钯催化芳基偶氮的氧化羰基化反应(英文)  

Palladium-Catalyzed Oxidative Carbonylation of Arylazos via N＝N Double Bond Cleavage

作　　者：陈向宁[1,2] 高宝[1,2] 解攀[1] 黄汉民[1] 

机构地区：[1]中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,甘肃兰州730000 [2]中国科学院大学,中国北京100049

出　　处：《分子催化》2016年第3期207-213,共7页Journal of Molecular Catalysis(China)

基　　金：supported by the Chinese Academy of Sciences and the National Natural Science Foundation of China(21172226 and21133011)

摘　　要：采用TBHP作为氧化剂,发展了钯催化芳基偶氮化合物N=N双键断裂的氧化羰基化反应.芳基偶氮的羰基化反应在Pd(OAc)2(5%),MeO-BIPHEP(5%),芳基偶氮(0.2 mmol),TBHP(2 equiv),H2O(1 equiv),DCE(1 mL),CO(3.0 MPa)的条件下110℃反应12 h后,经柱层析纯化分离得到31%-91%的芳基脲.初步的机理研究表明,芳基偶氮化合物的N=N双键断裂原位产生芳基胺,再进一步氧化羰基化生成芳基脲.A new palladium-catalyzed oxidative carbonylation of arylazos has been developed via cleavage of NN double bond with TBHP as oxidant,which provided an alternative method for synthesis of arylureas from simple arylazos. The desired products could be obtained in good to excellent yields（ 31% ~ 90%） catalyzed by the combination of Pd（ OAc）_2/ MeO-B IPHEP in the presence of TBHP at 110 ℃ under 3. 0 MPa of CO. The primary mechanistic studies demonstrated that amines might be first formed in situ from arylazos and then the oxidative carbonylation of amines occurs to give the urea products.

关 键 词：芳基偶氮 氧化羰基化 N=N键断裂 芳基脲 

分 类 号：O625.65[理学—有机化学]