新型杯[6]芳烃活化KOH催化合成(Z)-1,2-二芳硒基烯

KOH-Catalyzed Synthesis of (Z)-1,2-bis( arylseleno)-1-alkene Activated by Novel Calix [6] arenes

以对叔丁基苯酚为原料,经一步法制得对叔丁基杯[6]芳烃。通过逆傅克反应、亲核取代反应制得二烷基化杯[6]芳烃。最后通过磺化、亲核取代等反应,合成了下缘含喹啉基长链的新型夹状醚杯[6]芳烃化合物( 2a~ 2c ),其结构经 1 H NMR, 13 C NMR和HR-MS(ESI-QTOF)表征。以10.0 mol%杯[6]芳烃化合物( 2b )为相转移催化剂,20.0 mol%KOH为催化剂,THF为溶剂,较高产率和高选择性地合成了一系列( Z )-1,2-二芳硒基烯化合物,其结构经 1 H NMR和NOESY确证。 2b 重复使用6次,催化活性无明显降低。

p -Tert-butylcalix[6]arene was obtained by a one step reaction of p -tert-butylphenol with formaldehyde. 1,4-Dialkoxycalix[6]arene was prepared by reverse Friedel-Crafts reaction and nucleophilic substitution. Three novel calixarenes( 2a^2c ) containing quinolinyl in the lower rims were synthesized by sulfonation reaction and nucleophilic substitution. The structures were characterized by 1 HNMR, 13 C NMR and HR-MS(ESI-QTOF). Furthermore, using 10 mol%calix[6]arene( 2b ) as phase transfer catalyst and 20 mol%KOH as catalyst, the reactions of terminal alkyne with diselenides proceed efficiently in THF to obtain a series of ( Z )-1,2-bis(arylseleno)-1-alkenes. The structure was confirmed by 1 H NMR and NOESY. The catalytic activity of 2b remains stable after recycle for six times.