“一锅法”合成6-苯氧（苯硫）甲基-[1，3]二氧戊环并[4，5-g]喹啉-7-羧酸

以6-溴甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-羧酸乙酯和酚(或硫酚)为原料,首次采用一锅法高收率地合成了6-苯氧(苯硫)甲基-[1,3]-氧戊环并[4,5-g]喹啉-7-羧酸,其结构经1H NMR,IR和元素分析表征.     

“一锅法”合成2-[(2,4-二叔丁基苯氧基)甲基]-6,7-二氧戊环并[1,3-g]喹啉-3-羧酸(英文)

采用一锅法的合成方式有效地合成了2-(2,4-二叔丁基苯氧基)甲基-6,7-二氧戊环并[1,3-g]喹啉-3-羧酸,其特点是将威廉姆逊反应和碱水解这两步反应在"一锅里"进行.所得化合物的结构经IR、1 HNMR、MS和元素分析得以证实.     

2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并[9,11]二氧戊环-14（6H）-酮的合成

以2-溴甲基-6,7-亚甲二氧基-3-喹啉酸乙酯(1)为原料,经三步合成了2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并[9,11]二氧戊环-14(6H)-酮(4)。其中,6-(2-氟-4-叔丁基-苯氧甲基)-[1,3]二氧戊环并[4,5-g]喹啉-7-羧酸是经一锅法合成的。它的分子内闭环反应是在Eaton’s reagent(P2O5-CH3SO3H)的作用下,在较温和的条件下进行的。所得新化合物3和4的结构经IR1、H NMR和元素分析得以证实。     

2-溴甲基取代的[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯的合成(英文)

6-甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯(1)与N-溴代丁二酰亚胺(NBS)在150W白炽灯照射的条件下有效的发生自由基溴化反应,以较好的收率(75%)得到想要的单溴化产品6-(溴甲基)-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯(2)。本文所开发的自由基溴化方法与文献相比,单溴化产品的收率提高了46%。另外,该溴化反应中所生成的少量副产品也进行了分离提纯,其结构经波谱分析证实为9-溴-6-甲基-[1,3]二氧戊环并[4,5-g]喹啉-7-甲酸乙酯(3)。     

“一锅法”合成6-氯取代的2-苯氧甲基-3-喹啉甲酸衍生物（英文）

设计了以6-氯-2-氯甲基-3-喹啉甲酸乙酯(1)为起始化合物,在溶剂乙腈、缚酸剂无水碳酸钾的条件下,通过"一锅法"与苯酚及取代苯酚2a-o反应,合成了喹啉环上含有氯原子的6-氯-2-苯氧甲基-3-喹啉甲酸衍生物3a-o.所合成的化合物3a-o的结构经红外光谱、核磁共振氢谱、核磁共振碳谱和高分辨质谱得以证实.     

2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并

以2-溴甲基-6,7-亚甲二氧基-3-喹啉酸乙酯(1) 为原料,经三步合成了2-叔丁基-4-氟-苯并氧杂卓并[3,4-b]喹啉并[9,11]二氧戊环-14(6H)-酮(4).其中,6-(2-氟-4-叔丁基-苯氧甲基)-[1,3]二氧戊环并[4,5-g]喹啉-7-羧酸是经一锅法合成的.它的分子内闭环反应是在Eaton's reagent(P2O5-CH3SO3H)的作用下,在较温和的条件下进行的.所得新化合物3和4的结构经IR、1H NMR和元素分析得以证实.     

7,8-亚甲二氧基-4-氧代-3,4-二氢嘧啶并[4,5-b]喹啉衍生物的合成

为了寻找具有药理活性的喹啉衍生物, 我们合成了五个新的喹啉衍生物和十一个7,8--亚甲二氧基-4-氧代-3,4-二氢嘧啶并[4,5-b]喹啉衍生物. 这些化合物的结构均经核磁共振光谱, 红外光谱和元素分析予以证实 .     

新型萘并氧杂并喹啉酮和萘并吖啶二酮的合成及其荧光性质的研究

以2-溴甲基-3-喹啉甲酸乙酯(1)为底物, 分别与α-萘酚和β-萘酚“一锅法”高产率合成了2-(α-萘氧甲基)-3-喹啉甲酸(2a)和2-(β-萘氧甲基)-3-喹啉甲酸(2b). 化合物2a, 2b用Eaton试剂(五氧化二磷-甲基磺酸)作为环化试剂, 发生分子内Friedel-Crafts酰基化反应得到两种新型闭环产物: 萘并[2’,1’,6,7]氧杂并[3,4-b]喹啉-7(14H)-酮(3a)和萘并[1’,2’,6,7]氧杂并[3,4-b]喹啉-15(8H)-酮(3b). 化合物3a, 3b在氢氧化钾的乙醇-水溶液中经1,2-Wittig重排和空气氧化生成萘并[2,1-b]吖啶-7,14-二酮(4a)和萘并[1,2-b]吖啶-7,14-二酮(4b). 所合成新化合物2a～4a, 2b～4b的结构通过 IR, UV, 1H NMR, MS和元素分析进行了确认. 测定了化合物2a～4a, 2b～4b在三氯甲烷中的紫外光谱和化合物3a, 4a和3b, 4b的固体荧光光谱, 2a～4a, 2b～4b在三氯甲烷中的最大吸收峰分别位于280, 261, 312, 273, 256和313 nm; 3a, 4a和3b, 4b在固态状态下的最大发射波长分别为350, 300, 274和330 nm.     

4′,4″(5″)-{二-[1,3]二氧[4,5-g]喹啉}-二苯并-18-冠-6的合成

6-氨基胡椒醛与4′,4″(5″)-二乙酰基二苯并-18-冠-6进行Friedlander缩合得到新的冠醚衍生物——4′,4″(5″)-{二-[1,3]二氧[4,5-g]喹啉}-二苯并-18-冠-6(3),产率62%。3的结构经UV,1HNMR,13CNMR,IR和MS表征。     

硅胶键合N-丙基氨基磺酸催化合成8-芳基-7,8-二氢-[1,3]二氧杂环戊烯并[4,5-g]苯并吡喃-6-酮类化合物

120℃、无溶剂条件下,硅胶键合N-丙基氨基磺酸可有效催化芝麻酚、芳香醛和米氏酸三组分一锅法合成8-芳基-7,8-二氢-[1,3]二氧杂环戊烯并[4,5-g]苯并吡喃-6-酮类化合物.考察了温度及催化剂用量对产率的影响.产物的结构经1H NMR,13C NMR,质谱和元素分析进行了表征.     

4'',4″(5″)-{二-[1,3]二氧[4,5-g]喹啉}-二苯并-18-冠-6的合成

6-氨基胡椒醛与4',4″(5″)-二乙酰基二苯并-18-冠-6进行Friedlnder缩合得到新的冠醚衍生物--4',4″(5″)-{二-[1,3]二氧[4,5-g]喹啉}-二苯并-18-冠-6(3),产率62%.3的结构经UV, 1H NMR, 13C NMR, IR和MS表征.     

Studies on uricosuric diuretics. III. Substituted 1,3-dioxolo[4,5-f]-1,2-benzisoxazole-6-carboxylic acids and 1,3-dioxolo[4,5-g]-1,2-benzisoxazole-7-carboxylic acids.

A series of substituted 1,3-dioxolo[4,5-f]-1,2-benzisoxazole-6-carboxylic acids 13 and 1,3-dioxolo[4,5-g]-1,2-benzisoxazole-7-carboxylic acids 14 were synthesized and evaluated for diuretic and uricosuric activities in rats. Most of the benzisoxazole derivatives 13 and 14 showed potent diuretic activities. Moderate uricosuric activities were also found in 14a, 14b, and 14f.     

Synthesis and antibacterial activity of novel 7-substituted-6-fluoro-1- fluoromethyl-4-oxo-4H-[1,3thiazeto[3,2-a]quinoline-3-carboxylic acid derivatives

A series of 7-substituted-6-fluoro-1-fluoromethyl-4-oxo-4H- [1,3]thiazeto[3,2-a]quinoline-3-carboxylic acid derivatives (2a-1) was prepared and evaluated for antibacterial activity. These compounds were obtained by deacylation of 4-benzoyloxy-2-(1-chloro-2-fluoroethyl)thio-6,7- difluoroquinoline-3-carboxylate (10) and subsequent intramolecular cyclization followed by substitution with cyclic amines and then hydrolysis. The intramolecular cyclization reaction of 18, one of the diastereomers (17, 18) revealed that the cyclization reaction proceeded through an inversion to afford (-)-11a in good chemical and optical yield. The enantiomers of 2a were prepared from the enantiomers of 11a, which were obtained by the optical resolution of the racemate using high-performance liquid chromatography (HPLC). Compounds 2a,b showed excellent in vitro and in vivo antibacterial activity against both gram-negative and gram-positive bacteria including quinolone and Methicillin-resistant Staphylococcus aureus.     

Short syntheses of 1,2,3,5-tetrahydro-5-oxopyrrolo-[1,2-a]quinoline-4-carboxylic acid and 1,2,3,4-tetrahydro-6H-6-oxopyrido[1,2-a]quinoline-5-carboxylic acid derivatives

Short and efficient syntheses of 7-fluoro-8-(4-methylpiperazin-1-yl)-1,2,3,5-tetrahydro-5-oxopyrrolo[1,2-a]-quinoline-4-carboxylic acid and 8-fluoro-9-(4-methylpiperazin-1-yl)-1,2,3,4-tetrahydro-6H-6-oxopyrido[1,2-a]-quinoline-5-carboxylic acid are described. Both basic heterocycles were synthesized in two steps by the condensation of a benzoylacetate with an imino ether followed by an intramolecular nucleophilic displacement cyclization reaction.     

Syntheses of spiro[cyclopropane-1,3′-oxindole]-2-carboxylic acid and cyclopropa[c]quinoline-7b-carboxylic acid and their derivatives

The synthesis of spiro[cyclopropane-1,3′-oxindole]-2-carboxylic acid, including novel 3-(2- and 3-pyridyl)-substituted analogues and the novel cyclopropa[c]quinoline-7b-carboxylic acid and their ester and amide derivatives is described. These syntheses involve diastereoselective cyclopropanation reactions of methyl 2-(2-nitrophenyl)acrylate and (3E)-(pyridin-2-ylmethylene)- and (3E)-(pyridin-3-ylmethylene)-1,3-dihydro-2H-indol-2-one with ethyl (dimethyl sulfuranylidene) acetate (EDSA). The synthesis of methyl cyclopropa[c]quinoline-7b-carboxylate involves a regioselective reductive cyclization of a nitro-diester precursor. The relative stereochemistry of key compounds has been determined by single-crystal X-ray structural analysis.