二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基的合成

以1,4-环己二酮、丙二酸二乙酯及多元醇等为原料, 经过两次“一锅煮”法合成了六种二代螺环树形化合物1,2,3,4,5,6,7,8,9,10,11,12-十二氢-2,2;6,6;10,10-三[3,3-二(烷氧羰基)-1,1-环亚丁基二甲氧基]三亚苯基螺环树形化合物, 其中烷氧基为异戊氧基、三羟甲基甲氧基、2,2-二溴甲基-3-羟丙氧基、2,2-二羟甲基丙氧基、二羟甲基膦甲氧基和(N-羟甲基-N-二羟甲基氨基乙基)甲氧基. 利用IR, NMR, MS和元素分析对合成的化合物进行了结构认证, 对影响反应的因素进行了讨论.     

1-芳基-3，5-二甲基吡唑-4-羧酸有机锡酯的合成、结构及杀菌活性研究

由1-芳基-3,5-二甲基吡唑-4-羧酸与适当的有机锡反应,合成表征了一系列的1-芳基-3,5-二甲基吡唑-4-羧酸有机锡酯(1～14),并通过单晶衍射确定了1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯(7)的结构。该化合物与一分子水共同结晶,通过分子间O-H…O及O-H…N氢键形成二维网状结构。杀菌活性筛选表明新合成的化合物对于番茄早疫菌、花生褐斑菌、小麦赤霉菌、苹果轮纹菌及灰霉菌全部具有良好的生长抑制作用。1-苯基-3,5-二甲基吡唑-4-羧酸三乙基锡酯及1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯在50μg.mL-1浓度下的体外实验中表现出很高的生长抑制率。对于高活性的三取代锡羧酸酯进行了EC50值的测定,结果表明1-(2-吡啶基)-3,5-二甲基吡唑-4-羧酸三乙基锡酯对苹果轮纹菌的EC50值为0.06μg.mL-1,对小麦赤霉菌的EC50值为0.14μg.mL-1。     

2,3-二甲基-2-异丙基-丁酸的合成

二异丙基酮与MeMgBr反应制备2,3,4-三甲基-3-戊醇;再经Koch-Haaf羧化反应合成了2,3-二甲基-2-异丙基-丁酸,总收率51%,其结构经NMR,IR和GC-MS确证.     

(4-甲基-1,3-二噻烷-2-亚甲基)-1,7-二芳基-1,6-二烯-3,5-二酮的合成

从2,4-戊二酮和1,2,3-三溴丙烷出发合成了一类新的α-羰基二硫缩烯酮类化合物,并以其为底物合成了(4-甲基-1,3-二噻烷-2-亚甲基)-1,7-二芳基-1,6-二烯-3,5-二酮类化合物,通过IR和1H NMR方法对其进行了表征.     

Sc(OTf)_3催化的δ-三氟甲基-δ-芳基-双取代对亚甲基苯醌和硫醇的反应:高效合成二芳基甲烷硫醚化合物（英文）

报道了一种δ-三氟甲基-δ-芳基-二取代的对亚甲基苯醌和硫醇参与的1,6-共轭加成反应.在5mol%三氟甲基磺酸钪催化的条件下,得到了结构多样化的含有三氟甲基四级碳中心的二芳基甲烷硫醚.反应具有良好的官能团兼容性和底物范围.此外,烷基硫醇和苄硫醇也适用于该反应.鉴于二芳基甲烷硫醚骨架以及三氟甲基在生物活性分子中的重要性,发展的含有三氟甲基取代四级碳中心的二芳基甲烷硫醚的高效合成方法将为生物活性分子的发现提供一条简洁、高效的策略.     

氧气氧化2,6-二-(三甲基硅基)吡喃为6-三甲基硅基-α-吡喃酮

开发出一种合成6-三甲基硅基α-吡喃酮的有效方法.在无溶剂无任何催化剂的氧气气氛中,室温条件下温和地将2,6-二-(三甲基硅基)吡喃通过氧化反应转化成6-三甲基硅基α-吡喃酮,并且给出了该反应可能的机理.     

3-甲基-4-氨基-5-[二-(4-氟苯基)]甲硫基-1,2,4-三氮唑席夫碱的微波合成及表征

微波辐射下,二氨基硫脲与乙酸反应制得3-甲基-4-氨基-1,2,4-三氮唑-5-硫酮(1),在无水乙醇中以三乙胺作为反应的缚酸剂,1与[二-(4-氟苯基)]甲基氯经微波辐射制得中间体3-甲基-4-氨基-5-[二-(4-氟苯基)]甲硫基-1,2,4-三氮唑(2),然后中间体2与芳香醛经缩合反应制得了10个Schiff碱3a～3j.合成的10个目标化合物通过熔点测定和质谱、红外光谱、核磁共振氢谱分析、元素分析对其结构进行确证.     

水介质中1,4-二芳基喹啉-2,5-二酮衍生物的绿色合成

以芳醛、3-芳氨基-5,5-二甲基环己-2-烯酮和Meldrum酸为原料, 以水为溶剂, 在回流条件下以三乙基苄基氯化铵为催化剂通过三组分一步反应, 合成了一系列的7,7-二甲基-1,4-二芳基-1,2,3,4,5,6,7,8-八氢化喹啉-2,5-二酮衍生物. 该方法具有中性反应条件、产率高(80 %～92 %)、操作简单和环境友好等优点.     

无溶剂、无催化剂条件下5-[(3-吲哚基)-芳甲基]-2,2-二甲基- 1,3-二氧六环-4,6-二酮的合成

在无溶剂和催化剂条件下,由芳香醛、吲哚、丙二酸亚异丙酯的三组分缩合反应,制备了5-[(3-吲哚基)-芳甲基]-2,2-二甲基-1,3-二氧六环-4,6-二酮,产率为70%～85%,产物结构经1H NMR,IR确证.     

1,1-二氨基-2,2-二硝基乙烯的合成研究进展

1,1-二氨基-2,2-二硝基乙烯（FOX-7）是一种低感度高能量的新型含能材料.现有的1,1-二氨基-2,2-二硝基乙烯的合成包括以2-甲基咪唑、盐酸乙脒与乙二酸二乙酯、2-甲基-4,6-二羟基嘧啶为前体的三条合成路线.使用硫酸/硝酸体系硝化2-甲基-4,6-二羟基嘧啶可得到2-二硝基亚甲基-5,5-二硝基嘧啶-4,6-二酮,然后水解可得到FOX-7,正相硅胶薄层色谱可对该反应进行监测.使用曲拉通X-100/正己烷体系的反相微乳法可制备FOX-7球形纳米晶;FOX-7球形纳米晶具有良好的应用前景,对其合成工艺与路线进行探索和研究具有一定的意义.     

Structural studies of lithium 4,4-difluoro- and 4,4,4-trifluoro-3-oxybutenoates

The condensation of ethyl difluoroacetate or ethyl trifluoroacetate with ethyl acetate in the presence of lithium hydride afforded lithium ethyl 4,4-difluoro- and ethyl 4,4,4-trifluoro-3-oxybutenoates, respectively. The structures of the complexes were established by X-ray diffraction.     

Characteristic aroma compounds from different pineapple parts

Characteristic aroma volatile compounds from different parts of cayenne pineapple were analyzed by headspace-solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC/MS). The main volatile compounds were esters, terpenes, ketones and aldehydes. The number and content of aroma compounds detected in pulp were higher than those found in core. In pulp, the characteristic aroma compounds were ethyl 2-methylbutanoate, ethyl hexanoate, 2,5-dimethyl-4-hydroxy-3(2H)-furanone (DMHF), decanal, ethyl 3-(methylthio)propionate, ethyl butanoate, and ethyl (E)-3-hexenoate; while in core the main compounds were ethyl 2-methylbutanoate, ethyl hexanoate and DMHF. The highest odor units were found to correspond to ethyl 2-methylbutanoate, followed by ethyl hexanoate and DMHF. The odor units found for pulp were higher than those for core.     

Isobaric vapor–liquid equilibria of binary system ethyl acetate + ethyl benzene + lithium bromide

The isobaric vapor–liquid equilibrium (VLE) behaviors for binary system, ethyl acetate + ethyl benzene, and ethyl acetate + ethyl benzene + LiBr (at saturation) were studied at the local ambient pressure (707 ± 1 mmHg). Equilibrium still was used where both liquid and vapor were continuously circulated. The experimental results showed that salt-free ethyl acetate + ethyl benzene system does not form an azeotrope point. The experimental results for ethyl acetate + ethyl benzene system were in a very good agreement with the predicted results using UNIFAC, UNIQUAC, NRTL, and Wilson models. Adding LiBr, as a salt, did show slight effects on the VLE behavior of ethyl acetate + ethyl benzene system.     

Vapor-liquid equilibria for binary mixtures of carbon dioxide and fatty acid ethyl esters

Vapor-liquid equilibria were measured and correlated using the Peng-Robinson equation of state for five binary systems of carbon dioxide and fatty acid ethyl esters (ethyl stearate, ethyl oleate, ethyl linoleate, ethyl eicosapentanoate, ethyl docosahexanoate) at 313.15 K, 323.15 K and 333.15 K. Solubility in CO₂ of fatty acid ethyl esters of equal chain length but of various degrees of unsaturation was compared. Although there was no distinct difference in solubility at lower pressures, at higher pressures (more than 15 MPa), those with a higher degree of unsaturation showed a slightly higher solubility. When the solubility in CO₂ of methyl esters and the corresponding ethyl esters were compared, it was noted that the former showed a slightly higher solubility at all system pressures measured in this work.     

沙枣花净油化学成份的研究

用GC-MS-DS技术对沙枣花净油的化学成份进行了研究。其主要成份为反式肉桂酸乙酯。其它成份有:3-甲基己醛、苯甲醛、壬醛、苯甲酸乙酯、癸醛、苯乙酸乙酯、7-甲基十三烯-6、顺式肉桂酸乙酯、肉桂酸甲酯、肉桂酸异丙酯、正十七烷、苯乙烯基异丙基酮、6,10,14-三甲基十五酮-2、棕榈酸乙酯、棕榈酸、正二十一烷、油酸乙酯、硬酯酸乙酯、正二十八烷和花生油酸乙酯。     

A Novel One‐Pot Synthesis of Substituted Quinolines

A synthesis of quinoline derivatives is described via reaction between ethyl bromopyruvate (=ethyl 3‐bromo‐2‐oxopropanoate), acetylenedicarboxylate, and isatin (=1H‐indole‐2,3‐dione) in the presence of NaH as a base. Also, these reactions were performed without ethyl bromopyruvate. The reaction in the presence of ethyl bromopyruvate provides regioselectively a quinoline with the ethyl ester group in 4‐position. In the absence of ethyl bromopyruvate, the reaction leads to functionalized quinolines with the same ester groups in 2‐, 3‐, and 4‐positions.     

2-(4-羟基苯基)-3,3,3-三氟丙酸乙酯的合成研究

报道了以苯酚和三氟丙酮酸乙酯为起始原料,在温和条件下合成高产率的2-(4-羟基苯基)-3,3,3-三氟丙酸乙酯的一条新途径.该途径包括无水碳酸钾催化的苯酚与三氟丙酮酸乙酯间的亲电取代反应、由此形成的产物的选择性侧连羟基的氯代反应和随后的硼氢化钠还原反应.     

Determination of eight fatty acid ethyl esters in meconium samples by headspace solid‐phase microextraction and gas chromatography–mass spectrometry

A number of fatty acid ethyl esters (FAEEs) have recently been detected in meconium samples. Several of these FAEEs have been evaluated as possible biomarkers for in utero ethanol exposure. In the present study, a method was optimized and validated for the simultaneous determination of eight FAEEs (ethyl laurate, ethyl myristate, ethyl palmitate, ethyl palmitoleate, ethyl stearate, ethyl oleate, ethyl linoleate and ethyl arachidonate) in meconium samples. FAEEs were extracted by headspace solid‐phase microextraction. Analyte detection and quantification were carried out using GC‐MS operated in chemical ionization mode. The corresponding D5‐ethyl esters were synthesized and used as internal standards. The LOQ and LOD for each analyte were <150 and <100 ng/g, respectively. The method showed good linearity (r²>0.98) in the concentration range studied (LOQ – 2000 ng/g). The intra‐ and interday imprecision, given by the RSD of the method, was lower than 15% for all FAEEs studied. The validated method was applied to 63 authentic specimens. FAEEs could be detected in alcohol‐exposed newborns (>600 ng/g cumulative concentration). Interestingly, FAEEs could also be detected in some non‐exposed newborns, although the concentrations were much lower than those measured in exposed cases.     

6-氨基-2-取代吲哚-3-羧酸乙酯及其衍生物的合成与生物活性评价

以2,4-二硝基氯苯和乙酰乙酸乙酯为原料, 经过亲核置换、还原-环化协同反应, 合成了6-氨基-2-甲基吲哚-3-羧酸乙酯, 而后在催化剂作用下, 与乙酰乙酸乙酯反应生成烯胺, 环化合成9-羟基-2,7-二甲基吡咯(2,3-f)喹啉-3-羧酸乙酯; 类似地, 合成了6-氨基-2-苯基吲哚-3-羧酸乙酯和6-氨基-2-(呋喃-2'-基)吲哚-3-羧酸乙酯. 其结构均由¹H NMR, IR以及MS波谱数据表征. 所得化合物具有抑制肺癌A549细胞生长的活性, 其抑制效果具有浓度依赖性.     

Catalytic ketonization over oxide catalysts, Part VI.a Cross-ketonization of aliphatic and aromatic esters

Activity of 20 wt.% MO₂/Al₂O₃ catalysts, where M = Mn, Ce and Zr has been studied in cross-ketonization of ethyl esters of aliphatic and aromatic acids in a flow system. Pentan-3-one and tridecan-7-one were formed in ketonization of pure aliphatic esters, ethyl propanoate and ethyl heptanoate. Benzene was obtained instead of diphenylmethanone as the product of ethyl benzoate transformations. Only two ketones, dialkyl and aralkyl, were obtained from the cross-ketonization of a mixture of aliphatic and aromatic esters. The highest yield of 1-phenyl-1-heptanone (70%) from ethyl heptanoate and ethyl benzoate was reached at 698 K in the presence of MnO₂/Al₂O₃ catalyst. Under similar conditions cross-ketonization of a mixture of ethyl propanoate and ethyl benzoate led to 1-phenyl-1-propanone (60% at 673 K).