细交链孢菌酮酸及其衍生物的合成与杀虫活性

尤伟晨; 刘小雨; 刘现坤; 柴源卿; 王晓菲; 吕培; 花日茂

doi:10.16801/j.issn.1008-7303.2022.0001

细交链孢菌酮酸及其衍生物的合成与杀虫活性

doi: 10.16801/j.issn.1008-7303.2022.0001

1.
安徽农业大学资源与环境学院，合肥 230036

基金项目: 国家自然科学基金青年基金项目(31901906)；安徽省省级大学生创新创业训练计划项目(S202010364275).

详细信息

作者简介:
尤伟晨，you19950720@163.com

通讯作者:
吕培，lvpei@ahau.edu.cn.

中图分类号: O626.1；TQ450.11
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- 文章访问数: 643
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- 被引次数: 0
出版历程
- 收稿日期: 2021-07-16
- 录用日期: 2021-08-08
- 网络出版日期: 2022-03-06
- 刊出日期: 2022-04-01

Synthesis and insecticidal activity of tenuazonic acid and derivatives

1.
College of Resources and Environment, Anhui Agricultural University, Hefei 230036, China

Funds: the National Natural Science Foundation of China (31901906) and College student innovation and entrepreneurship training program of Anhui Province (S202010364275).

摘要

摘要: 为了寻找具有较高杀虫活性的特胺酸化合物，以天然活性产物细交链孢菌酮酸(TeA)作为先导化合物，利用酰基化米氏酸作为酰基化试剂，设计、合成了26个3-位不同酰基取代和5-位不同取代的含特胺酸骨架衍生物 4a~4s、5a~5g、7a 和 8a ，其中14个化合物未见文献报道，所有目标化合物的结构均经核磁共振氢谱、碳谱和高分辨质谱确证。初步杀虫活性测定结果表明，在100 μg/mL下处理72 h内，所有目标化合物对麦长管蚜Macrosiphum avenae (Fabricius)均表现出良好的杀虫活性，并具有内吸性，其中化合物 5d 和 7a 48 h致死率为100%，高于对照药剂螺虫乙酯，具有作为先导化合物进一步研究的价值。对处理后的小麦植株进行残留量测定，结果表明目标化合物 4e、5c、7a 和 8a 能被植株较好的吸收。该研究结果可为进一步研究具有特胺酸骨架化合物的构效关系提供参考。
- 特胺酸 /
- 细交链孢菌酮酸 /
- 衍生物 /
- 杀虫活性 /
- 构效关系
Abstract: In order to find tetramic acids with high insecticidal activity, the natural product tenuazonic acid (TeA) was used as lead compound, 26 tetramic acid derivatives 4a-4s , 5a-5g , 7a and 8a were designed and synthesized using acyl Meldrum's acid as acylation reagent with different substituted groups of tetramic acids at 3-position and 5-position, in which fourteen target compounds were not reported in the literature. The target compounds were confirmed by ¹H NMR, ¹³C NMR and HRMS. The preliminary insecticidal activity eveluation showed that the target compounds had good insecticidal activity against wheat aphids (Macrosiphum avenae (Fabricius)) with systemic action at 100 μg/mL concentration for 72 h. Compounds 5d and 7a showed excellent insecticidal activities with the lethal rate of 100% in 48 h at the concentration of 100 μg/mL, which was higher than that of spirotetramat. 5d and 7a could be used as lead compounds for further research. The residues of 4e , 5c , 7a and 8a in wheat plants showed that the target compounds could be well absorbed. The study may provide a guideline of further studies on for structure-insecticidal activity relationships of tetramic acid derivatives.
- tetramic acids /
- tenuazonic acid /
- derivatives /
- insecticidal activity /
- structure-insecticidal activity relationship

HTML全文

1 3-酰基特胺酸的生物合成^[4]

1. Biosynthetic route of 3-acylated tetramic acid^[4]

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2 TeA (1) 及其5R, 6S-异构体 (2) 的结构

2. Structures of tenuazonic acid and its 5R,6S-isomer

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3 目标化合物4a~4s和5a~5g的合成路线

3. The synthetic route of the target compounds 4a-4s and 5a-5g

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4 目标化合物7a和8a的合成路线

4. The synthetic route of the target compounds 7a and 8a

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5 3-酰基特胺酸互变异构^[18]

5. Tautomerism of 3-acylated tetramic acid^[18]

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表 1 目标化合物的质谱分析参数

Table 1. Mass spectrometry parameters of target compounds

化合物 Compd	保留时间 Retention time/min	母离子 Precursor ion, m/z	子离子 Product ion, m/z	驻留时间 Dwell time/s	锥孔电压 Declustering potential/V	碰撞能量 Collision energy/eV
4e	2.38	198.07	96.7	0.05	50	18
4e	2.38	198.07	138.8	0.05	50	16
5c	3.40	252.12	153.92	0.05	50	20
5c	3.40	252.12	177.89	0.05	50	22
7a	2.58	311.95	158.78	0.05	50	34
7a	2.58	311.95	196.62	0.05	50	26
8a	4.06	410.03	70.88	0.05	50	16
8a	4.06	410.03	311.9	0.05	50	16

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表 2 目标化合物在100 μg/mL下对麦蚜的杀虫活性

Table 2. Insecticidal activity of target compounds against wheat aphid under the concentration of 100 μg/mL

化合物 Compd.	校正死亡率 Corrected mortality/%
化合物 Compd.	24 h	48 h	72 h
4a	0	7	50
4b	0	17	72
4c	0	62	94
4d	0	41	90
4e	0	41	98
4f	0	68	90
4g	0	44	58
4h	0	55	82
4i	2	37	94
4j	3	38	72
4k	2	24	76
4l	30	70	91
4m	3	64	94
4n	0	72	100
4o	3	47	78
4p	4	66	94
4q	39	77	100
4r (TeA)	48	86	97
4s	44	81	100
5a	46	88	96
5b	82	68	94
5c	35	94	100
5d	77	100
5e	44	97	100
5f	54	73	100
5g	62	78	100
7a	1	100
8a	17	93	100
螺虫乙酯 spirotetramat	41	90	100

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表 3 目标化合物在麦苗中的平均添加回收率和相对标准偏差 (RSD) (n = 5)

Table 3. The average recoveries and RSD of target compounds in wheat seedlings (n = 5)

化合物 Compd.	添加水平 Spiked level/(mg/kg)	平均回收率 Average recovery/%	相对标准偏差 RSD/%
4e	10	95	0.4
	100	101	0.7
	500	100	2.4
5c	10	99	0.4
	100	101	0.5
	500	101	0.9
7a	10	110	0.06
	100	101	0.09
	500	96	2.3
8a	10	97	0.08
	100	101	0.2
	500	99	0.4

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表 4 目标化合物在麦苗中的残留量

Table 4. Residue of target compounds in wheat seedlings

化合物 Compd.	线性回归方程 Linear regression equation	决定系数 R²	残留量 Residue/(mg/kg)
4e	y=9538023.74x ‒ 5889.38	1.00	13.58
5c	y=39382191.04x ‒ 131984.32	1.00	22.67
7a	y=32284991.98x + 19998.06	1.00	0.97
8a	y=1358715.13x + 24016.24	1.00	358.52

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