【作者】 谢芳；

【导师】 李燕萍；

【作者基本信息】 新疆大学 ， 有机化学， 2007， 硕士

【摘要】 嘧啶酮和1,4-二氢吡啶都是具有重要应用价值和良好生物活性的含氮杂环化合物.许多取代嘧啶酮是一种广谱高效抗病毒的药物。二氢嘧啶酮类化合物具有广泛的治疗和药理性质,作为药物中间体,它具有抗病毒、抗肿瘤、抗菌和消炎作用,还被作为钙离子通道的调节剂、降血压、类肾上腺素和神经肽Y (NPY)拮抗剂等,Batzelladine A and B是文献中首次报道的能够抑制HIV gp-120与CD4细胞结合的小分子量天然产物,为AIDS治疗开拓了新的领域。1,4-二氢吡啶类化合物与嘧啶酮结构类似,具有扩张血管、抗高血压、抗动脉粥状硬化、抗肿瘤、抗糖尿病、抗衰老等作用,是一类新型高效的钙离子拮抗剂。它们独特的结构和在医疗方面所表现出的巨大潜力使许多含吡啶环的生物碱成了很多研究小组的理想合成目标。许多研究小组在合成方法的改进和寻找具有生物活性的药物先导分子方面做了很多工作,但含有1,2,3-三唑基的二氢嘧啶酮尚未见报道。为了寻找具有生物活性的药物先导分子,提高新化合物的药理活性,我们将1,2,3-三唑基引进二氢嘧啶酮和1,4-二氢吡啶分子,得到一系列新的三唑基二氢嘧啶酮类化合物、1,4-二氢吡啶类化合物和吡啶类化合物,同时,寻找到一种高效、高催化活性的催化剂。所有新化合物均未见文献报道,其结构经元素分析、IR和1HNMR谱进行确认。针对新疆地产柴油蜡含量较高的特点,以丙烯酸混合酯、苯乙烯、丙烯腈、马来酸混合酯四种单体为原料,采用自由基溶液聚合反应合成了柴油低温流动改进剂ASAMa。利用正交实验研究了单体配比,引发剂用量,溶剂用量及聚合温度对聚合物降凝效果的影响。共聚物用IR表征。针对独山子0#柴油进行降凝助滤测试,结果表明,添加剂量w (ASAMa) =5%时,对独山子0#柴油的纯降凝度可达10℃,冷滤点降低可达5℃。本论文的主要工作:1.以Sm(ClO4)3为催化剂,用1-苯基-1,2,3-三唑-4-醛与1,3-二羰基类化合物或环戊酮、脲或取代硫脲通过Biginelli反应合成3,4-二氢嘧啶-2-(1H)(硫)酮类化合物。2.用1-苯基-1,2,3-三唑-4-醛与1,3-二羰基类化合物、NH4OAc通过Hantzsch反应合成1,4-二氢吡啶类化合物并在Sm(ClO4)3催化下将部分产物芳构化为吡啶类化合物。3.先用丙烯酸、马来酸酐分别和高碳醇(十二醇、十四醇、十六醇、十八醇)反应得到相应的高碳酯,再与丙烯腈和苯乙烯以一定的摩尔比混合,在氮气保护下,恒温反应,得到ASAMa型聚合物,并针对独山子0#柴油作低温流动测试。本论文的创新点:1.寻找到一种新的适用于Biginelli反应和Hantzsch反应的催化剂;2.以往的Biginelli反应中用的都是脲或硫脲,本文采用了取代的苯基硫脲,拓展了硫脲的范围。更多还原

【Abstract】 Pyrimidone and dihydropyridine is important category of compounds including nitrogen which have applied values and biological activities. Many substituted pyrimidons are a broad highly active drug. Dihydropyrimidinones have broad therapeutic and pharmaceutical properties, as medical intermediate, which have antiviral, antitumour, antibacterial and anti-inflammatory activities, and have been used as potent calcium channel blockers, antihypertensive agents, adrenergic and neuropeptide Y (NPY) antagonist. Batzelladine A and B which are the first low molecular weight natural products reported in the literature to inhibit the binding of HIV gp-120 to CD4 cells, so disclosing a new field towards the development of AIDS therapy. 1,4-Dihydropyridines are analogy with Pyrimidones in the construction, which have expanding vascular, antihypertension, antiarteriosclerosis, antitumor, antimelituria and antifade activities. Many biologic alkalis including dihydropyridine have been used as perfect target of synthesis because of their specific construction and tremendous potentiality inhibited in medical field. Most of research groups have peoceeded a large quantity of studied in the method improvement of synthsis and in seek to leading molecules of drug with biological activity, but dihydropyrimidinones including 1,2,3-triazolyl were not reported. In order to find parent biological activity for new drugs, we designed and synthesized pyrimidone and dihydropyridine incorporating with bioactive 1,2,3-triazolyl in an effort to enhance their biological activity, a serise of desired triazolyl dihydropyrimidone compounds and 1,4-dihydropyridine compounds were obtained and seeked to an new catalyst of highly catalytic active. The structures of all the synthesized compounds were confirmed by analytical analysis and spectral data (IR, HNMR and MS).A low temperature flow improver (ASAMa) was synthesis by free radical copolymerization reaction of acrylate, styrene, acrylonitrile and maleric anhydride for Xinjiang high Wax content diesel. The influencing factors such as monomer ratio, mass fraction of initiator and solvent and reaction temperature on cold filter plugging point (CFPP) depressing effects were investigated by orthogonally designed experiments. The depressant was applied for 0# diesel fuels of Dushanzi refinery, the SP (solidifying point) of the 0# diesel fuel was lowered by 10℃and the CFPP (cold filter plugging point) 5℃.The major accomplishments of the thesis:1. A novel series of 3,4-dihydropyrimidin-2(1H)-(thio)ones including substituted triazolyl were synthesised by a one-pot three component cyclocondensation reaction with a 1,3-dicarbonyl compound or cyclopentanone, 2-phenyl-1,2,3-triazoly-4-formaldehyde and urea or thiourea (substituted thiourea) using Samarium perchlorate [Sm(ClO4)3] as an efficient catalyst.2. A novel series of 1,4-dihydropyridines including substituted triazolyl were synthesised by Hantzsch reaction with a 1,3-dicarbonyl compound, 2-phenyl-1,2,3-triazoly-4-formaldehyde and NH4Cl, and were partially aromatizated to pyridine using Samarium perchlorate [Sm(ClO4)3] as an efficient catalyst.3. First, acroleic esters and maleic esters were separately synthesised with corresponding alcohol (lauryl alcohol, tridecyl alcohol, hexadecyl alcohol, octadecanoic alcohol), then mixed with styrene and acrylon in some ratio and thermostatic reation under nitrogen protection. ASAMa polymer was obtained and proceeded cold flow testing against 0# diesel fuels of Dushanzi refinery.The major innovations of the thesis:1. Seeked to an new catalyst of highly catalytic active in application to Biginelli reaction and Hantzsch reaction.2. Only urea and thiourea were used in past Biginelli reaction, substituted thioureas were used in Biginelli reaction and continuated a field of thiourea.更多还原