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WO2017148226A1 - 一种氟苯噁唑类化合物及其用途 - Google Patents

一种氟苯噁唑类化合物及其用途 Download PDF

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WO2017148226A1
WO2017148226A1 PCT/CN2017/071633 CN2017071633W WO2017148226A1 WO 2017148226 A1 WO2017148226 A1 WO 2017148226A1 CN 2017071633 W CN2017071633 W CN 2017071633W WO 2017148226 A1 WO2017148226 A1 WO 2017148226A1
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compound
formula
fluorobenzoxazole
present
activity
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PCT/CN2017/071633
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许良忠
吴华龙
王明慧
李焕鹏
黄雪松
杨曦
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浙江博仕达作物科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles

Definitions

  • the present invention relates to the field of pesticide acaricides, and in particular to a fluorobenzoxazole compound and use thereof.
  • acaricides for controlling cockroaches such as acetylene, bromo oxime, avermectin, spironolactone, oxazolidine, hydrazine, and the like. Due to the long-term or frequent use of existing commercial acaricides, aphids have produced varying degrees of resistance and cross-resistance to existing insecticides. Therefore, the development of new or different activating agents with different mechanisms of action is an important means to control the resistance of cockroaches.
  • CN1038809A discloses an oxazole compound of the formula (I) which has strong insecticidal and acaricidal activity against pests and mites which are harmful to agriculture and horticulture, and which is almost phytotoxic to crops.
  • US5478855 discloses an oxazole compound of the formula III, which has excellent control effects on hawthorn leafhopper, citrus aphid, vegetable leafhopper, etc., and has the characteristics of super high efficiency, long-lasting effect, low toxicity and safety. .
  • the oxazole compound disclosed in the above patent has certain similarities with the compound of the present invention, but in the prior art, such as the fluorobenzoxazole compound of the present invention (Formula I) and its insecticidal and acaricidal activity No reports have been reported.
  • the compounds of formula I can be prepared by the following methods:
  • Ethylazole (Compound III) is a representative acaricide in oxazoline acaricides. It is a brand new uniquely synthesized compound developed by Sumitomo Chemical Co., Ltd., which is a new compound with leaf mites, leaves and leaves. Xenopus laevis, cinnabar leafhopper, citrus red spider, etc. have excellent control effect and excellent ovicidal activity. Not only the acaricide is ultra-efficient, but also has the characteristics of long-lasting effect and low pollution. The leader in the agent market, but due to the large number of frequent use of the acaricide in recent years, the mites have caused serious resistance to them, and the control effect and duration of action have been significantly reduced.
  • the present inventors have combined the years of research on the relationship between the efficacy of biologically active substances and the experience of bioresistant treatment to create a compound of the present invention (Formula I) by introducing a fluorine atom into the structure of the etoxazole.
  • acaricidal cough, scorpion egg
  • the compound of the present invention not only has an unexpected killing effect on the eggs (see Table 1), but also has good killing properties (see Table 2), and overcomes The disadvantage of acetoxime on the ineffectiveness of cockroach solves the shortcoming of the lack of quick-acting effect of acetoxime field control.
  • the compound of the present invention also has excellent insecticidal action (see Table 3).
  • the comprehensive control performance is significantly better than that of etoxazole.
  • the compound of the invention avoids the use of the highly toxic raw material diethyl sulfate in the synthesis process of oxazole, so that the production process is safer and more environmentally friendly; the introduction of fluorine atom is more beneficial to overcome or delay the generation of harmful drug resistance. Therefore, the compound of the present invention is a creative acaricide, and the commercialization thereof will be an ideal replacement product of an acaricide such as oxazole, and also an excellent insecticidal and acaricidal agent for the prevention and control of pests and cockroaches in China, and effectively promote the country. The development of the pesticide industry and the greening process of pesticides.
  • the present invention also encompasses acaricidal compositions of the compounds of formula I as active ingredients, which also include agriculturally or forestry acceptable carriers.
  • the compound of the present invention can be used alone or in combination with other active substances such as insecticides and acaricides in order to improve the comprehensive function of the product.
  • composition of the present invention can be administered in the form of a preparation, and the compound of the formula I is dissolved or dispersed in a carrier or a solvent as an active ingredient, and an appropriate surfactant is added to prepare an emulsifiable concentrate, an aqueous emulsion, a microemulsion, a suspending agent and the like.
  • the acaricidal egg activity was determined by the method of dipping and statistically correcting the mortality of the pest.
  • the specific process is: diluting the test agent to the required concentration according to the active ingredients, and injecting 50 mL of the drug solution into the culture dish under aseptic conditions, and then immersing them in the cinnabar eggs respectively (the eggs are normally reared according to the indoor standardized method)
  • the leaves were placed in a blank control with a plate containing 50 ml of sterilized water. Place the culture dish in a constant temperature incubator at 24 ⁇ 1 °C.
  • the mortality rate was investigated after 48 hours.
  • the activity data of the eggs and the mites are shown in Tables 1 and 2, respectively.
  • the compound I of the present invention has excellent acaricidal activity, and the activity of the compound I of the present invention is significantly superior to the known commercial acaricide (the compound of the formula III) at the same dose.
  • the compound I of the present invention has good killing properties, and overcomes the disadvantages of the compound of the formula III being ineffective.
  • Example 2 The activity of the compound of formula I to kill beet armyworm
  • the compound I of the present invention has excellent activity against Spodoptera exigua, and the activity of the compound I of the present invention is significantly superior to the known commercial acaricide (compound of the formula III) at the same concentration.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

本发明公开了一种结构如式I所示的一种氟苯噁唑类化合物及其用途，该化合物对害螨及螨卵有优异的抑杀作用，可作为杀螨剂用于防治农业害螨，同时具有优异的杀甜菜夜蛾活性。

Description

一种氟苯噁唑类化合物及其用途
本发明请求申请日为2016年03月01日、申请号为CN 201610114395.7的中国发明专利申请为优先权。
技术领域  本发明属于农药杀螨剂领域，具体涉及一种氟苯噁唑类化合物及其用途。
背景技术  防治螨害的杀螨剂有多种，如炔螨特、溴螨酯、阿维菌素、螺螨酯、唑螨酯、哒螨灵等。由于现有商品化的杀螨剂长期或频繁地使用，使螨虫对现有杀虫剂产生了不同程度地抗药性和交互抗性。因此开发新的或作用机制不同的杀螨剂，是治理害螨抗药性的重要手段。CN1038809A公开了结构如式II所示的噁唑类化合物，该化合物对有害于农业和园艺的虫和螨类具有较强的杀虫和杀螨活性，并且对农作物几乎没有植物毒性。US5478855公开了结构如式III的噁唑类化合物，该化合物对山楂叶螨、柑橘螨、蔬菜叶螨等有优异的防治效果，防治害螨具有超高效、长持效、低毒、安全等特点。上述专利公开的噁唑类化合物与本发明所述化合物具有一定的相似之处，但在现有技术中，如本发明的氟苯噁唑类化合物(式I)及其杀虫、杀螨活性未见报道。
发明内容  本发明的目的在于提供一种结构新颖、使用安全的更高活性杀虫、杀螨剂。
本发明的技术方案如下：
一种氟苯噁唑类化合物，结构如式I所示：
Figure PCTCN2017071633-appb-000002
式I化合物可由以下方法制备：
Figure PCTCN2017071633-appb-000003
以甲苯和DMF(1∶1)为溶剂，间叔丁基苯酚和二氟乙基甲磺酸酯在K2CO3存在下回流反应生成化合物IV，备用。冰浴搅拌下2，6-二氟苯甲酰胺与氯乙醛缩二甲醇在浓H2SO4存在下反应，生成化合物V。以二氯甲烷为溶剂，式V化合物在AlCl3存在下与化合物IV反应生成中间体VI；以甲醇为溶剂，NaOH或KOH存在下中间体VI环化生成本发明化合物(式I)，式IV、式V、式VI及本发明化合物(式I)的具体制备方法见本发明合成实例。
本发明的优点及积极效果：
乙螨唑(化合物III)是噁唑啉类杀螨剂中的代表性杀螨剂，是日本住友化学株式会社研究开发的一个全新的具有独特结构的化合物，对叶螨、始叶螨和全爪螨如三斑叶螨、朱砂叶螨、柑橘红蜘蛛等具有卓越防效，优异的杀卵活性，不仅该杀螨剂具有超高效，且具有长持效、低公害之特点，成为杀螨剂市场的佼佼者、但由于该杀螨剂近年来的大量频繁地使用，导致螨类均对其产生了严重抗药性，防效及持效期均显著降低。本发明人结合多年来生物活性物质功效关系研究及生物抗性治理经验，通过在乙螨唑结构中引入氟原子，创制出本发明化合物(式I)。经过杀虫、杀螨(成螨、螨卵)试验，本发明化合物不仅对螨卵具有出人意料的杀灭作用(见表1)，且具有良好的杀成螨性能(见表2)，克服了乙螨唑对成螨无效的弊端，解决了乙螨唑田间防治没有速效性的缺点，不仅如此，本发明化合物亦具有优良的杀虫作用(见表3)。综合防治性能显著优于乙螨唑。本发明化合物避免了乙螨唑合成过程中须用剧毒原料硫酸二乙酯，使生产过程更安全、环保；氟原子的引入，更有利于克服或延缓有害生物抗药性的产生。因此本发明化合物作为创制型杀螨剂，其商品化将是乙螨唑等杀螨剂的理想换代品种，也为我国有害虫、螨防治增添一个优秀杀虫杀螨剂品种，有效地推动我国农药产业的发展及农药的绿色化进程。
本发明还包括式I化合物作为活性组分的杀螨组合物，该组合物中还包括农业或林业上可接受的载体。
本发明化合物在防治螨害时可单独使用，也可与其它活性物质如杀虫、杀螨剂组合使用，以利于提高产品的综合功能。
本发明的组合物可以制剂的形式施用，式I化合物作为活性组分溶于或分散于载体或溶剂中，添加适当的表面活性剂配制成乳油、水乳剂、微乳剂、悬浮剂等。
应明确的是，在本发明的权利要求的限定的范围内，可进行各种变换和改动。
具体实施方式
下列合成实例及生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
合成实例
实例1、式I化合物的制备
(1)化合物IV的制备
Figure PCTCN2017071633-appb-000004
步骤：在250mL四口烧瓶中依次加入15.0g(0.1mol)间叔丁基苯酚，粉末K2CO316.6g(0.12mol)，甲苯和DMF各50mL，搅拌下加入二氟乙基甲磺酸酯20.8g(0.13mol)，缓慢升温回流4h，TLC跟踪反应完成。稍降温抽滤，滤饼用少量DMF洗涤，旋蒸除去溶剂，加入二氯甲烷和水各50mL，萃取分液，萃取液用50mL水洗二次。有机相用无水硫酸钠干燥，旋蒸，得到红褐色油状液体19.32g，收率97.6％，备用。
(2)化合物V的制备
Figure PCTCN2017071633-appb-000005
步骤：在250mL四口烧瓶中依次加入143g(0.1mol)2，6-二氟苯甲酰胺、氯乙醛缩二甲醇49.8g(0.4mol)，在冰浴中剧烈搅拌，在1h内滴加浓硫酸6mL，室温搅拌约2h，用TLC跟踪至2，6-二氟苯甲酰胺反应完全。反应液倒入分液漏斗中，加入水150mL、二氯甲烷150mL，萃取，萃取液用80mL水洗二次。旋蒸出二氯甲烷和过量的氯乙醛缩二甲醇，加入正己烷80mL，搅拌冷却过夜。结晶析出，过滤，干燥得18.3g白色化合物V，产率73.5％。
(3)化合物VI的制备
Figure PCTCN2017071633-appb-000006
步骤：将14.9g(0.06mol)化合物V与14.2g(0.072mol)化合物IV溶解在80mL二氯甲烷中，在10min内滴加到14.2g(0.108mol)三氯化铝溶解在80mL二氯甲烷的冰冷溶液中。缓慢升温至回流约2h，TLC跟踪至化合物V基本反应完成，将反应液加入到冰水中去，二氯甲烷层用50mL水洗涤2次，蒸去二氯甲烷，冷却过夜。析出结晶，过滤，少量冰冷甲醇洗涤，干燥得白色固体21.89g，产率87.9％。
(3)化合物I的合成
Figure PCTCN2017071633-appb-000007
步骤：将4.8g 20％NaOH溶液慢慢滴加到8.3g(0.02mol)化合物V溶解在60mL甲醇的溶液中去，混合物在70℃搅拌约1h，用TLC跟踪至化合物V基本反应完成。旋蒸出甲醇和水，加入水和苯各50mL，萃取分液，有机相用无水硫酸钠干燥，减压蒸馏蒸去低沸物，稍冷后加20mL温热的正己烷，搅拌，冷却过夜。析出结晶，过滤，干燥得6.95g白色化合物I，产率91.7％。熔点：82.5-85.2℃。
式I化合物氢核磁数据如下：
1H-NMR(500MHz，DMSO)：δ/ppm 1.257(s，9H)，4.085-4.118(t，1H)，4.378-4.436(m，2H)，4.780-4.838(t，1H)，5.525-5.563(t，1H)，6.274-6.499(t，1H)，7.025-7.663(m，6H)
生测实例
实例2式I化合物杀螨(卵)活性试验
采用浸渍法和统计校正害虫死亡率的方法测定杀螨卵活性。具体过程是：将供试药剂按有效成分分别稀释至所需浓度，在无菌条件下各取50mL药液注入培养皿内，再分别浸入朱砂螨卵(螨卵按室内标准化方法正常饲养的群体)的叶片，以添加50ml灭菌水的平板做空白对照。将培养皿放在24±1℃恒温培养箱内。48h后调查统计死亡率。对螨卵及成螨活性数据分别见表1和表2。
表1式I化合物杀螨卵试验结果
Figure PCTCN2017071633-appb-000008
根据表1测试结果可知，本发明化合物I具有优异的杀螨卵活性，在相同剂量下，本发明化合物I的活性显著优于已知商品化杀螨剂(式III化合物)。
表2式I化合物杀成螨试验结果
Figure PCTCN2017071633-appb-000009
根据表2测试结果可知，本发明化合物I具有良好的杀成螨性能，克服了式III化合物对成螨无效的弊端。
实例2式I化合物杀甜菜夜蛾活性试验
式I化合物对甜菜夜蛾活性测定：采用国际抗性行动委员会(IRAC)提出的浸叶法。用配制好的待测药液，用直头眼科镊子浸渍甘蓝叶片，时间3-5秒甩掉余液每次1片每个样品共3片，安样品标记顺序依次放在处理纸上。待药液干后，放入具有标记的10cm长的直型管内，接入2龄小甜菜夜蛾幼虫30头，用纱布盖好管口。将试验处理置于标准处理室内，48h检查结果以拔针轻触虫体，不动者为死亡。计算死亡率。(试验做3次重复，取平均值)。
表3式I化合物杀甜菜夜蛾试验结果
Figure PCTCN2017071633-appb-000010
根据表3测试结果可知，本发明化合物I具有优异的杀甜菜夜蛾活性，相同浓度下，本发明化合物I的活性显著优于已知商品化杀螨剂(式III化合物)。

Claims (3)

  1. 一种氟苯噁唑类化合物，结构如式Ⅰ所示：
    Figure PCTCN2017071633-appb-100001
  2. 根据权利要求1所述的一种氟苯噁唑类化合物的用途，其特征在于式I化合物可用作杀螨剂，用于防治农业害螨。
  3. 一种杀螨组合物，含有权利要求1所述的式I化合物作为活性组分和农业或林业上可接受的载体。
PCT/CN2017/071633 2016-03-01 2017-01-19 一种氟苯噁唑类化合物及其用途 WO2017148226A1 (zh)

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CN107365279A (zh) * 2017-08-15 2017-11-21 上海开荣化工科技有限公司 乙螨唑的合成工艺
CN108424400A (zh) * 2018-06-09 2018-08-21 石家庄市绿丰化工有限公司 一种提高乙螨唑含量的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1038809A (zh) * 1988-06-09 1990-01-17 八洲化学工业株式会社 唑啉或噻唑啉衍生物和其制法
US5478855A (en) * 1992-04-28 1995-12-26 Yashima Chemical Industry Co., Ltd. 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butylphenyl)-2-oxazoline
JPH0959115A (ja) * 1995-08-25 1997-03-04 Yashima Chem Ind Co Ltd 光安定性良好なる殺虫・殺ダニ組成物
CN105693648A (zh) * 2016-03-01 2016-06-22 浙江博仕达作物科技有限公司 一种氟苯噁唑类化合物及其用途

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE297910T1 (de) * 2001-03-14 2005-07-15 Lilly Co Eli Retinoid x rezeptormodulatoren

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1038809A (zh) * 1988-06-09 1990-01-17 八洲化学工业株式会社 唑啉或噻唑啉衍生物和其制法
US5478855A (en) * 1992-04-28 1995-12-26 Yashima Chemical Industry Co., Ltd. 2-(2,6-difluorophenyl)-4-(2-ethoxy-4-tert-butylphenyl)-2-oxazoline
JPH0959115A (ja) * 1995-08-25 1997-03-04 Yashima Chem Ind Co Ltd 光安定性良好なる殺虫・殺ダニ組成物
CN105693648A (zh) * 2016-03-01 2016-06-22 浙江博仕达作物科技有限公司 一种氟苯噁唑类化合物及其用途

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