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

Abstract

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

CLC Number:

TQ35

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.

Figures/Tables 2

Fig.1

Table 1

References 20

1	梁文平, 郑斐能, 王仪, 等. 21世纪农药发展的趋势:绿色农药与绿色农药制剂[J]. 农药, 1999, 38 (9): 1- 2.
	LIANG W P , ZHENG P N , WANG Y , et al. The trend of 21st gentury agrochemicals:Green agrochemicals and green agrochemical formulations[J]. Agrochemicals, 1999, 38 (9): 1- 2.
2	潘里, 陈有为, 刘卓, 等. 新型含三唑啉酮的磺酰脲类化合物的合成、晶体结构及除草活性研究[J]. 有机化学, 2013, 33 (3): 542- 550.
	PAN L , CHEN Y W , LIU Z , et al. Synthesis, crystal structure and herbicidal activity of novel sulfonylureas containing triazolinone moiety[J]. Chinese Journal of Organic Chemistry, 2013, 33 (3): 542- 550.
3	童建颖, 石延霞, 刘幸海, 等. 含邻氟苯基的1, 2, 4-三唑类衍生物的合成及杀菌活性研究[J]. 有机化学, 2012, 32 (12): 2373- 2377.
	TONG J Y , SHI Y X , LIU X H , et al. Synthesis and fungicidal activity of 1, 2, 4-triazole derivatives ontaining 2-fluorophenyl moiety[J]. Chinese Journal of Organic Chemistry, 2012, 32 (12): 2373- 2377.
4	TAN C X , SHI Y X , WENG J Q , et al. Synthesis and antifungal activity of novel 1, 2, 4-triazole derivatives containing 1, 2, 3-thiadiazole moiety[J]. Journal of Heterocyclic Chemistry, 2014, 51 (3): 690- 694. doi: 10.1002/jhet.1656
5	朱廷儒, 王素贤, 裴月湖, 等. 中药虎杖抗菌活性成分的研究[J]. 中草药, 1985, 16 (3): 21.
	ZHU T R , WANG S X , PEI Y H , et al. Study on antibacterial active ingredients of Polygonum cuspidatum[J]. Chinese Traditional and Herbal Drugs, 1985, 16 (3): 21.
6	徐艳, 曹松屹, 曲格霆. 大黄抑菌作用的体外研究[J]. 中国中医药信息杂志, 2007, 14 (2): 43- 44. doi: 10.3969/j.issn.1005-5304.2007.02.020
	XU Y , CAO S Y , QU G T . Effect of rheum on restraining bacterium in vitro[J]. Chinese Journal of Information on TCM, 2007, (2): 43- 44. doi: 10.3969/j.issn.1005-5304.2007.02.020
7	蔡可而, 王严飞, 陆豫. 大黄素甲醚衍生物的合成及抗肿瘤活性的研究[J]. 化学试剂, 2014, 36 (4): 313- 314, 377.
	CAI K W , WANG Y F , LU Y . Synthesis and anti-tumor activity of physcion derivatives[J]. Chemical Reagents, 2014, 36 (4): 313- 314, 377.
8	SEMPLE S J , PYKE S M , REYNOLDS G D , et al. In vitro antiviral activity of the anthraquinone chrysophanic acid against poliovirus[J]. Antiviral Research, 2001, 49 (3): 169- 178. doi: 10.1016/S0166-3542(01)00125-5
9	CHANG L C , SHEU H M , HUANG Y S , et al. A novel function of emodin:Enhancement of the nucleotide excision repair of UV-and cisplatin-induced DNA damage in human cells[J]. Biochemical pharmacology, 1999, 58 (1): 49- 57. doi: 10.1016/S0006-2952(99)00075-1
10	薛敏峰, 向礼波, 龚双军, 等. 0.5%大黄素甲醚水剂等药剂对水稻稻瘟病防治效果评价[J]. 湖北植保, 2017, (1): 14- 15, 56. doi: 10.3969/j.issn.1005-6114.2017.01.009
	XUE M F , XIANG L B , GONG S J , et al. 0.5% Other pharmaceutical agent physcion control effect against rice blast evaluation[J]. Hubei Plant Protection, 2017, (1): 14- 15, 56. doi: 10.3969/j.issn.1005-6114.2017.01.009
11	杨宇红, 龚惠之, 杨翠荣, 等. 植物源杀菌剂大黄素甲醚防治黄瓜白粉病研究[J]. 中国蔬菜, 2009, 1 (20): 23- 28.
	YANG Y H , GONG H Z , YANG C R , et al. Control of cucumber powdery mildew with physcion[J]. China Vegetables, 2009, 1 (20): 23- 28.
12	邓丽红, 谢臻, 麦蓝尹, 等. 蒽醌类化合物抗菌活性及其机制研究进展[J]. 中国新药杂志, 2016, 25 (21): 2450- 2455.
	DENG L H , XIE Z , MAI L Y , et al. Advances in studies on antibacterial activity and mechanismof anthraquinone compounds[J]. Chinese Journal of New Drugs, 2016, 25 (21): 2450- 2455.
13	杨森,丁成荣,刘幸海,等.手性芳氧苯氧丙酰胺类化合物的合成及除草活性研究[J/OL].有机化学, 2019, 39: 1-8[2019-07-11].http://kns.cnki.net/kcms/detail/31.1321.O6.20190620.1030.010.html.
	YANG S, DING C R, LIU X H, et al.Synthesis and herbicidal activity of chiral aryloxyphenoxypro-pionic amides compounds[J/OL]. Chinese Journal of Organic Chemistry, 2019, 39: 1-8[2019-07-11]. http://kns.cnki.net/kcms/detail/31.1321.O6.20190620.1030.010.html.
14	董存柱, 郭锦全, 周学明, 等. 山蒟中脂肪链酰胺类化合物的分离及杀虫活性[J]. 农药学学报, 2018, (5): 679- 683.
	DONG C Z , GUO J Q , ZHOU X M , et al. Isolation and insecticidal activity of fatty chain amides from hawthorn[J]. Chinese Journal of Pesticide Science, 2018, (5): 679- 683.
15	黄朋勉, 周智慧, 杜永磊, 等. N-烷氧基取代酰胺类化合物的合成及杀菌活性[J]. 有机化学, 2019, 39 (3): 867- 872.
	HUANG P M , ZHOU Z H , DU Y L , et al. Synthesis and fungicidal activity of N-alkoxyl amide derivatives[J]. Chinese Journal of Organic Chemistry, 2019, 39 (3): 867- 872.
16	贾红圣. 1-苯基-5-苯基吡唑基-3-氧乙酸乙酯的合成及晶体结构[J]. 化工时刊, 2016, 30 (10): 12- 16.
	JIA H S . Synthesis and structure characterization of ethyl-1-phenyl-5-phenylpyrazol-3-oxyacetate[J]. Chemical Industry Times, 2016, 30 (10): 12- 16.
17	YU L H , HUANG D , ZHU X , et al. Design, synthesis, phloem mobility, and bioactivities of a series of phenazine-1-carboxylic acid-amino acid conjugates[J]. Molecules (Basel, Switzerland), 2018, 23 (9): 2139- 2147. doi: 10.3390/molecules23092139
18	NIU J F , NIE D Y , YU D Y , et al. Synthesis, fungicidal activity and phloem mobility of phenazine-1-carboxylic acid-alanine conjugates[J]. Pesticide Biochemistry and Physiology, 2017, 143, 8- 13. doi: 10.1016/j.pestbp.2017.10.004
19	朱春雨,吴新平,徐文平,等.农药室内生物测定试验准则.杀菌剂.第2部分:抑制病原真菌菌丝生长试验.平皿法: NY/T 1156.2-2006[S].北京:中国农业出版社, 2006.
	ZHU, C Y, WU X P, XU W P, et al.Pesticides guidelines for laboratory bioactivity tests Part 2: Petri platetest for deter mining fungicide inhibition of mycelial growth: NY/T1156.2-2006[S]. Beijing: China Agriculture Press, 2006.
20	ZHU X , ZHANG M , YU L H , et al. Synthesis and bioactivities of diamide derivatives containing a phenazine-1-carboxamide scaffold[J]. Natural Product Research, 2019, 33 (17): 1- 8.

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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Synthesis and Fungicidal Activity of Physcion-amino Acid Derivatives

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