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磺酰氨基氯磺隆的合成、除草活性、作物安全性及其土壤降解研究

武磊 李永红 周莎 李正名 王忠文

武磊, 李永红, 周莎, 李正名, 王忠文. 磺酰氨基氯磺隆的合成、除草活性、作物安全性及其土壤降解研究[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0051
引用本文: 武磊, 李永红, 周莎, 李正名, 王忠文. 磺酰氨基氯磺隆的合成、除草活性、作物安全性及其土壤降解研究[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2022.0051
WU Lei, LI Yonghong, ZHOU Sha, LI Zhengming, WANG Zhongwen. Synthesis, herbicidal activity, crop safety and soil degradation of sulfonylamino-substituted chlorsulfuron[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0051
Citation: WU Lei, LI Yonghong, ZHOU Sha, LI Zhengming, WANG Zhongwen. Synthesis, herbicidal activity, crop safety and soil degradation of sulfonylamino-substituted chlorsulfuron[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2022.0051

磺酰氨基氯磺隆的合成、除草活性、作物安全性及其土壤降解研究

doi: 10.16801/j.issn.1008-7303.2022.0051
基金项目: 国家自然科学基金 (2021YFD1700103)资助项目.
详细信息
    作者简介:

    武磊,wl836929871@163.com

    通讯作者:

    王忠文,wzwrj@nankai.edu.cn

  • 中图分类号: TQ457.2

Synthesis, herbicidal activity, crop safety and soil degradation of sulfonylamino-substituted chlorsulfuron

Funds: the National Key Research and Development Program of China (No.2021YFD1700103).
  • 摘要: 基于活性亚结构拼接方法,在氯磺隆分子中苯环的5位引入不同磺酰氨基,设计合成了4个氯磺隆衍生物 ( H01 ~ H04 ),其结构经核磁共振氢谱(1H NMR)、碳谱(13C NMR)和高分辨质谱(HRMS)确证。初步的生物活性测试结果表明,目标化合物在150 g/hm2浓度下表现出较好的除草活性。苗前处理时, H01H02H04 对油菜生长的抑制率均高于85%, H01 对反枝苋的抑制率为100%,优于对照药剂氯磺隆 (68.8%);苗后处理时, H04 对油菜和反枝苋的抑制率均与氯磺隆相当,对稗草的抑制率 (85.5%) 优于对照药剂氯磺隆 (68.8%)。安全性测试结果表明,目标化合物对小麦和玉米生长的抑制率均低于氯磺隆。苗前处理时, H01H04 对小麦安全, H01 ~ H04 对玉米的抑制率均低于氯磺隆;苗后处理时, H01 ~ H04 对玉米生长无抑制作用。降解试验结果表明, H01 ~ H04 在碱性土壤 (pH 8.39) 中的降解半衰期为44.43~53.32 d,比氯磺隆的半衰期 (157.53 d) 明显缩短。研究结果表明, H01H04 可作为潜在的小麦田和玉米田磺酰脲类除草剂候选药物。本文可为进一步设计具有高效除草活性、降解速率快以及作物安全性高的新型磺酰脲类除草剂提供参考。
  • 1  目标化合物的设计

    1.  Design of the title compounds

    2  甲酰胺磺隆和甲磺胺磺隆的化学结构式.

    2.  Structural formula of mesosulfuron-methyl and foramsulfuron.

    3  目标化合物H01-H04的合成路线

    反应试剂和条件Reagents and conditions: (a) H2O, HCl, NaNO2→H2O, HCl, CuCl2, NaHSO3, -5 ℃; (b) 28% NH3•H2O, THF, 0 ℃→RT (room temperature), overnight; (c) Fe, HCl, C2H5OH, H2O, reflux; (d) DMF-DMA (N,N-dimethylformamide dimethyl acetal), CH2Cl2; (e) TFAA (trifluoroacetic anhydride), CH2Cl2, 0 ℃; (f) ICH3, K2CO3, DMF, 50 ℃; (g) pyridine, aryl sulfonyl chloride, CH2Cl2, 0 ℃, overnight; (h) 80% H2NNH2•H2O, C2H5OH; (i) 60% NaH, THF, 0 ℃→RT; (j) DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), CH3CN.

    3.  Synthetic route of the title compounds H01-H04

    表  1  土壤分析数据

    Table  1.   Analysis data of soils

    土壤
    Soil
    土壤质地
    Soil texture
    pH有机质含量
    Organic
    matter/
    (g/kg)
    阳离子交换量
    Cation exchange
    capacity/
    (cmol/kg)
    土壤粒级 (mm)/机械组成 (%)
    Soil separation (mm)/Mechanical composition (%)
    碱性土壤
    Alkaline soil
    轻粘土
    Loam
    8.3919.47.31~20.5~10.25~0. 50.05~0.020.02~0.002<0.0020.25~0.052.0~0.050.05~0.002
    0.7952.462.337.9028.628.229.735.336.5
    下载: 导出CSV

    表  2  不同处理方式下目标化合物H在15 g/hm2和150 g/hm2测试浓度下的除草活性

    Table  2.   Herbicidal activities of the target compounds H at concentration of 15 g/hm2 and 150 g/hm2 through different treatments

    化合物
    Compound
    施药剂量
    (有效成分)
    Concentration
    a.i/(g/hm2)
    抑制率 Inhibition rate/%
    苗前处理
    Pre-emergence treatment
    苗后处理
    Post-emergence treatment
    油菜
    Brassica
    campestris
    反枝苋
    Amaranthus
    tricolor
    稗草
    Echinochloa
    crusgalli
    马唐
    Digitaria
    sanguinalis
    油菜
    Brassica
    campestris
    反枝苋
    Amaranthus
    tricolor
    稗草
    Echinochloa
    crusgalli
    马唐
    Digitaria
    sanguinalis
    氯磺隆
    chlorslfuron
    15 94.8 62.1 43.8 32.4 100 100 60.0 0
    150 100 68.8 84.9 35.5 100 100 68.8 0
    H01 15 90.3 53.0 0.1 12.7 0 0 40.9 0
    150 94.8 100 14.6 31.1 62.0 97.6 61.5 0
    H02 15 83.5 50.0 3.6 5.3 0 13.3 37.2 0
    150 89.5 89.4 52.6 27.5 74.3 76.8 70.1 0
    H03 15 0 0 0 0 1.2 60.0 55.7 0
    150 16.8 0 5.7 2.9 72.6 94.6 90.7 2.3
    H04 15 0 58.3 40.1 0 54.4 87.5 47.0 0
    150 85.8 62.5 61.2 0.4 100 100 85.2 0
    下载: 导出CSV

    表  3  不同处理方式下目标化合物H在30 g/hm2和60 g/hm2剂量下的对小麦 (济麦22) 的安全性

    Table  3.   Crop safety of the target compounds H at concentration of 30 g/hm2 and 60 g/hm2 on wheat (Jimai 22) through different treatments

    化合物
    Compound
    施药剂量 (有效成分)
    Concentration
    a.i/(g/hm2)
    苗前处理
    Pre-emergence treatment
    苗后处理
    Post-emergence treatment
    鲜重/(g/10株)
    Fresh Weight/
    (g/10 Plants)
    方差分析a
    Analysis of
    Variance a
    抑制率
    Inhibition
    rate/%
    鲜重/(g/10株)
    Fresh Weight/
    (g/10 Plants)
    方差分析a
    Analysis of
    Variance a
    抑制率
    Inhibition
    rate/%
    5%1%5%1%
    0 2.013 abc A 0 4.030 a A 0
    氯磺隆
    chlorslfuron
    30 2.258 abc A 0 4.284 a A 0
    60 2.231 abc A 0 4.119 a A 0
    H01 30 2.065 abc A 0 4.682 a A 0
    60 1.824 c A 9.3 4.496 a A 0
    H02 30 1.878 bc A 6.7 4.667 a A 0
    60 1.799 c A 10.6 3.796 a A 5.8
    H03 30 2.407 ab A 0 3.863 a A 4.1
    60 2.524 a A 0 3.762 a A 6.6
    H04 30 2.167 abc A 0 4.264 a A 0
    60 2.209 abc A 0 4.104 a A 0
    a同一列内不同字母分别表示在5%或1%水平上差异显著性。有一个标记相同字母的即为差异不显著,具不同标记字母的即为差异显著。a Different letters within the same column indicate significant difference at 5% or 1% level, respectively. The same letter indicates that there was no significant difference, and different letters indicate that there was a significant difference
    下载: 导出CSV

    表  4  不同处理方式下目标化合物H在30 g/hm2和60 g/hm2剂量下的对玉米 (新单66) 的安全性

    Table  4.   Crop safety of the target compounds H at concentration of 30 g/hm2 and 60 g/hm2 on corn (Xindan 66) through different treatments

    化合物
    Compound
    施药剂量
    (有效成分)
    Concentration
    a.i/(g/hm2)
    苗前处理
    Pre-emergence treatment
    苗后处理
    Post-emergence treatment
    鲜重/(g/5株)
    Fresh weight/
    (g/5 Plants)
    方差分析a
    Analysis of
    variance a
    抑制率
    Inhibition
    rate/%
    鲜重/(g/5株)
    Fresh weight/
    (g/5 Plants)
    方差分析a
    Analysis of
    variance a
    抑制率
    Inhibition
    rate/%
    5%1% 5%1%
    0 6.141 a A 0 8.981 ab AB 0
    氯磺隆chlorslfuron 30 3.733 d BC 39.2 6.358 bc BC 29.2
    60 2.414 e CD 60.7 4.003 cd C 55.4
    H01 30 5.938 ab A 3.3 9.001 ab AB 0
    60 5.320 abc AB 13.4 10.038 a AB 0
    H02 30 4.725 bcd AB 23.1 9.078 ab AB 0
    60 4.563 cd AB 25.7 8.734 ab AB 2.8
    H03 30 5.847 ab A 4.8 10.865 a A 0
    60 4.963 abc AB 19.2 10.538 a AB 0
    H04 30 5.981 ab A 2.6 11.000 a A 0
    60 5.857 ab A 4.6 8.907 ab AB 0.8
    a同一列内不同字母分别表示在5%或1%水平上差异显著性。有一个标记相同字母的即为差异不显著,具不同标记字母的即为差异显著。a Different letters within the same column indicate significant difference at 5% or 1% level, respectively. The same letter indicates that there was no significant difference, and different letters indicate that there was a significant difference.
    下载: 导出CSV

    表  5  目标化合物的液相分析条件及其在土壤中的添加回收率

    Table  5.   HPLC analysis condition and recovery rate of taeget compounds

    化合物
    Compound
    HPLC 分析条件
    HPLC analysis condition
    提取溶剂
    Extraction solvent
    添加水平
    Spiked level/
    (mg/kg)
    平均添加
    回收率
    Average
    recovery/%
    相对标准偏差
    Relative standard
    deviation, RSD/%
    检测波长
    Wavelength/
    nm
    流速
    Flow rate/
    (mL/min)
    流动相
    Mobile phase
    V(甲醇) : V
    (磷酸水溶液) (pH 3.0)
    V(CH3OH) : V(H3PO4
    aqueous solution) (aq) (pH 3.0)
    V(丙酮) : V(二氯甲烷) : V(甲醇) :
    V(磷酸水溶液) (pH 1.5)
    V(CH3COCH3) : (CH2Cl2) :
    (MeOH) : (H3PO4 aq) (pH 1.5)
    H01 235 0.65 62 : 38 30 : 10 : 30 : 10 5 82 2.3
    2 77 2.3
    0.5 73 1.8
    H02 235 0.65 60 : 40 30 : 10 : 30 : 10 5 80 2.3
    2 84 1.4
    0.5 97 1.6
    H03 235 0.65 65 : 35 30 : 10 : 30 : 10 5 76 2.0
    2 73 1.2
    0.5 72 1.3
    H04 235 0.70 67 : 33 30 : 10 : 30 : 10 5 73 2.1
    2 81 2.1
    0.5 81 1.3
    氯磺隆
    chlorslfuron
    235 0.70 62 : 38 40 : 5 : 10 : 10 5 73 1.1
    2 73 2.4
    0.5 81 1.2
    下载: 导出CSV

    表  6  目标化合物在碱性土壤的降解

    Table  6.   Alkaline soil degradation results of the target compounds

    化合物
    Compound
    一级动力学方程
    First-order kinetic
    equation
    决定系数
    Coefficient of
    determination (R2)
    降解半衰期
    DT50/d
    H01Ct = 4.1074 e−0.0156t0.999144.43
    H02Ct = 4.0746e−0.0148t0.998646.83
    H03Ct = 3.9401e−0.0143t0.992948.47
    H04Ct = 3.5422e−0.0130t0.993353.32
    氯磺隆
    chlorslfuron
    Ct = 3.7060e−0.0044t0.9982157.53
    下载: 导出CSV
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  • 收稿日期:  2022-03-23
  • 录用日期:  2022-04-23
  • 网络出版日期:  2022-05-18

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