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 NN 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.
出处
《分子催化》
EI
CAS
CSCD
北大核心
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)