WO2017054524A1 - Nematicide of trans structure containing lactone ring and preparation method and use thereof - Google Patents

Abstract

Disclosed is a nematicide of trans structure containing a lactone ring, characterized in that the general structural formula I is as shown in (I). R₁, R₂, R₃, R₄ and R₅ are selected from hydrogen, cyano, fluorine, chlorine, bromine, an alkyl containing 1 to 4 carbon atoms, an alkoxy containing 1 to 4 carbon atoms, alkoxyphenyl, an alkoxy containing 1 to 4 carbon atoms and a hydrogen atom on the carbon atom substituted by one or more chlorine atoms, an alkoxy containing 1 to 4 carbon atoms and a hydrogen atom on the carbon atom substituted by one or more fluorin atoms, nitro or amino; R₆ is selected from hydrogen, fluorine and chlorine; the nematicide of trans structure containing the lactone ring is used for controlling agricultural nematode diseases; because the nematicide of trans structure containing the lactone ring comprises the structure of a polyfluorobutene and a lactone ring, the nematicide has a good control effect on eggs and the second-stage juveniles of a root-knot nematodes, and in particular can fully inhibit the hatching of crop root-knot nematode eggs; and same has a low toxicity, and less residue in crops, thus improving the safety of agricultural production.

Description

Nematic ring-containing nematicidal agent with trans structure, preparation method and use thereof Technical field

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.

technical background

Most of the 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.

Compared with 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.

Summary of the invention

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.

In order to achieve the above objects, the technical solution adopted by the present invention is:

A trans-structured nematicidal agent containing a lactone ring, the structural formula I of which is as follows:

结构通式I，

Structural formula I,

Wherein 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. 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;

R _{6 is} selected from the group consisting of hydrogen, fluorine, and chlorine.

Preferably, a lactone ring-containing nematicide of trans structure, R ₆ is a fluorine atom.

Preferably, a lactone ring-containing nematicide of trans structure, when R ₁ =CF ₃ , R ₂ =R ₃ =R ₄ =R ₅ =H.

Preferably, a lactone ring-containing nematicide of trans structure, when R ₁ =OCF ₃ , R ₂ =R ₃ =R ₄ =R ₅ =H.

Preferably, a lactone ring-containing nematicide having a trans structure, R ₁ = R ₂ = R ₅ = H, and when R ₃ = F, R ₄ = -OC ₆ H ₅ .

Preferably, a lactone ring-containing nematicide of trans structure, when R ₂ =R ₄ =CF ₃ , R ₁ =R ₃ =R ₅ =H. The invention also provides a preparation method of a lactone ring-containing nematicidal agent having a trans structure, comprising the following steps:

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

1 will have a cis-trans racemic acid

Adding to a sulfuric acid solution with a volume fraction of 40 to 70%, stirring at 50 to 70 ° C for 3 to 5 hours, filtering, adding the filter cake to ethyl acetate and water, extracting and collecting the organic phase, drying the organic phase with magnesium sulfate, and evaporating the solvent Recrystallized from toluene and dried to give the acid of the trans structure

和步骤①所得的反式结构的酸

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

和缚酸剂的摩尔比为1∶0.8～1.2∶3～5；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;

Wherein 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. 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 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 advantages of the invention are:

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.

detailed description

A trans-structured nematicidal agent containing a lactone ring, the structural formula I of which is as follows:

结构通式I，

Structural formula I,

Wherein 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. 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;

R _{6 is} selected from the group consisting of hydrogen, fluorine, and chlorine.

Preferably, the nematicide containing an anti-lactone ring structure of formula, R ₆ is a fluorine atom.

Preferably, a lactone ring-containing nematicide of trans structure, when R ₁ =CF ₃ , R ₂ =R ₃ =R ₄ =R ₅ =H.

Preferably, a lactone ring-containing nematicide of trans structure, when R ₁ =OCF ₃ , R ₂ =R ₃ =R ₄ =R ₅ =H.

Preferably, a lactone ring-containing nematicide having a trans structure, R ₁ = R ₂ = R ₅ = H, and when R ₃ = F, R ₄ = -OC ₆ H ₅ .

Preferably, a lactone ring-containing nematicide of trans structure, when R ₂ =R ₄ =CF ₃ , R ₁ =R ₃ =R ₅ =H. The invention also provides a preparation method of a lactone ring-containing nematicidal agent having a trans structure, comprising the following steps:

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

1 will have a cis-trans racemic acid

Adding to a sulfuric acid solution with a volume fraction of 40 to 70%, stirring at 50 to 70 ° C for 3 to 5 hours, filtering, adding the filter cake to ethyl acetate and water, extracting and collecting the organic phase, drying the organic phase with magnesium sulfate, and evaporating the solvent Recrystallized from toluene and dried to give the acid of the trans structure

和步骤①所得的反式结构的酸

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

和缚酸剂的摩尔比为1∶0.8～1.2∶3～5；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;

Wherein 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. 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;

Its reaction formula is:

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.

可在市场上购买，或采用以下步骤制备：将

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

其中

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：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:

Example 1

The preparation of the compound of No. 2 in Table 1 comprises the following steps:

1 1 mol of o-methylbenzaldehyde, 0.8 mol of succinic anhydride and 1 mol of anhydrous zinc chloride were added to 300 ml of dichloromethane, and 3 mol of triethylamine was added dropwise at 0 ° C, and the reaction liquid was obtained by dropwise addition, and the reaction liquid was placed. After stirring at 20 ° C for 10 h, hydrochloric acid was added thereto to adjust the pH of the reaction mixture to 2, and extracted with 200 ml of ethyl acetate. The organic phase was collected, and 200 ml of toluene was added to the organic phase to recrystallize to give 5-oxo-2-(2-methylphenyl)tetrahydrofuran-3-carboxylic acid;

2 The 5-oxo-2-(2-methylphenyl)tetrahydrofuran-3-carboxylic acid obtained in the step 1 was added to a 40% sulfuric acid solution, stirred at 50 ° C for 3 h, filtered, and the filter cake was added to ethyl acetate and water. The organic phase is extracted and dried over magnesium sulfate, the solvent is evaporated, and the remaining organics are recrystallized from toluene and dried to give 5-methoxy-2-(2-methylphenyl)tetrahydrofuran-3- carboxylic acid.

3 0.5 mol of trans-structured 5-oxo-2-(2-methylphenyl)tetrahydrofuran-3-carboxylic acid obtained in step 2 and 0.4 mol of 4-bromo-1,1-difluoro-1-butene After adding 500 ml of methanol, 1.5 mol of potassium carbonate was added, and the reaction was stirred at 20 ° C for 22 hours. At a vacuum of 0.08 kPa, methanol was distilled off, and the residue was added to 100 ml of dichloromethane and 50 ml of water, and the mixture was uniformly stirred. The methylene chloride phase was collected, and the collected dichloromethane phase was distilled off at a vacuum of 0.08 kPa to obtain a product, that is, a compound of the formula 2 in Table 1.

Elemental analysis results: C, 61.93; H, 5.20; F, 12.25; O, 20.62.

Nuclear magnetic analysis results: δ2.24, 2H; δ 2.34, 3H; δ 2.52-2.77, 2H; δ3.31, 1H; δ 4.12, 2H; δ 4.28, 1H; δ 6.21, 1H; δ 7. 19-7.26, 3H; δ 7.39, 1H.

Example 2

The preparation of the compound of No. 26 in Table 1 comprises the following steps:

1 1 mol of 4-fluoro-5-phenoxybenzaldehyde, 1.2 mol of succinic anhydride and 3 mol of anhydrous zinc chloride were added to 400 ml of dichloromethane, and 5 mol of triethylamine was added dropwise at 5 ° C, and the reaction liquid was obtained by dropwise addition. The reaction solution was stirred at 30 ° C for 20 h, hydrochloric acid was added thereto to adjust the pH of the reaction mixture to 2, and extracted with 250 ml of ethyl acetate. The organic phase was collected, and the organic phase was recrystallized by adding 250 ml of toluene to give 5-oxo-2. -(2-(4-fluoro-5-phenoxy)phenyl)tetrahydrofuran-3-carboxylic acid;

2 The 5-oxo-2-(2-(4-fluoro-5-phenoxy)phenyl)tetrahydrofuran-3-carboxylic acid obtained in the step 1 was added to a 70% sulfuric acid solution, stirred at 40 ° C for 5 h, and filtered. The filter cake was added to ethyl acetate and water, and the organic phase was extracted and dried. The organic phase was dried over magnesium sulfate, and the solvent was evaporated, and the remaining organics were recrystallized from toluene and dried to give 5-oxy-2-(2-) (4-Fluoro-5-phenoxy)phenyl)tetrahydrofuran-3-carboxylic acid.

3 0.5 mol of the 5-methoxy-2-(2-(4-fluoro-5-phenoxy)phenyl)tetrahydrofuran-3-carboxylic acid obtained in the step 2 and 0.6 mol of 4-bromo-1, 1-Difluoro-1-butene was added to 400 ml of ethanol, 2.5 mol of sodium carbonate was added, and the reaction was stirred at 30 ° C for 26 hours. At a vacuum of 0.10 kPa, ethanol was distilled off, and the residue was added to 120 ml of dichloromethane and 80 ml. The water was stirred well, and the layers were allowed to stand, and the dichloromethane phase was collected. The collected dichloromethane phase was distilled off at a vacuum of 0.12 kPa to give the product, that is, the compound of No. 26 in Table 1.

Elemental analysis results: C, 59.44; H, 3.80; F, 17.91; O, 18.85.

Nuclear magnetic analysis results: δ2.24, 2H; δ 2.52-2.77, 2H; δ 3.31, 1H; δ 4.12, 2H; δ 6.21, 1H; δ7.06-7.14, 5H; δ 7.27, 1H; δ 7.41, 2H.

Example 3

The preparation of the compound of No. 41 in Table 1 includes the following steps:

1 1 mol of o-trifluoromethylbenzaldehyde, 1 mol of succinic anhydride and 2 mol of anhydrous zinc chloride were added to 300 ml of dichloromethane, 4 mol of triethylamine was added dropwise at 5 ° C, and the reaction liquid was obtained after the dropwise addition, and the reaction liquid was placed. After stirring at 25 ° C for 15 h, hydrochloric acid was added thereto to adjust the pH of the reaction mixture to 2, and extracted with 220 ml of ethyl acetate. The organic phase was collected, and the organic phase was recrystallized by adding 220 ml of toluene to give 5-oxo-2-(2- (trifluoromethoxy)phenyl)tetrahydrofuran-3-carboxylic acid;

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.

3 0.5 mol of trans-structured 5-oxo-2-(2-(trifluoromethoxy)phenyl)tetrahydrofuran-3-carboxylic acid obtained in step 2 and 0.5 mol of 4-bromo-1,1,2- Trifluoro-1-butene was added to 380 ml of acetone, 2.0 mol of pyridine was added, and the reaction was stirred at 25 ° C for 24 hours. The acetone was distilled off under a vacuum of 0.10 kPa, and the residue was added to 120 ml of dichloromethane and 100 ml of water and stirred well. The mixture was allowed to stand for stratification, the dichloromethane phase was collected, and the collected dichloromethane phase was distilled off at a vacuum of 0.10 kPa to obtain a product, that is, a compound of the formula 41 in Table 1.

Elemental analysis results: C, 48.25; H, 3.04; F, 28.62; O, 20.09.

Nuclear magnetic analysis results: δ2.24, 2H; δ 2.52-2.77, 2H; δ 3.31, 1H; δ 4.12, 2H; δ 6.21, 1H; δ 6.92-6.96, 3H; δ 7.25, 1H.

Example 4

The preparation of the compound of No. 46 in Table 1 includes the following steps:

1 1 mol of o-trifluoromethylbenzaldehyde, 1.1 mol of succinic anhydride and 2.5 mol of anhydrous zinc chloride were added to 300 ml of dichloromethane, and 3.5 mol of triethylamine was added dropwise at 3 ° C, and the reaction liquid was obtained by dropwise addition. Reaction solution After stirring at 22 ° C for 12 h, hydrochloric acid was added thereto to adjust the pH of the reaction mixture to 2, and extracted with 250 ml of ethyl acetate. 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;

2 The 5-oxo-2-(2-(trifluoromethyl)phenyl)tetrahydrofuran-3-carboxylic acid obtained in the step 1 was added to a 40% sulfuric acid solution, stirred at 70 ° C for 4 h, filtered, and the filter cake was added to acetic acid. The organic phase is extracted with ethyl acetate and water. The organic phase is dried over magnesium sulfate, and the solvent is evaporated. The remaining organics are recrystallized from toluene and dried to give 5- thio-2-(2-(trifluoromethyl) )phenyl)tetrahydrofuran-3-carboxylic acid.

3 0.5 mol of trans-structured 5-oxo-2-(2-(trifluoromethyl)phenyl)tetrahydrofuran-3-carboxylic acid obtained in step 2 and 0.5 mol of 4-bromo-1,1,2-tri Fluor-1-butene was added to 380 ml of acetone, 2.0 mol of triethylamine was added, and the reaction was stirred at 25 ° C for 22 hours. At a vacuum of 0.10 kPa, acetone was distilled off, and the residue was added to 120 ml of dichloromethane and 100 ml of water and stirred. The product was homogeneous, and the mixture was allowed to stand for separation. The methylene chloride phase was collected, and the collected methylene chloride phase was distilled off at a vacuum of 0.10 kPa to obtain a product, that is, the compound of No. 46 in Table 1.

Elemental analysis results: C, 50.28; H, 3.16; F, 29.82; O, 16.73.

Nuclear magnetic analysis results: δ2.24, 2H; δ 2.52-2.77, 2H; δ 3.31, 1H; δ 4.12, 2H; δ 6.21, 1H; δ 7.29-7.38, 3H; δ 7.55, 1H.

Example 5

The preparation of the compound of No. 48 in Table 1 comprises the following steps:

1 1 mol of 3,5-bistrifluoromethylbenzaldehyde, 0.9 mol of succinic anhydride and 2.5 mol of anhydrous zinc chloride were added to 300 ml of dichloromethane, and 3.5 mol of triethylamine was added dropwise at 4 ° C, and the addition was completed. The reaction solution was stirred at 22 ° C for 16 h, hydrochloric acid was added thereto to adjust the pH of the reaction mixture to 2, and extracted with 250 ml of ethyl acetate. The organic phase was collected, and the organic phase was recrystallized by adding 250 ml of toluene to obtain 5-oxo. 2-(2-(3,5-bistrifluoromethyl)phenyl)tetrahydrofuran-3-carboxylic acid;

2 The 5-oxo-2-(2-(3,5-bistrifluoromethyl)phenyl)tetrahydrofuran-3-carboxylic acid obtained in the step 1 was added to a 70% sulfuric acid solution, stirred at 70 ° C for 5 h, and filtered. The filter cake was added to ethyl acetate and water, and the organic phase was extracted and dried. The organic phase was dried over magnesium sulfate, and the solvent was evaporated, and the remaining organics were recrystallized from toluene and dried to give 5-oxy-2-(2-) (3,5-Bistrifluoromethyl)phenyl)tetrahydrofuran-3-carboxylic acid.

3 0.5 mol of trans-structured 5-oxo-2-(2-(3,5-bistrifluoromethyl)phenyl)tetrahydrofuran-3-carboxylic acid and 0.5 mol of 4-bromo-1 obtained in step 2. 1,2-Trifluoro-1-butene was added to 380 ml of acetone and added 2.0 mol of triethylamine, the reaction was stirred at 25 ° C for 22 hours, the acetone was distilled off under a vacuum of 0.10 kPa, and the residue was added to 120 ml of dichloromethane and 100 ml of water, stirred uniformly, and allowed to stand for separation. The collected dichloromethane phase was distilled off at a vacuum of 0.10 kPa to give the product, that is, the compound of No. 48 in Table 1.

Elemental analysis results: C, 45.35; H, 2.46; F, 37.98; O, 14.21.

Nuclear magnetic analysis results: δ2.24, 2H; δ 2.52-2.77, 2H; δ 3.31, 1H; δ 4.12, 2H; δ 6.21, 1H; δ 7.62, 2H; δ 7.94, 1H.

Nematicidal test

The compounds in Table 1 were tested by the immersion method for the inhibition of phytopathogenic nematodes to determine the activity of the above compounds against the second instar larvae, and tested in accordance with NY/T 1154.5-2006 (Part 5: Oviposition activity test impregnation method) The inhibitory activities of the above compounds on the hatching of nematode eggs are shown in Table 2:

Table 2: Inhibition of phytopathogenic nematodes by compounds of nematicides containing trans lactone ring

It can be seen from the data in Table 1 that 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.

Toxicity test

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:

Table 2 Results of toxicity test of nematicidal compound of trans lactone ring

Toxicity LC50 Soil microbial toxicity (15d)

(14d) (unit: mg/L) (The suppression rate when the amount is 100 times constant) Compound 1 >10, low toxicity Less than 50%, low toxicity Compound 2 >10, low toxicity Less than 50%, low toxicity Compound 3 >10, low toxicity Less than 50%, low toxicity Compound 4 >10, low toxicity Less than 50%, low toxicity Compound 5 >10, low toxicity Less than 50%, low toxicity Compound 6 >10, low toxicity Less than 50%, low toxicity Compound 7 >10, low toxicity Less than 50%, low toxicity Compound 8 >10, low toxicity Less than 50%, low toxicity Compound 9 >10, low toxicity Less than 50%, low toxicity Compound 10 >10, low toxicity Less than 50%, low toxicity Compound 11 >10, low toxicity Less than 50%, low toxicity Compound 12 >10, low toxicity Less than 50%, low toxicity Compound 13 >10, low toxicity Less than 50%, low toxicity Compound 14 >10, low toxicity Less than 50%, low toxicity Compound 15 >10, low toxicity Less than 50%, low toxicity Compound 16 >10, low toxicity Less than 50%, low toxicity Compound 17 >10, low toxicity Less than 50%, low toxicity Compound 18 >10, low toxicity Less than 50%, low toxicity Compound 19 >10, low toxicity Less than 50%, low toxicity Compound 20 >10, low toxicity Less than 50%, low toxicity Compound 21 >10, low toxicity Less than 50%, low toxicity Compound 22 >10, low toxicity Less than 50%, low toxicity Compound 23 >10, low toxicity Less than 50%, low toxicity Compound 24 >10, low toxicity Less than 50%, low toxicity Compound 25 >10, low toxicity Less than 50%, low toxicity Compound 26 >10, low toxicity Less than 50%, low toxicity Compound 27 >10, low toxicity Less than 50%, low toxicity Compound 28 >10, low toxicity Less than 50%, low toxicity

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 toxicity Compound 44 >10, low toxicity Less than 50%, low toxicity Compound 45 >10, low toxicity Less than 50%, low toxicity Compound 46 >10, low toxicity Less than 50%, low toxicity Compound 47 >10, low toxicity Less than 50%, low toxicity Compound 48 >10, low toxicity Less than 50%, low toxicity Compound 49 >10, low toxicity Less than 50%, low toxicity Compound 50 >10, low toxicity Less than 50%, low toxicity Compound 51 >10, low toxicity Less than 50%, low toxicity Compound 52 >10, low toxicity Less than 50%, low toxicity Compound 53 >10, low toxicity Less than 50%, low toxicity Compound 54 >10, low toxicity Less than 50%, low toxicity Compound 55 >10, low toxicity Less than 50%, low toxicity Compound 56 >10, low toxicity Less than 50%, low toxicity Compound 57 >10, low toxicity Less than 50%, low toxicity

Compound 58 >10, low toxicity Less than 50%, low toxicity Compound 59 >10, low toxicity Less than 50%, low toxicity Compound 60 >10, low toxicity Less than 50%, low toxicity

As can be seen from the data in Table 2, 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.

Claims (8)

A trans-structured nematicidal agent containing a lactone ring, characterized in that the structural formula I is as follows:

Structural formula I, Wherein 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. 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; R _{6 is} selected from the group consisting of hydrogen, fluorine, and chlorine. The transestera-containing nematicidal agent according to claim 1, wherein R ₆ is a fluorine atom. The transestera-containing nematicide according to claim 2, wherein when R ₁ = CF ₃ , R ₂ = R ₃ = R ₄ = R ₅ = H. The transestera-containing nematicide according to claim 2, wherein when R ₁ = OCF ₃ , R ₂ = R ₃ = R ₄ = R ₅ = H. The transestera-containing nematicide according to claim 2, wherein R ₁ = R ₂ = R ₅ = H, and when R ₃ = F, R ₄ = -OC ₆ H ₅ . The transestera-containing nematicide according to claim 2, wherein when R ₂ = R ₄ = CF ₃ , R ₁ = R ₃ = R ₅ = H. The method for preparing a transestera-containing nematicidal agent according to claim 1, which comprises the steps of: 1 will have a cis-trans racemic acid

Adding to a sulfuric acid solution with a volume fraction of 40 to 70%, stirring at 50 to 70 ° C for 3 to 5 hours, filtering, adding the filter cake to ethyl acetate and water, extracting and collecting the organic phase, drying the organic phase with magnesium sulfate, and evaporating the solvent Recrystallized from toluene and dried to give the acid of the trans structure

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; Wherein 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. 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 one of methanol, ethanol, acetone or N,N-dimethylformamide; The acid binding agent is one of potassium carbonate, sodium carbonate, pyridine or triethylamine. The use of the transesteroester-containing nematicide of the trans structure of claim 1 for controlling agricultural nematode diseases.