6-烷氧基-7-乙基-4-羟基-3-喹啉羧酸乙酯的合成及抗球虫活性研究

本文设计并合成了2个新的6-烷氧基-7-乙基-4-羟基-3-喹啉羧酸乙酯化合物.所有化合物的结构均经HRMS,1H NMR,IR和元素分析所证实.对2个化合物进行了抗球虫活性实验,结果表明,化合物6-正十四烷氧基-7-乙基-4-羟基-3-喹啉羧酸乙酯具有抗球虫效果,并有可能作为抗球虫药物使用.目标物制备方法具有合成路线短、产率高、原料易得和总生产成本低的优点.     

5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯的合成

5-溴苯并呋喃-2-甲酸乙酯与4-叔丁氧基羰基哌嗪进行Buchwald-Hartwig偶联反应,若催化剂是Pd(OAc)2/BINAP,碱是Cs2CO3,则产物主要是5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯,转化率达70%;若催化剂是Pd(dba)2/P(t-Bu)3,碱是叔丁醇钾,则产物中几乎没有5-(4-叔丁氧基羰基哌嗪基)苯并呋喃-2-甲酸乙酯.文中讨论了影响这个Buchwald-Hartwig偶联反应的因素.     

5-卤代-1H-1,2,4-三氮唑-3-羧酸乙酯及其衍生物的合成

以5-氨基-1H1,2,4-三氮唑-3-羧酸乙酯为原料,经Sandmeyer反应合成了5-X-1H-1,2,4-三氮唑-3-羧酸乙酯(X=C1,Br,I)(1a-1c),1a-1c再分别与α-2′,4′-二氟苯乙酮反应合成了3个5-卤代-1-1H-1,2,4-三氮唑-3-羧酸乙酯衍生物(2a-2c),其结构通过元素分析,IR,UV和^1H NMR进行了表征。     

11-脱氧甘草次酸乙酯3-单糖链皂苷的合成及其活性研究

合成了5种11-脱氧甘草次酸3-单糖链皂苷并初步探讨其生物活性.以苯甲酰基保护的糖基三氯乙酰亚胺酯为供体,在三氟甲磺酸三甲基硅脂(TMSOTf)的催化作用下与11-脱氧甘草次酸乙酯C(3)位羟基发生糖苷化反应,以较好的产率制备得苯甲酰基保护的11-脱氧甘草次酸乙酯3-单糖链皂苷7a～7e,用NaOMe/MeOH溶液脱除苯甲酰基得11-脱氧甘草次酸乙酯3-单糖链皂苷8a～8e.合成的5个11-脱氧甘草次酸3-单糖链皂苷均为新化合物,结构经1H NMR、质谱、元素分析确证,活性实验表明化合物8a对高浓度N,N-二甲基甲酰胺(DMF)中枯草芽孢杆菌的生长具有保护作用,化合物8e对高浓度DMF中大肠杆菌、酵母菌的生长具有保护作用.     

6-芳氧基-4-羟基-3-喹啉羧酸乙酯的合成及抗球虫活性的研究

设计并合成了8个新的6-芳氧基-4-羟基-3-喹啉羧酸乙酯类化合物. 合成路线短, 产率高, 原料易得, 易实现工业化. 所有化合物的结构均经¹H NMR, MS, IR和元素分析所证实. 并选择了其中3个化合物进行抗球虫活性实验, 结果表明. 化合物6-(2-甲氧苯氧基)-4-羟基-3-喹啉羧酸乙酯具有抗球虫效果, 并有可能作为抗球虫药物使用.     

(R)-4-氰基-3-羟基丁酸乙酯的合成

研究了一条新的路线用于他汀类药物的重要中间体(R)-4-氰基-3-羟基丁酸乙酯的合成. 以廉价、易得的L-(－)-苹果酸为起始原料, 经酯化、还原、溴代和氰化四步反应得到目标化合物(R)-4-氰基-3-羟基丁酸乙酯, 合成总收率为56.7%. 所有中间体和最终产物均由ESI-MS, 1H NMR和13C NMR光谱及比旋光度表征并与文献值比较. 该方法原料易得、操作简便、收率良好, 产物容易分离纯化, 是一条适合大规模制备(R)-4-氰基-3-羟基丁酸乙酯的新合成工艺路线.     

(±)-6,7-丙酮缩二醇-3-酮-庚酸乙酯合成研究

用对甲苯磺酸-2,3-丙酮缩甘油酯(2)与乙酰乙酸乙酯盐、碳酸二乙酯反应, 制备β-酮酯类衍生物1. 以(±)-1,2-丙酮缩甘油为起始物, 经对甲苯磺酰化、亲核取代、脱羧等反应, 方便、高产率地合成了6,7-丙酮缩二醇-3-酮-庚酸乙酯(1). 试图通过对甲苯磺酸-2,3-丙酮缩甘油酯(2)和乙酰乙酸乙酯双阴离子反应制备6,7-丙酮缩二醇-3-酮-庚酸乙酯(1)未获成功. 所合成的化合物经元素分析, IR, ¹H NMR, ¹³C NMR和MS光谱表征.     

3-亚甲基异苯并呋喃-1(3H)-酮的合成新方法

本文报道了3-亚甲基异苯并呋喃-1(3H)-酮的高效合成方法。其特点是以邻甲基苯甲酸为原料,采用"一锅法"经过酯化,自由基溴代,形成季鏻盐三步反应得到2-[(溴三苯基正膦基)甲基]苯甲酸甲酯;随后经过改进的Wittig反应,酯水解合成了邻乙烯基苯甲酸;再与KI/I2溶液发生环合反应生成3-碘甲基异苯并呋喃-1(3H)-酮;最后发生消除反应得到所需要的产物。该方法具有原料易得、价格低廉、反应条件温和、收率高等优点。化合物结构用1H NMR、13C NMR和IR表征。     

3-亚甲基异苯并呋喃-1(3H)-酮及其衍生物的合成研究

以2-乙烯基苯甲酸甲酯及其衍生物为原料,经过酯水解反应,随后发生环氧化、环合反应制备了3-羟甲基异苯并呋喃-1(3H)-酮及其衍生物;再和三溴化磷或者对甲苯磺酰氯发生亲核取代,最后通过消除反应合成了3-亚甲基异苯并呋喃-1(3H)-酮及其衍生物.在亲核取代和消除反应中,对甲苯磺酰氯法比三溴化磷法产率高.目标产物及其中间体有10个是新化合物.化合物结构用1H NMR,13C NMR,MS和IR表征.目标产物在空气中长期放置没有发生二聚.     

2-甲硫基-4-羟基-5-嘧啶甲酸乙酯的工艺优化

以S-甲基异硫脲半硫酸盐和乙氧基亚甲基丙二酸二乙酯为主要原料,乙醇为溶剂,合成出2-甲硫基-4-羟基-5-嘧啶甲酸乙酯,研究了2-甲硫基-4-羟基-5-嘧啶甲酸乙酯的工艺优化,考察了投料比、反应温度、反应时间等因素对产率的影响。 获得较好的反应条件:n(C₂H₆N₂S·1/2H₂SO₄):n(C₁₀H₁₆O₅):n(NaOH)=1.2:1:1.8,在室温下缓慢滴加NaOH溶液,搅拌反应6 h,酸化得白色固体产物,产率为81.1%。产物结构经熔点测定仪、¹H NMR、ESI-MS、FT-IR等技术手段得到验证。     

Le polyphosphate d'éthyle,un réactif de choix pour la synthèse de dérivés du benzo[b]furanne dicarboxylate-2,3 de méthyle

The aim of this work is to develop a fast and effective method for the synthesis of methylated derivatives of dimethylbenzo[b]furan-2,3-dicarboxylate. With this end in view, we can suggest significant improvements to the Koelsch and Whitney method, especially by using ethyl polyphosphate. This reagent is indeed well adapted to the cyclodehydration of the methyl 2-aryloxy-3-hydroxymaleate intermediates into benzofuran compounds, since the yield is often better than 80%.     

Electrochemical synthesis of 5,6-dihydroxy-2-methyl-1-benzofuran-3-carboxylate derivatives

Electrochemical oxidation of catechols (1a-c) has been studied in the presence of methyl acetoacetate (2a) and ethyl acetoacetate (2b) as nucleophiles in aqueous solution using cyclic voltammetry and controlled-potential coulometry. The results indicate that the quinones derived from catechols (1a-c) participate in Michael addition reactions with 2a and 2b to form the corresponding benzofuran derivatives (3a-f). The electrochemical synthesis of 3a-f has been successfully performed in an undivided cell in good yield and purity. The oxidation mechanism was deduced from voltammetric data and by coulometry at controlled potential. The products have been characterized after purification by IR, ¹H NMR, ¹³C NMR, MS, and single crystal X-ray diffraction.     

A Novel and Facile Synthesis of 2‐(Benzofuran‐2‐yl)benzo[h]quinoline‐3‐carboxylic Acid Derivatives

A simple and concise approach for the synthesis of a series of new heterocyclic systems of 2‐(benzofuran‐2‐yl)benzo[h]quinoline‐3‐carboxylic acid derivatives ( 3a–3g ) is described. The synthetic strategy features the one‐pot reaction of ethyl 2‐(chloromethyl)benzo[h]quinoline‐3‐carboxylate ( 2 ) with various substituted salicylaldehydes as well as 2‐hydroxy‐1‐naphthaldehyde as a key step. The substrate 2 was prepared in good yield by a mild, efficient and direct reaction of 1‐naphthylamine ( 1 ) with Vilsmeier‐Haack reagent. The structures of all the new compounds were identified by spectral data and elemental analysis.     

2,4-二甲基吡咯-3,5-二羧酸二乙酯的合成——推荐一个大学有机化学实验

采用Knorr吡咯合成法，以乙酰乙酸乙酯和亚硝酸钠为原料，在醋酸和锌粉作用下采用“一锅法”得到2,4-二甲基吡咯-3,5-二羧酸二乙酯。本实验涉及到控温、回流、重结晶、熔点测定、红外光谱及核磁共振等实验操作和分析检测方法。该实验原料简单易得、产物收率高，结合波谱解析方法，可以培养和提高学生合成实验的能力，加强学生对杂环合成和波谱解析的理解与分析。     

Efficient Synthesis of 4,5‐Disubstituted‐3‐Toluenesulfonyl Glutarimides. Application to the Formal Synthesis of Mappicine Ketone

Various 4,5‐disubstituted‐3‐sulfonyl glutarimides 3 were synthesized from α‐sulfonyl acetamide 1 and ethyl α,β‐disubstituted acrylate esters 2 via stepwise facile [3+3] annulation in moderate yield. The synthesis of pyridin‐2‐one 9 , a key intermediate for mappicine ketone ( 4 ) synthesis, was also reported.     

Electrochemical Activation of CO2 for the Synthesis of Ethyl Carbanilate under Mild Conditions

A novel electrochemical procedure for the synthesis of ethyl carbanilate from aniline and carbon dioxide was developed via the selective cathodic reduction of carbon dioxide in CO2-saturated DMF solution containing 0.1 mol/L TEABr at room temperature,followed by the addition of EtI as an alkylating agent.The synthesis was carried out under mild[p(CO2)=1.0×105 Pa,t=20 ℃] and safe conditions.Influences of the nature of the electrodes,the current densities,the passed charges during electrolysis,temperatures,and supporting electrolytes on the yield of ethyl carbanilate were studied to optimize the electrolytic conditions.The selectivity of ethyl carbanilate is 100%.     

橙花素的催化合成研究

将研制得的季鏻盐型高聚物相转移催化剂用于橙花素(即β-萘乙醚)的催化合成。研究结果表明,在β-萘酚∶溴乙烷为1∶1.3(摩尔比),通N2保护,反应温度为75℃,反应时间为5 h的条件下,可获得81.7%的收率。此法具有操作简便、反应温和、催化剂能重复使用、效果良好的优点。     

芳并呋喃类化合物的一锅化合成法

本文报道用KF/Al~2O~3作为碱催化剂，由水杨醛或2-羟基-1-萘醛分别和α-溴代乙酸酯、α-溴代苯乙酮、苄基氯、4,4'-二氯甲基联苯和1,5-二氯甲基萘等进行一锅化缩合反应，以38～89%的产率合成了14种芳并呋喃化合物。     

Practical and Scalable Synthesis of Ethyl (R)-Piperidine-3-acetate

A practical and scalable synthesis of ethyl (R)-piperidine-3-acetate was achieved from commercially available 3-pyridylacetic acid in 76% overall yield. The practical synthesis was demonstrated on 100-g scale. One-pot reductive N-ethylation of the pyridinium salt with acetonitrile gave an N-ethyl piperidine derivative.     

Regioselective ring opening of β-phenylglycidate and aziridine-2-carboxylates with N-alkylhydroxylamines: synthesis of isoxazolidinones

A simple and efficient method for the synthesis of 4-hydroxy or 4-alkylamino isoxazolidin-3-ones and 4-hydroxy isoxazolidin-5-ones is described. The synthesis involved the ring opening of ethyl β-arylglycidates or ethyl N-alkylaziridine-2-carboxylates by free N-alkylhydroxylamines or hydroxylamine anions, followed by cyclization to give the title isoxazolidinones in moderate to good yields.