苯并-10-氮杂-15-冠-5取代的单Schiff碱的合成及其锰(Ⅲ)配合物的催化环氧化性能

由苯并-10-氮杂-15-冠-5经Mannich反应、还原和缩合制得了含单氮杂冠醚的水杨醛亚胺单Schiff碱HL^1和HL^2。研究了它们的锰(Ⅲ)配合物MnL2^1Cl和MnL2^2Cl的仿酶催化性能，并与非冠醚类似物MnL2^3Cl比较，考察了配体芳环上挂接氮杂冠醚环对锰(Ⅲ)配合物的催化环氧化性能的影响。结果表明，在常温常压下，MnL2^1Cl和MnL2^2Cl比MnL2^3Cl的催化活性。其中，具有正庚氧基的MnL2^2烯转化率52．6％，环氧化选择性96．2％，摩尔转化频率(TOF)17．5h^-1。

Synthesis of Salicylaldimine Mono-Schiff Bases with a Pendant Benzo-10-aza15-crown-5 and Catalytic Epoxidation Performance of Their Mn(III) Complexes

The aza-crown ether substituted salicylaldimine mono-Schiff bases HL~(1) and HL~(2) were synthesized from benzo-10-aza-15-crown-5 via Mannich reaction, reduction and condensation. Their Mn(III) complexes were employed as models to mimic monooxygenase in catalytic epoxidation of styrene.The effect of the azacrown ether in the ligands of MnL_(2)()~1Cl and MnL_(2)()~2Cl on the catalytic activity were also examined through comparing with uncrowned analogue MnL_(2)()~3Cl. The results indicated that MnL_(2)()~1Cl and MnL_(2)()~2Cl containing two azacrown rings were superior to the uncrowned analogue MnL_(2)()~3Cl. The MnL_(2)()~2Cl containing two heptyloxyl groups showed the best activity, its conversion and selectivity were up to 52.6 % and 96.2% respectively at ambient temperature and pressure.