CN104592183A - N-酰基-n-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途 - Google Patents

N-酰基-n-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途 Download PDF

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CN104592183A
CN104592183A CN201510018894.1A CN201510018894A CN104592183A CN 104592183 A CN104592183 A CN 104592183A CN 201510018894 A CN201510018894 A CN 201510018894A CN 104592183 A CN104592183 A CN 104592183A
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fluorobenzyl
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aminocoumarin
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CN104592183B (zh
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郝双红
王栋
魏艳
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Qingdao Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
    • C07D311/18—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted otherwise than in position 3 or 7
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom

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Abstract

本发明（名称为：N-酰基-N-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途）涉及18种N-酰基-N-间氟苄基-8-氨基香豆素类化合物及其制备方法，以及在除草方面的用途。18种化合物均可通过N-间氟苄基-8-氨基香豆素与不同酰氯缩合制备，这些化合物可作为除草剂防治杂草马唐、反枝苋。

Description

N-酰基-N-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途
技术领域
本发明为N-酰基-N-间氟苄基-8-氨基香豆素类化合物及其制备与除草用途，具体的涉及除草剂领域。
背景技术
天然产物香豆素和酰基芳胺类化合物均是已知的具有生物活性的化合物，该专利涉及的化合物中既有香豆素的结构，又有酰基芳胺的结构，是一种具有优异除草活性的的新化合物。
发明内容
本发明的目的在于提供N-酰基-N-间氟苄基-8-氨基香豆素类化合物及其制备，它可应用于防治杂草马唐和反枝苋。
本发明的技术方案如下：
     本发明提供N-酰基-N-间氟苄基-8-氨基香豆素类化合物，其结构通式如下：
R选自C1-C17烷基、C3-C6环烷基、C2-C17烯基、C1-C18卤代烷基、C2-C20烷氧基甲基、卤代苯氧基甲基；及其异构体。
N-酰基-N-间氟苄基-8-氨基香豆素类化合物合成反应式：
 
式中R定义如上
     通式化合物制备方法：在适当溶剂中，适当温度下，加入适当催化剂，2和3发生缩合，反应一定时间后，处理即得目的产物1。
适当溶剂可选自苯、甲苯、二甲苯、二氯甲烷、氯仿、四氢呋喃、乙酸乙酯、丙酮、乙腈、乙醇、甲醇等。
适当温度指0℃至溶剂的沸点温度。
适当催化剂指无水碳酸钾、哌啶、吡啶、无水碳酸钠、碳酸氢钠、三乙胺、氢氧化钠、甲醇钠、乙醇钠、叔丁醇钾等。
反应时间为30分钟至20小时。
本发明的化合物对马唐、反枝苋种子根茎的生长有很好的抑制作用。
具体实施方式
实例1
     化合物1-a的制备
     将0.269g（1mmol）N-间氟苄基-8-氨基香豆素，30mL二氯甲烷，0.086g（1.1 mmol）乙酰氯，加入到100mL三口瓶中，再滴加0.202g（2 mmol）三乙胺，室温搅拌，TLC跟踪反应。反应完毕，水洗至中性，分液，浓缩得褐色油状液体，通过柱层析[流动相为V（石油醚）：V（乙酸乙酯）=4：1]分离获得。1H NMR (500 MHz, TMS/CD3Cl), δ: 7.60(d, J=9.5Hz, 1H, H-4), 7.31(d, J=8.55Hz, 1H, PhH), 7.24(d, J=6.75Hz, 1H, PhH), 7.16(d, J=8.6Hz, 1H, PhH), 7.13(s, 1H, PhH), 6.96(d, J=8.65Hz, 3H, PhH), 6.47(d, J=9.4Hz, 1H, H-3), 4.89(s, 2H, PhCH2), 1.92(s, 3H, CH3)。
化合物1-b~1-r按照与1-a相似的方法合成，相关数据列于表1中。
表1
         
 （续表1）
         
      实例2 除草活性测定
     称取0.015g化合物，加入5mL丙酮，溶解配制成3000mg/L浓度的药液；取1mL3000mg/L的溶液，加入4mL丙酮，溶匀配制成600mg/L浓度的药液。两种药液各取1mL分别加入到30mL 0.5%的琼脂溶液中，充分混匀，然后分别倒入3个10mL小烧杯中，制成带毒培养基，每个浓度重复3次。取1mL丙酮加入培养基中做空白对照（CK)。把催芽露白的马唐和反枝苋种子分别接到培养基上培养，每个小杯接种10粒，将接种后的小杯放入培养箱（27℃，相对湿度90%，L/D=8h:16h）中培养，当空白对照根长到合适长度时测量种子根、茎长度。按照下式计算根茎生长抑制率：
       抑制率/%=[对照根（茎）长-处理根（茎）长]/对照根（茎）长×100
       化合物1-a~1-r的除草活性数据列于表2中。
表2 1-a ~1-r的除草活性
         

Claims (3)

1.N-酰基-N-间氟苄基-8-氨基香豆素类化合物，如通式所示：
R选自C1-C17烷基、C3-C6环烷基、C2-C17烯基、C1-C18卤代烷基、C2-C20烷氧基甲基、卤代苯氧基甲基；及其异构体。
2.权利要求1所述的化合物可通过下列反应制备：
式中R定义如上。
3.权利要求1所述的化合物防治杂草马唐和反枝苋的用途。
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CN106749144A (zh) * 2016-12-27 2017-05-31 江苏大学 7‑芳氧乙酰氧基香豆素类化合物及其在农药上的应用
CN106831683A (zh) * 2016-12-27 2017-06-13 江苏大学 一种香豆素‑芳氧羧酸酯类化合物及其在农药上的应用
CN106967028A (zh) * 2017-04-07 2017-07-21 青岛农业大学 一类新型含氟酰胺基香豆素化合物及其制备与除草用途
CN108017607A (zh) * 2017-12-11 2018-05-11 青岛农业大学 一类新型n-取代胺基香豆素及其除草与杀菌用途
CN108148034A (zh) * 2018-01-12 2018-06-12 青岛农业大学 一类新型含氟取代脲基香豆素衍生物及其除草与杀菌用途
CN110563730A (zh) * 2019-07-29 2019-12-13 江苏理工学院 高纯度n10-三氟乙酰蝶酸的制备方法

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
CN106749144A (zh) * 2016-12-27 2017-05-31 江苏大学 7‑芳氧乙酰氧基香豆素类化合物及其在农药上的应用
CN106831683A (zh) * 2016-12-27 2017-06-13 江苏大学 一种香豆素‑芳氧羧酸酯类化合物及其在农药上的应用
CN106749144B (zh) * 2016-12-27 2019-06-28 江苏大学 7-芳氧乙酰氧基香豆素类化合物及其在农药上的应用
CN106831683B (zh) * 2016-12-27 2019-06-28 江苏大学 一种香豆素-芳氧羧酸酯类化合物及其在农药上的应用
CN106967028A (zh) * 2017-04-07 2017-07-21 青岛农业大学 一类新型含氟酰胺基香豆素化合物及其制备与除草用途
CN106967028B (zh) * 2017-04-07 2019-08-30 青岛农业大学 一类含氟酰胺基香豆素化合物及其制备与除草用途
CN108017607A (zh) * 2017-12-11 2018-05-11 青岛农业大学 一类新型n-取代胺基香豆素及其除草与杀菌用途
CN108017607B (zh) * 2017-12-11 2019-10-29 青岛农业大学 一类n-取代胺基香豆素及其除草与杀菌用途
CN108148034A (zh) * 2018-01-12 2018-06-12 青岛农业大学 一类新型含氟取代脲基香豆素衍生物及其除草与杀菌用途
CN108148034B (zh) * 2018-01-12 2021-06-01 青岛农业大学 一类含氟取代脲基香豆素衍生物及其除草与杀菌用途
CN110563730A (zh) * 2019-07-29 2019-12-13 江苏理工学院 高纯度n10-三氟乙酰蝶酸的制备方法
CN110563730B (zh) * 2019-07-29 2022-03-25 江苏理工学院 高纯度n10-三氟乙酰蝶酸的制备方法

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