【作者】 马楠；

【导师】 王洪星；

【作者基本信息】 天津大学 ， 有机化学， 2008， 硕士

【摘要】 本文从呋喃甲醛出发,设计合成了三个系列共8个呋喃亚胺类化合物,两个系列共5个呋喃叔胺类化合物,并分别研究了这些亚胺和叔胺的钯化反应及其反应机理。1.在甲醇水溶液中,呋喃甲醛分别与取代苯胺、取代苄胺、手性苄胺作用分别得到席夫碱,它们在甲醇/二氯甲烷作溶剂,四氯钯钠作钯化试剂的情况下进行钯化反应得到钯化物。2.呋喃甲醛与取代苄胺、手性苄胺得到的席夫碱在甲醇/硼氢化钠的还原作用下得到相应的仲胺化合物。仲胺化合物在乙腈作溶剂,氰基硼氢化钠/水合甲醛溶液的还原甲基化作用下,得到相应的叔胺化合物。叔胺化合物在甲醇/二氯甲烷作溶剂,四氯钯钠作钯化试剂的情况下进行环钯化反应,得到环钯化物。以上亚胺、亚胺钯化物,仲胺、叔胺及其环钯化物均经元素分析、红外、核磁证实。此外,其中3个钯化产物经过单晶衍射的证实,并对环钯化反应的区域选择性进行了讨论。更多还原

【Abstract】 This thesis summarized in detail the progress of palladation reactions of N-donor ligands particularly for those bearing 2-furfuryl group. Based on the previous studies, three series, eight furfurylideneamines and two series, total five ter-amines were synthesized from the starting material furfural. Their palladation reactions and characterizations were discussed.1. Synthesis, characterization of imines and their palladated complexesCondensation of furfural with substituted benzylamines, chiral benzylamines and anilines in methanol or water at room temperature resulted in aldimines. Treatment of these imines with sodium tetrachloropalladate in methanol and dichloromethane led to the corresponding palladated complexes.2. Synthesis,characterization of [(N-methyl-N-2-furfuryl)-(α)-methylbenzyl]amines and their cyclopalladated complexesReduction of the imines resulted from by furfural and substituted benzyl- amines, chiral benzylamines with sodium borohydride in methanol produced quantitative sec-amines. Reductive methylation of these sec-amines with sodiumcyanoborohydride, formaldehyde in acetonitrile and acetic acid gave out the corresponding ter-amines. Cyclopalladation of these amines with sodium tetra- chloropalladate in methanol and dichloromethane led to cyclopalladated complexesThe imines and ter-amines as well as their palladated complexes were characterized by elemental analysis, IR and 1HNMR. The structures of three of the palladated complexes were confirmed by X-Ray single crystal diffraction. The possible mechanism for the formation of cyclopalladated complexes was discussed.更多还原