利用三组分串联反应合成3-苯并[d]咪唑啉取代的吡喃并[3,2-c]色烯-2-酮衍生物

苯并咪唑和香豆素并吡喃衍生物具有重要的生物活性.目前制备兼具苯并咪唑和香豆素并吡喃骨架的杂环化合物尚缺乏有效的方法.报道了在醋酸促进下芳醛、2-氰甲基苯并咪唑和4-羟基香豆素的三组分串联环化反应,合成了一系列3-苯并咪唑啉取代的吡喃并[3,2-c]色烯-2-酮衍生物,收率为58％～84％.该反应采用兼容各种官能化的芳醛...     

水中"一锅法"合成2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-4H-5,6,7,8-四氢苯并[b]吡喃

报道了以十二烷基苯磺酸(DBSA)为催化剂,芳醛、丙二腈和5,5-二甲基-1,3-环己二酮为原料于水中一步生成2-氨基-3-氰基-4-芳基-7,7-二甲基-5-氧代-4H-5,6,7,8-四氢苯并[b]吡喃.该方法具有产率高、操作简便、对环境友好、催化剂可重复使用等优点.     

水介质中吡喃并[3,2-c]吡喃-5-酮衍生物的三组分一锅合成

水介质中在氯化三乙基苄基铵(TEBAC)催化下, 芳醛与丙二腈和4-羟基-6-甲基吡喃-2-酮三组分一锅反应合成了一系列2-氨基-3-氰基-4-芳基-4H,5H-吡喃-5-酮. 该反应具有产率高、污染少、操作简单、环境友好等优点.     

离子液体中一步合成14-芳基-1,6,7,14-四氢二苯并[a, i]吖啶-1,6-二酮衍生物

室温条件下在离子液体[bmim]BF4中合成了14-芳基-1,6,7,14-四氢二苯并[a, i]吖啶-1,6-二酮类衍生物,该方法具有产率高,反应介质可回收使用,反应底物范围广,反应时间短,操作简单等优点。     

2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂-6,11-二酮的合成与杀菌活性

以蒽醌为原料,经Schmidt重排为5,6-二氢-二苯并[b,e]氮杂-6,11-二酮,再经氯磺酰化和胺化合成了一系列新颖的2-(烃基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂-6,11-二酮.结构经1H NMR,13C NMR和高分辨质谱确证.初步的生测结果表明,它们对棉花立枯病菌、油菜菌核病菌和芦笋茎枯病菌具有一定的杀菌活性.其中,2-(3-三氟甲基-4-溴苯基胺磺酰基)-5,6-二氢-二苯并[b,e]氮杂-6,11二酮(4u)对芦笋茎枯病菌有良好的杀菌活性,在50μg/m L浓度下抑制率达96.3%,与对照药剂百菌清基本相当(在50μg/m L浓度下的抑制率为98.8%).初步的构效关系分析指出,氟原子的引入有利于杀菌活性的提高.     

两种苯并二氢吡喃-4-酮衍生物的合成

分别以间甲氧基苯酚与间苯二酚为原料,经过3步合成了(E)-7-甲氧基-3(4-甲氧基苯哑甲基)与(E)-7-羟基-3-(3',4',5'-三甲氧基苯哑甲基)取代的苯并二氢吡喃-4-酮.合成路线简单,易于操作,两者的最终收率分别为20.1%和15.3%.     

由N-苯基[1,3]苯并噁嗪正离子与烯烃[4+2]反应合成喹啉并[1,2-c][1,3]苯并噁嗪-6-酮衍生物

以BF3·OEt2 为催化剂, 在室温下通过4-羟基-N-苯基[1,3]苯并噁嗪-2-酮的脱羟基产生N-苯基[1,3]苯并噁嗪正离子, 然后与富电子烯烃发生Diels-Alder反应, 合成出了一系列喹啉并[1,2-c][1,3]苯并噁嗪-6-酮和喹啉并[1,2-c][1,3]萘并噁嗪-6-酮衍生物.     

苯并[b][1,4]二氮杂衍生物的合成及其应用新进展

苯并[b][1,4]二氮杂衍生物是一类含有两个氮杂原子的苯并七元杂环化合物,以其特殊的结构特点和广泛的生理及药理活性而备受关注,因此其合成和活性研究也是有机化学及药学领域的研究热点.就近10年来苯并[b][1,4]二氮杂衍生物在抑菌、抗神经炎和抗癌活性等方面的应用进展进行了归纳总结;综述了其不同催化体系下合成及机理的最新研究进展,同时对本课题组的研究成果做了阐述,并对其合成及应用前景进行了展望.     

区域选择性合成二苯并[d,f][1,3]二噁烷

针对二苯并[d,f][1,3]二噁烷传统制备方法中易产生二羟基联苯乙烯副产物的缺点,本文以路易斯酸性胍盐离子液体为催化剂,2,2'-二羟基联苯和端基炔为原料,高区域选择性的合成了二苯并[d,f][1,3]二噁烷,收率39%~84%。 本方法适用于各种端基炔。路易斯酸性胍盐离子液体循环利用5次,活性不变。     

L-脯氨酸催化一锅法合成4 H-吡喃并[2,3-c]吡唑衍生物

以L-脯氨酸为绿色催化剂,3-甲基-5-吡唑酮(或1-苯基取代物)和芳醛及丙二腈为原料,就微波辅助的一锅法成环缩合反应进行研究。实验结果表明,乙醇/水为溶剂,催化剂用量10mol%,微波功率300W和80℃下反应10～15 min,即可得到4H-吡喃并[2,3-c]吡唑类化合物(4a～4j),合成收率达85～94%。该方法具有产率高、反应时间短、操作简单等优点。     

Synthesis,Crystal Structure and Properties of Ethyl 3,9-Dimethyl-7-phenyl- 6H-dibenzo[b,d]pyran-6-one-8-carboxylate

Ethyl 3,9-dimethyl-7-phenyl-6H-dibenzo[b,d]pyran-6-one-8-carboxylate(C24H20O4, Mr = 372.40) has been synthesized and its structure was determined by 1H and 13C NMR, ESI-MS, elemental analysis, and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/n, with a = 8.3674(11), b = 10.6683(14), c = 11.3817(15) , α = 95.596(2), β = 109.866(2), γ = 94.495(2)°, V = 944.2(2)3, Z = 2, Dc = 1.310 g/cm3, μ = 0.089 mm-1, F(000) = 392, R = 0.0482 and wR = 0.1281 for 2916 observed reflections with I 2σ(I). In the crystal structure, the fused tricyclic nucleus of the title compound is not fully coplanar. Analysis of the crystal packing indicates aromatic π-π stacking interactions occurring between the fused tricyclic aromatic rings of neighboring molecules in which a maximum overlap of the π-electron systems was achieved. Fluorescence and thermal studies indicate that compound 3 has good optical properties and thermal stability.     

Modified Coumarins. 6. Synthesis of Substituted 5,6-Benzopsoralens

Substituted 5H-benzo[c]furo[3,2-g]chromen-5-ones, modified analogs of psoralen that contain a benzene ring annelated at the 5,6-position of a furo[3,2-g]chromen-7-one system, were synthesized from 3-hydroxy- 6H-benzo[c]chromen-6-ones.     

Synthesis of nitro-substituted dioxotetrahydrodioxapyrenes and 6H-dibenzo[b,d]pyran-6-one

Methods for the synthesis of tri- and tetranitro-substituted 5,9-dioxo-4,5,9,10-tetrahydro-4,10-dioxapyrenes, 5,10-dioxo-4,5,9,10-tetrahydro-4,9-dioxapyrenes, and 6H-dibenzo[b,d]pyran-6-one were developed in a search for effective sensitizers for electrophotographic layers based on carbazole-containing polymers. The possibility of the production of nitro compounds that contain three vicinal nitro groups was demonstrated. Under severe nitration conditions 2,4,8-trinitro-6H-dibenzo[b,d]pyran-6-one is cleaved to give 2-hydroxy-2-carboxy-3,5,4-trinitro-biphenyl, which is resistant to cyclization to give the starting compound, evidently because of the existence of an intramolecular hydrogen bond between the hydroxy group and the nitro group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 463–467, April, 1985.     

Synthesis of some 5H-benzo[a]phenothiazin-5-one derivatives

Several substituted 6-anilino-5H-benzo[a]phenothiazin-5-one derivatives were prepared by condensation of substituted 1,4-naphthoquinones with 2-aminobenzenethiol in pyridine. The reduction and acetylation of the resulting compounds were also investigated.

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Synthese einiger 5H-Benzo[a]phenothiazin-5-on-Derivate

Zusammenfassung Es wurden mittels Kondensation substituierter 1,4-Naphthochinone mit 2-Aminothiophenol in Pyridin einige substituierte 6-Anilino-5H-benzo[a]phenothiazin-5-one dargestellt. Die Reduktion und Acetylierung der resultierenden Verbindungen wurde ebenfalls untersucht.

     

Synthesis of substituted 6h-dibenzo[b,d]pyran-6-one

Chemistry of Heterocyclic Compounds -     

2-羟基-1O,11-二氢-5H-二苯并[a,d]环庚烯-5-酮的合成

以2－羟基苯甲醛和3－甲氧基苯乙酸为原料,经3步反应合成2－羟基－10,11－二氢－5H－二苯并[a,d]环庚烯－5－酮。     

Modified coumarins. 26. Synthesis of angular dihydrooxazinocoumarins from 3-hydroxy[<Emphasis Type="Italic">b,d</Emphasis>]pyran-6-one

N-Substituted angular pyranodihydrobenzoxazines were prepared by condensation of 3-hydroxy-dibenzo[b,d]pyran-6-one with various primary amines and two equivalents of formaldehyde in the presence of 4-N,N-dimethylaminopyridine as base. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 14–17, January–February, 2007.     

Synthesis and Theoretical Study of Intramolecular Hydrogen Bond at Two Possible Positions in Pyrazolo[1,2‐b]phthalazine

Properties of dimethyl 3‐(alkylamino)‐5,10‐dioxo‐5,10‐dihydro‐1H‐pyrazolo[1,2‐b]phthalazine‐1,2‐dicarboxylate and its derivatives were studied by means of ab initio method. NO₂ derivative of title compound was synthesized and the nature of its intramolecular hydrogen bond (HB) was investigated. Furthermore, the topological properties of the electron density distributions for N? H···O intramolecular bridges were analyzed in terms of the Bader theory of atoms in molecules (AIM). The electron density (ρ) and Laplacian (?²ρ) properties, estimated by AIM calculations, indicated that O···H bond possesses low ρ and positive ?²ρ values which are in agreement with electrostatic character of the HBs, whereas N? H bonds have covalent character (?²ρ<0). Moreover, steric effect of the t‐Bu group on structure and topological parameters of pyrazolo[1,2‐b]phthalazine conformers was studied. Finally, the powerful method of Espinosa was used to obtain the H‐bond energy.