CN106243039A - Preparation method and application containing the pyrazoles oxime compound of 1 methyl 3 ethyl 4 chlorine 5 formoxyl pyrrazole structure - Google Patents

Abstract

The present invention relates to a kind of pyrazoles oxime compound (I) containing 1 methyl 3 ethyl 4 chlorine 5 formoxyl pyrrazole structure and its preparation method and application.It is condensed to yield with 1 methyl 3 ethyl 4 chlorine pyrazoles 5 formoxyl chlorine (III) by pyrazoles oxime (II).The described pyrazoles oxime compound (I) containing 1 methyl 3 ethyl 4 chlorine 5 formoxyl pyrrazole structure has prevention effect to harmful insect, and the type compound can be used for preparing the insecticide in the fields such as agricultural, gardening.

Description

Pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure The preparation method and application of

technical field

The invention belongs to the field of pesticides, and in particular relates to a pyrazole oxime compound containing a 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure and a preparation method and application thereof.

Background technique

Pest control has always been the core field of pesticide scientific research, and the widespread use of insecticides has enabled most pests to be effectively controlled. However, with the continuous expansion of the application scale of pesticides, the problem of resistance to traditional pesticides has become increasingly prominent, coupled with the continuous emergence of new pests and diseases, making the continued research and development of new pesticides an inevitable choice.

Pyrazole oxime compounds are an important class of nitrogen-containing heterocyclic compounds, and their representative compounds, such as pyraflux, play an important role in killing insects in the field of pesticides.

In recent years, some related studies have reported that pyrazole oxime compounds show excellent insecticidal effects. For example, Shi et al. found that pyrazole oxime compound A containing a furan heterocyclic structure exhibited insecticidal activity against diamondback moth. When the test concentration was 400 μg/mL, the control effect of compound A on Plutella xylostella was 71% (Chin.J.Org.Chem.2015,35,1785-1791); the pyrazole containing pyridine heterocyclic structure reported by Dai et al. Oxime compound B has a good inhibitory effect on aphids. When the test dose of compound B is 400 μg/mL, the killing rate of aphids is 90% (Chin. J. Org. Chem. 2015, 35, 2399-2404).

Pyrazole rings are widely used in agricultural production. Pyrazole compounds have excellent insecticidal and acaricidal activities. Pyrazole heterocycles are widely introduced into pesticide compound molecules, such as pyrazole amide insecticide and acaricide It has excellent killing activity against mites and aphids (Biochim. Biophys. Acta 1998, 1364, 236-244).

Therefore, in order to find and discover compounds with better biological activity from pyrazole oxime, pyrazole oxime and substituted pyrazole heterocyclic units are rationally spliced together with pyrazole oxime as the parent, and it is expected to obtain insecticidal activity. of new compounds.

Contents of the invention

The object of the present invention is to provide a class of pyrazoles containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure that have excellent control effects against various pests, and are highly efficient, safe and environmentally friendly. Oxime compounds to meet the demand for high-efficiency insecticides for crop protection.

Another object of the present invention is to provide the preparation method of the above compound.

Another object of the present invention is to provide the use of the above compounds in the preparation of insecticides.

The object of the present invention can be achieved through the following measures:

The pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure of the present invention is characterized in that it has the following structure:

The preparation method of this type of pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure is characterized in that compounds Ia-Ie can be synthesized by the following reactions:

Among them, intermediates IIa-IIe can be synthesized by referring to the method in the literature (J.Agric.Food Chem.2008,56,10805-10810); the synthesis of intermediate III can be obtained by referring to the conventional method reported in the literature (J.Agric.Food Chem. 2013, 61, 8730-8736).

The compound of general formula I has excellent control activity on insects, so the compound of the present invention can be used to prepare insecticides, and further protect plants such as agriculture and gardening. The insects include armyworm, rice planthopper, aphid and the like. Of course, the harmful organisms that can be controlled by the compounds of the present invention are not limited to the scope of the above examples.

When the compound of the present invention represented by general formula I is used as an insecticide in fields such as agriculture and horticulture, it can be used alone or in the form of an insecticidal composition, such as using formula I as an active ingredient, plus the field Commonly used pesticide adjuvants are processed into aqueous emulsions, suspension concentrates, water-dispersible granules, emulsifiable concentrates, etc.

Commonly used pesticide adjuvants include: liquid carriers, such as water; organic solvents such as toluene, xylene, cyclohexanol, methyl alcohol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and Vegetable oils and fatty acids; commonly used surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; other additives, such as wetting agents, thickeners, etc. .

When the compound of the present invention represented by general formula I is used as an active ingredient in an insecticide, the content in the insecticide can be selected within the range of 0.1% to 99.5%, and can be selected according to the formulation form and application Methods to determine the appropriate active ingredient content. Usually, contain 5% to 50% (weight percentage, the same below) described active component in aqueous emulsion, preferably its content is 10% to 40%; Contain 5% to 50% active component in suspension concentrate, preferably Its content is 5% to 40%.

For the use of the insecticide of the present invention, commonly used pesticide application methods can be selected, such as stem and leaf spray, water surface application, soil treatment and seed treatment and the like. For example, when spraying stems and leaves, the compound represented by the general formula I as an active ingredient can be used in aqueous emulsions, suspensions, water-dispersible granules, and emulsifiable concentrates in a concentration range of 1 to 1000 μg/mL, preferably at a concentration of 1 to 500 μg/mL.

The pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure disclosed by the present invention has excellent control effect on harmful insects, so it can be used to prepare Insecticides in horticulture and other fields.

detailed description

In order to facilitate a further understanding of the present invention, the examples provided below illustrate it in more detail. These examples are for illustration only and are not intended to limit the scope or practice principles of the present invention.

Example 1:

5 mmol of compound IIa was dissolved in 20 mL of dichloromethane, followed by the addition of 15 mmol of pyridine. Add 6mmol of intermediate III to it under ice-bath conditions, and after the addition is complete, continue to stir in ice-bath for 5 hours. The reaction solution was rotary evaporated to dryness under reduced pressure, and the obtained residue was separated and purified by column chromatography to obtain the target compound Ia. ¹ H NMR (400MHz, CDCl ₃ ): δ8.18(s, 1H, CH=N), 7.29-7.35(m, 1H, Ar-H), 6.71-6.90(m, 3H, Ar-H), 4.11 (s, 3H, N-CH ₃ ), 3.63 (s, 3H, N-CH ₃ ), 2.65 (q, J=7.6Hz, 2H, CH ₂ ), 2.52 (s, 3H, CH ₃ ), 1.23 ( t,J=7.6Hz,3H,CH ₃ ).

Example 2:

6 mmol of compound IIb was dissolved in 30 mL of tetrahydrofuran, followed by the addition of 24 mmol of triethylamine. 9mmol of Intermediate III was added thereto under ice-bath conditions, and after the addition was complete, stirring was continued for 9 hours in ice-bath. The reaction solution was rotary evaporated to dryness under reduced pressure, and the obtained residue was separated and purified by column chromatography to obtain the target compound Ib. ¹ H NMR (400MHz, CDCl ₃ ): δ8.17(s, 1H, CH=N), 7.27-7.31(m, 1H, Ar-H), 7.14(d, J=8.0Hz, 1H, Ar-H ),6.83-6.99(m,2H,Ar-H),4.11(s,3H,N-CH ₃ ),3.63(s,3H,N-CH ₃ ),2.65(q,J＝7.6Hz,2H, CH ₂ ), 2.52(s,3H,CH ₃ ), 1.23(t,J=7.6Hz,3H,CH ₃ ).

Example 3:

4 mmol of compound IIc was dissolved in 25 mL of chloroform, followed by the addition of 20 mmol of triethylamine. At room temperature, 5 mmol of intermediate III was added thereto, and after the addition was completed, the reaction was heated under reflux for 10 hours. The reaction solution was rotary evaporated to dryness under reduced pressure, and the obtained residue was separated and purified by column chromatography to obtain the target compound Ic. ¹ H NMR (400MHz, CDCl ₃ ): δ8.15(s, 1H, CH=N), 7.65(d, J=9.2Hz, 2H, Ar-H), 6.74(d, J=8.8Hz, 2H, Ar-H), 4.11 (s, 3H, N-CH ₃ ), 3.62 (s, 3H, N-CH ₃ ), 2.64 (q, J=7.6Hz, 2H, CH ₂ ), 2.51 (s, 3H, CH ₃ ), 1.24(t, J=7.6Hz, 3H, CH ₃ ).

Example 4:

8 mmol of compound IId was dissolved in 30 mL of acetonitrile, followed by the addition of 20 mmol of pyridine. At room temperature, 10 mmol of intermediate III was added thereto, and after the addition was completed, the reaction was heated under reflux for 12 hours. The reaction solution was rotary evaporated to dryness under reduced pressure, and the obtained residue was separated and purified by column chromatography to obtain the target compound Id. ¹ H NMR (400MHz, CDCl ₃ ): δ8.17(s, 1H, CH=N), 7.22(d, J=8.4Hz, 2H, Ar-H), 6.98(d, J=9.2Hz, 2H, Ar-H), 4.10 (s, 3H, N-CH ₃ ), 3.64 (s, 3H, N-CH ₃ ), 2.65 (q, J=7.6Hz, 2H, CH ₂ ), 2.51 (s, 3H, CH ₃ ), 1.23(t, J=7.6Hz, 3H, CH ₃ ).

Example 5:

5 mmol of compound IIe was dissolved in 25 mL of chloroform, followed by the addition of 25 mmol of triethylamine. At room temperature, 8 mmol of intermediate III was added thereto, and after the addition was completed, the reaction was heated under reflux for 13 hours. The reaction solution was rotary evaporated to dryness under reduced pressure, and the obtained residue was separated and purified by column chromatography to obtain the target compound Ie. ¹ H NMR (400MHz, CDCl ₃ ): δ8.11(s, 1H, CH=N), 7.15(d, J=8.4Hz, 2H, Ar-H), 6.85(d, J=8.8Hz, 2H, Ar-H), 4.10 (s, 3H, N-CH ₃ ), 3.62 (s, 3H, N-CH ₃ ), 2.64 (q, J=7.6Hz, 2H, CH ₂ ), 2.52 (s, 3H, CH ₃ ), 2.33(s,3H,Ar-CH ₃ ), 1.23(t,J=7.6Hz,3H,CH ₃ ).

Embodiment 6:

Screening of samples for insecticidal activity against armyworm

The leaf soaking method proposed by the International Resistance Action Committee (IRAC) was adopted: the target of the test was armyworm, that is, an appropriate amount of corn leaves were fully infiltrated in the prepared medicinal solution, dried naturally in the shade, put into a petri dish lined with filter paper, and inoculated. 10 mid-instar larvae of Armyworm larvae were cultured in an observation room at 24-27°C, and the results were observed after 2 days. Touch the insect body with a brush, and if there is no response, it is regarded as a dead insect. The test concentration is 500 μg/mL (other concentrations of the drug solution can be obtained by diluting the 500 μg/mL drug solution).

Embodiment 7:

Insecticidal activity screening of samples against aphids and brown planthoppers

The spraying method proposed by the International Resistance Action Committee (IRAC) was adopted: the test targets were aphids and rice brown planthoppers, that is, the broad bean leaves inoculated with aphids and the rice seedlings inoculated with brown planthoppers were sprayed under the Potter spray tower, and the cinnabar leaves were treated. The mites and brown planthoppers were cultured in the observation room at 24-27°C, and the aphids were cultured in the observation room at 20-22°C, and the results were investigated after 48 hours. Touch the insect body with a brush, and if there is no response, it is regarded as a dead insect. The test concentration is 500 μg/mL (other concentrations of the drug solution can be obtained by diluting the 500 μg/mL drug solution).

Insecticidal activity test results showed that all compounds exhibited insecticidal activity. When the test dose was 500 μg/mL (Table 1), the inhibitory effect of compound Ⅰb on armyworm was 60%; the killing effects of compounds Ⅰa and Ⅰb on aphids were 100% and 90% respectively; The inhibition rates were 80%, 90% and 80%, respectively.

Table 1. Insecticidal activity data for Ia-Ie

The above experimental data show that the pyrazole containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure is obtained by rationally combining multi-substituted pyrazole groups and pyrazole oxime active units. Oxime compounds show good insecticidal activity. These experimental data provide an important structure selection model and theoretical basis for continuing to engage in the synthesis and biological activity of new pyrazole oxime compounds in the future.

Claims (3)

1. the pyrazoles oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formoxyl pyrrazole structure, it is characterised in that possess Following structure:

2. a preparation method for the pyrazoles oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formoxyl pyrrazole structure, it is special Levy and be that compound Ia～Ie shown in claims 1 obtains by being synthesized as follows:

3. the purposes in terms of preparing insecticide of the compound as shown in claim 1.