三氟羧草醚类似物的合成及除草活性

赵卓然; 李佳康; 李占斌; 陈雨; 黄玉乾; 李文琪; 姬志勤; 魏少鹏

doi:10.16801/j.issn.1008-7303.2022.0019

三氟羧草醚类似物的合成及除草活性

doi: 10.16801/j.issn.1008-7303.2022.0019

赵卓然^1,,
李佳康¹,
李占斌¹,
陈雨¹,
黄玉乾¹,
李文琪¹,
姬志勤^{1, 2},
魏少鹏^{1, 2, ,}

1.
西北农林科技大学植物保护学院，陕西杨凌 712100
2.
陕西省植物源农药研究与开发重点实验室，陕西杨凌 712100

基金项目: 国家自然科学基金(31872011).

详细信息

作者简介:
赵卓然，zhaozhuoran@nwafu.edu.cn

通讯作者:
魏少鹏，weishaopeng@nwsuaf.edu.cn.

中图分类号: O625.5；TQ450.11
计量
- 文章访问数: 45
- HTML全文浏览量: 20
- PDF下载量: 5
- 被引次数: 0
出版历程
- 收稿日期: 2021-11-03
- 录用日期: 2022-01-21
- 网络出版日期: 2022-03-01

Synthesis and herbicidal activity of acifluorfen analogues

1.
College of Plant Protection, Northwest A&F University, Yangling 712100, Shaanxi Province, China
2.
Shaanxi Province Key Laboratory Research & Development on Botanical Pesticides, Yangling 712100, Shaanxi Province, China

Funds: the National Natural Science Foundation of China (31872011).

摘要

摘要: 以2,5-二羟基苯甲酸甲酯和三氟羧草醚为起始原料，设计合成了3个系列20个新的三氟羧草醚类似物，通过核磁共振氢谱、碳谱对其结构进行了表征。分别采用小杯法和室内盆栽法测定了目标化合物的除草活性。结果表明，化合物 III-02 [5-(2-氯-4-三氟甲基苯氧基)-2-硝基苯甲酸-(6-甲基苯并噻唑-2-基)酯]对单子叶杂草的除草活性明显高于对照药剂三氟羧草醚，其对稗草Echinochloa crusgalli和马唐Digitaria sanguinalis根茎生长的EC₅₀值分别为2.03、0.93 μg/mL和1.49、0.52 μg/mL；在有效成分100 g/hm²的施药剂量下，化合物 III-02 对单子叶杂草稗草、马唐及狗尾草Setaria viridis的防治效果均在85%以上，明显高于三氟羧草醚，对阔叶杂草马齿苋Portulaca oleracea、反枝苋Amaranthus retroflexus及苘麻Abutilon theophrasti的防治效果可达100%。初步构效关系表明，2-硝基苯甲酰衍生物的除草活性明显优于其2-甲氧基衍生物，三氟羧草醚苯甲酸酯衍生物对单子叶杂草的除草活性明显高于其苯甲酰胺衍生物。
- 三氟羧草醚 /
- 类似物 /
- 合成 /
- 除草活性 /
- 构效关系
Abstract: Three series of twenty new acifluorfen analogues were designed and synthesized using methyl 2,5-dihydroxybenzoate and acifluorfen as starting materials. Their structures were characterized by ¹H NMR and¹³C NMR. The herbicidal activities of the compounds were determined by methods of petri dish and greenhouse potted. The results showed that the herbicidal activity of compound III-02 [6-methylbenzo[d]thiazol-2-yl 5-(2-chloro-4-(trifluoromethyl)phenoxy)-2-nitrobenzoate] against monocotyledonous weeds was significantly higher than that of acifluorfen, and its EC₅₀ values were 2.03, 0.93 μg/mL and 1.49, 0.52 μg/mL against the roots and stems of Echinochloa crusgalli and Digitaria sanguinalis, respectively. Additionally, at the dosage of 100 g a.i./ha, the efficacy of compound III -02 against monocotyledonous weeds E. crusgalli, S. sanguinalis and Setaria viridis was above 85%, which was significantly higher than that of acifluorfen, and a 100% control effect on broadleafs Portulaca oleracea, Amaranthus retroflexus and Abutilon theophrasti. The structure-activity relationship showed that the herbicidal activity of 2-NO₂ benzoyl derivatives was significantly higher than that of 2-OCH₃ analogues, and the herbicidal activity of acifluorfen benzoate derivatives against monocotyledons was significantly higher than that of benzamide derivatives.
- acifluorfen /
- analogues /
- synthesis /
- herbicidal activity /
- SAR

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1 化合物A27、I-00、氟吡酰草胺和三氟羧草醚的化学结构式

1. The structural formulas of A27, I-00, picolinafen and acifluorfen

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2 目标化合物I-01~I-06的合成路线

2. The synthetic routes of target compounds I-01 to I-06

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3 目标化合物II-01~II-10和III-01~III-04的合成路线

3. The synthetic routes of target compounds II-01 to II-10 and III-01 to III-04

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表 1 目标化合物中取代基R的结构

Table 1. The structural formulas of target compounds

化合物 Compd.	R	化合物 Compd.	R	化合物 Compd.	R	化合物 Compd.	R
I-01	—	I-06		II-05	4-Cl	II-10	6-Br
I-02		II-01	—	II-06	6-Me	III-01	H
I-03		II-02	H	II-07	6-OMe	III-02	6-Me
I-04		II-03	4-Me	II-08	6-OEt	III-03	6-Cl
I-05		II-04	4-OMe	II-09	6-Cl	III-04	6-Br

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表 2 目标化合物在5.0 μg/mL下的除草活性 (小杯法)

Table 2. Herbicidal activities of target compounds at 5.0 μg/mL (petri dish assay)

化合物 Compounds	抑制率 Inhibition rate/%^*
	稗草 E. crusgalli	马唐 D. sanguinalis	马齿苋 P. oleracea	野油菜 B. juncea
	根/茎 Root/Stem	根/茎 Root/Stem	根/茎 Root/Stem	根/茎 Root/Stem
I-01	3.2/8.6	4.8/11.9	14.5/30.9	17.2/31.1
I-02	2.3/7.1	2.0/5.6	12.9/36.8	20.7/49.8
I-03	1.7/5.1	3.7/8.4	6.7/21.5	10.9/25.6
I-04	3.5/9.9	7.2/17.1	16.3/40.1	26.5/58.8
I-05	0.2/1.2	4.7/9.3	15.0/39.4	5.9/21.5
I-06	1.6/4.5	2.5/6.6	6.2/23.3	3.5/9.3
II-01	13.2/34.0	85.0/93.4	100/100	96.9/97.6
II-02	4.3/11.7	10.3/19.2	100/100	96.2/100
II-03	0.2/1.3	2.7/6.5	11.8/30.2	10.4/29.9
II-04	5.9/20.6	3.8/9.1	80.3/85.9	89.2/94.5
II-05	1.0/3.2	3.0/6.7	23.8/58.5	32.6/69.4
II-06	2.8/9.1	13.9/22.0	98.3/99.2	100/100
II-07	6.5/22.6	5.2/11.1	10.4/36.8	12.5/41.9
II-08	4.7/20.3	0.2/1.2	71.7/75.9	77.2/79.2
II-09	5.6/13.5	6.2/15.9	20.2/46.5	22.8/54.9
II-10	3.3/12.8	10.8/22.2	80.6/83.9	97.0/97.5
III-01	10.8/32.1	87.2/91.4	100/100	100/100
III-02	72.7/85.5	90.3/96.9	100/100	100/100
III-03	20.6/42.9	16.0/41.2	100/100	100/100
III-04	59.8/74.6	76.5/87.9	100/100	100/100
三氟羧草醚 acifluorfen	52.5/64.7	47.7/65.8	100/100	100/100
注：^表中数据为 3 次重复平均值。Note: ^ The data in the table is the average of the three repeats.

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表 3 部分化合物对四种供试杂草的EC₅₀值

Table 3. EC₅₀ value of selected compounds against four tested weeds

化合物 Compound		EC₅₀值 (95% 置信区间) EC₅₀ value (95% confidence interval)/(μg/mL)
化合物 Compound		稗草 E. crusgalli	马唐 D. sanguinalis	马齿苋 P. oleracea	野油菜 B. juncea
II-01	茎 Stem	7.48(5.67~9.88)	1.14(0.99~1.31)	0.14(0.11~0.18)	0.50(0.40~0.63)
II-01	根 Root	12.56(11.51~13.72)	1.67(1.45~1.92)	0.23(0.18~0.30)	0.54(0.42~0.71)
III-01	茎 Stem	8.60(6.65~11.12)	1.46(1.28~1.66)	0.12(0.10~0.15)	0.38(0.29~0.50)
III-01	根 Root	13.13(12.03~14.34)	1.53(1.33~1.77)	0.20(0.16~0.24)	0.43(0.35~0.54)
III-02	茎 Stem	0.93(0.74~1.17)	0.52(0.43~0.63)	0.07(0.06~0.09)	0.26(0.20~0.35)
III-02	根 Root	2.03(1.71~2.42)	1.49(1.30~1.70)	0.14(0.11~0.18)	0.32(0.25~0.41)
III-03	茎 Stem	5.88(4.78~7.23)	6.38(4.85~8.40)	0.21(0.16~0.26)	0.61(0.49~0.75)
III-03	根 Root	10.72(9.68~11.87)	15.90(13.88~18.25)	0.21(0.17~0.27)	0.62(0.49~0.79)
III-04	茎 Stem	1.97(1.59~2.43)	2.03(1.79~2.31)	0.10(0.08~0.12)	0.34(0.27~0.42)
III-04	根 Root	3.61(3.10~4.19)	3.77(3.41~4.17)	0.18(0.15~0.23)	0.42(0.32~0.54)
三氟羧草醚 acifluorfen	茎 Stem	3.29(2.88~3.77)	3.92(3.45~4.44)	0.09(0.07~0.11)	0.31(0.24~0.39)
三氟羧草醚 acifluorfen	根 Root	4.33(3.67~5.11)	5.77(4.94~6.75)	0.17(0.14~0.20)	0.35(0.28~0.44)

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表 4 部分化合物苗后处理的除草活性

Table 4. Post-emergence herbicidal activity of selected compounds

化合物 Compound	剂量 Dose, a.i./ (g/hm²)	防治效果 Control efficacy/%
化合物 Compound	剂量 Dose, a.i./ (g/hm²)	稗草 E. crusgalli	马唐 D. sanguinalis	狗尾草 S. viridis	马齿苋 P. oleracea	反枝苋 A. retroflexus	苘麻 A. theophrasti
II-01	100	41.2 ± 2.1 f	87.4 ± 1.2 bc	58.1 ± 2.2 d	85.2 ± 2.0 b	75.2 ± 2.5 c	80.8 ± 2.4 d
II-01	50	23.3 ± 1.8 g	73.3 ± 1.9 d	41.3 ± 3.8 f	73.6 ± 3.2 c	66.3 ± 1.8 d	71.2 ± 2.3 e
III-01	100	43.0 ± 2.1 f	82.7 ± 2.0 c	44.4 ± 3.4 f	100 ± 0.0 a	100 ± 0.0 a	91.2 ± 1.5 c
III-01	50	20.5 ± 1.3 g	72.1 ± 1.6 d	33.4 ± 2.2 g	100 ± 0.0 a	100 ± 0.0 a	79.5 ± 2.3 d
III-02	100	88.7 ± 1.2 a	92.8 ± 2.5 a	87.5 ± 2.4 a	100 ± 0.0 a	100 ± 0.0 a	100 ± 0.0 a
III-02	50	74.0 ± 3.1 b	89.6 ± 1.6 ab	73.2 ± 2.8 b	100 ± 0.0 a	100 ± 0.0 a	100 ± 0.0 a
III-03	100	51.9 ± 1.7 e	52.1 ± 3.6 f	50.2 ± 2.3 e	100 ± 0.0 a	87.9 ± 1.4 b	91.1 ± 3.1 c
III-03	50	43.1 ± 2.4 f	45.5 ± 2.5 g	42.1 ± 1.4 f	100 ± 0.0 a	72.0 ± 2.1 c	81.2 ± 1.7 d
III-04	100	76.1 ± 1.5 b	75.5 ± 2.7 d	65.1 ± 3.7 c	100 ± 0.0 a	96.9 ± 3.3 a	93.7 ± 2.7 bc
III-04	50	60.6 ± 2.3 d	62.6 ± 2.1 e	53.5 ± 1.9 de	100 ± 0.0 a	87.8 ± 3.0 b	83.0 ± 2.4 d
三氟羧草醚 acifluorfen	100	64.9 ± 1.6 c	86.3 ± 2.5 bc	69.4 ± 1.1 bc	100 ± 0.0 a	100 ± 0.0 a	100 ± 0.0 a
三氟羧草醚 acifluorfen	50	53.7 ± 1.2 e	70.8 ± 1.6 d	53.9 ± 2.0 de	100 ± 0.0 a	100 ± 0.0 a	96.6 ± 2.6 ab
注: 表中数据为 3 次重复平均值 ± 标准偏差。不同字母表示经Duncan’s新复极差测验, 在 P_0.05水平差异显著。
Note: Data in the table are mean ± SD, and repeated for three times. Different letters indicate that there are significant differences at the level of P_0.05 after Duncan’s multiple range test.

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