桧木醇酯类衍生物的设计合成及抑菌活性

Design,synthesis and antifungal activity of hinokitiol ester derivatives

为了丰富天然单萜桧木醇的结构多样性、拓宽其活性范围,在前期研究的基础上,以桧木醇为先导化合物,设计并合成了15个新型桧木醇羧酸酯类化合物(3)以及20个桧木醇磺酸酯类化合物(异构体5和6)。抑菌活性测定结果表明,大部分目标化合物在50μg/mL下对苹果树腐烂病菌Valsa mali、水稻纹枯病菌Rhizoctonia solani、番茄灰霉病菌Botrytis cinerea及黄瓜炭疽病菌Colletotrichum orbiculare均表现出良好的抑菌活性,其中羧酸酯类衍生物3a、3f、3g、3o对水稻纹枯病菌的EC50值分别为0.96、1.05、1.29和1.88μg/mL,3a、3e、3j对苹果树腐烂病菌的EC50值分别为3.60、3.28和3.48μg/mL,3d、3f、3g对黄瓜炭疽病菌的EC50值分别为0.77、0.51和0.67μg/mL,均优于桧木醇。总体来说,羧酸酯类衍生物的抑菌活性明显优于磺酸酯类衍生物,但磺酸酯类衍生物酯基位置的异构体抑菌活性存在较大差异,构型为1时抑菌活性更好。

As a continuous research on structure derivation and activity of natural monoterpenoid hinokitiol,15 novel hinokitol carboxylic acid esters(3)and 20 hinokitol sulfonate esters(isomers 5 and 6)were designed and synthesized from hinokitiol as a lead compound.The results of fungicidal activity showed that most of the target compounds at 50μg/mL exhibited good fungicidal activity against Valsa mali,Rhizoctonia solani,Botrytis cinerea,and Colletotrichum orbiculare.The EC50 values of 3a,3f,3g,3o against R. solani were 0.96, 1.05, 1.29 and 1.88 μg/mL, respectively, the EC50 values of 3a, 3e and 3j were 3.60, 3.28 and 3.48 μg/mL against V. mali, and the EC50 values of 3d, 3f and 3g were 0.77, 0.51 and 0.67 μg/mL against C. orbiculare, respectively, which were superior to hinokitol. In general, the fungicidal activity of carboxylate derivatives was significantly better than that of sulfonate derivatives. The position isomers of sulfonate derivatives possessed different fungicidal activities, among which the compound with configuration 1 has better activities.