【作者】 曾国平；

【导师】 丁明武；

【作者基本信息】 华中师范大学 ， 有机化学， 2007， 硕士

【摘要】 含氮杂环化合物由于具有广泛的生物活性倍受重视，现已开发出许多含氮杂环类的杀菌剂、除草剂、杀虫剂及医用药物，此类化合物已成为农用化学和医药的研究热点，具有广阔的应用前景。本论文运用原料易得、条件温和及收率较高的氮杂wittig反应方法合成了4个系列43个未见报道的四氢吡啶并噻吩并嘧啶酮衍生物，并探索和分析了所合成化合物的成环反应条件、波谱性质。具体研究内容如下：1、利用羟醛缩反应合成二苄叉丙酮。2、由二苄叉丙酮与甲胺合成取代哌啶酮。3、应用Gewald反应合成了2-氨基四氢吡啶并噻酚甲酸乙酯。4、进一步合成了重要中间体膦亚胺。5、通过中间体膦亚胺与芳基异氰酸酯反应合成了活性中间体碳二亚胺。6、应用氮杂Wittig反应，用碳二亚胺与仲胺及伯胺类化合物在醇钠催化条件下的成环反应，合成了2—取代烷氨基四氢吡啶并噻吩并嘧啶酮衍生物34个。其中仲胺类28个，伯胺类6个。7、应用氮杂Wittig反应方法，用碳二亚胺与醇在碱（醇钠）催化条件下的成环反应，合成了2—取代烷氧基四氢吡啶并噻吩并嘧啶酮衍生物6个。8、应用氮杂Wittig反应，用碳二亚胺与酚类化合物在碱（无水K₂CO₃固体）催化条件下的成环反应合成了2—取代芳氧基四氢吡啶并噻吩并嘧啶酮衍生物3个。9、研究了碳二亚胺与胺、醇和酚的成环规律，发现胺和醇的关环需要醇钠的催化，且伯胺的关环选择性与空间位阻和电子效应有关；而酚则需碳酸钾的催化才能关环。更多还原

【Abstract】 Many azole compounds have been found to show widespread biological activities. Some of them have been used as fungicide, herbicide, pesticide and medicine .In this paper, a new synthetic method to 2-substituted -5,6,7,8-tetrahydropyrido[3’ ,4’ :5,4] thieno [2,3-d] pyrimidin-4 (3H)-one derivatives was proposed. This synthetic method has the advantage of easily accessible starting material, mild condition and good yields. The reactions of aza-Wittig were studied further. The spectral properties were also researched and some of them were found to show good fungicidal activities. More than forty unreported compounds in four parts were synthesized, it may be summarized as follows:1. 1,5-diphenylpenta-1,4dien-3-one is synthesized using Claisen-Schmidt reaction.2. 1-methyl-2,6-diphenylpiperidin-4-one is synthesized using 1,5-diphenylpenta-1,4-dien-3-one and methylamine3. Gewald reaction was utilized to obtain ethyl 2 -amino -6-methyl -5,7-diphenyl -4,5,6,7- tetrahydrothieno pyridine -3- carboxylate4. Had synthesized iminophosphorane as an important intermediate.5. The iminophosphorane reacted with aryl isocyanates to give carbodimide as actived intermediate.6. The carbodimide reacted with second amines and primary amines to give 2-alkylamino -3-aryl-7- methyl -6,8- diphenyl -5,6,7,8- tetrahydropyrido[3’ ,4 :5,4] thieno [2,3-d] pyrimidin - 4(3H)-one derivatives via aza-Wittig reaction catalyzed by NaOEt7. The carbodimide reacted with alcohols to give 2-alkyloxyl-3-aryl -7- methyl- 6,8-diphenyl -5,6,7,8-tetrahydropyrido[3’ ,4’ :5,4] thieno [2,3-d] pyrimidin - 4(3H)-one derivatives via aza-Wittig reaction catalyzed by NaOEt8. The carbodimide reacted with phenols to give 2-aryloxyl-3-aryl -7- methyl -6,8-diphenyl -5,6,7,8- tetrahydropyrido [3,4’.5,4] thieno [2,3-d] pyrimidin - 4(3H)-one derivatives via aza-Wittig reaction catalyzed by solid K2CO3.9. The cyclization of carbodiimide with second amines and alcohols was in presence of sodium alkoxide .But the cyclization of carbodiimide with phenols was in presence of solid potassium carbonate.更多还原