WO2017054523A1 - 一种含内酯环的杀线虫剂及其制备方法和用途 - Google Patents

一种含内酯环的杀线虫剂及其制备方法和用途 Download PDF

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WO2017054523A1
WO2017054523A1 PCT/CN2016/086426 CN2016086426W WO2017054523A1 WO 2017054523 A1 WO2017054523 A1 WO 2017054523A1 CN 2016086426 W CN2016086426 W CN 2016086426W WO 2017054523 A1 WO2017054523 A1 WO 2017054523A1
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lactone ring
carbon atoms
nematicide
hydrogen
group
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PCT/CN2016/086426
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English (en)
French (fr)
Inventor
唐剑峰
潘光民
刘杰
赵恭文
吴建挺
李冬蓉
牛芳
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山东省联合农药工业有限公司
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Application filed by 山东省联合农药工业有限公司 filed Critical 山东省联合农药工业有限公司
Priority to AU2016333198A priority Critical patent/AU2016333198B2/en
Priority to EP16850148.4A priority patent/EP3279189B1/en
Priority to US15/572,669 priority patent/US10111428B2/en
Priority to BR112017025877-3A priority patent/BR112017025877B1/pt
Priority to ES16850148T priority patent/ES2772713T3/es
Publication of WO2017054523A1 publication Critical patent/WO2017054523A1/zh

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    • 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
    • A01N43/06—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 five-membered rings
    • A01N43/08—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 five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P5/00—Nematocides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form

Definitions

  • the invention relates to the field of agrochemical and medical technology, in particular to a nematicide containing a lactone ring, a preparation method thereof and use thereof.
  • nematodes live in the soil, some parasitic in plants, spread through soil or seeds, can destroy the roots of plants, or invade the organs of the aboveground parts, affect the growth and development of crops, and indirectly spread the diseases caused by other microorganisms, resulting in agriculture. A big economic loss.
  • the existing nematicides are toxic by the penetration of the nematode epidermis.
  • nematicides and fungicides there are few nematicidal agents with good effects in the world.
  • There are only ten kinds of nematicides and because the existing nematicides have better toxicity to humans and animals, Some varieties have phytotoxicity to crops and affect their use, so new, efficient and environmentally friendly nematicides are urgently needed.
  • the object of the present invention is to provide a lactone ring-containing nematicidal agent, a preparation method thereof and use thereof for the problems existing in the prior art, and the nematicide ring-containing nematicidal agent of the invention has good insecticidal activity against nematodes And is less toxic to humans and animals.
  • R 1 , R 2 , R 3 , R 4 and R 5 are selected from the group consisting of hydrogen, cyano, fluorine, chlorine, bromine, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 6 is selected from the group consisting of hydrogen, fluorine, and chlorine.
  • a lactone ring-containing nematicide wherein R 6 is a fluorine atom is preferably, a lactone ring-containing nematicide wherein R 6 is a fluorine atom.
  • R 3 F
  • the invention also provides a preparation method of a nematicide ring-containing nematicidal agent, comprising the following steps: Adding to the solvent, adding an acid binding agent, stirring the reaction at 20 to 30 ° C for 22 to 26 hours, distilling off the solvent under a vacuum of 0.08 to 0.10 kPa, adding methylene chloride and water, stirring uniformly, and standing to separate the layer to remove water. Distilling off methylene chloride at a vacuum of 0.08 to 0.10 kPa to obtain a lactone ring-containing nematicide of the formula I;
  • the molar ratio to the acid binding agent is 1:0.8 to 1.2:3 to 5;
  • R 1, R 2, R 3, R 4, R 5 is selected from hydrogen, cyano, fluoro, chloro, bromo, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, Alkoxyphenyl, an alkoxy group having from 1 to 4 carbon atoms and having a hydrogen atom on the carbon atom substituted by one or more chlorine atoms, having from 1 to 4 carbon atoms and having one or more hydrogen atoms on the carbon atom a fluorine atom-substituted alkoxy group, a nitro group or an amine group; and R 6 is selected from the group consisting of hydrogen, fluorine, and chlorine;
  • the solvent is methanol, ethanol, acetone, N,N-dimethylformamide or N,N-dimethylformamide;
  • the acid binding agent is potassium carbonate, sodium carbonate, pyridine or triethylamine.
  • the invention also provides the use of a lactone ring-containing nematicide for controlling agricultural nematode diseases.
  • the lactone ring-containing nematicide of the present invention contains a structure of a polyfluorobutene and a lactone ring, it has a good control effect on the eggs of the root-knot nematode and the second instar larvae, and particularly inhibits the cucumber, Incubation of root-knot nematode eggs such as tomato, tobacco, soybean, etc.; and the lactone ring-containing nematicide of the present invention has low toxicity, less residue in crops, and less harm to humans and animals, and is well solved.
  • the existing nematicide is more toxic and has more residual residues in the crop, which improves the safety of agricultural production; the use of pests over a longer period of time does not produce antibodies to the nematicidal agent of the present invention, and has good The insecticidal effect; the invention also provides a preparation method of the lactone ring-containing nematicidal agent, the preparation method has few steps, the process is easy to operate, and is suitable for large-scale industrial production.
  • R 1 , R 2 , R 3 , R 4 and R 5 are selected from the group consisting of hydrogen, cyano, fluorine, chlorine, bromine, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 6 is selected from the group consisting of hydrogen, fluorine, and chlorine.
  • a lactone ring-containing nematicide wherein R 6 is a fluorine atom is preferably, a lactone ring-containing nematicide wherein R 6 is a fluorine atom.
  • R 3 F
  • the invention also provides a preparation method of a nematicide ring-containing nematicidal agent, comprising the following steps: Adding to the solvent, adding an acid binding agent, stirring the reaction at 20 to 30 ° C for 22 to 26 hours, distilling off the solvent under a vacuum of 0.08 to 0.10 kPa, adding methylene chloride and water, stirring uniformly, and standing to separate the layer to remove water. Distilling off methylene chloride at a vacuum of 0.08 to 0.10 kPa to obtain a lactone ring-containing nematicide of the formula I;
  • the molar ratio to the acid binding agent is 1:0.8 to 1.2:3 to 5;
  • R 1 , R 2 , R 3 , R 4 and R 5 are selected from the group consisting of hydrogen, cyano, fluorine, chlorine, bromine, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.
  • R 6 is selected from the group consisting of hydrogen, fluorine, and chlorine;
  • the solvent is methanol, ethanol, acetone, N,N-dimethylformamide or N,N-dimethylformamide;
  • the acid binding agent is potassium carbonate, sodium carbonate, pyridine or triethylamine.
  • the invention also provides the use of a lactone ring-containing nematicide for controlling agricultural nematode diseases.
  • Raw materials in the preparation method of the invention Can be purchased on the market or prepared by the following steps: And anhydrous zinc chloride is added to dichloromethane in turn, triethylamine is added dropwise at 0 to 5 ° C, the reaction solution is obtained after the dropwise addition, and the reaction solution is stirred at 20 to 30 ° C for 10 to 20 hours. , adding hydrochloric acid to adjust the pH of the reaction solution to 2, extracting with ethyl acetate, collecting the organic phase,
  • Table 1 Structural measurement analysis table of a nematicide-containing nematicide-containing compound
  • a lactone ring-containing nematicide of the present invention can be obtained according to the preparation method of the present invention.
  • the following are specific examples of the compounds in Table 1:
  • the preparation of the compound of No. 2 in Table 1 comprises the following steps:
  • the preparation of the compound of No. 26 in Table 1 comprises the following steps:
  • the preparation of the compound of No. 41 in Table 1 includes the following steps:
  • the preparation of the compound of No. 46 in Table 1 includes the following steps:
  • reaction solution was stirred at 22 ° C for 12 h, hydrochloric acid was added thereto to adjust the pH of the reaction mixture to 2, and extracted with ethyl acetate (250 ml), and the organic phase was collected, and the organic phase was recrystallized by adding 250 ml of toluene to give 5-oxo-2- (2-(trifluoromethyl)phenyl)tetrahydrofuran-3-carboxylic acid;
  • the preparation of the compound of No. 48 in Table 1 comprises the following steps:
  • the nematicide-containing nematicidal compound of the present invention has a good control effect on the second instar larvae and eggs of the nematode, and the hatching inhibition rate of the nematode eggs is better than that of the second instar larvae. The effect is good.
  • the cockroach toxicity test and the soil microbial toxicity test of the compounds 1 to 60 in Table 1 of the present invention are carried out according to the steps of the cockroach toxicity test and the soil microbial toxicity test in the chemical pesticide environmental safety evaluation test standard, wherein the commonly used pesticide amount in the soil microbial test is simulated. At 40 ppm, the results of the two tests are as follows:
  • the lactone ring-containing nematicide-containing compound of the present invention has low toxicity to organisms in the soil environment, is safe to use, and is an environmentally friendly compound.

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

Abstract

本发明公开了一种含内酯环的杀线虫剂及其制备方法和用途，包括氢、氰基、氟、氯、溴、含1～4个碳原子的烷基、含1～4个碳原子的烷氧基、烷氧苯基、含1～4个碳原子并且碳原子上氢原子被一个或多个氯原子取代的烷氧基、含1～4个碳原子并且碳原子上氢原子被一个或多个氟原子取代的烷氧基、硝基或胺基；R6选自氢、氟、氯。本发明对根结线虫的卵与二龄幼虫有很好的防治效果，尤其能很好地抑制黄瓜、番茄、烟草、大豆等根结线虫卵的孵化；在较长时间内使用害虫不会对本发明的杀线虫剂产生抗体，具有很好的杀虫效果；本发明还提供了该含内酯环的杀线虫剂的制备方法，该制备方法步骤少，工艺易于操作，适合大规模的工业生产。

Description

一种含内酯环的杀线虫剂及其制备方法和用途 技术领域
本发明涉及农化与医药技术领域，具体涉及一种含内酯环的杀线虫剂及其制备方法和用途。
技术背景
线虫大多生活在土壤中，有的寄生在植物体内，通过土壤或种子传播，能破坏植物的根系，或侵入地上部分的器官，影响农作物的生长发育，并且间接传播其他微生物引起的病害，造成农业上很大的经济损失。现有的杀线虫剂是通过线虫表皮透入起毒杀作用。
和杀线虫剂、杀菌剂相比，目前世界上专用的效果比较好的杀线虫剂很少，仅有十余种，并且由于现有的效果较好的杀线虫剂对人畜的毒性较高，有些品种对作物有药害，影响其使用，所以新型、高效、对环境友好的杀线虫剂亟待开发。
发明内容
本发明的目的是针对现有技术中存在的问题，提供一种含内酯环的杀线虫剂及其制备方法和用途，本发明含内酯环的杀线虫剂对线虫有良好的杀虫活性，并且对人畜毒性小。
本发明为实现以上目的，所采取的技术方案是：
一种含内酯环的杀线虫剂，其结构通式I如下所示：
Figure PCTCN2016086426-appb-000001
结构通式I，
其中，R1、R2、R3、R4、R5选自氢、氰基、氟、氯、溴、含1～4个碳原子的烷基、含1～4个碳原子的烷氧基、烷氧苯基、含1～4个碳原子并且碳原子上氢原子被一个或多个氯原子取代的烷氧基、含1～4个碳原子并且碳原子上氢原子被一个或多个氟原子取代的烷氧基、硝基或胺基；
R6选自氢、氟、氯。
优选的，一种含内酯环的杀线虫剂，R6为氟原子。
优选的，一种含内酯环的杀线虫剂，R1＝CF3时，R2＝R3＝R4＝R5＝H。
优选的，一种含内酯环的杀线虫剂，R1＝OCF3时，R2＝R3＝R4＝R5＝H。
优选的，一种含内酯环的杀线虫剂，R1＝R2＝R5＝H，R3＝F时，R4＝-O-C6H5。
优选的，一种含内酯环的杀线虫剂，R2＝R4＝CF3时，R1＝R3＝R5＝H。
本发明还提供了含内酯环的杀线虫剂的制备方法，包括以下步骤：将
Figure PCTCN2016086426-appb-000002
加入溶剂中，加入缚酸剂，在20～30℃下搅拌反应22～26小时，在真空度0.08～0.10kPa下，蒸馏除去溶剂，加二氯甲烷和水搅拌均匀，静置分层除去水，在真空度0.08～0.10kPa下，蒸馏除去二氯甲烷得到通式I所示的含内酯环的杀线虫剂；其中
Figure PCTCN2016086426-appb-000003
和缚酸剂的摩尔比为1∶0.8～1.2∶3～5；
其中，R1、R2、R3、R4、R5选自氢、氰基、氟、氯、溴、含1～4个碳原子的烷基、含1～4个碳原子的烷氧基、烷氧苯基、含1～4个碳原子并且碳原子上氢原子被一个或多个氯原子取代的烷氧基、含1～4个碳原子并且碳原子上氢原子被一个或多个氟原子取代的烷氧基、硝基或胺基；R6选自氢、氟、氯；
所述的溶剂为甲醇、乙醇、丙酮、N,N-二甲基甲酰胺或N,N-二甲基甲酰胺；
所述的缚酸剂为碳酸钾、碳酸钠、吡啶或三乙胺。
本发明还提供了含内酯环的杀线虫剂的用途，用于防治农业线虫类病害。
本发明的优点在于：
本发明的含内酯环的杀线虫剂由于含有多氟丁烯和内酯环的结构，因而对根结线虫的卵与二龄幼虫有很好的防治效果，尤其能很好地抑制黄瓜、番茄、烟草、大豆等根结线虫卵的孵化；并且本发明的含内酯环的杀线虫剂的毒性较低，在农作物中的残留少，对人、畜的危害性小，很好解决了现有的杀线虫剂毒性较大，在作物中的残留较多的问题，提高了农业生产的安全性；在较长时间内使用害虫不会对本发明的杀线虫剂产生抗体，具有很好的杀虫效果；本发明还提供了该含内酯环的杀线虫剂的制备方法，该制备方法步骤少，工艺易于操作，适合大规模的工业生产。
具体实施方式
一种含内酯环的杀线虫剂，其结构通式I如下所示：
Figure PCTCN2016086426-appb-000004
结构通式I，
其中，R1、R2、R3、R4、R5选自氢、氰基、氟、氯、溴、含1～4个碳原子的烷基、含1～4个碳原子的烷氧基、烷氧苯基、含1～4个碳原子并且碳原子上氢原子被一个或多个氯原子取代的烷氧基、含1～4个碳原子并且碳原子上氢原子被一个或多个氟原子取代的烷氧基、硝基或胺基；
R6选自氢、氟、氯。
优选的，一种含内酯环的杀线虫剂，R6为氟原子。
优选的，一种含内酯环的杀线虫剂，R1＝CF3时，R2＝R3＝R4＝R5＝H。
优选的，一种含内酯环的杀线虫剂，R1＝OCF3时，R2＝R3＝R4＝R5＝H。
优选的，一种含内酯环的杀线虫剂，R1＝R2＝R5＝H，R3＝F时，R4＝-O-C6H5。
优选的，一种含内酯环的杀线虫剂，R2＝R4＝CF3时，R1＝R3＝R5＝H。
本发明还提供了含内酯环的杀线虫剂的制备方法，包括以下步骤：将
Figure PCTCN2016086426-appb-000005
加入溶剂中，加入缚酸剂，在20～30℃下搅拌反应22～26小时，在真空度0.08～0.10kPa下，蒸馏除去溶剂，加二氯甲烷和水搅拌均匀，静置分层除去水，在真空度0.08～0.10kPa下，蒸馏除去二氯甲烷得到通式I所示的含内酯环的杀线虫剂；其中
Figure PCTCN2016086426-appb-000006
和缚酸剂的摩尔比为1∶0.8～1.2∶3～5；
其中，R1、R2、R3、R4、R5选自氢、氰基、氟、氯、溴、含1～4个碳原子的烷基、含1～4个碳原子的烷氧基、烷氧苯基、含1～4个碳原子并且碳原子上氢原子被一个或多个氯原子取代的烷氧基、含1～4个碳原子并且碳原子上氢原子被一 个或多个氟原子取代的烷氧基、硝基或胺基；R6选自氢、氟、氯；
其反应通式为：
Figure PCTCN2016086426-appb-000007
所述的溶剂为甲醇、乙醇、丙酮、N,N-二甲基甲酰胺或N,N-二甲基甲酰胺；
所述的缚酸剂为碳酸钾、碳酸钠、吡啶或三乙胺。
本发明还提供了含内酯环的杀线虫剂的用途，用于防治农业线虫类病害。
本发明制备方法中的原料
Figure PCTCN2016086426-appb-000008
可在市场上购买，或采用以下步骤制备：将
Figure PCTCN2016086426-appb-000009
和无水氯化锌依次加入到二氯甲烷中，在0～5℃下，滴加三乙胺，滴加完毕后得到反应液，将反应液置于20～30℃下搅拌10～20小时，向其中加入盐酸调节反应液的pH至2，加入乙酸乙酯萃取，收集有机相，
加入甲苯重结晶得到
Figure PCTCN2016086426-appb-000010
其中
Figure PCTCN2016086426-appb-000011
无水氯化锌和三乙胺的摩尔比为1∶0.8～1.2∶1～3∶3～5；其反应通式为：
Figure PCTCN2016086426-appb-000012
表1一种含内酯环的杀线虫剂的化合物的结构测量分析表
Figure PCTCN2016086426-appb-000013
Figure PCTCN2016086426-appb-000014
Figure PCTCN2016086426-appb-000015
Figure PCTCN2016086426-appb-000016
Figure PCTCN2016086426-appb-000017
Figure PCTCN2016086426-appb-000018
Figure PCTCN2016086426-appb-000019
本发明的一种含内酯环的杀线虫剂均可按照本发明的制备方法得到，下面为表1中化合物的具体实施例：
实施例1
制备表1中序号2的化合物包括下述步骤：
①将1mol邻甲基苯甲醛、0.8mol琥珀酐和1mol无水氯化锌加入300ml二氯甲烷中，在0℃下滴加3mol三乙胺，滴加完毕得到反应液，将反应液置于20℃下搅拌10h，向其中加入盐酸调节反应液的pH至2，加入200ml乙酸乙酯萃取，收集有机相，向有机相中加入200ml甲苯重结晶得到5-氧代-2-(2-甲基苯基)四氢呋喃-3-羧酸；
②将步骤①所得0.5mol 5-氧代-2-(2-甲基苯基)四氢呋喃-3-羧酸和0.4mol4-溴-1,1-二氟-1-丁烯加入500ml甲醇中，加入1.5mol碳酸钾，在20℃下搅拌反应22小时，在真空度0.08kPa下，蒸馏除去甲醇，将剩余物加入100ml二氯甲烷和50ml水搅拌均匀，静置分层，收集二氯甲烷相，将收集的二氯甲烷相在真空度0.08kPa下蒸馏除去二氯甲烷得到产品，即表1中序号2的化合物。
元素分析结果：C,61.93；H,5.20；F,12.25；O,20.62。
核磁分析结果：δ2.24，2H；δ2.34,3H；δ2.52-2.77,2H；δ3.31,1H；δ4.12,2H；δ4.28,1H；δ6.21,1H；δ7.19-7.26，3H；δ7.39,1H。
实施例2
制备表1中序号26的化合物包括下述步骤：
①将1mol4-氟-5-苯氧基苯甲醛、1.2mol琥珀酐和3mol无水氯化锌加入400ml二氯甲烷中，在5℃下滴加5mol三乙胺，滴加完毕得到反应液，将反应液置于30℃下搅拌20h，向其中加入盐酸调节反应液的pH至2，加入250ml乙酸乙酯萃取，收集有机相，向有机相中加入250ml甲苯重结晶得到5-氧代-2-(2-(4-氟-5-苯氧基)苯基)四氢呋喃-3-羧酸；
②将步骤①所得0.5mol5-氧代-2-(2-(4-氟-5-苯氧基)苯基)四氢呋喃-3-羧酸和0.6mol 4-溴-1,1-二氟-1-丁烯加入400ml乙醇中，加入2.5mol碳酸钠，在30℃下搅拌反应26小时，在真空度0.10kPa下，蒸馏除去乙醇，将剩余物加入120ml二氯甲烷和80ml水搅拌均匀，静置分层，收集二氯甲烷相，将收集的二氯甲烷相在真空度0.12kPa下蒸馏除去二氯甲烷得到产品，即表1中序号26的化合物。
元素分析结果：C,59.44；H,3.80；F,17.91；O,18.85
核磁分析结果：δ2.24，2H；δ2.52-2.77,2H；δ3.31,1H；δ4.12,2H；δ6.21,1H；δ7.06-7.14，5H；δ7.27,1H；δ7.41,2H。
实施例3
制备表1中序号41的化合物包括下述步骤：
①将1mol邻三氟甲基苯甲醛、1mol琥珀酐和2mol无水氯化锌加入300ml二氯甲烷中，在5℃下滴加4mol三乙胺，滴加完毕得到反应液，将反应液置于25℃下搅拌15h，向其中加入盐酸调节反应液的pH至2，加入220ml乙酸乙酯萃取，收集有机相，向有机相中加入220ml甲苯重结晶得到5-氧代-2-(2-(三氟甲氧基)苯基)四氢呋喃-3-羧酸；
②将步骤①所得0.5mol5-氧代-2-(2-(三氟甲氧基)苯基)四氢呋喃-3-羧酸和0.5mol 4-溴-1,1,2-三氟-1-丁烯加入380ml丙酮中，加入2.0mol吡啶，在25℃下搅拌反应24小时，在真空度0.10kPa下，蒸馏除去丙酮，将剩余物加入120ml二氯甲烷和100ml水搅拌均匀，静置分层，收集二氯甲烷相，将收集的二氯甲烷相在真空度0.10kPa下蒸馏除去二氯甲烷得到产品，即表1中序号41的化合物。
元素分析结果：C,48.25；H,3.04；F,28.62；O,20.09。
核磁分析结果：δ2.24，2H；δ2.52-2.77,2H；δ3.31,1H；δ4.12,2H；δ6.21,1H；δ6.92-6.96，3H；δ7.25,1H。
实施例4
制备表1中序号46的化合物包括下述步骤：
①将1mol邻三氟甲基苯甲醛、1.1mol琥珀酐和2.5mol无水氯化锌加入300ml二氯甲烷中，在3℃下滴加3.5mol三乙胺，滴加完毕得到反应液，将反应液置于22℃下搅拌12h，向其中加入盐酸调节反应液的pH至2，加入250ml乙酸乙酯萃取，收集有机相，向有机相中加入250ml甲苯重结晶得到5-氧代-2-(2-(三氟甲基)苯基)四氢呋喃-3-羧酸；
②将步骤①所得0.5mol5-氧代-2-(2-(三氟甲基)苯基)四氢呋喃-3-羧酸和0.5mol 4-溴-1,1,2-三氟-1-丁烯加入380ml丙酮中，加入2.0mol三乙胺，在25℃下搅拌反应22小时，在真空度0.10kPa下，蒸馏除去丙酮，将剩余物加入120ml二氯甲烷和100ml水搅拌均匀，静置分层，收集二氯甲烷相，将收集的二 氯甲烷相在真空度0.10kPa下蒸馏除去二氯甲烷得到产品，即表1中序号46的化合物。
元素分析结果：C,50.28；H,3.16；F,29.82；O,16.73。
核磁分析结果：δ2.24，2H；δ2.52-2.77,2H；δ3.31,1H；δ4.12,2H；δ6.21,1H；δ7.29-7.38，3H；δ7.55,1H。
实施例5
制备表1中序号48的化合物包括下述步骤：
①将1mol 3,5-双三氟甲基苯甲醛、0.9mol琥珀酐和2.5mol无水氯化锌加入300ml二氯甲烷中，在4℃下滴加3.5mol三乙胺，滴加完毕得到反应液，将反应液置于22℃下搅拌16h，向其中加入盐酸调节反应液的pH至2，加入250ml乙酸乙酯萃取，收集有机相，向有机相中加入250ml甲苯重结晶得到5-氧代-2-(2-(3,5-双三氟甲基)苯基)四氢呋喃-3-羧酸；
②将步骤①所得0.5mol5-氧代-2-(2-(3,5-双三氟甲基)苯基)四氢呋喃-3-羧酸和0.5mol 4-溴-1,1,2-三氟-1-丁烯加入380ml丙酮中，加入2.0mol三乙胺，在25℃下搅拌反应22小时，在真空度0.10kPa下，蒸馏除去丙酮，将剩余物加入120ml二氯甲烷和100ml水搅拌均匀，静置分层，收集二氯甲烷相，将收集的二氯甲烷相在真空度0.10kPa下蒸馏除去二氯甲烷得到产品，即表1中序号48的化合物。
元素分析结果：C,45.35；H,2.46；F,37.98；O,14.21。
核磁分析结果：δ2.24，2H；δ2.52-2.77,2H；δ3.31,1H；δ4.12,2H；δ6.21,1H；δ7.62，2H；δ7.94,1H。
杀线虫试验
对表1中的化合物采用浸虫法进行了抑制植物病原线虫试验，以测定以上化合物对二龄幼虫的活性，同时参照NY/T 1154.5-2006(第5部分：杀卵活性试验浸渍法)测试以上化合物对线虫卵孵化的抑制活性，结果如表2所示：
表2含内酯环的杀线虫剂的化合物抑制植物病原线虫试验结果
Figure PCTCN2016086426-appb-000020
Figure PCTCN2016086426-appb-000021
Figure PCTCN2016086426-appb-000022
Figure PCTCN2016086426-appb-000023
Figure PCTCN2016086426-appb-000024
Figure PCTCN2016086426-appb-000025
由表1中的数据可知，本发明含内酯环的杀线虫剂的化合物对线虫二龄幼虫及卵均有较好的防治效果，并且对线虫卵的孵化抑制率要比对二龄幼虫的效果好。
毒性试验
根据化学农药环境安全评价试验准则中的蚯蚓毒性试验和土壤微生物毒性试验的步骤对本发明表1中的化合物1～60进行蚯蚓毒性试验和土壤微生物毒性试验，其中土壤微生物试验中模拟的农药常用量为40ppm，两个试验的结果如下：
表2含内酯环的杀线虫剂的化合物的毒性试验结果
Figure PCTCN2016086426-appb-000026
Figure PCTCN2016086426-appb-000027
Figure PCTCN2016086426-appb-000028
由表2中的数据可知，该本发明含内酯环的杀线虫剂的化合物对土壤环境中的生物的毒性低，使用安全，属于环境友好型化合物。

Claims (8)

  1. 一种含内酯环的杀线虫剂，其特征在于：其结构通式I如下所示：
    Figure PCTCN2016086426-appb-100001
    结构通式I，
    其中，R1、R2、R3、R4、R5选自氢、氰基、氟、氯、溴、含1～4个碳原子的烷基、含1～4个碳原子的烷氧基、烷氧苯基、含1～4个碳原子并且碳原子上氢原子被一个或多个氯原子取代的烷氧基、含1～4个碳原子并且碳原子上氢原子被一个或多个氟原子取代的烷氧基、硝基或胺基；
    R6选自氢、氟、氯。
  2. 根据权利要求1所述的含内酯环的杀线虫剂，其特征在于：R6为氟原子。
  3. 根据权利要求2所述的含内酯环的杀线虫剂，其特征在于：R1＝CF3时，R2＝R3＝R4＝R5＝H。
  4. 根据权利要求2所述的含内酯环的杀线虫剂，其特征在于：R1＝OCF3时，R2＝R3＝R4＝R5＝H。
  5. 根据权利要求2所述的含内酯环的杀线虫剂，其特征在于：R1＝R2＝R5＝H，R3＝F时，R4＝-O-C6H5。
  6. 根据权利要求2所述的含内酯环的杀线虫剂，其特征在于：R2＝R4＝CF3时，R1＝R3＝R5＝H。
  7. 权利要求1所述的含内酯环的杀线虫剂的制备方法，其特征在于：包括以下步骤：将
    Figure PCTCN2016086426-appb-100002
    加入溶剂中，加入缚酸剂，在20～30℃下搅拌反应22～26小时，在真空度0.08～0.10kPa下，蒸馏除去溶剂，加二氯甲烷和水搅拌均匀，静置分层除去水，在真空度0.08～0.10kPa下，蒸馏除去二氯甲烷得 到通式I所示的含内酯环的杀线虫剂；其中
    Figure PCTCN2016086426-appb-100003
    和缚酸剂的摩尔比为1∶0.8～1.2∶3～5；
    其中，R1、R2、R3、R4、R5选自氢、氰基、氟、氯、溴、含1～4个碳原子的烷基、含1～4个碳原子的烷氧基、烷氧苯基、含1～4个碳原子并且碳原子上氢原子被一个或多个氯原子取代的烷氧基、含1～4个碳原子并且碳原子上氢原子被一个或多个氟原子取代的烷氧基、硝基或胺基；R6选自氢、氟、氯；
    所述的溶剂为甲醇、乙醇、丙酮、N,N-二甲基甲酰胺或N,N-二甲基甲酰胺；
    所述的缚酸剂为碳酸钾、碳酸钠、吡啶或三乙胺。
  8. 权利要求1所述的含内酯环的杀线虫剂的用途，其特征在于：用于防治农业线虫类病害。
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