辛弗林衍生物的合成

以苯甲醚为起始原料,与乙酰氯发生付-克酰基化后脱甲基得到4-羟基苯乙酮,然后与液溴进行α-溴代得到2-溴-1-(4-羟苯基)乙酮,再与叔丁胺进行胺化得到1-(4-羟基苯基)-2-(叔丁基氨基)乙酮,最后用氢硼化钠还原合成目标产物1-(4-羟基苯基)-2-(叔丁基氨基)乙醇,总收率约为42.3%。     

3-(4-氨基苯基偶氮)苯磺酸钠的合成

氨基甲基苯基偶氮苯磺酸钠;3-(4-氨基苯基偶氮)苯磺酸钠的合成     

1-(2-氯-4-吡啶基)-3-苯基脲的合成

氯氨基吡啶;氯吡啶基苯基脲;1-(2-氯-4-吡啶基)-3-苯基脲的合成     

4-丁酰氨基乙酰氧基苯的合成

以对氨基苯酚和正丁酸为原料，合成了4-丁酰氨基乙酰氧基苯，讨论了反应的影响因素。本方法收率高，易于纯化。     

2-[(4-羟基苯基)砜基]苯酚的合成及其精制新工艺

2-[(4-羟基苯基)砜基]苯酚的合成及其精制新工艺; [(羟基苯基)砜基]苯酚;苯酚;亚磷酸;偏三甲苯     

2-氰基-3-取代氨基-3-(2-甲基苯基)丙烯酸乙酯的合成和杀菌活性

2-甲基苯甲酰氯与氰乙酸乙酯反应得到2-氰基-3-羟基-3-(2-甲基苯基)丙烯酸乙酯, 经氯化得到2-氰基-3-氯-3-(2-甲基苯基)丙烯酸乙酯, 再用三乙胺处理合成了11个2-氰基-3-取代氨基-3-(2-甲基苯基)丙烯酸乙酯类目标化合物. 生物活性研究表明这类新化合物具有良好的杀菌活性.     

D-脯氨酸催化的(3S,4S)-4-氨基-3-羟基-5-苯基戊酸衍生物的合成

报道了一条合成(3S,4S)-4-氨基-3-羟基-5-苯基戊酸(Ahppa)衍生物的新路线。以氨基保护的L-苯丙氨酸为起始原料,依次经Weinreb胺缩合、还原、aldol缩合及溴仿4步反应合成了3个Ahppa衍生物,总收率5.8%~6.7%,其结构经¹H NMR, ¹³C NMR和ESI-MS确证。对反应条件进行了探讨,结果表明：催化剂D-脯氨酸用量对反应收率影响不大,对立体选择性影响较大;氨基上保护基体积较大有利于提高反应立体选择性。     

2-对乙酰氨基苯基-4,5-二对硝基苯基咪唑的合成及性能

咪唑化合物;非线性光学活性有机化合物;2-对乙酰氨基苯基-4;5-二对硝基苯基咪唑的合成及性能     

(S)-2-乙氧基-3-(4-羟基苯基)丙酸乙酯的合成

(S)-2-乙氧基-3-(4-羟基苯基)丙酸乙酯的合成;二乙氧基乙酸乙酯;Horner Wadswordth Emmons反应;催化氢化;化学拆分;（S） 乙氧基（羟基苯基）     

三步缩合法合成2-苯基-1-羟基联三苯叉

以邻羟基苯乙酮为原料,与N,N-二甲基甲酰胺-二甲基缩醛(DMF-DMA)分子间缩合合成(E)-3-二甲氨基-1-(2'-羟基苯基)-1-丙烯酮中间体(2);中间体2与1,3-二苯基丙酮在以DMF为溶剂,K2CO3存在下发生缩合反应生成4'-苯基-2,3'-羟基-1,1':2',1'-三联苯类化合物(3);化合物3以乙腈-1%HCl(V∶V=1∶1)为溶剂,汞灯500 W照射分子内脱水关环合成2-苯基-1-羟基联三苯叉类化合物(4).三步缩合法合成2-苯基-1-羟基联三苯叉具有操作简单、无需氧化剂与催化剂、原子利用率高等优点.采用FT-IR,1H NMR,13C NMR和HRMS对化合物3和4进行了表征.     

Studies on pyrazines. 14 The syntheses of 2,5-dihydroxypyrazines and their derivatives

Reaction of phenylglycinamide ( 1c ) with ethyl benzoylformate ( 2c ) in the presence of refluxing ethanolic sodium ethoxide gave 2,5-dihydroxy-3,6-diphenylpyrazine ( 3i ) in 19% yield. This synthetic method, however, was limited to the preparation of 3i . On the other hand, α-aminoamides 1 condensed with α-ketoesters 2 to give the intermediates 5 , which were also prepared by condensation of 1 with α-ketalesters 6 , followed by hydrolysis of the ketal moeity. Cyclization of 5 with refluxing methanolic sodium methoxide gave only disubstituted 2,5-dihydroxypyrazines 3 . Acetylation of 5 with refluxing acetic anhydride/acetic acid led to direct formation of 2,5-diacetoxypyrazines 9 . Similarly, compounds 5 could be converted into 2,5-dichloropyrazines 4 .     

Friedländer reaction of 3-acetyltropolone: Synthesis of 3-(2-quinolyl)tropolones

3-Acetyltropolone ( 1a ) reacted with 2-aminobenzaldehydes in the presence of sodium ethoxide to afford 3-(2-quinolyl)tropolone ( 3aa ) in 96% yield. Methyl- and isopropyl-substituted tropolones 1b,c also gave six 3-(2-quinolyl)tropolones in excellent yields. The compound 3aa was allowed to stand in 40% aqueous methylamine solution to give 7-methylamino-2-(2-quinolyl)tropone ( 4 ).     

Benzofuran derivatives. Part 3 On the reactivities of the intermediates in benzofuran synthesis

3-Methyl-5-nitrobenzofuran ( 2 ) and 3-methyl-5-nitrobenzofuran-2-carboxylic acid ( 3 ) were obtained by heating 2-acetyl-4-nitrophenoxyacetic acid ( 1 ) with various bases in acetic anhydride. It appeared that 3-hydroxy-3-methyl-5-nitro-2,3-dihydrobenzofuran-2-carboxylic acid ( 4 ) was the intermediate in the benzofuran synthesis. The properties of 4 were examined under various conditions. Using strong bases such as triethyl-amine in place of sodium acetate, 3-methyl-5-nitrobenzofuran-2-carboxylic acid ( 3 ) was obtained exclusively. However, in the presence of acetic acid in the reaction mixture 3-methyl-5-nitrobenzofuran ( 2 ) was obtained in good yield. The reaction pathways for the formation of 2 and 3 are discussed.     

4-甲基-7，10-二氢苯并[h]香豆素的合成研究

以1-萘酚(6)为起始原料，经过Birch还原得到5，8-二氢-1-萘酚(7)；7与乙酰 乙酸乙酯在不同条件下缩合合成了4-甲基-7，10-二氢苯并[h]香豆素(4)．研究结 果表明，无氧和酸催化的反应条件对缩合反应是至关重要的．在没有酸催化的条件 下，反应生成3-乙酰基-2-羟基-6-甲基-吡喃-4-酮(8)，并通过单晶X射线衍射分析 确定了产物的结构；在酸催化的条件下，除了生成产物4外，还伴随生成脱氢芳构 化产物4-甲基苯并[h]香豆素(5)，而且在不同条件下二者的比例不同，其中以甲磺 酸为催化剂、在氮气保护下并加入抗氧化剂无水Na_2SO_3为最佳反应条件，化学选 择性约为70：30(4：5)，收率49．1％．     

Syntheses of substituted 1-methyl-2-(1,3,4-thiadiazol-2-yl)-4-nitropyrroles and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-4-nitropyrroles

Starting from readily available ethyl-4-nitropyrrole-2-carboxylate ( 1 ), substituted 1-methyl-2-(1,3,4-thiadiazol-2-yl)-4-nitropyrroles and 1-methyl-2-(1,3,4-oxadiazol-2-yl)-4-nitropyrroles were prepared. The reaction of 1 with diazomethane gave ethyl 1-methyl-4-nitropyrrole-2-carboxylate ( 2 ). Reaction of compound 2 with hydrazine hydrate afforded the corresponding hydrazide 3 . The reaction of 3 with formic acid yielded 1-(1-methyl-4-nitropyrrole-2-carboxyl)-2-(formyl)hydrazine ( 7 ). Refluxing of the latter with phosphorus pentasulfide in xylene yielded compound 6 in 40% yield. Reaction of compound 7 with phosphorus pentoxide afforded compound 9 . Reaction of compound 3 with 1,1′-carboxyldiimidazole in the presence of triethylamine yielded 2-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-oxadiazoline-4(H)-5-one ( 11 ). Refluxing compound 3 with cyanogen bromide in methanol gave compound 12 . Compound 13 could be obtained through the reaction of compound 3 with carbon disulfide in basic medium. Alkylation of compound 13 afforded the correspanding alkylthio derivative 14 . Reaction of 1-methyl-4-nitropyrrole-2-carboxylic acid ( 15 ) with thiosemicarbazide and phosphorus oxychloride gave 2-amino-5-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazole ( 16 ). Sandmeyer reaction of compound 16 yielded 2-chloro-5-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazole ( 17 ). Refluxing of the latter with thiourea afforded 2-(1-methyl-4-nitro-2-pyrrolyl)-1,3,4-thiadiazoline-4(H)-5-thione ( 18 ). Alkylation of compound 18 gave the corresponding alkylthio derivative 19 . Oxidation of the latter with hydrogen peroxide in acetic acid yielded 2-(1-methyl-4-nitro-2-pyrrolyl)-5-methylsulfonyl-1,3,4-thiadiazole ( 20 ).     

Preparation of 7-hydroxy-2-oxoindolin-3-ylacetic acid and its [13C2], [5-n-3H], and [5-n-3H]-7-O-glucosyl analogues for use in the study of indol-3-ylacetic acid catabolism

An improved synthesis of 7-hydroxy-2-oxoindolin-3-ylacetic acid via the base-induced condensation reaction between oxalate esters and 7-benzyloxyindolin-2-one is described. 7-Benzyloxyindolin-2-one was prepared in four steps and 50% overall yield from 3-hydroxy-2-nitrotoluene. The yield of the title compound from 7-benzyloxyindolin-2-one was 56%. This route was used to prepare 7-hydroxy-2-oxoindolin-3-yl[13C2]acetic acid in 30% yield from [13C2]oxalic acid dihydrate. The method could not be extended to the preparation of the corresponding [14C2]-compound. However, an enzyme preparation from Zea mays roots catalysed the conversion of carrier-free [5-n-3H]indol-3-ylacetic acid with a specific activity of 16.7 Ci mmol-1 to a mixture of 7-hydroxy-2-oxo[5-n-3H]indolin-3-ylacetic acid and its [5-n-3H]-7-O-glucoside in ca. 3 and 40% radiochemical yield respectively. The glucoside was converted into the 7-hydroxy compound in 80% yield by means of beta-glucosidase.     

9, 9-二(3-氨基-4-羟基苯基)呫吨的合成

以醋酸酐为溶剂, 将9, 9-二(4-羟基苯基)呫吨与浓硝酸在15 ℃左右发生硝化反应1.5 h, 形成中间体-9, 9-二(3-硝基-4-羟基苯基)呫吨, 产率为88.5%;继而以Pd/C 为催化剂, 80%的水合肼为还原剂, 在乙醇和1, 4-二氧六环混合溶剂中, 于70 ℃将中间体进行还原反应10 h, 得到目标产物9, 9-二(3-氨基-4-羟基苯基)呫吨, 产率为90.8%, 两步反应总收率为80.4%。 中间体与目标化合物经NMR、FTIR和元素分析等确定了它们的结构。     

Synthesis and biological assessment of some fused Pyran derivatives

Pyran was formed by reacting methyl 3-methoxyacrylate (1) with 2-benzylidenemalanonitrile to form compound 2 . The pyrano derivatives 3–6 were obtained by reacting the second molecule with 2-benzylidenemalanonitrile, carbon disulfide, formamide, and benzylidene cyclohexanone. Compound (2) interacted with ethyl chloroacetate to form compound 8 , which then cyclized in the presence of sodium ethoxide to form compound 9 . Compound 7 was formed when compound (2) was treated with acetic acid in the presence of sulfuric acid and reacted with ethylchloroacetate to form compound 10 and then was converted to compound 11 by the addition of sodium ethoxide. Analytical and spectral data have been used to determine the structures of the newly synthesized substances and they were then tested for their antibacterial and antioxidant activities. In terms of antioxidant activity, compounds 2 and 8 were found to have the greatest and lowest levels, respectively, against Enterobacter aerogenes.     

Merrifield树脂负载的固相法合成1-氨基-2,4-咪唑二酮

设计了两条新的固相有机合成路线合成了1-氨基-2,4-咪唑二酮化合物4. 一条是由Merrifield树脂负载的羟基苯甲醛1a～1c和氨基脲反应得到缩氨基脲树脂2a～2c, 再在乙醇钠存在下和氯乙酸乙酯成环, 经盐酸切割得到1-氨基-2,4-咪唑二酮; 另一条是将Merrifield树脂用二甲基亚砜氧化氯甲基末端醛化后, 与氨基脲反应得到负载的缩氨基脲6, 经环化、切割得到目标产物4. 这两种方法中用1 mol/L的盐酸代替三氟乙酸作为切割剂, 产物单一、操作简便、可定量反应, 是合成1-氨基-2,4-咪唑二酮化合物的新方法.     

Synthesis and characterization of quinoline derivatives via the Friedländer reaction

A rapid and efficient method for the synthesis of various poly-substituted quinolines has been developed via the Friedländer condensation of 2-aminoarylaldehyde with a carbonyl compound containing a reactive α-methylene group in the presence of sodium ethoxide (10 mol %). The new tetrahydroacridine derivatives and 11H-indeno[1,2-b]quinolines were synthesized in high yield with sodium ethoxide as a catalyst via the Friedländer reaction. The conditions of reaction were discussed and the possible reaction mechanism was proposed.