Ringschlüsse an Chinonylmethanfarbstoffen und analogen Merocyaninen. 3. Mitteilung. Chinoide Derivate des anellierten Tetrahydro-isochinolino-chinoxalins. Ringschluss nach 1,7-Verschiebung von Wasserstoff?

Cyclization Reactions of Quinonylmethane Dyes and Analogous Merocyanines. 3. Communication. Quinoid Derivatives of the Anellated Tetrahydro-quinoxalino-quinoxaline. Cyclization Following 1,7-Hydrogene-Shift? The title compounds were obtained by proton catalyzed cyclization of the corresponding 2-(1-alkyl-3-methyl-1,2-dihydroquinoxalin-2-ylidenmethyl)-1,4-naphtho- and 1,4-anthraquinones. The visible and ¹H-NMR.- and some mass spectra of the dyes are given. Mechanistic aspects of the new-type cyclization reaction are discussed.     

Reaction of thiosalicylic acid with 1,4-quinones and cyclization of the resulting arylsulfanylbenzoic acids

Thiosalicylic acid reacts with 1,4-benzoquinone to give 2-(1,4-dihydroxyphenylsulfanyl)benzoic acid which undergoes intramolecular cyclization to 1,4-dihydroxythioxanthen-9-one in the presence of dehydrating agents. Cyclization of arylsulfanylbenzoic acids obtained by reaction of thiosalicylic acid with 1,4-naphtho- and anthraquinones leads to 1,4-quinone derivatives, benzo- and naphthothioxanthenetriones.     

Interlayer Energy Transfer from Naphthalene to Anthracene Chromophores Organized in Langmuir—Blodgett Films

Interlayer energy transfer between 2,3-naphthol-10-hexadecylaza-15-crown-5(NC16) and N-[1-(9-methoxyanthryl)] decylaza-15-crown-5(A10C) within multilayer Langmuir-Blodgett films has been studied by steady-state fluorescence spectra. The donor and acceptor could be separated precisely by inserting stearic acid (SA) spacers. The efficiency of the energy transfer increases with the decrease in the donor-acceptor distance by a quadratic manner, suggesting the donor excitations are delocalized in the layer.     

基于2，3-萘-18-冠-6单元的共轭高分子对金属离子的荧光传感器

能发射蓝绿色荧光的共轭高分子由单体1,4-二溴-2,3-萘-18-冠-6(M-2)与1,4-二乙烯基-2,5-二丁氧基苯(M-3)通过Pd催化的Heck偶联反应合成制得。通过荧光和紫外-可见光谱探讨了高分子对金属离子的响应性质,其中Hg²⁺能使高分子荧光淬灭、吸收增强,但As^Ⅲ、Pb²⁺和K⁺对高分子的荧光光谱改变很小。结果表明以2,3-萘-18-冠-6作为荧光团和识别位点的共轭高分子可作为有效识别Hg²⁺的荧光化学传感器。     

Acetylenchemie 12. Mitt.: Weitere studien über die phasentransfer-katalysierte umsetzung des 9(10H)-acridinons mil alkinylhalogeniden

By the phase transfer catalyzed reaction of 9(10H)-acridinone with 1-bromo-2-propyne, 10-(2-propynyl)-9(10H)-acridinone is synthesized. As prototropic rearrangement products of this 10-(1,2-propadienyl)-9(10H)-acridinone and 10-(1-propynyl)-9(10H)-acridinone are obtained, Under the given conditins 1-bromo-2butyne leads to 10-(2-butynyl)-9(10H)-acridinone and 2-chloro-3-butyne leads to 10-(1-methyl-1,2-propddienyl)-9(10H)-acridinone, 10-(1-methyl-2-propynyl)-9(10H)-acridinone, 9-(1-methyl-2-propynyloxy)acridine and 10-[1-methyl-3-(3,4-dimethylphenyl-2-propynyl)]-9(10H)-acridinone. The formation of the products is experimentally confirmed and with published work compared.     

1-O-Substituted derivatives of murrayafoline A and their antifungal properties

The synthesis of some 1-oxygenated derivatives of murrayafoline A (1) and their antifungal properties is reported. Three derivatives, 1-hydroxy-3-methyl-9H-carbazole (2), 1-(3-methylbut-2-enyloxy)-3-methyl-9H-carbazole (3) and 1-(2,3,4,6,-tetra-O-acetyl-alpha-D-O-glucopyranosyl)-3-methyl-9H-carbazole (4), of murrayafoline A were synthesized. Compounds 1 and 2 exhibit strong fungicidal activity against Cladosporium cucumerinum at the dose of 12.5 microg.     

Synthesis of substituted methyl 5,5-polymethylene-2,4-dioxotetrahydropyran-3-carboxylates

Dimethyl 2-(1-bromocyclohexylcarbonyl)-, 2-(1-bromocyclopentylcarbonyl)-, and 2-(1-bromocyclobutylcarbonyl)-2-methylmalonates reacted with zinc and aromatic aldehydes to give the corresponding methyl 1-aryl-4-methyl-3,5-dioxo-2-oxaspiro[5.5]undecane-4-, 6-aryl-9-methyl-8,10-dioxo-7-oxaspiro[4.5]-decane-9-, and 5-aryl-8-methyl-7,9-dioxo-6-oxaspiro[3.5]nonane-8-carboxylates.     

Synthesis of unsaturated derivatives of 2,5-dimethyl-4-phenylpyridine and 3-methyl-2-azafluorene

A substituted butadiene — 1-phenyl-4-(5-methyl-4-phenyl-2-pyridyl)buta-1,3-diene with a trans, trans configuration — was obtained by condensation of 2,5-dimethyl-4-phenylpyridine with cinnamaldehyde. Two 3-methyl-9-cinnamylidene-2-azafluorene isomers are formed as a result of condensation of the same aldehyde with 3-methyl-2-azafluorene. Data from the PMR and IR spectra were used to prove the configuration of the compounds obtained. It was established that the condensation of 3-methyl-2-azafluorene with salicylaldehyde gives 3-methyl-9-(2-hydroxybenzylidene)-2-azafluorene, which has a zwitterionic structure, and 1,2-bis(3-methyl-2-aza-9-fluorenylidene)ethane. Ideas regarding the chemical mechanism of the formation of the latter are presented. The preparation of an unsaturated alcohol — 3-methyl-9-allyl-2-aza-9-fluorenol — is described.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 82–86, January, 1978.     

Photo-induced Coupling Reaction of 1, 1-Diphenyl-2, 2-dicyanoethylene with 10-Methyl-9, 10-dihydroacridine

In a previous communication1, we reported a novel photo-induced coupling of 9-fluorenylidenemalononitrile 1 with the coenzyme NADH model 10-methyl-9, 10-dihydroacridine (AcrH2) to give 9-dicyanomethyl-9-(10-methyl-9-acridinyl)fluorene and proposed a mechanism involving photo-induced electron transfer-proton transfer and radical coupling. This is a scarce mechanism for the reaction of NADH models2, which usually takes place by a formal hydride transfer pathway3. In view of the novelty of t…     

Synthesis of two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids

[structures: see text] Two naturally occurring 3-methyl-2,5-dihydro-1-benzoxepin carboxylic acids, 6-hydroxy-3-methyl-8-(phenylethyl)-2,5-dihydro-1-benzoxepin-9-carboxylic acid (radulanin E) (1) and 9-hydroxy-3-methyl-2,5-dihydro-1-benzoxepin-7-carboxylic acid (2), were synthesized using Stille coupling followed by Mitsunobu cyclization.     

Tetrahydro- and octahydropyrido[1,2-a]pyrimidin-4-ones

The catalytic hydrogenation of 2-methyl-, 1 2,8-dimethyl-, 2 , 2,9-dimethyl-, 3 , 9-methyl-2-propyl-, 4 , 2,3,9-trimethyl-, 5 , 9-methyl-2-phenyl-, 6 , 9-hydroxy-2-methyl-, 7 , 9-acetoxy-2-methyl, 8 , 9-carboxy-2-methyl-, 16 , 9-carboethoxy-2-methyl-, 17 , 9-carbomethoxy-2-methyl-, 18 , and several 9-carboxamido-2-methyl-, 19, 20 , and 21 , derivatives of the pyrido[1,2-a]pyrimidin-4-one heterocycle has led to a series of novel 6,7,8,9-tetrahydro- and fully saturated, octahydro analogs. In deuteriochloroform or DMSO-d₆ solution, the pmr spectra of the tetrahydro derivatives derived from 1-7 revealed only the 6,7,8,9-tetrahydro structures. In the pmr spectra of 16-21 , there was evidence of a facile 1,3-prototropic shift of the proton from position-9 to position-1, resulting in equilibria between tautomeric species, i.e., . The ratio of tautomers present at equilibrium, with the esters, favored the enamine conformation, whereas, with both the carboxylic acid and the amides, the imine structure predominated. Supportive evidence for the enamine structure with the esters was derived also from the ir spectra. Alkylation of the anion derived from the tetrahydro 9-carbomethoxy derivative with sodium hydride led exclusively to derivatives of 6,7,8,9-tetrahydro system.     

Skeletal transformations of perfluoro-1-ethyl-1-phenylbenzocyclobutene in the reaction with antimony pentafluoride

Interaction of perfluoro-1-ethyl-1-phenylbenzocyclobutene with SbF₅ at room temperature gives, after treatment of the reaction mixture with H₂O, perfluoro-4-[1-(2-methylphenyl)propylidene]cyclohexa-2,5-dienone as a main product. The reaction at 90-95 °C leads, after treatment with H₂O, to a mixture of perfluorinated 9-ethyl-9-methyl-1,2,3,4-tetrahydro-9H-fluorene, 9-ethyl-4a-methyl-4,4a-dihydrofluoren-1-one, 3-ethyl-3-phenylphthalide, 1-hydroxy-2-methyl-1-phenylindan, 3-methyl-2-phenylindenone and small amounts of other products.     

1, 3-dipolar cycloaddition of diazomethane to azolopyridazines. The synthesis of 8-methyl-8H- and 9-methyl-9H-pyrazolo[3, 4-d]-s-triazolo[4, 3-b]pyridazine and 1-methyl-1H- and 2-methyl-2H-imidazo[1, 2-b]pyrazolo[3, 4-b]pyridazine derivatives

The transformations of 7-methyl-7H- and 8-methyl-8H-pyrazolo[4, 3-d]tetrazolo[1, 5-b]pyridazines 1, 2, 9 and 10 into 8-methyl-8H- and 9-methyl-9H-pyrazolo[3, 4-H]-s-triazolo[4, 3-b]pyridazines 7 and 8 , and 1-methyl-1H-and 2-methyl-2H-imidazo[1, 2-b]pyrazolo[3, 4-d]pyridazines 13 and 14 are described.     

Synthesis of 9-chloropyrazolo[4,3-b]quinolines

A series of 1-methyl-4-arylaminopyrazole-3- and -5-carboxylic acids were synthesized by the reaction of 1-methyl-4-halopyrazole-3- and -5-carboxylic acids with aromatic amines in the presence of a copper catalyst; treatment with phosphorus oxychloride converted them to the corresponding 9-chlorosubstituted 1-methyl-1H- and 2-methyl-2H-pyrazolo[4,3-b]quinolines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1123–1125, August, 1984.     

重氮萘酮在环醚中热解反应研究

三种带有不同取代基的重氮萘酮(la～1c)在THF和二氧六环中加热分解给出不同的产物。1-重氮-4-萘酮(1a)的热解产物主要是重氮萘酮热解后产生的烯酮卡宾(2a)与环醚开环后形成的聚合物;3-甲基-1-重氮-4-萘酮(1b)的热解产物比较复杂,除冠醚类产物之外,还有烯酮卡宾对四氢呋喃和二氧六环的C-H键的插入反应产物、螺环化合物、2-甲基萘酚以及难以分离的聚合物;3-硝基-1-重氮-4-萘酮(1c)的热解产物主要是聚合物,此外还有少量C－H键的插入反应产物和2-硝基萘酚。对重氮萘酮热解反应的机理作了讨论。     

Studies on antibacterial agents. I. Synthesis of substituted 6,7-dihydro-1-oxo-1H,5H-benzo[i,j]quinolizine-2-carboxylic acids

A series of substituted 6,7-dihydro-1-oxo-1H,5H-benzo[i,j]quinolizine-2-carboxylic acids was synthesized and tested for antibacterial activities. Among them, 9-fluoro-6,7-dihydro-5-methyl-8-(4-methyl-1-piperazinyl)-1-oxo-1H,5H- benzo[i,j]quinolizine-2-carboxylic acid (OPC-7241) exhibited potent antibacterial activity against gram-positive and -negative bacteria, including Staphylococcus aureus and Pseudomonas aeruginosa, and 9-fluoro-6,7-dihydro-8-(4-hydroxy-1-piperidyl)-5-methyl-1-oxo-1H, 5H-benzo[i,j]quinolizine-2-carboxylic acid (OPC-7251) showed potent activity characteristically against Propionibacterium acnes.     

Isolation of tetraprenyltoluquinols from the brown alga Sargassum thunbergii

Thunbergols A (4) and B (5), tetraprenyltoluquinols, along with three known compounds (1-3) have been isolated from the brown alga Sargassum thunbergii. The structures of these two new compounds were determined to be 9-(3,4-dihydro-2,8-dimethyl-6-hydroxy-2H-1-benzopyran-2-yl)-6-methyl-2-(4-methyl-3-pentenyl)-(2E,6E)-nonadienoic acid (4) and 10-(2,3-dihydro-5-hydroxy-7-methyl-1-benzofuran-2-yl)-10-hydroxy-6-methyl-2-(4-methyl-3-pentenyl)-(2E,6E)-undecadienoic acid (5), respectively, by combined spectroscopic methods. Both of them exhibited significant scavenging activities on radical and potently inhibited generation of ONOO(-) from morpholinosydnonimine (SIN-1).     

Synthesis and Antibacterial Activity of New N9-Substituted Acridine-9-amines

Russian Journal of General Chemistry - A method for the synthesis of N9-substituted acridine-9-amines by reacting 9-chloroacridines with 2-(2-methyl-5- nitro-1H-imidazol-1-yl)ethanamine was...     

Novel Synthesis of 1,2,3,4-Tetrahydropyrazino[1,2-a]indoles

Condensation of 2-(3-methyl-1H-indol-1-yl)ethylamine (7) with benzotriazole and formaldehyde gave 2-(1H-1,2,3-benzotriazol-1-ylmethyl)-10-methyl-1,2,3,4-tetrahydropyrazino[1,2-a]indole (8) in 96% yield. Nucleophilic substitutions of the benzotriazolyl group in 8 with NaBH(4), NaCN, triethyl phosphite, allylsilanes, silyl enol ether and Grignard reagents afforded novel 10-methyl-1,2,3,4-tetrahydropyrazino[1,2-a]indoles 9a-i in 78-95% yields.     

南海红树林内生真菌No．ZZF71代谢产物研究

由于海洋环境的特殊性和微生物在生态系统的功能,海洋微生物已经发展出独特的代谢方式,提供了在陆地微生物中未遇到过的代谢产物。研究海洋微生物的活性物质,不但能发现结构新颖的化合物,丰富和发展有机化学理论,而且为寻找新的强效活性药物及其它有用物质提供了一个重要途径[1