Thiophene systems. 6. An unexpected bromine migration during the synthesis of thieno[3,4-b][1,5]benzoxazepin-10-ones

7-Bromothieno[3,4-b][1,5]benzoxazepin-10-one ( 1a ) was unexpectedly formed upon acid catalyzed ring closure of 5-bromo-4-ethoxy-2′-hydroxy-3-thiophenecarboxanilide ( 2a ). Ring closure of the chlorine analogue 2c proceeded normally to give 3-chlorothieno[3,4-b][1,5]benzoxazepin-10-one ( 1b ).     

新型1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂-2-酮的合成

取代苯并二氢吡喃 4 酮 ( 1)的芳腙在冰醋酸中与KNCO发生 [3 2 ]环加成反应 ,加成产物经KMnO4氧化开环得偕偶氮异氰酸酯 ( 3 ) .3在HBF4的催化下发生环化 -重排反应 ,合成得到一系列新型 6 7 5三环系 1,2 ,4 三唑并 [3 ,2 d] [1,5 ]苯并氧氮杂 2 酮 ( 5a～ 5g) .由X单晶衍射测定了化合物 5a的晶体结构     

Thiophene systems. 4. Selective syntheses of thieno[3,4-b][1,4]- and [1,5]benzodiazepinones

Novel syntheses of thiophene fused tricyclic systems 1 and 2 are reported. The methods use intermediates 4-ethoxy-3-thiopheneamine, 4-ethoxy-3-thiophenecarbonyl aside and 4-ethoxy-3-thiophenecarbonyl chloride to effect selective, high yield syntheses of the target compounds in two steps. These methods allow preparation of thiophene systems without substitution at the normally reactive C-1 and C-3 positions.     

Annulated 1,2,3-triazoles. 3. Synthesis of 1,2,3-triazolo[4,5-b][1,5]benzoxazepin-10(9H)-ones and 10-(4-substituted-1-piperazinyl)-1,2,3-triazolo[4,5-b][1,5]benzoxazepines

10-(4-Substituted-1-piperazinyl)-1,2,3-triazolo[4,5-b][1,5]benzoxazepines 11 were prepared in a three-step synthesis starting from easily available 5-chloro-1,2,3-triazole-4-carbonyl chlorides 7 by titanium tetrachloride catalyzed condensation of N-(substituted)piperazines with 1,2,3-triazolo[4,5-b][1,5]benzoxazepin-10(9H)-ones 10 formed by ring closure of the intermediate amides 9 . Although lactams 10 were obtained as the sole product of the cyclisation at 80°, the unexpected by-products 13 and 14 were formed in addition to 10c at 150° from 9c . The 4-methoxybenzyl group in 11j was easily removed by solvolyses in TFA. Compounds 11d-f and 11i were tested for psychotropic activity.     

Synthesis of 10-(4-methyl-1-piperazinyl)thieno[3,2-b][1,5]benzoxazepines

A series of the title compounds has been synthesized starting from methyl 3-hydroxythiophene-2-carboxylate. Its condensation with 2,4-dinitrochlorobenzene provides through compound 4e a way to introduce 7-substituents by means of diazonium salts reactions.     

Synthesis of novel quino[2,3-b][1,5]benzodiazepin-12-ones

The synthesis of potentially biologically biologically active quino[2,3-b][1,5]benzodiazepin-12-ones has been reported for the first time by the reaction of 2-chloroquinoline-3-carboxylic acids with o-phenylenediamine.     

13C NMR spectra of thieno[2,3-b][1,5]benzodiazepine neuroleptics

The ¹³C NMR spectra of five thieno[2,3-b][1,5]benzodiazepines and two related benzodiazepinones have been recorded at 22.64 MHz using broad band and off-resonance proton decoupling techniques. Spectral interpretation is facilitated by the presence of one (or more) fluorine substituents in the benzo-ring.     

Synthesis of 10-(4-methyl-1-piperazinyl)thieno[3,2-b][1,5]benzothiazepines

A series of the title compounds has been synthesized by two alternative methods in order to study their potential neuroleptical activity and to compare it with the pharmacological data already obtained for compounds of other isomeric or related series.     

Selenium heterocycles. XXXIII. Synthesis of thieno[3,4-b]furan,seleno[3,4-b]furan,thieno[3,4-b]indole and seleno[3,4-b]indole. four novel heterocycles

Starting from the readily available 2-methyl-3-benzoylfuran, 1-phenylthieno[3,4-b]furan and 1-phenyl-seleno[3,4-b]furan were prepared. Also, starting from phenyl 3-methylindol-2-yl ketone and aryl 2-methyl-indole-3-yl ketones a series of substituted thieno[3,4-b]indoles and substituted seleno[3,4-b]indoles were prepared.     

Synthesis and opening of the thiadiazine ring in 6,7-dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines

A reaction of 3-benzylthiotriazole-4-amines with aromatic aldehydes leads to the formation of 6,7-dihydro-5H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazines. A dihydrothiadiazine ring opening along the N-N bond occurs by the action of strong bases. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1249–1252, June, 2008.     

新型1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂(艹卓)-2-酮的合成

取代苯并二氢吡喃-4-酮(1)的芳腙在冰醋酸中与KNCO发生[3 2]环加成反应,加成产物经KMnO4氧化开环得偕偶氮异氰酸酯(3).3在HBF4的催化下发生环化-重排反应,合成得到一系列新型6-7-5三环系1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂(艹卓)2-酮(5a～5g).由X单晶衍射测定了化合物5a的晶体结构.     

Synthesis of thieno[3,4-c] and thieno[3,2-c][2,1]benzothiazepines

Starting from [4,3-c] and [3,2-c] methyl chlorosulfonylthiophenecarboxylates the synthesis of ketones 7 and 8 is described. These compounds are the first two representatives of the new thieno[3,4-c] and thieno-[3,2-c][2,1]benzothiazepine ring systems. The formation of methyl 3-chlorosulfonylthiophene-2-carboxy-late is also revised.     

Synthesis of pyrazolo[3,4-b][1,4]diazepines and pyrazolo[3,4-b]pyrazines

The synthesis and structure elucidation of new pyrazolo[3,4-b][1,4]diazepines and pyrazolo[3,4-b]pyrazines are reported and the characterisation of isomers and tautomers by proton and carbon-13 nmr are discussed. In some case only NOE experiments allow us to identify the isomeric structure.     

Condensed heterocycles with a thiazole ring. 10. Thiazolo[3,4-b][1,2,4]triazines

Derivatives of a new heterocyclic system, viz., the thiazolo[3,4-b][1,2,4]triazinium ion, were obtained by condensation of cyanobenzyl benzenesulfonate with substituted N-dithiocarboxyhydrazones of 1,2-diketones and -isonitroso ketones.See [1] for communication 9.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 498–501, April, 1985.     

Synthesis of some novel 2-phenylpyridazino[4,5-b][1,5]thiazepines

Synthesis of some derivatives of the pyridazino[4,5-b][1,5]thiazepine ring system is reported. Thus, 5-benzyl-8-methyl-2-phenyl-2,3.4,5-tetrahydro-5H-pyridazino[4,5-b][1,5]thiazepin-9(8H)-one ( 5 ) was prepared by an intramolecular S-alkylation reaction, whereas the thiazepine ring of sulfone analogue 21 , and that of the novel tricyclic pyrrolidino fused ring system 22 was elaborated by an intramolecular C-alkylation reaction. Unexpected formation of bicyclic pyrido- and thiazine fused pyridazine systems are also discussed.     

Chemistry of thienopyridines. XV. Syntheses of thieno [3,4-b] - and thieno[3,4-c] pyridines

Thieno [3,4-b] pyridine (5) was synthesized by means of the successive steps of (a) photochlorination of 2,3-dimethylpyridine to the bis(chloromethyl) compound, (b) condensation with sodium sulfide, (c) oxidation to the sulfoxide, and (d) catalytic dehydration by means of alumina. Thieno[3,4-c]pyridine (6) was obtained in an analogous manner. Spectral properties indicate that 5 and 6 have aromatic character.     

Synthesis of 4-aryl-1,3-diphenyl-1,4,5,10-tetrahydropyrazolo-[3,4-b][1,5]benzodiazepines

A convenient method is proposed for the synthesis of the previously unknown 4-aryl-1,3-diphenyl-1,4,5,10-tetrahydropyrazolo[3,4-b][1,5]benzodiazepines by cyclocondensation of 5-(2-aminoanilino)-1,3-diphenylpyrazole with aromatic aldehydes. The reaction only takes place very selectively with aldehydes which contain electron acceptor substituents in the aryl fragment. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 913–918, June, 2006.     

Synthesis of 1H-thieno[3,4-c]pyrazoles,thieno[3,4-b]furans,selenolo[3,4-b]furans and pyrrolo[3,4-d]thiazoles

Starting from the readily available aryl 2-methyl-5-phenyl-3-furyl ketones, 5-methyl-1H-1-phenylpyrazole-4-yl ketones and 4-methyl-2-phenyl-5-thiazolylcarboxaldehyde, a series of 2-phenyl-4-arylthieno[3,4-b]-furan, 2-phenyl-4-(p-methoxyphenyl)selenolo[3,4-b]furan, 4-aryl-1H-1-phenylthieno[3,4-c]pyrazole and 5-benzyl-2-phenylpyrrolo[3,4-d]thiazole were prepared in high yield.     

Synthesis and anticancer evaluation of some new pyrazolo[3,4-d][1,2,3]triazin-4-ones,pyrazolo[1,5-a]pyrimidines,and imidazo[1,2-b]pyrazoles clubbed with carbazole

Carbazole represents as a promising template for cancer treatment as it exists in the skeleton of numerous man-made and natural anticancer agents. In this regard, new sets of novel functionalized pyrazolo[3,4-d][1,2,3]triazin-4-ones 6a-e and 10a-e , pyrazolo[1,5-a]pyrimidines 16a,b and imidazo[1,2-b]pyrazoles 20a,b and 23a-c having carbazole moiety were efficiently synthesized, characterized, and mechanistically discussed. They were also evaluated against three human cancer cell lines (HCT-116, HepG-2, and MCF-7) and one standard human cell line (REP1) for their in vitro anticancer activity. The results declared that seven compounds 10d , 10e , 12b , 12d , 12e , 16a , and 23a had potent anticancer activity, having IC₅₀ values in the range 2.97 to 10.31 μM. The most effective compounds 10d and 10e inhibited the growth of all screened cancer cell lines and did not reveal human toxicity.     

Selenium heterocycles XXV. Synthesis of thieno[3,4-d][1,2,3]-thiadiazole,selenolo[3,4-d][1,2,3]thiadiazole and pyrrolo[3,4-d][1,2,3]-thiadiazole. Three novel ring systems

Starting from the readily available 4-bromomethyl-5-benzoyl-1,2,3-thiadiazole and 5-bromomethyl-4-benzoyl-1,2,3-thiadiazole; thieno[3,4-d][1,2,3]thiadiazole, selenolo[3,4-d][1,2,3]-thiadiazole and pyrrolo[3,4-d][1,2,3]thiadiazole were synthesized in good yield.