CN110804040B - Preparation method and application of pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl - Google Patents
Preparation method and application of pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl Download PDFInfo
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- CN110804040B CN110804040B CN201911164766.2A CN201911164766A CN110804040B CN 110804040 B CN110804040 B CN 110804040B CN 201911164766 A CN201911164766 A CN 201911164766A CN 110804040 B CN110804040 B CN 110804040B
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
Abstract
The invention relates to a preparation method and application of a pyrazole oxime compound (I) containing difluoromethyl pyrazole bipyridyl. By 1-substituted pyridyl-3-difluoroMethyl pyrazole-4-formyl chloride (II) and 1, 3-dimethyl-5-aryloxy pyrazole oxime (III) react to obtain the compound. The difluoromethyl pyrazole bipyridyl-containing pyrazole oxime compound has an effective control effect on harmful insects, and can be used for preparing pesticides in the fields of agriculture, horticulture and the like.
Description
Technical Field
The invention relates to the field of chemical pesticides, in particular to a preparation method and application of a pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl.
Background
The prevention and control of pests are always the core field of pesticide science research, and the wide use of pesticides enables most pests to be effectively treated. However, with the continuous expansion of the application scale of the pesticide, the problem of drug resistance of the traditional pesticide varieties becomes more and more prominent, and the continuous research and development of new pesticides become necessary choices due to the continuous emergence of new plant diseases and insect pests.
The heterocyclic compound is widely applied in the aspect of agricultural production, and the pyrazole oxime derivative has excellent insecticidal effect as an important heterocyclic compound, wherein a representative compound is fenpyroximate and plays an important role in the field of pesticides.
Substituted pyrazolyl units as important heterocyclic ring segments are often introduced into pesticide compound molecules, such as pyrazole insecticides tebufenpyrad, chlorantraniliprole and the like, and show good insecticidal action.
In view of the above, in order to further find and discover a compound with good insecticidal activity from pyrazole oxime compounds, a substituted pyrazolyl skeleton and a pyrazole oxime unit are connected together, and the invention discloses a difluoromethyl pyrazole bipyridyl-containing pyrazole oxime compound with agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl, which has excellent control effect on pests such as armyworm and the like, is efficient, safe and environment-friendly, and meets the requirement of crop protection on efficient pesticides.
It is a further object of the present invention to provide the use of the above compounds in the preparation of insecticides.
Another object of the present invention is to provide a process for the preparation of the above compounds.
In order to solve the above technical problems, a first aspect of the present invention provides a difluoromethylpyrazole bipyridyl-containing pyrazole oxime compound having the structure of formula I,
preferably, the difluoromethyl pyrazole bipyridyl-containing pyrazole oxime compound has the following structure:
the second aspect of the present invention provides a method for producing the above difluoromethyl pyrazole bipyridyl-containing pyrazole oxime compound, which comprises the steps of:
dissolving a compound III in an organic solvent, adding an acid-binding agent, dropwise adding a mixed solution of an intermediate II and a small amount of solvent, reacting for a period of time after dropwise adding, concentrating mother liquor under reduced pressure, separating and purifying an obtained crude product to obtain a target compound I,
preferably, the preparation method of the pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl comprises the following steps:
among them, 1-substituted pyridyl-3-difluoromethylpyrazole-4-formyl chloride intermediates were synthesized according to conventional methods reported in the literature (organic chemistry, 2011,31, 1943-; the synthesis of 1, 3-dimethyl-5-aryloxypyrazole oxime intermediates is according to the conventional methods reported in the literature (J.Agric.food chem.2008,56, 10805-10810).
The compound of the general formula I has excellent control activity on insects, so that the compound can be used for preparing pesticides to protect plants in agriculture, horticulture and the like. The insects include armyworms and the like. Of course, the pests which the compounds of the invention can control are not limited to the above exemplified ranges.
When the compound of the invention represented by the general formula I is used as an insecticide in the fields of agriculture, horticulture and the like, the compound can be used alone or in the form of an insecticidal composition, for example, the compound is prepared into an aqueous emulsion, a suspending agent, a water dispersible granule, an emulsion and the like by taking the formula I as an active ingredient and adding pesticide auxiliaries commonly used in the field.
Commonly used pesticide adjuvants include liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; common surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants; other adjuvants, such as wetting agents, thickeners, and the like.
When the compound of the present invention represented by the general formula I is used as an active ingredient in an insecticide, the content in the insecticide is selected in the range of 0.1% to 99.5%, and an appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous emulsion contains 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably 10% to 40%; the suspension concentrate contains 5% to 50% of active ingredient, preferably 5% to 40%.
For the use of the insecticide of the present invention, a commonly used application method such as stem and leaf spraying, water surface application, soil treatment, seed treatment, and the like can be selected. For example, when spray application from stems and leaves is employed, the compounds represented by the general formula I as active ingredients can be used in the form of aqueous emulsions, suspensions, water-dispersible granules, emulsifiable concentrates in the concentration range of 1 to 1000. mu.g/mL, preferably in the concentration range of 1 to 500. mu.g/mL.
The pyrazole oxime compound containing difluoromethyl pyrazole bipyridyl disclosed by the invention has good control effect on harmful insects such as armyworm and the like, and therefore, can be used for preparing pesticides used in the fields of agriculture, horticulture and the like.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1:
adding 8mmol of III into a reaction bottlea. 30mmol sodium acetate and 20mL acetonitrile. A mixed solution of 8mmol of intermediate II and 2mL of acetonitrile was slowly dropped thereinto with stirring in an ice bath. After dropping, the mixture was stirred under reflux for 16 hours. Removing the solvent under reduced pressure, and separating the obtained crude product by column chromatography to obtain a target compound Ia;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.14(s,1H,Pyrazole-H),8.11(s,1H,CH＝N),7.96～7.98(m,1H,Py-H),7.67～7.69(m,1H,Ar-H),7.24～7.52(m,3H,Py-H,Ar-H and CHF2),6.76～7.10(m,2H,Ar-H),3.67(s,3H,CH3),2.55(s,3H,CH3).
example 2:
a reaction flask was charged with 7mmol IIIb, 35mmol triethylamine and 30mL tetrahydrofuran. While stirring in an ice bath, a mixed solution of 9mmol of intermediate II and 5mL of tetrahydrofuran was slowly dropped thereinto. After the addition, stirring in ice bath was continued for 10 hours. Removing the solvent under reduced pressure, and separating the obtained crude product by column chromatography to obtain a target compound Ib;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.18(s,1H,CH＝N),8.15(s,1H,Pyrazole-H),7.95～7.98(m,1H,Py-H),7.13～7.53(m,5H,Py-H,Ar-H and CHF2),6.88～6.91(m,1H,Ar-H),3.64(s,3H,CH3),2.54(s,3H,CH3).
example 3:
a reaction flask was charged with 10mmol IIIc, 30mmol pyridine and 20mL dichloromethane. To this was slowly dropped a mixed solution of 15mmol of intermediate II and 6mL of dichloromethane while stirring at room temperature. After dropping, the reaction was heated under reflux for 15 hours. Removing the solvent under reduced pressure, and separating the obtained crude product by column chromatography to obtain a target compound Ic;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.18(s,1H,CH＝N),8.14(s,1H,Pyrazole-H),7.95～7.97(m,1H,Py-H),7.49～7.52(m,1H,Py-H),7.26～7.36(m,2H,Ar-H and CHF2),6.71～6.91(m,3H,Ar-H),3.64(s,3H,CH3),2.54(s,3H,CH3).
example 4:
a reaction flask was charged with 9mmol of IIId, 30mmol of triethylamine and 20mL of N, N-Dimethylacetamide (DMA). While stirring in an ice bath, a mixture of 8mmol of II and 6mL of N, N-Dimethylacetamide (DMA) was slowly dropped thereinto. After the completion of the dropwise addition, the reaction mixture was heated to 85 ℃ to react for 12 hours. After the solvent is removed, the obtained crude product is separated by column chromatography to obtain a target object Id;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.15(s,1H,CH＝N),8.13(s,1H,Pyrazole-H),7.95～7.97(m,1H,Py-H),7.25～7.51(m,2H,Py-H and CHF2),6.93～7.09(m,4H,Ar-H),3.65(s,3H,CH3),2.53(s,3H,CH3).
example 5:
a reaction flask was charged with 6mmol IIIe, 36mmol N, N-Diisopropylethylamine (DIPEA) and 20mL acetone. While stirring in an ice bath, a mixture of 9mmol of II and 5mL of acetone was slowly dropped thereinto. After the completion of the dropwise addition, the reaction was continued at room temperature for 22 hours. After the solvent is removed, the obtained crude product is separated by column chromatography to obtain a target object Ie;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.14(s,1H,CH＝N),8.12(s,1H,Pyrazole-H),7.95～7.97(m,1H,Py-H),7.48～7.51(m,1H,Py-H),7.15～7.40(m,4H,Ar-H and CHF2),6.97(d,J＝8.0Hz,2H,Ar-H),3.64(s,3H,CH3),2.55(s,3H,CH3).
example 6:
a reaction flask was charged with 8mmol of IIIf, 30mmol of 4-Dimethylaminopyridine (DMAP) and 25mL of DMF. While stirring in an ice bath, a mixture of 10mmol of II and 5mL of DMF was slowly dropped thereinto. After the completion of the dropwise addition, the reaction was continued at room temperature for 28 hours. After the solvent is removed, the obtained crude product is separated by column chromatography to obtain a target object If;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.16(s,1H,CH＝N),8.14(s,1H,Pyrazole-H),7.95～7.97(m,1H,Py-H),7.48～7.52(m,1H,Py-H),7.26～7.39(m,3H,Ar-H and CHF2),6.91(d,J＝9.2Hz,2H,Ar-H),3.64(s,3H,CH3),2.53(s,3H,CH3).
example 7:
a reaction flask was charged with 6mmol IIIg, 25mmol N, N-Diisopropylethylamine (DIPEA) and 20mL N, N-Dimethylacetamide (DMA). While stirring in an ice bath, a mixture of 8mmol of II and 5mL of N, N-Dimethylacetamide (DMA) was slowly dropped thereinto. After the completion of the dropwise addition, the reaction mixture was heated to 90 ℃ and reacted for 19 hours. After the solvent is removed, the obtained crude product is separated by column chromatography to obtain a target product Ig;1H NMR(400MHz,CDCl3)δ:8.53～8.55(m,1H,Py-H),8.16(s,1H,CH＝N),8.14(s,1H,Pyrazole-H),7.95～7.97(m,1H,Py-H),7.66(d,J＝8.4Hz,2H,Ar-H),7.26～7.52(m,2H,Py-H and CHF2),6.74(d,J＝8.8Hz,2H,Ar-H),3.63(s,3H,CH3),2.53(s,3H,CH3).
example 8:
insecticidal activity screening of samples against armyworm
The leaf soaking method proposed by the International Resistance Action Committee (IRAC) was adopted: the target for testing is armyworm, namely, a proper amount of corn leaves are fully soaked in prepared liquid medicine and then naturally dried in the shade, the corn leaves are placed into a culture dish filled with filter paper, 10 heads/dish of armyworm larvae in the 3-instar middle stage are connected, the corn leaves are placed into an observation room for culture at 24-27 ℃, and the result is investigated after 2 days. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The assay concentration was 500. mu.g/mL.
Example 9:
screening of insecticidal Activity of samples against aphids
The spray method proposed by the International Resistance Action Committee (IRAC) was used: the test target is aphid, namely broad bean leaves connected with the aphid are sprayed under a Potter spray tower, the processed aphid is cultured in an observation room at 20-22 ℃, and the result is investigated after 2 days. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration was 500. mu.g/mL (other concentrations of drug solution could be diluted with 500. mu.g/mL).
The result of the insecticidal activity test shows that the target objects Ia, Ib, ic, id, ie, if and Ig all show excellent insecticidal activity to armyworms. At a test concentration of 500. mu.g/mL (Table 1), the target substances Ia, Ib, ic, id, ie, if and Ig gave pesticidal rates of 100%, 100%, 100%, 100%, 100%, 100% and 100% for armyworm, respectively; in addition, the target substance Ia also shows good insecticidal effect on aphids, and the insecticidal rate reaches 100%.
TABLE 1 Primary insecticidal Activity data for Ia-Ig
"-" means not determined
The test results show that the novel pyrazole oxime compound obtained by combining the difluoromethyl pyrazole bipyridyl framework and the pyrazole oxime fragment has excellent insecticidal effect, and provides important test data for continuously researching novel pyrazole oxime derivatives in the future.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A difluoromethyl pyrazole bipyridyl-containing pyrazole oxime compound I is characterized by having the following structure:
2. a process for the preparation of difluoromethyl pyrazole bipyridyl-containing pyrazole oxime compound I according to claim 1, which comprises the following steps:
3. use of difluoromethyl pyrazole bipyridyl-containing pyrazole oxime compound I as claimed in claim 1 for the preparation of a pesticidal agent.
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