carboxyl)-2-(formyl)hydrazine ( 8 ) in high yield. Refluxing of the latter with phosphorus pentasulfide in xylene yielded compound 4 in 50% yield. Reaction of compound 8 with phosphorus pentoxide afforded compound 10 in 60% yield.     

Synthesis and Crystal Structure of 2（1-Phenyl-3-methyl-5-chloro-1H-pyrazol-4-yl）-3-（1-naphthoylamido）-4-thiazolidinone

1INTRODUCTIONManypyrazolederivativeshavebeenreportedtoshowvariousbiologicalactivitiestobeusedasbactericide[1],fungicide[2],herbicide[3],insecticide[4]andvirucide[5]agents.Inaddition,4-thiazolidinoneplaysavitalroleowingtoitswiderangeofbiologi-calactivities…     

Synthesis and Crystal Structure of 4-Bromo-5-ethoxy-3-methyl-5- （naphthalen- 1-yl）- 1-tosyl- 1H-pyrrol-2（5H）- one

The title compound 4-bromo-5-ethoxy-3-methyl-5-(naphthalen-1-yl)-1-tosyl-1H- pyrrol-2(5H)-one 1 (C24H22BrNO4S, Mr = 500.40) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 8.8562(15), b = 18.118(3), c = 14.055(2) , β = 99.855(3)o, V = 2221.9(6) 3, Z = 4, Dc = 1.496 g/cm3, μ = 1.975 mm-1, λ = 0.71073 , F(000) = 1024, R = 0.0607 and wR = 0.1371.     

Syntheses of 3-[5-Methyl-1-(4-Methylphenyl)-1,2,3-Triazol-4-yl]-6-Substituted-s-Triazolo[3,4-b]-1,3,4-Thiadiazoles

1,2,3-Triazole derivatives have been reported as inhibiting tumor proliferation, invasion, and metastasis^[1]. The fused l,3,4-triazolo[3,4-b]-1,3,4-thiadiazoles derivatives show various biological effects such as antifungal^[2], antibacterial, hypotensive and CNS depressant activities^[3]. We have reported several 6-aryl-3-[5-methyl-1-(4-methylphenyl)-1,2,3-triazol-4-yl]-s-triazolo[3,4-b]-1,3,4-thiadiazoles in the previous paper^[4]. The novel 6-aryl-3-[5-methyl-1-(4-methylphenyl)-1,2,3-triazol-4-yl]-s-triazolo[2,4-b]-1,3,4-thiadiazoles 6a-j have been synthesized by the condensation of 4-amino-5-mercapto-3-[5-methyl-1-(4-methylphenyl)-1,2,3-triazol-4-yl]-s-triazole 5 with various aromatic carboxylic acids in the presence of phosphorus oxychloride. The mercaptotriazole 5 was prepared from 4,the latter being prepared from 1 throng 2 and 3. The title compounds 6 were depicted in scheme 1. The structures of these compounds were established by elemental analysis, NMR, MS and IR techniques.     

Unusual result of the reaction of 4-(1-methyl-1H-imidazol-2-yl)methylene-substituted 2-alkylthioimidazol-5(4H)-one with copper(ii) chloride

A reaction of potassium ({(4Z)-4-[(1-methyl-1H-imidazol-2-yl)methylene]-5-oxo-1-phenyl-4,5-dihydro-1H-imidazol-2-yl}thio)acetate with copper(II) chloride in methanol leads to bis(5-anilino-7-methoxycarbonyl-1-methyl-1H-imidazo[1,2-c]pyrimidin-4-ium) tetrachloro-cuprate(II), whose structure was confirmed by the X-ray diffraction studies.     

Synthesis and structure of 1-(4-chlorophenyl)-3-(5-methyl-1, 3-dioxan-5-yl)-(1,2),(3,4)-diepoxybutane

The synthesis and X-ray structural study of 1-(4-chlorophenyl)-3-(5-methyl-1,3-dioxan-5-yl)-(1,2), (3,4)-diepoxybutane are described.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 715–718, April, 1995.     

Synthesis and photochromic and fluorescence properties of 3-(1-benzyl-5-methoxy-2-methylindolyl)-4-thienyl-substituted furan(pyrrole)-2,5-diones

New nonsymmetrical dihetarylethenes, 3-(1-benzyl-5-methoxy-2-methyl-1H-indol-3-yl)-4-(3-thienyl)furan-2,5-dione and 1-alkyl- and (1-aryl)-3-(1-benzyl-5-methoxy-2-methyl-1H-indol-3-yl)-4-(3-thienyl)-1H-pyrrole-2,5-dione, exhibiting photochromic properties in solutions were synthesized. Noncyclic isomers of dihetarylethenes show fluorescence with quantum yields up to 0.13.     

Synthesis of 3-methyl-4-(5-R-1H-1,2,4-triazol-3-yl)-1,2,5-oxadiazoles

A number of 3-methyl-4-(5-R-1H-1,2,4-triazol-3-yl)-1,2,5-oxadiazoles were obtained in high yields by thermal dehydration of acylated 4-methyl-1,2,5-oxadiazole-3-carboxamide hydrazones.