CN106967028B - 一类含氟酰胺基香豆素化合物及其制备与除草用途 - Google Patents

一类含氟酰胺基香豆素化合物及其制备与除草用途 Download PDF

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CN106967028B
CN106967028B CN201710222166.1A CN201710222166A CN106967028B CN 106967028 B CN106967028 B CN 106967028B CN 201710222166 A CN201710222166 A CN 201710222166A CN 106967028 B CN106967028 B CN 106967028B
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fluorine
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CN106967028A (zh
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郝双红
乔丽丽
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
    • C07D311/16—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 in position 7
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    • 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
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    • 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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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

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Abstract

本发明涉及11种含氟酰胺基香豆素化合物及其制备方法，以及在除草方面的应用。11种化合物可通过4‑三氟甲基‑7‑甲氧基‑6‑（N‑间氟苄基）‑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单子叶杂草马唐、稗草及双子叶杂草灰藜、荠菜等。

Description

一类含氟酰胺基香豆素化合物及其制备与除草用途
技术领域
本发明涉及一类新型含氟酰胺基香豆素类化合物及其制备与除草用途，具体的涉及农用除草剂领域。
背景技术
4-甲基-7-羟基-香豆素（羟甲基香豆素）是合成药物、染料的重要中间体，还可作为利胆药-胆通的原料药。该化合物及其衍生物在农药领域也有多样生物活性，如杀虫、抑菌及除草作用等。酰基芳胺类化合物也具有广泛生物活性，如杀菌剂甲霜灵、萎锈灵，除草剂乙草胺、氟吡草胺等。该专利基于活性亚结构拼接思想，以4-甲基-7-羟基-香豆素为先导，同时引入三氟甲基等含氟基团，设计合成了一类新型含氟酰胺基香豆素类化合物，并筛选了该类化合物的除草活性。
发明内容
本发明的目的在于提供一类新型含氟酰胺基香豆素类化合物及制备方法，它可应用于农业上以防治田间杂草。
本发明的技术方案如下：
本发明提供的新型含氟酰胺基香豆素类化合物，其结构通式如下：
R选自：正丙基、3-氯丙基、环丙基、2-甲基烯丙基、4-甲基苯基、苯乙基、4-甲氧基苯基、3-氟苯基、萘-2-基、噻吩-2-基或2-氯吡啶-5-基；
新型含氟酰胺基香豆素类化合物合成反应式：
式中R定义如上；
制备方法：在适当溶剂中，适当温度下，加入适当催化剂，Ⅱ和Ⅲ发生缩合，反应一定时间后，处理即得目的产物Ⅰ；
适当溶剂可选自苯、甲苯、二甲苯、二氯甲烷、三氯甲烷、二氯乙烷、乙酸乙酯、丙酮、乙腈等；
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、无水碳酸钠、碳酸氢钠、氢氧化钠、哌啶、吡啶、三乙胺等；
反应时间为2小时至20小时；
本发明的化合物对马唐、稗草、灰藜、荠菜等杂草种子萌发后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Ⅰ-1的制备
将0.734 g（2 mmol）4-三氟甲基-7-甲氧基-N-间氟苄基-6-氨基香豆素，50 mL二氯甲烷，0.265 g（2.5 mmol）丁酰氯，加入到100 mL三口瓶中，再滴加3滴三乙胺，室温搅拌，TLC跟踪反应。反应完毕，水洗至中性，分液，浓缩得黄色油状液体，通过柱层析[流动相为V（石油醚）：V（乙酸乙酯）=5：1]分离获得；
化合物Ⅰ-2~Ⅰ-11按照与Ⅰ-1相似的方法合成，合成化合物MS及1H NMR数据列于表1；
表1 目标化合物MS及1H NMR数据
（续表1）
I-9 522.00 <sup>1</sup>H NMR (500 MHz, DMSO) δ 7.98 – 7.69 (m, 4H), 7.49 (s, 2H),7.38 (dd, J = 14.6, 7.7 Hz, 2H), 7.25 – 7.06 (m, 5H), 6.74(s, 1H), 5.47 (d, J = 14.7 Hz, 1H), 4.56 (d, J = 14.7 Hz,1H), 3.87 (s, 3H)
I-10 478.13 <sup>1</sup>H NMR (500 MHz, CDCl<sub>3</sub>) δ 7.29 (d, <i>J</i> = 4.9 Hz, 1H), 7.25 –7.14 (m, 3H), 7.02 (dd, <i>J</i> = 12.9, 8.8 Hz, 2H), 6.96 (dd, <i>J</i>=11.7, 5.2 Hz, 1H), 6.90 (s, 1H), 6.85 (t, <i>J</i> = 4.3 Hz, 1H),6.63 (s, 1H), 5.51 (d, <i>J</i> = 14.1 Hz, 1H), 4.42 (d, <i>J</i> =14.0Hz, 1H), 3.78 (s, 3H)
I-11 507.10 <sup>1</sup>H NMR (500 MHz, CDCl<sub>3</sub>) δ 8.26 (s, 1H), 7.69 (d, <i>J</i> = 7.6Hz, 1H), 7.26 – 7.16 (m, 2H), 7.12 (s, 1H), 7.06 – 6.89 (m,3H), 6.76 (s, 1H), 6.60 (s, 1H), 5.36 (d, <i>J</i> = 14.3 Hz,1H), 4.61 (d, <i>J</i> = 14.3 Hz, 1H), 3.78 (s, 3H)
实例2 除草活性初筛
称取0.015 g化合物，加入5 mL丙酮，溶解配制成3000 mg/L浓度的药液；取1 mL3000 mg/L的溶液，加入4 mL丙酮，溶匀配制成600 mg/L浓度的药液。两种药液各取1 mL分别加入到30 mL 0.5%的琼脂溶液中，充分混匀，然后分别倒入3个10 mL小烧杯中，制成带毒培养基，每个浓度重复3次。取1 mL丙酮加入培养基中做空白对照（CK)；
把催芽露白的马唐和灰藜种子分别接到培养基上培养，选长势相同的种子每个小杯接种10粒，将接种后的小杯放入培养箱（28 ℃，相对湿度90%，L/D=12h:12h）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Ⅰ-1~Ⅰ-11的除草活性数据列于表2中；
表2 目标化合物除草活性初筛（mg/L）
。
实例3 除草活性复筛
将40~50粒荠菜、灰藜、马唐及稗草种子播于直径8 cm的塑料盆中，覆土1~2 mm，放入装有水的搪瓷盘中，让水逐渐渗入，等水渗到土表后转移入玻璃温室培养，待杂草2~3叶期间苗定株，每盆定株30棵，定期从盆钵底部渗灌补水，以保持土壤湿度；
每化合物分别设100、500 g a. i. / hm2 处理。待测化合物用适量丙酮溶解，然后用0.1%吐温-80水溶液稀释至合适浓度。于上述杂草2~3片真叶期茎叶均匀喷雾处理，施药后20 d称量各处理杂草地上部分鲜重，计算鲜重防效。按公式计算各处理的鲜重防效：
抑制率/ % = [对照区鲜重-处理区鲜重]/ 对照区鲜重×100
表3 目标化合物盆栽除草活性（g. a. i. / hm2）

Claims (2)

1.一种含氟酰胺基香豆素类化合物结构如通式所示：
R选自正丙基、3-氯丙基、环丙基、2-甲基烯丙基、4-甲基苯基、苯甲基、4-甲氧基苯基、3-氟苯基、萘-2-基、噻吩-2-基或2-氯吡啶-5-基。
2.权利要求1所述化合物在防治杂草方面的用途，所述的杂草包括单子叶植物马唐、稗草及双子叶植物灰藜、荠菜。
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