2-Amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile and ethyl-2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxylate were synthesised by reaction of cyclohexanone and sulphur with malononitrile and ethyl cyanoacetate respectively. These 2-aminothiophene derivatives were diazotised and coupled with a variety of coupling components to give azo dyes. The spectral properties of these dyes are reported. The dyes had generally good colouration and fastness properties on polyester. 相似文献
Syntheses of C-Nucleosides and Analogs of C-Nucleosides. I. Preparation of 1-(D-galacto-2,3,4,5,6-Pentakisacetoxy-hexanoyl)-3-alkyl-or arylamino-6,6-dimethyl-4,5,6,7-tetrahydro-benzo[c] thiophene-4-ones 2-(Alkyl- or Arylamino-mercapto-methylen)-5,5-dimethyl-cyclohexane-1,3-diones 1 react in alkaline medium with 3,4,5,6,7-penta-O-acetyl-1-bromo-1-deoxy-D-galacto-heptulose 2b to give the title compounds 6d-g . 相似文献
A series of novel 3-[6-(4-substituted phenyl)-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazol-3-ylmethyl]-5,6,7,8-tetrahydro[1]benzothieno[2,3-d]pyrimidin-4(3H)-one derivatives (7a–7h) have been synthesized from 2-amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile (1) through a multi-step reaction sequence. The key intermediate (6) on condensation with various substituted aromatic carboxylic acids in the presence of phosphorus oxychloride afforded the series of title compounds (7a–7h). The structures of all newly synthesized compounds were established on the basis of their IR, 1H-NMR, 13C-NMR and liquid chromatography mass spectrometry spectral data. 相似文献
The [2+3] dipolar cycloaddition of nitrile oxides to the double C = C bonds of thiophene-1, 1-dioxides leads to formation of the fused isoxazolines-2 (1, 2). Tumor growth inhibition of these compounds strongly depends on the nature of group IV A element increasing from slightly active tert-butyl derivatives to silicon and germanium containing analogues. The products of benzonitrile oxide cycloaddition have greater cytotoxic effect than the compounds obtained from the cycloaddition reaction of 2, 5-disubstituted thiophene-1, 1-dioxides with acetonitrile oxide. Fused silyl substituted isoxazolines-2 are stronger NO-inducers than their germyl and tert-butyl analogues. 相似文献
The synthetic utility of 3,3'-(3,4-dimethylthieno[2,3-b]thiophene-2,5-diyl)bis (3-oxopropanenitrile) (1) in the synthesis of some novel bis-[1,3,4-thiadiazole] 6a-g and bis-thiazole 10 and 13 derivatives with thieno[2,3-b]thiophene moiety is reported. Antimicrobial evaluation of some selected examples from the synthesized products was carried out and showed promising results. 相似文献
The Reaction of 2-Aminothiophene-3-carbonitriles with Heterocumulenes . The reaction of 2-aminothiophene-3-carbonitriles ( 1 ) with phenyl isothiocyanate does not yield the expected thieno[2,3-d]pyrimidine derivatives but the substituted dithieno-[2′,3′:4, 3][2′,3′:8, 9]pyrimido[3, 4-a]pyrimid-7-thiones ( 4 ). The compounds 4 also may be synthesized from 1 and thiophosgene. Analogously, from 1 and phenyl isocyanate the substituted dithieno[2′,3′:4, 3][2′,3′:8, 9]pyrimido[3, 4-a]pyrimid-7-ones ( 9 ) arise in small yields. They are better obtainable from 1 and phosgene. Carbon disulphide react with 1 in pyridine to form a mixture of the thieno[2, 3-d]pyrimid-2, 4-dithione ( 10 ) and the condensed compound 4 . The ratio of products depends on the substituents in the 4, 5-position of 1 . The structures are investigated by n.m.r.-spectroscopy. 相似文献
The synthesis of the new heterocycle benzo[d]naphtho[1,2-b]thiophene-9,10-dicarboxylic anhydride is described. Yellow dyes for synthetic-polymer fibres result from the condensation of this intermediate with alkylamines, arylamines and o-diamines. The colour, dyeing and fastness properties of these compounds are described, and compared with those of the isomeric derivatives from benzo[k,1]thioxanthene-3,4-dicarboxylic anhydride. 相似文献
The course of the four-component reactions of (2-benzimidazolyl) acetonitrile, carbondisulfide, isothiocyanate, and sulfur and selenium, respectively, is quite different. Whereas in the case of sulfur a tetracyclic [1,3]thiazolo[4′,5′:4,5]pyrimido[1,6-a]benzimidazol-2(3H)-thione is formed, a zwitterionic 7-(benzimidazolium-2-yl)-[1,2]thiaselenolo[2,3-b][1,2,4]thiaselenazole-6-thiolate (an azaselenadithiapentalene) is the product in the case of selenium. The structures of the products have been established by X-ray crystallography, and reaction mechanisms for their formation are proposed. 相似文献
Addition of α-Ketoenamines to 2-Acetyl-p-benzoquinone Addition of 2-morpholino-2-cyclohex-1-en-one 2 to 2-acetyl-quinone 1 yields benzo[c][4 H]chromen-4,7,10-trion 4 which is unstable and rearranges to 5. 4 is converted to 3-(2,5-dihydroxy-phenyl)-2-morpholino-2-cyclohex-1-en-on 3 thermically and to dibenzo[b,d]furan-4-on 7 acid catalyzed. The structure of 7 is secured by independent synthesis. Dibenzo[b,d]furan-4-on 14 is the product of reaction from 2-(p-toluidino)-2-cyclohex-1-en-on 9 and 1 with benzo[c][4 H]chromen-4,7,10-trion 10 as intermediate. By proton catalysis 5-acetyl-6-hydroxy-carbazol-1-on 13 and 4-oxo-cyclohexa[c]isochinolinium hydrochlorid 15 is obtained from 10 . 1 H-cyclopenta[d]furan-3-on 17 is formed by addition of 2-(p-toluidino)-2-cyclopent-1-en-on 16 to 1 . It is rearranged by proton catalysis to 3-oxo-1 H-cyclopenta[c]isochinolinium salt 18 . Reaction of cyclopentan-1,2-dione and 1 yields 3 aH-cyclopenta[c]isochromen-3,6,9-trion 20 , rearranging to 1 H-cyclopenta[b]benzo[d]furan-3-on 21 . The stereochemistry of adducts is discussed in connection with the course of the reaction, spectroscopical evidence, molecular modelling and calculation of HOMO/LUMO and AO-coefficients. 相似文献
4-Nitroso-1-phenyl-3-methyl-5-aminopyrazole ( 1 ) was condensed with ethylcyanoacetate ( 2 ), malononitrile ( 4a ) and 2-cyanomethylbenzimidazole ( 4b ) to yield 6-hydroxy-5-cyano, 6-amino-5-cyano and 6-amino-5-(benzimidazol-2-yl)-3-methylpyrazolo [3,4-b]pyrazines 3, 5a and 5b , respectively. 5-Cyano-6-chloro derivative 6 obtained from 3 was converted to 3-aminopyrazolo[4′,3′:5,6]pyrazino[2,3-c]pyrazoles 8a and 8b by the treatment with hydrazin hydrate ( 7a ) and phenylhydrazine ( 7b ), respectively. Compound 5a was treated with formamide ( 9a ), urea ( 9b ) and thiourea ( 9c ) to give 4-aminopyrazolo[4′,3′:5,6]pyrazino[2′3′-d]pyrimidines 10a–10c. With refluxing acetic anhydride compounds 8a, 8b and 10a gave corresponding acetamido derivatives 8c, 8d and 10d. Compound 5a was treated with ethylorthoformate ( 11 ), acetic anhydride ( 12 ) or benzoylchloride ( 13 ) to give fused benzimidazopyrazolo[4′,3′:5,6]pyrazino[2′,3′-d]pyrimidines, viz., benzimidazol[1,2-c]pyrazolo[4,3-g]pteridines ( 14a–14c ). Some of the compounds 8, 10 and 14 were applied to polyester as disperse dyes and their fastness properties were studied. 相似文献
Lipoxygenases are lipid-peroxidizing enzymes that have been implicated in the pathogenesis of inflammatory diseases and lipoxygenase inhibitors may be developed as anti-inflammatory drugs. Structure comparison with known lipoxygenase inhibitors has suggested that (2Z)-2-(3-benzylidene)-3-oxo-2,3-dihydrobenzo[b]thiophene-7-carboxylic acid methyl ester might inhibit the lipoxygenase pathway but we found that it exhibited only a low inhibitory potency for the pure 12/15-lipoxygenase (IC(50) = 0.7 mM). However, photoactivation, which induces a Z-to-E isomerization of the double bond, strongly augmented the inhibitory potency and an IC(50) value of 0.021 mM was determined for the pure E isomer. Similar isomer-specific differences were observed with the recombinant enzyme and its 12-lipoxygenating Ile418Ala mutant, as well as in intracellular lipoxygenase activity. Structure modeling of the enzyme/inhibitor complex suggested the molecular reasons for this isomer specificity. Since light-induced isomerization may proceed in the skin, such photoreactive compounds might be developed as potential drugs for inflammatory skin diseases. 相似文献
Treatment of fac-[W(CO)3(NCMe)3] (prepared in situ) with three equivalents of thiophene-3-acetonitrile {NCCH2(3-C4H3S)} at 0°C, followed by stirring for 2 h at room temperature gave a quantitative yield of the tris{thiophene-3-acetonitrile} complex fac-[W(CO)3{NCCH2(3-C4H3S)}3] (1). The crystal structure of 1 was determined, and has an almost perfect octahedral geometry with three facial carbonyl groups and three facial thiophene-3-acetonitrile ligands. The versatility of 1 as a starting material is discussed. 相似文献
Amino-thieno[2,3–c]pyrazoles and Amino-thieno[2,3–b]pyrroles The synthesis of thieno[2,3–c]pyrazoles and thieno[2,3–b]pyrroles is described. From the dithioliumsalt ( 1 ) and potassium hydroxide the potassium-(2,2-dicyan-1-methylthio-ethen-1-yl)-thiolate ( 2 ) is formed. This reacts with hydrazine hydrate to form the 3-amino-5-thioxo-pyrazol-4-carbonitrile ( 3 ) S-Alkylation with α-chlorocarbonyl compounds yielding ( 6a–c ) leads via Thorpe-Ziegler-cyclization to 3,4-diamino-thieno[2,3–c]pyrazoles ( 9 ) if the position 1 is alkylated ( 8 ). Acetyl acetone yields 2-mercapto-pyrazolo[1,5–a]pyrimidine ( 5 ). After S-alkylation ( 10a–d ) are immediately cyclized to thieno [2′,3′:3,4]pyrazolo[1,5-a]pyrimidine ( 11a–d ). The ketone ( 6a ) can be cyclized to the pyrazolo [5,1–b]thiazole ( 12 ). 3 reacts with oxalyl chloride to form the 2,3-dioxo-6-thioxo-imidazo[1,2-b]pyrazole ( 13 ) of which S-phenacyl derivative ( 14 ) because the NH-proton cannot be cyclized. The 5-amino-3,4-dicyano-pyrrol-2-thiolate ( 16 ) shows the analogous behaviour. The S-alkylation is followed by cyclization, and 3,5-diamino-thieno[2,3–b]pyrroles ( 18a–b ) arise. Reaction of 5-amino-2-alkylthio-pyrrol-3,5-dicarbonitrile ( 17 ) with acetyl acetone provides pyrrolo[1,2-a]pyrimidine ( 20a–c ) which can be cyclized to form thieno[3′,2′:4,6]pyrimidines ( 21a–c ) very easily. 相似文献
3-Amino-thieno[2,3-b]furans and 3-Amino-thieno[3,2-b]furans The O-alkylation of 2-hydroxy-thiophene-3-carbonitriles ( 1 ) with α-bromocarbonyl compounds yields the 2-alkoxy-thiophene-3-carbonitriles ( 2a–f ) among them 2-benzoylmethoxy-thiophene-3-carbonitriles ( 2a–c ) which undergo Thorpe-Ziegler-cyclization to form the 3-amino-2-benzoyl-thieno[2,3–b]furans ( 3 ) in low yields. The 2-acyl-3-amino-thieno[3,2–b]furans and ethyl 3-amino-thieno[3,2–b]furan-2-carboxylates ( 6 ) are synthesized in similar manner from 3-hydroxy-thiophene-2-carbonitriles ( 4 ) and α-halogencarbonyl compounds via 3-acylmethoxy- and 3-ethoxycarbonylmethoxy-thiophene-2-carbonitriles ( 5 ) with high yields. 相似文献
Synthesis of 6-(4-pyridinyI)-substituted Pyrido[2,3-d]pyrimidines and 1,8-Naphthyridinms A series of new 6-(4-pyridinyl)-substituted pyrido-[2,3-d]pyrimidines 2 – 4 and 1,8-naphthyridines 6 , respectively, is described. Cyclisation of 2-amino-5-(4-pyridinyl)-pyridinm-3-carboxamide 1a with diethyl oxalate gives the pyrido-[2,3-d]pyrimidinm 2a . Alkylation of( 2a ) yields the 3-ethylaminoxyrido[2,3-d]pyrimidine derivative 2b . Saponification of 2a , b gives the corresponding carboxylic acids 3a , b , which are decarboxylated by heating above the melting point to give 4a , b . The 2-amino-5-(4-pyridinyl)-pyridinm carboxylic acid derivatives 1 b – e react with ethylmalonylchloridm and diethyl malonate to afford the 1,8-naphthyridines 6b – e . The 1-oxide 7 in a similar reaction gives 8 and the oxdiazole( 9 ) which is converted by ring transformation to the 1,8-naphthyridine 10 . 相似文献
Benzo[b]naphtho[2,3-d]thiophene-6,7-dicarboxylic anhydride (I) is obtained y Pschorr intramolecular cyclisation of 2-(2-aminophenylthio)-1,8-naphthalic anhydride. Condensation with alkylamines and arylamines gives the corresponding imides, which colour synthetic-polymer fibres in greenish-yellow hues, and reaction with o-phenylenediamines affords the isomer mixtures of derivatives of benzimidazo[1,2-b]-dibenzothiopheno-[4,3,2-d,e] isoquinolin-10-one and of benzimidazo-[2,1-a] dibenzothiopheno-[4,3,2-d,e]isoqumolin-10-one, which dye polyester fibres bright reddish-orange. Both series of dyes have excellent fastness to light and sublimation. The colour of the dyes is discussed in relation to the isomeric compounds derived from benzo[k,1]thioxanthene-3,4-dicarboxylic anhydride (III) and from benzo[d]naphtho[1,2-b]thiophene-9,10-dicarboxylic anhydride (II). The synthesis of the individual isomers resulting from reaction of I with o-phenylenediamine is reported and their absorption maxima related to polar factors operative within each isomer. 相似文献