Syntheses of Examples of the 5,6-dihydro-4H-[1,2,3]triazolo[4,5,1-ij]quinoline, 4,5,6,7-tetrahydro[1,2,3]triazolo[4,5,1-jk][1,4]benzodiazepine,and 5,6,7,8-tetrahydro-4H-[1,2,3]triazolo[4,5,1-kl][1]benzazocine ring systems

Lithiation of 1-vinylbenzotriazole 9 with n-BuLi (2 equiv) generates dianion 10, which upon subsequent reaction with 1,2- and 1,4-diketones affords 14 and 13, representatives of the 5,6-dihydro-4H-[1,2,3]triazolo[4,5,1-ij]quinoline 1 and 5,6,7,8-tetrahydro-4H-[1,2,3]triazolo[4,5,1-kl][1]benzazocine 2 ring systems, respectively. Reactions of dianion 10 with isocyanates give 15a,b, which contain the 4,5,6,7-tetrahydro[1,2,3]triazolo[4,5,1-jk][1,4]benzodiazepine 3 ring system.     

Derivatives of 5,6-Dimethoxybenzo[b]thiophen-2-(3H)one. Synthesis of 5,6-Dimethoxybenzo[b]thieno[2,3-b]quinoline

Substituted-3-benzylidenebenzo[b]thiophen-2-ones have been synthesized. 5,6-Dimethoxybenzo[b]-thiophen-2-(3H)one with aniline and triethyl orthoformate gives the 3-anilinomethylene compound, which can be hydrolysed to give the corresponding 3-hydroxymethylene derivative. Dimethoxybenzo[b]thieno[2,3-b]-quinoline has been synthesized.     

吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶化合物的合成与生物活性

应用串联氮杂Wittig反应设计合成了一系列新的2-烷氨(芳氧)基-3,8-二苯基-5-芳基-6-甲基-5,8-二氢-4H-吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶-4(3H)-酮衍生物。通过氢核磁共振谱仪(1H NMR)、傅里叶变换红外光谱仪(FTIR)和元素分析等方法对所合成的化合物进行了结构表征,用X射线单晶衍射确证了化合物2-二正丙基氨基-3,8-二苯基-5-(4-甲基苯基)-6-甲基-5,8-二氢-4H-吡唑并[4',3':5,6]吡喃并[2,3-d]嘧啶-4(3H)-酮(Ⅲi)晶体结构。室内的杀菌和杀虫活性测试结果表明:目标化合物具有一定的杀菌活性,其中部分化合物对黄瓜灰霉菌(Botrytis cinereapers)在50 mg/L剂量下抑制率达到90%以上,显示了优异的杀菌活性;对水稻褐飞虱无明显的杀虫活性,但发现对粘虫具有较高的杀灭效果,大多数抑制率达到90%以上。     

Studies on Condensed Heterocyclic Compounds XVII. Synthesis of 6-(1-Aryl-5-methyl-1,2,3-triazol-4-yl)-3-phenyl-s-triazolo[3,4-b]-1,3,4-thiadiazoles

Treatment of 4-amino-5-mercapto-3-phenyl-1,2,4-triazole 2 with 1-aryl-4-carboxy-5-methyl-1,2,3-triazoles 1a-1j in a one-step reaction yielded several 6-(1-aryl-5-methyl-1,2,3-triazol-4-yl)-3-phenyl-s-triazolo[3,4-b]-1,3,4-thiadiazoles 3a-3j . The structures of all the products were established on the basis of elemental analyses and spectral data. The fragmentation of the mass spectra of 3a-3j under electron impact was discussed.     

Pyrrolocarbazoles. 4. Acetylation of 3H-pyrrolo[2,3-c]carbazole

It is shown that 1-acetyl and 1-chloroacetyl derivatives are formed in the Vilsmeier acylation of 3H-pyrrolo[2,3-c]carbazole. The 3,6-diacetyl derivative is formed by the action of Ac₂O without a catalyst, whereas the presence of catalytic amounts of H₃PO₄ leads to 1,6-diacetyl-3H-pyrrolo[2,3-c]carbazole. Only one reaction product, viz., the 9-acetyl derivative, is formed when AlCl₃ is used as the catalyst, while a mixture of acylation products was obtained in the presence of SnCl₄.See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 497–500, April, 1980.     

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.     

Derivatives of benzo[5,6]cyclohepta[1,2-b]thiophene. Synthesis of 2,3,7,8-tetrahydro-3-oxothieno[1,2-b]cyclohepta[5,6,7-de]isoquinoline and 1,2,3,7,8,11b-hexahydro-3-oxothieno[1,2-b]cyclohepta[5,6,7-de]isoquinoline

The synthesis of the title compounds was carried out by cyclization via isocyanate of (E)-4,5-dihydro-10H-benzo[5,6]cyclohepta[1,2-b]-thiophene-10-ylideneacetic acid and 4,5-dihydro-10H-benzo[5,6]cyclohepta[1,2-b]-thiophene-10-ylacetic acid respectively, which were obtained by the Wadsworth-Emmons modification of the Wittig reaction of 4,5-dihydro-10H-10-oxobenzo[5,6]cyclohepta[1,2-b]thiophene and triethyl phosphonacetate. The structures of these new compounds are described.     

Synthesis and spectroluminescent properties of 4-oxo-1,2,3,3a-tetrahydropyrimido[1,2,3-Z,m]-α-carbolines

The reaction of 1-acetyl-2-arylpyrazolidines with the DMF-POCl₃ complex and subsequent treatment of the iminium salts formed with the potassium enolates of -substituted acetate esters yielded a series of previously unknown -carboline derivatives. The spectroluminescent properties of these compounds were studied. Some of the -carbolines synthesized have a laser effect.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 82–83, January, 1985.     

Syntheses based on dimethylpyrazoles. 9. Synthesis and spectral peculiarities of isomeric pyrazolo[3′,4′-5,6]- and-[5′,4′-5,6]-pyrimido[1,2-b]benzo[d,e]isoquinoline-4,12-diones

2-Methyl-2,4,12,13H-pyrazolo[3,4-5,6]pyrimido[1,2-b]benzo[d,e]isoquinoline-4,12-dione and its 8-nitro- and 8-amino-substituted derivatives were obtained starting from 4-amino-3-carbamoyl-1-methylpyrazole and naphthalic and 4-nitronaphthalic anhydrides. The spectral properties of the synthesized compounds were studied.See [1] for Communication 8.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 237–241, February, 1990.     

A novel synthesis of 6,7,8,9-tetrahydro-5H-dibenzo[c,g]carbazole

The synthesis of the title compound from 2-tetralone and thiosemicarbazide is reported. The structure was obtained by X-ray crystallography and its evaluation in certain anticonvulsant, cytotoxic and DNA binding screens is described.     

Chemistry of 1,2,3-thiadiazole. IV. Synthesis of [1]benzoxepino-[3,4-d][1,2,3]thiadiazole, [1]benzothiepino-[3,4-d][1,2,3]thiadiazole, [1]benzoxepino[4,3-d][1,2,3]thiadiazole, [1]benzoxepino[4,3-d]oxazole and [1]benzoxepino[4,3-d]oxazole. Four novel heterocycles

Starting from the readily available 4-bromomethy-5-carbethoxy 1,2,3-thiadiazole (V), 5-bromomethy-4-carbethoxy-1,2,3-thiadiazole (IX) and ethyl 2-aryl-5-bromomethyloxazole-4-carboxylate (XIV), 4,10-dihydro-10-oxo[1]benzoxepino[3,4-d][1,2,3]thiadiazole (Ia), 4,10-dihydro-10-oxo[1]benzothiepino[3,4-d][1,2,3]thiadiazole (Ib), 4,10-dihydro-4-oxo[1]benzothiepino[4,3-d] [1,2,3]thiazole (II), 2-aryl-4,10-dihydro-4-oxo[1]benzoxepino[4,3-d]oxazoles (XIXa-XIXc) and 2-aryl-4,10-dihydro-4-oxo[1]benzothiepino[4,3-d]oxazoles (XIXd-XIXf) were prepared.     

Benzo[b]thiophene derivatives. XXIII. Derivatives of 5,6-dihydroxy-3-benzo[b] thienylacetic acid

A series of 5,6-disubstituted benzo[b]thiophenes have been synthesized for biological evaluation. These include analogs of tryptamine, melatonin and harmaline types, having hydroxy, methoxy, methoxymethyloxy, or isopropylidenedioxy groups at both the 5- and 6- positions. In order to synthesize these, the appropriate mercaptoguaiacols were prepared, and condensed with chloroacetoacetic esters to the 4-arylthioacetoacetic esters. Cyclization of these ketones was best accomplished when the free phenolic groups were masked by methoxymethyl groups. The benzo[b] thienylacetic esters were then converted to corresponding amides, reduced to tryptamine analogs, acetylated to melatonin analogs, and cyclized to harmaline analogs. N-Acetyltryptamine and 1-methylmelatonin were also synthesized for comparison. Preliminary bioassay results on the melatonin analogs, which showed activity, are reported.     

Derivatives of benzo[4,5]cyclohepta[1,2-b]thiophene. 4. Synthesis of 1-(9,10-dihydro-4H-benzo[4,5]cyclohepta[1,2-b]thiophen-4-yl)-3-alkylaminoazetidines

Thirteen 1-(9,10-dihydro-4H-benzo[4,5]cyclohepta[1,2-b]thiophen-4-yl)-3-alkylaminoazetidines 11 have been synthesized in three steps from 4-amino-9,10-dihydro-4H-benzo[4,5]cyclohepta[1,2-b]thiophene ( 6 ), which was obtained from the reduction of either 4-azido 4 or 4-hydroxyimino 5 derivatives. All the compounds have been evaluated as potential antidepressive agents.     

Synthesis of 3- [ 1- (4-Ethoxyphenyl)-5-methyl-1,2,3-triazol-4-yl ]-6- substituted- s-triazolo [ 3,4- b ] -1,3,4-thiadiazoles

Several 3- [ 1- (4-ethoxyphenyl)-5-methyl- 1,2, 3-triazol-4-yl ]-6-substituted-s-triazolo [ 3,4- b ]- 1,3,4-thiadia zoles have been synthesized and the structures of these compounds were established by MS, IR and 1H NMR spectral data.     

Diastereoselective Manipulations of Bicyclo[m.1.0]alkane Derivatives. 4. Reactions of Nucleophiles with Bicyclo[m.1.0]alk-3-en-2-ones

Enantiomerically enriched bicyclo[m.1.0]alk-3-en-2-ones possessing 8-, 12-, and 15-membered rings were prepared and subjected to additions of nucleophiles. 1,2-Additions of n-butyllithium were highly diastereoselective for all cyclopropyl enones examined. Reactions of (Z)-bicyclo[6.1.0]non-3-en-2-one and (E)-bicyclo[13.1.0]hexadec-3-en-2-one with dimethyloxosulfonium methylide were highly diastereoselective, while reaction of (E)-bicyclo[10.1.0]tridec-3-en-2-one with this reagent was not diastereoselective. In contrast, 1,4-additions of lithium diorganocuprates were highly diastereoselective for the 8- and 12-membered enones but were not diastereoselective for the 15-membered enone. All reactions were chemically efficient. The diastereoselectivities observed for 1,2-additions, which are thought to involve early transition states, can be rationalized by consideration of the low-energy conformations of each cyclopropyl enone. The diastereoselectivities observed for 1,4-additions, which may involve late transition states, do not correlate simply with the lowest energy conformations of these enones.