WO2017054524A1 - 一种反式结构的含内酯环的杀线虫剂及其制备方法和用途 - Google Patents

一种反式结构的含内酯环的杀线虫剂及其制备方法和用途 Download PDF

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WO2017054524A1
WO2017054524A1 PCT/CN2016/086427 CN2016086427W WO2017054524A1 WO 2017054524 A1 WO2017054524 A1 WO 2017054524A1 CN 2016086427 W CN2016086427 W CN 2016086427W WO 2017054524 A1 WO2017054524 A1 WO 2017054524A1
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low toxicity
carbon atoms
hydrogen
group
nematicide
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French (fr)
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唐剑峰
潘光民
刘杰
赵恭文
吴建挺
李冬蓉
牛芳
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SHANDONG PROVINCE LIANHEN PESTICIDE INDUSTRY Co Ltd
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SHANDONG PROVINCE LIANHEN PESTICIDE INDUSTRY Co Ltd
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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
    • 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 transesterification agent containing a lactone ring having a trans structure, 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 transesterification agent containing a lactone ring, a preparation method and use thereof, and a lactone ring-containing nematicide agent of the trans structure of the present invention, in view of the problems in the prior art. It has good insecticidal activity against nematodes and is less toxic to humans and animals.
  • a trans-structured nematicidal agent containing a lactone ring the structural formula I of which is as follows:
  • 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.
  • R 6 is a fluorine atom.
  • the invention also provides a preparation method of a lactone ring-containing nematicidal agent having a trans structure, comprising the following steps:
  • step 2 will And the acid of the trans structure obtained in step 1. 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 trans structure represented by 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 one of methanol, ethanol, acetone or N,N-dimethylformamide
  • the acid binding agent is one of potassium carbonate, sodium carbonate, pyridine or triethylamine.
  • the invention also provides the use of a lactone ring-containing nematicide having a trans structure for controlling agricultural nematode diseases.
  • the lactone ring-containing nematicide of the trans structure of the present invention has a good control effect on the eggs of the root knot nematode and the second instar larvae due to the structure containing the polyfluorobutene and the lactone ring, especially good.
  • Inhibiting the hatching of root-knot nematode eggs such as cucumber, tomato, tobacco, soybean, etc.; and the lactone ring-containing nematicide of the trans structure of the present invention is less toxic, has less residue in crops, and is suitable for humans and animals. The harm is small, which solves the problem that the existing nematicide is more toxic, and the residue in the crop is more, which improves the safety of agricultural production; the use of pests in a long time does not kill the invention.
  • the nematode produces antibody and has good insecticidal effect; the invention also provides a preparation method of the transester structure containing a lactone ring-containing nematicide, the preparation method has few steps, the process is easy to operate, and is suitable for large-scale industry. produce.
  • a trans-structured nematicidal agent containing a lactone ring the structural formula I of which is as follows:
  • 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 nematicide containing an anti-lactone ring structure of formula, R 6 is a fluorine atom.
  • the invention also provides a preparation method of a lactone ring-containing nematicidal agent having a trans structure, comprising the following steps:
  • step 2 will And the acid of the trans structure obtained in step 1. 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 trans structure represented by 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 one of methanol, ethanol, acetone or N,N-dimethylformamide
  • the acid binding agent is one of potassium carbonate, sodium carbonate, pyridine or triethylamine.
  • the invention also provides the use of a lactone ring-containing nematicide having a trans structure 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. Add hydrochloric acid to adjust the pH of the reaction solution to 2, extract with ethyl acetate, collect the organic phase, and recrystallize by adding toluene. among them The molar ratio of anhydrous zinc chloride to triethylamine is from 1:0.8 to 1.2:1 to 3:3 to 5; the reaction formula is:
  • Table 1 Structural measurement analysis table of a trans-seed nematicide-containing compound of trans structure
  • a lactone ring-containing nematicide of the trans structure 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:
  • step 2 The 5-oxo-2-(2-(trifluoromethoxy)phenyl)tetrahydrofuran-3-carboxylic acid obtained in step 1 was added to a 50% sulfuric acid solution, stirred at 70 ° C for 5 h, filtered, and the filter cake was added. The organic phase is extracted with ethyl acetate and water, and the organic phase is dried over magnesium sulfate. The solvent is evaporated, and the remaining organics are recrystallized from toluene, and dried to give 5-oxy-2-(2-(trifluoro) Oxy)phenyl)tetrahydrofuran-3-carboxylic acid.
  • the preparation of the compound of No. 46 in Table 1 includes the following steps:
  • the preparation of the compound of No. 48 in Table 1 comprises the following steps:
  • the lactone ring-containing nematicidal compound of the trans structure 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 higher than that. Good effect on second instar larvae.
  • 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:
  • Compound 29 >10, low toxicity Less than 50%, low toxicity Compound 30 >10, low toxicity Less than 50%, low toxicity Compound 31 >10, low toxicity Less than 50%, low toxicity Compound 32 >10, low toxicity Less than 50%, low toxicity Compound 33 >10, low toxicity Less than 50%, low toxicity Compound 34 >10, low toxicity Less than 50%, low toxicity Compound 35 >10, low toxicity Less than 50%, low toxicity Compound 36 >10, low toxicity Less than 50%, low toxicity Compound 37 >10, low toxicity Less than 50%, low toxicity Compound 38 >10, low toxicity Less than 50%, low toxicity Compound 39 >10, low toxicity Less than 50%, low toxicity Compound 40 >10, low toxicity Less than 50%, low toxicity Compound 41 >10, low toxicity Less than 50%, low toxicity Compound 42 >10, low toxicity Less than 50%, low toxicity Compound 43 >10, low toxicity Less than 50%, low
  • the transestericide-containing nematicidal 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
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  • Wood Science & Technology (AREA)
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Abstract

一种反式结构的含内酯环的杀线虫剂，其特征在于：其结构通式Ｉ如（Ｉ）所示。其中，R 1、R 2、R 3、R 4、R 5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；R 6选自氢、氟、氯；反式结构的含内酯环的杀线虫剂用于防治农业线虫类病害；反式结构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，尤其能很好地抑制农作物根结线虫卵的孵化；并且毒性较低，在农作物中的残留少提高了农业生产的安全性。

Description

一种反式结构的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，具体涉及一种反式结构的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，提供一种反式结构的含内酯环的杀线虫剂及其制备方法和用途，本发明反式结构的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：
一种反式结构的含内酯环的杀线虫剂，其结构通式I如下所示：
Figure PCTCN2016086427-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，一种反式结构的含内酯环的杀线虫剂，R6为氟原子。
优选的，一种反式结构的含内酯环的杀线虫剂，R1＝CF3时，R2＝R3＝R4＝R5＝H。
优选的，一种反式结构的含内酯环的杀线虫剂，R1＝OCF3时，R2＝R3＝R4＝R5＝H。
优选的，一种反式结构的含内酯环的杀线虫剂，R1＝R2＝R5＝H，R3＝F时，R4＝-O-C6H5。
优选的，一种反式结构的含内酯环的杀线虫剂，R2＝R4＝CF3时，R1＝R3＝R5＝H。本发明还提供了反式结构的含内酯环的杀线虫剂的制备方法，包括以下步骤：
①将具有顺反式外消旋的酸
Figure PCTCN2016086427-appb-000002
加入到体积分数为40～70％的硫酸溶液，50～70℃搅拌3～5小时，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，用甲苯重结晶，干燥得到反式结构的酸
Figure PCTCN2016086427-appb-000003
②将
Figure PCTCN2016086427-appb-000004
和步骤①所得的反式结构的酸
Figure PCTCN2016086427-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所示的反式结构的含内酯环的杀线虫剂；其中
Figure PCTCN2016086427-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；
所述的溶剂为甲醇、乙醇、丙酮或N,N-二甲基甲酰胺中的一种；
所述的缚酸剂为碳酸钾、碳酸钠、吡啶或三乙胺中的一种。
本发明还提供了反式结构的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：
本发明的反式结构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；并且本发明的反式结构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；本发明还提供了该反式结构的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
一种反式结构的含内酯环的杀线虫剂，其结构通式I如下所示：
Figure PCTCN2016086427-appb-000007
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，一种反式结构的含内酯环的杀线虫剂，R6为氟原子。
优选的，一种反式结构的含内酯环的杀线虫剂，R1＝CF3时，R2＝R3＝R4＝R5＝H。
优选的，一种反式结构的含内酯环的杀线虫剂，R1＝OCF3时，R2＝R3＝R4＝R5＝H。
优选的，一种反式结构的含内酯环的杀线虫剂，R1＝R2＝R5＝H，R3＝F时，R4＝-O-C6H5。
优选的，一种反式结构的含内酯环的杀线虫剂，R2＝R4＝CF3时，R1＝R3＝R5＝H。 本发明还提供了反式结构的含内酯环的杀线虫剂的制备方法，包括以下步骤：
①将具有顺反式外消旋的酸
Figure PCTCN2016086427-appb-000008
加入到体积分数为40～70％的硫酸溶液，50～70℃搅拌3～5小时，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，用甲苯重结晶，干燥得到反式结构的酸
Figure PCTCN2016086427-appb-000009
②将
Figure PCTCN2016086427-appb-000010
和步骤①所得的反式结构的酸
Figure PCTCN2016086427-appb-000011
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所示的反式结构的含内酯环的杀线虫剂；其中
Figure PCTCN2016086427-appb-000012
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 PCTCN2016086427-appb-000013
所述的溶剂为甲醇、乙醇、丙酮或N,N-二甲基甲酰胺中的一种；
所述的缚酸剂为碳酸钾、碳酸钠、吡啶或三乙胺中的一种。
本发明还提供了反式结构的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 PCTCN2016086427-appb-000014
可在市场上购买，或采用以下步骤制备：将
Figure PCTCN2016086427-appb-000015
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 PCTCN2016086427-appb-000016
其中
Figure PCTCN2016086427-appb-000017
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 PCTCN2016086427-appb-000018
表1一种反式结构的含内酯环的杀线虫剂的化合物的结构测量分析表
Figure PCTCN2016086427-appb-000019
Figure PCTCN2016086427-appb-000020
Figure PCTCN2016086427-appb-000021
Figure PCTCN2016086427-appb-000022
Figure PCTCN2016086427-appb-000023
Figure PCTCN2016086427-appb-000024
Figure PCTCN2016086427-appb-000025
本发明的一种反式结构的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5-氧代-2-(2-甲基苯基)四氢呋喃-3-羧酸加入40％的硫酸溶液中，50℃搅拌3h，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，剩余的有机物用甲苯重结晶，干燥得到反式结构的5-氧代-2-(2-甲基苯基)四氢呋喃-3-羧酸。
③将步骤②所得0.5mol反式结构的5-氧代-2-(2-甲基苯基)四氢呋喃-3-羧酸和0.4mol 4-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5-氧代-2-(2-(4-氟-5-苯氧基)苯基)四氢呋喃-3-羧酸加入70％的硫酸溶液中，40℃搅拌5h，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，剩余的有机物用甲苯重结晶，干燥得到反式结构的5-氧代-2-(2-(4-氟-5-苯氧基)苯基)四氢呋喃-3-羧酸。
③将步骤②所得0.5mol反式结构的5-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5-氧代-2-(2-(三氟甲氧基)苯基)四氢呋喃-3-羧酸加入50％的硫酸溶液中，70℃搅拌5h，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，剩余的有机物用甲苯重结晶，干燥得到反式结构的5-氧代-2-(2-(三氟甲氧基)苯基)四氢呋喃-3-羧酸。
③将步骤②所得0.5mol反式结构的5-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5-氧代-2-(2-(三氟甲基)苯基)四氢呋喃-3-羧酸加入40％的硫酸溶液中，70℃搅拌4h，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，剩余的有机物用甲苯重结晶，干燥得到反式结构的5-氧代-2-(2-(三氟甲基)苯基)四氢呋喃-3-羧酸。
③将步骤②所得0.5mol反式结构的5-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5-氧代-2-(2-(3,5-双三氟甲基)苯基)四氢呋喃-3-羧酸加入70％的硫酸溶液中，70℃搅拌5h，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，剩余的有机物用甲苯重结晶，干燥得到反式结构的5-氧代-2-(2-(3,5-双三氟甲基)苯基)四氢呋喃-3-羧酸。
③将步骤②所得0.5mol反式结构的5-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含反式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 PCTCN2016086427-appb-000026
Figure PCTCN2016086427-appb-000027
Figure PCTCN2016086427-appb-000028
Figure PCTCN2016086427-appb-000029
Figure PCTCN2016086427-appb-000030
由表1中的数据可知，本发明反式结构的含内酯环的杀线虫剂的化合物对线虫二龄幼虫及卵均有很好的防治效果，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反式内酯环的杀线虫剂的化合物的毒性实验结果
  蚯蚓毒性LC50 土壤微生物毒性(15d)
  (14d)(单位：mg/L) (加量为常量100倍时的抑制率)
化合物1 ＞10，低毒 低于50％，低毒
化合物2 ＞10，低毒 低于50％，低毒
化合物3 ＞10，低毒 低于50％，低毒
化合物4 ＞10，低毒 低于50％，低毒
化合物5 ＞10，低毒 低于50％，低毒
化合物6 ＞10，低毒 低于50％，低毒
化合物7 ＞10，低毒 低于50％，低毒
化合物8 ＞10，低毒 低于50％，低毒
化合物9 ＞10，低毒 低于50％，低毒
化合物10 ＞10，低毒 低于50％，低毒
化合物11 ＞10，低毒 低于50％，低毒
化合物12 ＞10，低毒 低于50％，低毒
化合物13 ＞10，低毒 低于50％，低毒
化合物14 ＞10，低毒 低于50％，低毒
化合物15 ＞10，低毒 低于50％，低毒
化合物16 ＞10，低毒 低于50％，低毒
化合物17 ＞10，低毒 低于50％，低毒
化合物18 ＞10，低毒 低于50％，低毒
化合物19 ＞10，低毒 低于50％，低毒
化合物20 ＞10，低毒 低于50％，低毒
化合物21 ＞10，低毒 低于50％，低毒
化合物22 ＞10，低毒 低于50％，低毒
化合物23 ＞10，低毒 低于50％，低毒
化合物24 ＞10，低毒 低于50％，低毒
化合物25 ＞10，低毒 低于50％，低毒
化合物26 ＞10，低毒 低于50％，低毒
化合物27 ＞10，低毒 低于50％，低毒
化合物28 ＞10，低毒 低于50％，低毒
化合物29 ＞10，低毒 低于50％，低毒
化合物30 ＞10，低毒 低于50％，低毒
化合物31 ＞10，低毒 低于50％，低毒
化合物32 ＞10，低毒 低于50％，低毒
化合物33 ＞10，低毒 低于50％，低毒
化合物34 ＞10，低毒 低于50％，低毒
化合物35 ＞10，低毒 低于50％，低毒
化合物36 ＞10，低毒 低于50％，低毒
化合物37 ＞10，低毒 低于50％，低毒
化合物38 ＞10，低毒 低于50％，低毒
化合物39 ＞10，低毒 低于50％，低毒
化合物40 ＞10，低毒 低于50％，低毒
化合物41 ＞10，低毒 低于50％，低毒
化合物42 ＞10，低毒 低于50％，低毒
化合物43 ＞10，低毒 低于50％，低毒
化合物44 ＞10，低毒 低于50％，低毒
化合物45 ＞10，低毒 低于50％，低毒
化合物46 ＞10，低毒 低于50％，低毒
化合物47 ＞10，低毒 低于50％，低毒
化合物48 ＞10，低毒 低于50％，低毒
化合物49 ＞10，低毒 低于50％，低毒
化合物50 ＞10，低毒 低于50％，低毒
化合物51 ＞10，低毒 低于50％，低毒
化合物52 ＞10，低毒 低于50％，低毒
化合物53 ＞10，低毒 低于50％，低毒
化合物54 ＞10，低毒 低于50％，低毒
化合物55 ＞10，低毒 低于50％，低毒
化合物56 ＞10，低毒 低于50％，低毒
化合物57 ＞10，低毒 低于50％，低毒
化合物58 ＞10，低毒 低于50％，低毒
化合物59 ＞10，低毒 低于50％，低毒
化合物60 ＞10，低毒 低于50％，低毒
由表2中的数据可知，该本发明反式结构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. 一种反式结构的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 PCTCN2016086427-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所述的反式结构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所述的反式结构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所述的反式结构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所述的反式结构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所述的反式结构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所述的反式结构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：
    ①将具有顺反式外消旋的酸
    Figure PCTCN2016086427-appb-100002
    加入到体积分数为40～70％的硫酸溶液，50～70℃搅拌3～5小时，过滤，将滤饼加入乙酸乙酯和水中，萃取收集有机相将有机相经硫酸镁干燥，蒸掉溶剂，用甲苯重结晶，干燥得到反式结构的酸
    Figure PCTCN2016086427-appb-100003
    ②将
    Figure PCTCN2016086427-appb-100004
    和步骤①所得的反式结构的酸
    Figure PCTCN2016086427-appb-100005
    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所示的反式结构的含内酯环的杀线虫剂；其中
    Figure PCTCN2016086427-appb-100006
    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、丙酮或N,N-二甲基甲酰胺中的一种；
    所述的缚酸剂为碳酸钾、碳酸钠、吡啶或三乙胺中的一种。
  8. 权利要求1所述的反式结构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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