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2A series of alternating polyamide-imideswith fluorenyl cardo structure was synthesized by "one-pot" polycondensation of cardo diamines,trimellitic anhydride and various aromatic diamines including p-phenylene diamine,m-phenylene diamine, 4,4\'-oxydianiline,3,4\'-oxydianiline,2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane respectively using triphenyl phosphite as condensing agents.

采用"一锅法"(One—pot Synthesis),由Cardo二胺、偏苯三酸酐和不同二胺包括对苯二胺、间苯二胺、4,4\'—二氨基二苯醚、3,4\'—二氨基二苯醚、2,2—双[4—(4—氨基苯氧基苯基]丙烷和2,2—双[4—(3—氨基苯氧基)苯基]丙烷合成了一系列含有芴基Cardo结构的交替聚酰胺酰亚胺。

The title compound (C21H15N5O) was obtained by the reaction of 3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and 4-(2,2-dicyanovinyl)benzonitrile in water in the presence of TEBA and by recrystallization from EtOH(95%) and DMF.

水溶剂中,在三乙基苄基氯化铵存在下,由3-甲基-1-苯基-1H-吡唑-5(4H)-酮和4-(2,2-二氰基)苯基氰合成并经N,N-二甲基甲酰胺与95%乙醇的混合溶剂重结晶得到化合物C21H15N5O的晶体。

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%。

In this thesis,the AM1,MNDO,MINDO/3(mainly AM1)and INDO/S-CI semiempirical MO methods were used toinvestigate the excited-state intramolecular protontransfer reactions of salicylic acid derivatives—salicylic acid,methyl salicylate,salicylaldehyde,o-hydroxyaceto-phenone,salicylamide and 3-hydroxy-picolinamide (6 conformers and 2-3 anion species);2-(2'-hydroxy-5' methylphenyl) benzotriazole(4 conformers),2-(2' hydroxyphenyl) benzimidazole (3 conformers and 3anion species),Bis-2,5-(2-benzoxazolyl)hydroquinone(3 conformers),2-(2'-hydroxyphenyl)benzothiazole(2conformers) and 7-azaindole dimer (2 conformers).Theinvestigations were described as follows.Geometry optimization,relative stability andhydrogen bonding energy First,for sylicylic acid derivative molecules,the AM1,MNDO and MINDO/3 methods were used toinvestigate ground-state geometry optimization,energies,relative stabilities and hydrogen-bondingenergies on the five kinds of the molecules(designing 6 conformers and 2-3 anion species).Comparing with experimental data,the optimizedgeometry,the order of stability,the hydrogen-bonding energies and the distances between O-O in O-H..O hydrogen bonds by AM1 method were in agreementwith the experimental data,however,the C-C bondlengths optimized by MNDO and MINDO/3 were longer,C-O and O-H bond lengths were shorter;for C-N bondlengths,the results opitimized by MNDO method werethe same as those by AM1 method,nevertheless the C-Nbond lengths given by MINDO/3 method were muchshorter.For some sylicylic acid derivatives(e.g.methyl salicylate,salicylamide),the order ofstabilities on the conformers given by MNDO andMINDO/3 methods were not in agreement with theexisting conformers deduced by experimental methods,and the hydrogen bonding energies calculated by MNDO.and MINDO/3 methods were smaller.Second,the studyon the other systems found that the optimizedgeometry of the proton-transfered product with INDOmethod could not be obtained,only could theoptimized geometry of reactant be obtained,and thecalculated hydrogen bonding energies were greater.Many results of calculation indicated that the studyon the excited-state intramolecular proton transferreaction system using AM1 method was suitable andreliable.

本论文用AM1、MNDO、MINDO/3(主要是AM1)和INDO/S-CI半经验分子轨道方法对水杨酸衍生物系列——水杨酸、水杨酸甲酯、水杨醛、O-羟基乙酰苯酮、水杨酰胺和3-羟基吡啶酰胺(6种异构体和2-3种阴离子);2-(2'-羟基-5'-甲基苯基)苯并三〓唑(4种异构体);2-(2'-羟基苯基)苯并咪唑(3种异构体和3种阴离子);2,5-二间氮杂氧茚氢醌(3种异构体);2-(2'-羟基苯基)间〓杂硫茚(2种异构体)和7-〓吲哚二体(2种异构体)的激发态分子内质子转移反应在以下几个方面进行了较系统的理论研究:几何构型优化和相对稳定性及氢键能首先以水杨酸衍生物系列分子为例,用AM1、MNDO和MINDO/3方法考察了5种分子(每种分子设计6种异构体和2-3种阴离子)的基态几何构型优化,能量、相对稳定性和氢键能计算,通过和实验数据进行比较,AM1方法给出的优化几何构型、稳定性次序、氢键能和O—H。。。O氢键的0—0距离与实验数据吻合最好,MNDO和MINDO/3方法优化的C-C键长偏长,C-O键和O-H键长偏短;对于C-N键长,MNDO和AM1优化结果差别不大,而MINDO/3给出了过短的C-N键长,MNDO和MINDO/3方法给出的有些水杨酸衍生物分子(如水杨酸甲酯和水杨酰胺)异构体的稳定性次序和实验上推测的可存在异构体结果不一致,MNDO和MINDO/3方法给出的氢键能偏低,对其他体系的研究发现INDO方法常常不能得到质子转移产物的优化几何构型,只能得到反应物的优化构型,并且估算的氢键能偏高,大量的计算结果表明AM1方法对本论文研究的激发态分子内质子转移反应体系是适宜和可靠的。

2A series of alternating polyamide-imideswith fluorenyl cardo structure was synthesized by "one-pot" polycondensation of cardo diamines,trimellitic anhydride and various aromatic diamines including p-phenylene diamine,m-phenylene diamine, 4,4\'-oxydianiline,3,4\'-oxydianiline,2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane respectively using triphenyl phosphite as condensing agents.

采用&一锅法&(One—pot Synthesis),由Cardo二胺、偏苯三酸酐和不同二胺包括对苯二胺、间苯二胺、4,4\'—二氨基二苯醚、3,4\'—二氨基二苯醚、2,2—双[4—(4—氨基苯氧基苯基]丙烷和2,2—双[4—(3—氨基苯氧基)苯基]丙烷合成了一系列含有芴基Cardo结构的交替聚酰胺酰亚胺。

2A series of alternating polyamide-imideswith fluorenyl cardo structure was synthesized by "one-pot" polycondensation of cardo diamines,trimellitic anhydride and various aromatic diamines including p-phenylene diamine,m-phenylene diamine, 4,4\'-oxydianiline,3,4\'-oxydianiline,2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane respectively using triphenyl phosphite as condensing agents.

采用&一锅法&O(来源:88AB57C论文网www.abclunwen.comne—pot Synthesis,由Cardo二胺、偏苯三酸酐和不同二胺包括对苯二胺、间苯二胺、4,4\'—二氨基二苯醚、3,4\'—二氨基二苯醚、2,2—双[4—(4—氨基苯氧基苯基]丙烷和2,2—双[4—(3—氨基苯氧基)苯基]丙烷合成了一系列含有芴基Cardo结构的交替聚酰胺酰亚胺。

Fourteen new pyrethroids containing isoxazole were designed and synthesized from 4-isopropyl-3-substituted phenyl-5-hydroxyl isoxazoles as major material, whose structures were also characterized by IR, 1H NMR and elemental analysis.

以4-异丙基-3-取代苯基-5-羟基异噁唑和3-苯氧基苄基溴为原料,三乙胺为缚酸剂,设计并合成了14个未见报道的4-异丙基-3-取代苯基-5-异噁唑基-(3'-苯氧基)苄基醚。通过红外光谱、核磁共振、元素分析等手段,确证了它们的化学结构。

The fluorescence spectra of 4- 5 '-p-biphenylyloxadiazolyl-2' benzyl ω-p-biphenylyl polymethylene car-boxylate have been determined. The results of experi-ment show that they can form not only intramolecularexciplex but also intermolecular excimer and triplex.

测定了ω-对联苯基多亚甲基羧酸4-[5'-对联苯基〓二唑-2']苄酯的荧光发射光谱,从实验结果得到,它们不但可以形成分子内激基复合物,而且可以形成分子间激基缔合物和三分子激基复合物。

Four chalcones were synthesized by aldol condensation reaction of acetophenone or para-substituted acetophenones with 2-phenyl-1,2,3-triazol-4-carboxaldehyde, which reacted with three hydrazines in glacial acetic acid under refluxing to give a series of pyrazoline derivatives.

以2-苯基-1,2,3-三唑基-4-甲醛为原料,与苯乙酮[或取代苯乙酮(1a~1d)]发生羟醛缩合,生成相应的查尔酮(2a~2d),再与不同的肼反应,合成了12种新的5位含2-苯基-1,2,3-三唑基的吡唑啉衍生物3a~3d,4a~4d,5a~5d。

First, by using p-methoxybenzaldehyde , p-hydroxybenzaldehyde and pyrrole as raw materials, 5-(p-hydroxyphenyl)-10,15,20-tri(p-methoxyphyenyl)porpyrin was prepares under acidity condition and the let reacted with benzoyl chloride, o-nitrobenzoyl chloride, m- nitrobenzoyl chloride and p- nitrobenzoyl chloride respectively under alkalinity condition with DMF as solvent.

以对-甲氧基苯甲醛、对-羟基苯甲醛和吡咯为原料,在酸性条件下合成了5-对羟苯基10,15,20-三对甲氧苯基卟啉,再以该化合物为原料分别与苯甲酰氯、邻-硝基苯甲酰氯、间-硝基苯甲酰氯和对-硝基苯甲酰氯反应,在碱性条件下以DMF为溶剂合成了四种目前尚未见文献报道的对-甲氧基卟啉硝基苯甲酸酯类化合物。

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