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Eleven novel 2-alkylthio-5-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-5-yl)-1,3,4-oxadiazole derivatives (5) and six novel 2-alkylthio-5-(5,7-dimethyl-1,2,4-triazolo[1,5-a]pyrimidine-5-yl)-1,3,4-thia- diazole derivatives (8) have been designed and synthesized by using 5-amino-3-ethoxycarbonyl-1H-1,2,4-triazole as a starting material.

以5-氨基-1H-1,2,4-三唑-3-羧酸乙酯为起始原料,设计合成了11个新型的2-取代硫醚-5-(5,7-二甲基-1,2,4-三唑并[1,5-a]嘧啶基)-1,3,4-恶二唑类化合物(5)和6个新型的2-取代硫醚-5-(5,7-二甲基-1,2,4-三唑并[1,5-a]嘧啶基)-1,3,4-噻二唑类化合物(8)。

After esterification, the ethyl-2-chloro-3-phenylpropionate reacts with diethyl malonate under the catalysis of sodium ethylate, and we obtain the corresponding triethyl ester. The-benzylsuccinic acid is formed by the triethyl ester reacting with concentrate hydrochloric acid and taking place hydrolyzation and decarboxylation reaction at the same time. In order to avoid the formation of cinnamic acid, the sodium ethylate and diethyl malonate must be react sufficiently. The course has simple operation, inexpensive materials and better yield.

具体制备工艺为:首先以L-苯丙氨酸为原料采用重氮化方法得到-2-氯-3-苯基丙酸,再经酯化得到-2-氯-3-苯基丙酸乙酯后在乙醇钠催化作用下和丙二酸二乙酯缩合,发生SN2反应,得到相应的三乙酯,然后经水解和脱羧,得到-苄基丁二酸;在实验中乙醇钠要和丙二酸二乙酯充分反应,避免生成肉桂酸乙酯;该过程操作简单,原料便宜,产率较高,总收率可达到26.8%。

They have close relationship as the former may provide new ideas and approaches for the later, while the later may be the simulation for the former and gives it helps in degradation products identification and mechanism explanation. It is necessary to choose a suitable system, which has high potential of treating EDs and close relationship to the natural environment, to combine the researches in the two aspects. Our group has been engaged in researches on the photochemical properties and application to water pollution control of different ferric species including Fe -OH complexes, Fe -polycarboxylate complexes, Ferric oxides and Fe -humic acid complexes. Fe -oxalate complexes system has higher efficiency than the other ferric species systems in photooxidation and degradation of organic compounds. This thesis is focused on the photodegradation of nine EDs estradiol (E2), estrone (E1), 17α-ethynyl estradiol (EE2), diethylstilbestrol , bisphenol-A , 4-Nonylphenol , 4-Octylphenol , di-n-butyl phthalate , and di (2-ethylhexyl) phthalate .

因此从处理效率和环境化学意义两方面考虑,结合本课题组在不同铁形态(包括Fe-OH配合物、Fe-多羧酸配合物、Fe氧化物、Fe-腐殖酸配合物等)的光化学特性及其在水污染控制中的应用方面较系统的研究工作基础,本论文选择了四类共9种典型的内分泌干扰物(雌二醇(E2)、雌酮(E1)、17α-乙炔基雌二醇(EE2)己雌酚、双酚A、壬基酚、辛基酚、酞酸二丁酯和酞酸二乙基己基酯),研究了它们在Fe-草酸盐配合物体系中的光降解效果,推测其降解机理,探索环境内分泌干扰物光氧化处理的新体系,同时为预测其在环境中的光降解行为提供了依据。

ABSTRACT Immobilized penicillin acylase (from E.coli) was used to catalyze 7 phenylacetamido 3 E propenyl cephalosporanic acid hydrolyzation into 7 amino 3 E propenyl cephalosporanic acid. Then, trans APRA was acylated with hydroxyethyl ester of 4 hydroxy D phenylglycine to obtain trans cefprozil.

以7 苯乙酰氨基 3 E 丙烯基 3 头孢菌素 4 羧酸为原料,在青霉素酰化酶作用下,首先酶法水解得到3 E 丙烯基 3 头孢菌素 4 羧酸,过滤固相酶,滤液调pH分离得到反式APRA固体;在青霉素酰化酶作用下,反式APRA再与对羟基苯甘氨酸乙二醇酯缩合,得到反式头孢丙烯;酶法合成所得的产品与进口反式头孢丙烯对照品一致。

Methacryloyloxydecyl-2-thiouracil-5-carboxylate was synthesized from the reaction of thiouracil with diethyl ethoxymethylene malonate and ω-hydroxy-decyl-methacrylate.

以硫脲、乙氧基次甲基丙二酸二乙酯和甲基丙烯酸ω-羟癸酯为主要原料合成了一种新的粘接性单体10-甲基丙烯酰氧癸基-2-硫脲嘧啶-5-羧酸酯。

A novel liquid crystalline compound named p-phenylenediamine di 4-[2- benzamide] was synthesized from allyl 2-hydroxyethylether, ethyl 4-hydroxybenzoate and p-phenylenediamine.

以乙二醇单烯丙基醚、对羟基苯甲酸乙酯、对苯二胺为原料合成了末端为不饱和双键的芳香聚酰胺溶致型液晶化合物——二对烯丙氧基乙氧基苯甲酰对苯二胺,最佳合成的摩尔比为∶羧酸∶对苯二胺∶吡啶=2。

Firstly, 3-ethylthiobutanal was prepared from crotonaldehyde reacting with ethanehiol in triethylamine with high yield. Secondly, methyl acetoacetate was converted to 6-ethylthiohept-3-en-2-one by three steps via hydrolysis, condensation with 3-ethyltio-butanal and dehydration, then 6-ethylthiohept-3-en-2-one was cycloco ndensed with dimethyl malonate by Michael addition and Claisen condensation, followed by saponification and decarboxylation to give the intermediate of 5-(2-ethylthiopropyl)-cyclohexane-1,3-dione.

首先,以巴豆醛与乙硫醇为原料,在三乙胺的催化作用下高收率制得3-乙硫基丁醛;然后从乙酰乙酸甲酯出发,通过碱水解、与3-乙硫基丁醛缩合、脱水三步反应合成6-乙硫基-3-烯-2-庚酮,接着6-乙硫基-3-烯-2-庚酮与丙二酸二甲酯通过Michael加成和Claisen缩合成环,再通过皂化和脱羧反应生成中间体5-[2-丙基]-1,3-环己二酮;再与丙酸酐反应丙酰化,最后与0-3-氯-2-丙烯基羟胺肟化,得到目标化合物烯草酮。

Based on the problem of various types of catalyst and according to the features of carbonylation catalysts reactions, our team has been designed a series of new metal complexes of benimidazoles, which can be used for carbonylation catalyst of industry. Seven new benzimidazole derivatives were prepared by the o-phenylenediamine、oxalic acid、glycolic acid、monomethyl monopotassium malonate、ethyl cyanoacetate、succinic anhydride. The structures of them were confirmed by IR、Elemental analsis. The crystal structures of d and e were determined by X-ray single crystal diffraction of Germanic Bruker Smart APEX II CCD. The catalysis of them was tested by carbonylation reactions.

本文设计以邻苯二胺和草酸、羟基乙酸、丙二酸单甲酯、氰基乙酸乙酯、丁二酸单甲酯为原料采用PPA催化和无机酸催化法,合成了4种苯并咪唑-2-羧酸衍生物并进行了表征;培养了2个化合物d、e的晶体并测定和讨论了晶体结构;制备了3种未见报道的苯并咪唑金属配合物,对配合物在羰基化法制醋酐-醋酸反应的催化作用进行了初步试验。

In the presence of catalytic rhodium acetate, ethyl 2-diazo-3-oxo-per fluoroalkanoates, reacted readily with nitriles to give a series of 5-fluoroalkyl substituted 1, 3oxazoles with high regio-selectivity through a metal carbenoid intermediate. The reactions of carbenoids with noncyclic vinyl ethers or cyclic vinyl ethers afforded dihydrofuroates in good to excellent yields. Interestingly, only vinyl C-H insertion compound was obtained concerning of the reaction of carbenoids with 2, 5dimethylfuran due to the steric hindrance of methyl group

醋酸铑分解2-重氮-3-氧代-全氟羧酸乙酯形成的金属卡宾作为1,3-偶极体,可以与一系列芳基或烷基取代的腈反应,高度区域选择性地生成一系列4-乙氧羰基-5-氟烷基取代的噁唑化合物;也可以与富电子的链状和环状的烯基醚反应,以优良的产率得到一系列氟烷基取代的二氢呋喃类化合物;而与2,5-二甲基呋喃的反应,由于甲基的位阻作用,只得到金属卡宾对呋喃3-位烯基碳氢键插入产物。

By utilizing three benezenemulticarboxylate derivatives (H2chdc, H2aip, NaH2sip), we obtain 12 coordination polymers. Especially, compelexes 1 and 2 are based on one-dimensional ···OHInOHIn···chains as building units, while complex 3 is based on double four-ring [In8(μ2-O)4(μ2-H2O)8]16+, complex 4 is based on trinuclear In3(μ3-O)(CO2)6, complexes 11 and 12 are both based on nested bistranded helices.

选择了三类取代苯羧酸配体: 2,5-二羟基-1,4-对苯二甲酸(2,5-H2chdc); 5-氨基间苯二甲酸(5-H2aip); 5-磺酸基间苯二甲酸钠盐(5-NaH2sip)和InCl3反应合成了十二个配位化合物:其中1、2以···OHInOHIn···链为构筑单元, 3以双四元环[In8(μ2-O)4(μ2-H2O)8]16+为构筑单元,4以棱柱状三核铟In3(μ3-O)(CO2)6为构筑单元,而11、12以嵌套的双股螺旋链为构筑单元。

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