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N-((5-烷硫基-1,3,4-噁二唑)-2-基)甲基溴代吡咯腈的合成及生物活性

周蒲 黄俊杰 何昌文 郭倩男 游江 刘一凡 徐志红

周蒲, 黄俊杰, 何昌文, 郭倩男, 游江, 刘一凡, 徐志红. N-((5-烷硫基-1,3,4-噁二唑)-2-基)甲基溴代吡咯腈的合成及生物活性[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0065
引用本文: 周蒲, 黄俊杰, 何昌文, 郭倩男, 游江, 刘一凡, 徐志红. N-((5-烷硫基-1,3,4-噁二唑)-2-基)甲基溴代吡咯腈的合成及生物活性[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0065
ZHOU Pu, HUANG Junjie, HE Changwen, GUO Qiannan, YOU Jiang, LIU Yifan, XU Zhihong. Synthesis and biological activity of N-((5-alkylthio-1,3,4-oxadiazole)-2-ylmethyl) tralopyril[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0065
Citation: ZHOU Pu, HUANG Junjie, HE Changwen, GUO Qiannan, YOU Jiang, LIU Yifan, XU Zhihong. Synthesis and biological activity of N-((5-alkylthio-1,3,4-oxadiazole)-2-ylmethyl) tralopyril[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0065

N-((5-烷硫基-1,3,4-噁二唑)-2-基)甲基溴代吡咯腈的合成及生物活性

doi: 10.16801/j.issn.1008-7303.2022.0065
基金项目: 国家自然科学基金 (31772170).
详细信息
    作者简介:

    周蒲,445826340@qq.com

    黄俊杰,huangjunjie58@163.com

    通讯作者:

    徐志红,x_u_78@sina.com

  • 中图分类号: O626.27;TQ450.11

Synthesis and biological activity of N-((5-alkylthio-1,3,4-oxadiazole)-2-ylmethyl) tralopyril

Funds: National Natural Science Foundation of China (31772170).
  • 摘要: 为了发现农药活性的新化合物,以溴代吡咯腈为原料,通过亲核取代、肼解和成环等反应,设计合成了一系列N-((5-烷硫基-1,3,4-噁二唑)-2-基)甲基溴代吡咯腈目标化合物( 5a ~ 5t ),所有化合物的结构均得到核磁共振氢谱和高分辨质谱确证。杀菌活性测定结果显示:在浓度为0.20 mmol/L时,大部分目标化合物具有一定的抑菌活性,其中化合物 5h 对水稻稻瘟病菌Magnaporthe oryzae的抑制率为60.07%,优于对照药剂咯菌腈(58.21%)。杀虫与杀螨活性测定结果显示:在浓度为0.20 mmol/L时,大部分目标化合物对斜纹夜蛾Spodoptera litura和朱砂叶螨Tetranychus cinnabarinus雌成螨具有一定的杀虫和杀螨活性,但均低于对照药剂虫螨腈(100%)。杀线虫生物测定结果显示:在浓度为0.20 mmol/L时,大部分目标化合物表现出优异的杀线虫活性,其中化合物 5k5r5s 对秀丽隐杆线虫Caenorhabditis elegans的LC50值分别为0.0918、0.0733和0.0810 mmol/L,优于对照药剂噻唑膦(0.2798 mmol/L)。本研究所合成的目标化合物具有一定的杀菌、杀虫、杀螨和杀线虫活性,可为溴代吡咯腈衍生物的设计和合成提供参考。
  • 1  目标化合物的合成路线

    1.  Synthetic routes of target compounds

    表  1  目标化合物对5种植物病原菌菌丝生长的抑制作用

    Table  1.   Inhibition of target compounds against five pathogenic fungi in vitro

    化合物
    Compound
    抑制率 Inhibition rate/%
    水稻纹枯病菌
    Rhizoctonia solani
    油菜菌核病菌
    Sclerotinia sclerotiorum
    玉米小斑病菌
    Bipolaris maydis
    香樟炭疽病菌
    Colletotrichum gloeosporioides
    水稻稻瘟病菌
    Magnaporthe oryzae
    243.08 ± 2.0567.62 ± 1.8835.11 ± 1.7539.85 ± 0.6581.72 ± 0.65
    457.71 ± 0.6877.05 ± 0.7137.79 ± 2.3871.05 ± 1.7220.52 ± 1.94
    5a3.95 ± 0.0016.39 ± 3.2513.74 ± 0.6614.66 ± 0.6523.13 ± 0.65
    5b21.34 ± 1.377.79 ± 2.1319.08 ± 0.6612.03 ± 1.1313.43 ± 1.71
    5c0.40 ± 1.198.20 ± 3.0918.70 ± 3.445.64 ± 2.3516.42 ± 2.82
    5d1.58 ± 2.0513.52 ± 2.5620.99 ± 1.9813.53 ± 0.6523.13 ± 1.71
    5e1.19 ± 2.4715.98 ± 3.5516.03 ± 2.389.40 ± 0.6517.16 ± 2.24
    5f12.65 ± 1.3725.82 ± 1.4210.31 ± 2.6411.28 ± 0.6517.16 ± 1.12
    5g9.09 ± 0.6812.70 ± 1.2310.69 ± 1.157.52 ± 1.1318.66 ± 2.33
    5h11.86 ± 1.8129.51 ± 2.8431.68 ± 0.6616.54 ± 1.1360.07 ± 0.65
    5i9.88 ± 1.1913.11 ± 2.8419.85 ± 1.9810.53 ± 2.3524.63 ± 1.71
    5j3.56 ± 0.689.84 ± 1.884.58 ± 1.752.26 ± 0.656.34 ± 0.65
    5k0.40 ± 3.146.15 ± 1.423.82 ± 1.156.02 ± 0.6511.57 ± 2.24
    5l1.58 ± 1.193.69 ± 1.428.02 ± 2.389.40 ± 1.308.58 ± 0.65
    5m4.35 ± 0.6826.23 ± 3.258.78 ± 3.3114.66 ± 0.6523.13 ± 1.29
    5n9.49 ± 1.3716.80 ± 1.8814.89 ± 0.666.77 ± 0.6510.82 ± 0.65
    5o24.90 ± 3.4223.77 ± 3.6912.74 ± 0.6612.78 ± 1.7217.54 ± 2.82
    5p16.09 ± 2.6717.21 ± 3.763.82 ± 1.159.77 ± 1.1317.91 ± 2.33
    5q9.09 ± 0.6812.70 ± 2.131.53 ± 1.159.02 ± 1.7219.79 ± 0.65
    5r15.42 ± 0.689.43 ± 1.8812.21 ± 1.3213.53 ± 0.6522.39 ± 2.33
    5s11.86 ± 1.3710.25 ± 0.001.53 ± 1.154.89 ± 1.3015.3 ± 0.65
    5t4.74 ± 1.3713.11 ± 0.714.58 ± 2.889.02 ± 0.655.60 ± 1.71
    溴代吡咯腈
    tralopyril
    61.66 ± 2.7488.11 ± 0.7185.88 ± 1.3266.54 ± 0.65100.00 ± 0.00
    咯菌腈
    fludioxonil
    100.00 ± 0.00100.00 ± 0.00100.00 ± 0.0076.69 ± 0.6558.21 ± 0.65
    注:每个处理重复 3 次 (平均值 ± 标准差)。化合物浓度为 0.20 mmol/L。
    Note: Each treatment had three replicates (Mean ± SD). Inhibition rate was measured at a concentration of 0.20 mmol/L.
    下载: 导出CSV

    表  2  目标化合物对斜纹夜蛾杀虫活性

    Table  2.   Insecticidal activity of target compounds against Spodoptera litura

    化合物
    Compound
    校正死亡率
    Corrected mortality/%
    化合物
    Compound
    校正死亡率
    Corrected mortality/%
    2 15.56 ± 5.09 5j 23.33 ± 2.89
    4 100.00 ± 0.00 5k 0.00 ± 0.00
    5a 0.00 ± 0.00 5l 18.65 ± 5.63
    5b 0.00 ± 0.00 5m 23.48 ± 4.73
    5c 36.67 ± 5.77 5n 26.67 ± 2.89
    5d 13.43 ± 2.89 5o 12.63 ± 1.59
    5e 29.52 ± 0.82 5p 19.63 ± 2.80
    5f 12.04 ± 0.80 5q 13.33 ± 5.77
    5g 0.00 ± 0.00 5r 10.83 ± 1.44
    5h 36.94 ± 3.37 5s 13.10 ± 1.03
    5i 0.00 ± 0.00 5t 14.48 ± 2.09
    溴代吡咯腈 tralopyril 100.00 ± 0.00 虫螨腈 chlorfenapyr 100.00 ± 0.00
    注:每个处理重复3次 (平均值 ± 标准差)。化合物浓度为0.20 mmol/L。Note: Each treatment had three replicates (Mean ± SD). Corrected mortality was measured at a concentration of 0.20 mmol/L.
    下载: 导出CSV

    表  3  化合物4对斜纹夜蛾的 LC50

    Table  3.   The LC50 value of compound 4 against Spodoptera litura

    化合物
    Compound
    回归方程
    Regression equation
    相关系数
    Correlation coefficient, r
    LC50/(mmol/L)95% 置信限
    95% Confidence limit/(mmol/L)
    4y = 9.4038 + 4.6278x0.97750.11180.0990~0.1263
    虫螨腈 chlorfenapyry = 14.9148 + 4.4421x0.95650.00590.0049~0.0070
    下载: 导出CSV

    表  4  目标化合物对朱砂叶螨雌成螨杀螨活性

    Table  4.   Insecticidal activity of some target compounds against adult mite of Tetranychus cinnabarinus

    化合物
    Compound
    校正死亡率
    Corrected mortality/%
    化合物
    Compound
    校正死亡率
    Corrected mortality/%
    2 31.47 ± 2.73 5j 15.37 ± 1.21
    4 0.00 ± 0.00 5k 15.27 ± 1.71
    5a 2.30 ± 1.99 5l 9.26 ± 0.67
    5b 2.56 ± 2.27 5m 31.05 ± 2.39
    5c 3.96 ± 1.53 5n 7.72 ± 2.00
    5d 4.53 ± 1.67 5o 6.31 ± 2.37
    5e 5.88 ± 2.03 5p 11.91 ± 3.01
    5f 6.91 ± 3.33 5q 9.29 ± 1.89
    5g 5.27 ± 2.00 5r 9.18 ± 2.78
    5h 30.69 ± 1.61 5s 9.94 ± 3.60
    5i 7.95 ± 3.92 5t 10.41 ± 0.99
    溴代吡咯腈
    tralopyril
    94.79 ± 1.96 虫螨腈
    chlorfenapyr
    100.00 ± 0.00
    注:每个处理重复3次 (平均值 ± 标准差)。化合物浓度为0.20 mmol/L。Note: Each treatment had three replicates (Mean ± SD). Corrected mortality was measured at a concentration of 0.20 mmol/L.
    下载: 导出CSV

    表  5  目标化合物对秀丽隐杆线虫杀线虫活性

    Table  5.   Nematicidal activity of target compunds against C. elegans

    化合物
    Compound
    校正死亡率%
    Corrected mortality/%
    化合物
    Compound
    校正死亡率%
    Corrected mortality/%
    2 100.00 ± 0.00 5j 31.18 ± 3.39
    4 25.19 ± 4.81 5k 85.14 ± 2.78
    5a 77.16 ± 3.59 5l 79.54 ± 4.00
    5b 73.50 ± 3.18 5m 29.54 ± 2.10
    5c 63.24 ± 1.20 5n 41.22 ± 2.14
    5d 30.74 ± 1.45 5o 49.00 ± 6.51
    5e 25.65 ± 1.65 5p 50.66 ± 2.68
    5f 51.34 ± 3.52 5q 74.36 ± 3.33
    5g 48.96 ± 3.08 5r 90.47 ± 4.48
    5h 73.25 ± 2.59 5s 87.99 ± 2.37
    5i 30.96 ± 3.70 5t 49.26 ± 2.85
    溴代吡咯腈
    tralopyril
    100.00 ± 0.00 噻唑膦
    fosthiazate
    43.89 ± 2.78
    注:每个处理重复3次 (平均值 ± 标准差);化合物浓度为0.20 mmol/L。Note: Each treatment had three replicates (Mean ± SD). Corrected mortality was measured at a concentration of 0.20 mmol/L.
    下载: 导出CSV

    表  6  部分目标化合物对秀丽隐杆线虫的 LC50

    Table  6.   The LC50 value of some target compounds against Caenorhabditis elegans

    化合物
    Compound
    回归方程
    Regression equation
    相关系数
    Correlation cofficient, r
    LC50/
    (mmol/L)
    95%置信区间
    95% Confidence limit/(mmol/L)
    2y = 13.4860 + 4.5436x0.94330.01360.0071~0.0260
    5ky = 7.1526 + 2.0754x0.95270.09180.0605~0.1392
    5ry = 7.5282 + 2.2273x0.99250.07330.0633~0.0848
    5sy = 7.0517 + 1.8797x0.97330.08100.0605~0.1084
    噻唑膦 fosthiazatey = 6.5220 + 2.7518x0.99350.27980.2426~0.3227
    溴代吡咯腈 tralopyrily = 12.7985 + 2.2790x0.98890.00040.0003~0.0005
    下载: 导出CSV
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  • 收稿日期:  2022-05-03
  • 录用日期:  2022-06-24
  • 网络出版日期:  2022-07-15

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