【作者】 庄俊鹏；

【导师】 张文勤；

【作者基本信息】 天津大学 ， 化学工艺， 2003， 博士

【摘要】 本文研究了含氮杂芳基乙烯类化合物的交叉光二聚反应。在长波长紫外光（中压汞灯，玻璃冷却夹套过滤后，波长>310 nm）的照射下含有苯并口恶唑、苯基口恶唑和吡啶基的含氮杂芳基乙烯类化合物在酸性水溶液中发生分子间的光二聚反应，生成光二聚体。通过不同种单体分子间的交叉光反应，合成了八种未见文献报道的交叉光二聚体，分别为rctt-1-(2-苯并口恶唑基)- 2-苯基-3-(4-吡啶基)-4-苯基环丁烷(BOPY)、rctt-1-(2-苯并口恶唑基)-2-苯基-3-(5-苯基口恶唑基)-4-苯基环丁烷(BOPO)、rctt-1-(5-苯基口恶唑基)- 2-苯基-3-(4-吡啶基)-4-苯基环丁烷(POPY)、rctt-1-(2-苯并口恶唑基)- 2-联苯基-3-(4-吡啶基)-4-苯基环丁烷(BOPYbi)、rctt-1-(2-苯并口恶唑基)- 2-(4-氯苯基)-3-(4-吡啶基)-4-苯基环丁烷(BOPYCl)、rctt-1-(2-苯并口恶唑基)-2-苯基-3-(4-吡啶基)-4-(4-氯苯基)环丁烷(ClBOPY)、rctt-1-(2-苯并口恶唑基)- 2-(4-氯苯基)-3-(5-苯基口恶唑基)-4-苯基环丁烷(BOPOCl) 和rctt-1-(2-苯并口恶唑基)- 2-苯基-3-(5-苯基口恶唑基)-4-(4-氯苯基)环丁烷(ClBOPO)。所有八种交叉光二聚体都以外消旋体形式存在，后五种化合物为带有四种不同取代芳基的环丁烷类化合物。用紫外、红外、核磁共振氢谱、核磁共振碳谱、质谱、元素分析以及晶体结晶表征了化合物的结构，证明其具有头尾相对的构型。对质谱的解析证明了杂芳基乙烯类化合物的光二聚体在质谱裂分时主要按纵向裂分，同时有少量横向裂分。研究了所合成的交叉光二聚体在稀溶液中，在短波长紫外光（波长=254 nm）照射下的光解开环反应。用紫外光谱和高效液相色谱跟踪了反应进程。研究发现，交叉光二聚体在紫外光解时仅发生纵向裂分，而生成原来的两种单体，没有横向裂分存在。所生成的单体在紫外光照射下发生顺反异构化反应，最终建立起顺反异构化平衡。用高效液相色谱跟踪研究了2-(苯乙烯基)苯并口恶唑（BOEP）与2-(苯乙烯基)-5-苯基口恶唑（POEP）在HCl水溶液中在中压汞灯照射下的交叉光二聚反应。结果发现，只有三种光二聚体生成。其中两种二聚体分别为BOEP和POEP自身的光二聚体，另一种为交叉光二聚体BOPO。本文合成了以BOEP作为配体，分别与CoCl2和AgClO4反应的配合物，通过X-射线衍射测定了其单晶体结构。在配合物分子中，两个BOEP配体中苯并口恶唑环上的氮原子同时与一个金属离子配位。与钴的配合物中，两分子BOEP具有顺式结构，而在银的配合物中，两分子BOEP以反式结构存在。本文合成了BOEP光二聚体DBOEP分别与CuCl2和AgClO4的配合物，以及POEP光二聚体DPOEP与CuCl2和CoCl2的配合物。由于所用的光二聚体分子含有两个氮原子，同时分子具有头尾相对构型，另外光二聚体中的环丁烷结构为刚性结构，所以所合成的四种配合物具有一维线性结构。本文探索了含有苯乙烯基吡啶盐光敏基团的单组份丝网印刷感光胶(PVA-SBQ)的工业化研究。改进了关键感光单体N-甲基-4-[2-(4-甲酰基苯基)乙烯基]吡啶甲基硫酸盐的合成路线，制备出性能优良的丝网印刷单组份感光胶。更多还原

【Abstract】 Eight cross-photodimers of heteroarylethene, rctt-1-(2-benzoxazolyl)-2-phenyl-3- (4-pyridinyl)-4-phenylcyclobutane(BOPY), rctt-1-(2-benzoxazolyl)-2-phenyl-3- (5-phenyl oxazolyl)-4-phenylcyclobutane(BOPO), rctt-1-(5-phenyloxazolyl)-2-phenyl- 3-(4-pyridinyl) -4-phenylcyclobutane(POPY), rctt-1-(2-benzoxazolyl)-2-biphenyl-3-(4-pyridinyl)-4- phenylcyclobutane(BOPYbi), rctt-1-(2-benzoxazolyl)-2-(4-chlorophenyl)-3-(4-pyridinyl) -4-phenylcyclobutane(BOPYCl), rctt-1-(2-benzoxazolyl)-2-phenyl-3-(4-pyridinyl)-4- (4-chlorophenyl)cyclobutane(ClBOPY), rctt-1-(2-benzoxazolyl)-2-(4-chlorophenyl)-3- (5-phenyloxazolyl)-4-phenylcyclobutane(BOPOCl) and rctt-1-(2-benzoxazolyl)-2-phenyl- 3-(5-phenyloxazolyl)-4-(4-chlorophenyl)cyclobutane(ClBOPO), were synthesized from different heteroarylethene monomers in aqueous acidic solution upon the irradiation of Medium-Pressure Mercury Lamp (MPML, wave length>310nm). Their structures were determined by UV, IR, 1H NMR, 13C NMR, MS, Elemental analysis and single crystal structure. The photochemical properties of the cross-photodimers upon the irradiation of Low-Pressure mercury lamp (LPML) in dilute methanol solution was studied using UV and HPLC. It was found that the cross-photodimers underwent photolysis reaction in solution and it was proved that the cross-photodimer was only photolysized into the original monomers which have formed the cross-photodimer and no other monomers were detected in the solution.Two coordination complexes of 2-styrylbenzoxazole(BOEP) with CoCl2 and AgClO4 were synthesized, respectively. Four coordination complexes of photodimers of BOEP with CuCl2 and AgClO4 and photodimers of 2-styryl-5-phenyloxazole(POEP) with CuCl2 and CoCl2 were synthesized respectively. Their structures were determined by IR and X-ray crystal diffraction. It was found that the two ligands has a cis conformation in BOEPCo, whereas an anti conformation in BOEPAg. It was found that all of the four photodimmer coordination complexes are one-dimensional coordination polymers with a line structure. The cyclobutane ring of the photodimers was distorted because of the coordination.The industrialization of one-pot photosensitive emulsion containing polyvinyl alcohol- styrylpyridinium resins used for Silk Screen Printing were studied in this paper. The synthesis of the key intermediate, N-methyl-4-[2-(4-formylphenyl)ethenyl]pyridinium methosulfate was improved greatly to give a cleaner process. The improvement of the quality of the final product was also discussed.更多还原