大黄素甲醚氨基酸衍生物的合成及其杀菌活性

doi:10.3969/j.issn.0253-2417.2020.01.016

摘要/Abstract

摘要：

为寻找具有高杀菌活性的新型蒽醌类化合物，通过活性亚结构拼接的方法，经醚化水解和酰氯化反应，将氨基酸片段引入先导化合物大黄素甲醚中，合成了一系列结构新颖的酰胺衍生物2a~6p，目标化合物的结构均经过¹H NMR和HRMS确证。研究结果表明：在0.2 mmoL/L下，目标化合物对6种植物病原菌表现出不同程度的抑菌活性，其中1（8）-大黄素甲醚氧乙酰基亮氨酸（6e）对水稻纹枯病菌和香樟炭疽病菌的抑制率最高，分别为69.93%和67.18%；1（8）-大黄素甲醚氧乙酰基甘氨酸乙酯（5a）、1（8）-大黄素甲醚氧乙酰基甘氨酸（6a）与1（8）-大黄素甲醚氧乙酰基苯丙氨酸（6c）对水稻纹枯病菌的活性较好，抑制率分别为60.51%、53.28%和58.50%；化合物6a和6c对香樟炭疽病菌的抑制率分别为49.25%和47.61%；均显著优于先导化合物大黄素甲醚。初步构效关系分析表明：在大黄素甲醚的羟基位置上引入氨基酸可增强其对水稻纹枯病菌、水稻稻瘟病菌、菜菌核病菌、草莓灰霉病菌、烟草赤星病菌和香樟炭疽病菌的抑菌活性。

关键词: 蒽醌, 合成, 酰胺, 抑菌活性

Abstract:

In order to find novel anthraquinone compounds with high fungicidal activity, a series of novel physcion-amino acid derivatives 2a-6p were designed and synthesized by introducing the amino acids into the lead compound physcion by etherification, hydrolysis and acid chloride reaction according to the method of active substructure combination. The structures of the target compounds were confirmed by ¹H NMR and HRMS. The preliminary bioassay data showed that all the target products exhibited certain fungicidal activities against the six kinds of plant pathogens at 0.2 mmoL/L. Compounds 6e had the highest inhibitory activities against Rhizoctonia solani and Colletotrichum gloeosporioides with 69.93% and 67.18%, respectively. Compounds 5a, 6a and 6c had moderate inhibitory activities against R. solani with 60.51%, 53.28% and 58.50%, respectively. The inhibitory activities of compounds 6a and 6c against C. gloeosporioides were 49.25% and 47.61%, respectively. The above compounds showed significantly higher fungicidal activities than the lead compound physcion. The preliminary analysis of structure effective relationship showed that the introduction of amino acids at the hydroxyl position of physcion could enhance its fungicidal activity against R. solani, Pyricularia oryzae, Sclerotinia sclerotiorum, Botrytis cinerea Alteraria alternate and C. gloeosporioide.

Key words: anthraquinone, synthesis, amide, fungicidal activity

中图分类号:

TQ35

孟振国,朱祥,赵炽娜,常悦,吴清来,李俊凯. 大黄素甲醚氨基酸衍生物的合成及其杀菌活性[J]. 林产化学与工业, 2020, 40(1): 113-119.

Zhenguo MENG,Xiang ZHU,China ZHAO,Yue CHANG,Qinglai WU,Junkai LI. Synthesis and Fungicidal Activity of Physcion-amino Acid Derivatives[J]. Chemistry and Industry of Forest Products, 2020, 40(1): 113-119.

图/表 2

图1

表1

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化合物 compourd	水稻纹枯病菌 R. solani	水稻稻瘟病菌 P. oryzae	油菜菌核病菌 S.asclerotiorum	草莓灰霉病菌 B. cinerea	烟草赤星病菌 A. alternata	香樟炭疽病菌 C. gloeosporioides
2a	(43.64±0.07)^f	—	—	—	(23.44±0.27)^cd	(38.78±0.34)^e
3a	(48.18±0.06)^e	(15.48±0.52)^g	(43.24±0.01)^a	(15.93±0.11)^d	(25.81±0.26)^b	(36.85±0.14)^f
5a	(60.51±0.17)^b	(16.04±0.33)^f	(25.17±0.12)^de	—	(18.88±0.55)^ghi	(35.20±0.23)^g
5b	(32.34±0.06)^m	(21.09±0.12)^b	—	—	(18.40±0.33)ⁱ	(35.93±0.18)^fg
5c	(31.76±0.04)^m	—	—	—	(16.30±1.65)^k	(34.92±0.17)^g
5d	(24.95±0.20)ⁿ	(26.02±0.33)^a	(24.36±0.35)^e	—	(19.38±0.20)^ghi	(37.12±0.20)^f
5e	(40.79±0.03)^h	(16.35±0.09)^ef	(16.38±0.83)^j	—	(18.47±0.30)^hi	(27.85±0.14)ⁱ
5f	(36.19±0.05)^l	(16.23±0.56)^ef	(31.57±0.16)^b	—	(18.37±0.60)ⁱ	(31.75±0.18)^h
5g	(39.30±0.08)^j	—	(17.56±0.17)ⁱ	—	(21.58±0.21)^ef	(36.06±0.16)^fg
5h	(40.26±0.24)^hi	—	(15.18±0.30)^l	—	(17.51±0.32)^j	(31.22±0.24)^h
5i	(42.05±0.01)^g	(18.20±0.36)^c	—	—	(19.51±0.06)^gh	(26.21±0.15)^j
6a	(53.28±0.28)^d	(16.55±0.56)^e	(15.77±0.44)^k	—	(21.50±0.21)^ef	(49.25±0.12)^b
6b	(48.76±0.34)^e	(17.55±0.21)^d	(21.12±0.16)^g	(16.77±0.76)^c	(19.66±0.20)^g	(39.42±0.38)^e
6c	(58.50±0.21)^c	(20.76±0.37)^b	(25.99±0.22)^cd	(19.78±0.25)^b	(21.09±0.09)^f	(47.61±0.63)^c
6d	(43.06±0.34)^f	—	(22.45±0.45)^f	—	(15.21±0.66)^l	(19.22±0.45)^k
6e	(69.93±0.04)^a	(25.35±0.17)^a	(31.32±0.18)^b	(28.74±0.16)^a	(35.60±0.08)^a	(67.18±0.21)^a
6f	(37.64±0.41)^k	(20.62±0.35)^b	(27.05±0.14)^c	(19.90±0.30)^b	(22.63±0.10)^de	(45.37±0.10)^d
6g	(40.43±0.37)^hi	(20.82±0.23)^b	(20.20±0.21)^h	—	(19.56±0.33)^gh	(35.27±0.25)^g
6h	(39.79±0.16)^ij	(20.78±0.43)^b	(25.31±0.09)^de	—	(24.74±0.11)^bc	(26.06±0.30)^j
大黄素甲醚physcion	(28.70±0.08)^f	—	—	—	—	—
空白对照CK	0	0	0	0	0	0

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