CN109912585B - Pyridine pyrazole-4-formamide compound based on sulfur-containing functional group and preparation method and application thereof - Google Patents
Pyridine pyrazole-4-formamide compound based on sulfur-containing functional group and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a pyridine pyrazole-4-carboxamide compound based on sulfur-containing functional groups and a preparation method and application thereof, wherein the pyridine pyrazole-4-carboxamide compound is subjected to further structural modification, fatty amide is latent in 1,3, 4-oxadiazole and dihydrazide, and the sulfur-containing functional groups are connected by an active substructure splicing method, so that a series of pyridine pyrazole-4-carboxamide compounds with sulfur-containing functional groups, which are not reported in documents, are obtained. The compound has great change on the lead chlorantraniliprole, has excellent effect of preventing harmful insects, can be used as an active ingredient of various agricultural and horticultural crop insecticides, and has the advantages of high efficiency, low toxicity and environmental friendliness.
Description
Technical Field
The invention relates to the field of pesticides, in particular to a pyridine pyrazole-4-formamide compound based on a sulfur-containing functional group, and a preparation method and application thereof.
Technical Field
With the wide application of pesticides, people have more and more profound understanding on the pesticides. The continuous progress and development of society has led to the profound change of the concept of pesticide. The traditional pesticide in the past can not meet the development requirements of the current society, and the discovery of novel broad-spectrum pesticide with high efficiency, low toxicity and low residue, which is environment-friendly, is an urgent problem to be solved before scientific researchers.
The formanilide compound is an effective pesticide for lepidoptera pests which is developed in recent years. A new class of compounds targeted at the ryanodine receptor was developed by Dupont, USA in 2000. The compound has the characteristics of high efficiency, low toxicity, broad spectrum, safety, environmental friendliness and the like. It represents a compound Chlorantraniliprole (common name: Chlorantraniliprole, trade name: Aliaco, Coragen, Rynaxypyr) having excellent insecticidal activity against various agricultural and horticultural lepidopteran pests.
The formanilide compound has attracted the general attention of scientific researchers in the creation field as a pesticide, and is rapidly one of the latest hotspots for the creation research of new pesticides. Formanilide compounds can be divided into three groups according to their structural features, as shown in the following formula: a benzene ring moiety (A), an aromatic amine moiety (B), and an aliphatic amine moiety (C).
In the structural modification of the benzene ring part (A), the most successful representative is cyantraniliprole (WO 2004067528), the cyantraniliprole is a second-generation ryanodine receptor inhibitor pesticide successfully developed by Dupont company after chlorantraniliprole, and the cyantraniliprole is formed by changing various polar groups on the benzene ring, has higher efficiency, is more widely applicable to crops, and can effectively control lepidoptera, hemiptera and coleopteran pests. DuPont also reports structural transformations of benzene ring, substituted benzene ring, naphthalene ring, heterocycle, fused heterocycle, etc., in the literature (Bioorg Med Chem Lett,2007,17(22): 6274-. In addition, CN 102924433A reports that a benzene ring is replaced by methyl to synthesize a series of pyridine-containing pyrazole formyl acetyl derivatives, and the compounds have agricultural insecticidal efficacy.
In the structural modification of the aromatic amine moiety (B), the main groups are derivatization of an amide bond and R2A change in (c). Derivatisation at amide groupsIn the publication, US 20040186141 reports that the position of pyridylpyrazole in chlorantraniliprole is changed, and a pyridine ring is directly connected to an N atom of the chlorantraniliprole to show certain insecticidal activity; US 2004192731 reports substitution of the amide group with a sulfonamide group, these compounds have less activity analysis but none of them has been shown to be as active as chlorantraniliprole from preliminary activity tests; WO 2007043677 reports that converting amide groups to thioamide groups, exhibit a certain insecticidal activity; WO 2012163095A1 reports that amide is modified into carbonyl thiourea, and the control of part of compounds on plutella xylostella, corn borer, plutella xylostella and beet armyworm can reach 100% at lower concentration; at R2In the variation (2), the U.S. DuPont company WO 0170671A 2 first reported R in 20012The influence of substituents on the activity of such compounds, R is stated in the patent2The activity of the group is obviously improved when N, S-containing heterocyclic rings (such as pyridine, pyrazole, oxazole, triazole and thiazole) are taken as substituent groups, and the activity is also obviously improved when heterocyclic-benzene ring or heterocyclic-heterocyclic ring is taken as substituent groups, wherein R2The most active substituent is the pyridylpyrazole group. Lahm et al, 2007 on R2The structure-activity relationship research of the compound with pyridine pyrazole substituent is carried out, and the result shows that when the 3-position of pyrazole is different substituent, the activity size relationship is as follows: OCH (OCH)3<OCHF2<OCH2CF3，Cl<Br≈CF3(Bioorg Med Chem,2009,174: 127-4133.). The group of Li's famous academy subjects in 2010 replaced the bromine at the 3-position of pyrazole with azidomethyl group, and showed some activity against diamond back moth at 80ppm (J.Agric.food chem.2010,58(23), 12327-12336.). CN 103467380A replaces the pyridine group with the nitro-substituted phenyl group, and shows excellent insecticidal effect on diamondback moth and armyworm at low concentration.
In the structural modification of the fatty amine moiety (C), the main groups are the derivatization of an amide bond and R3A change in (c). In the derivatization of amide bonds, US 2004192731 reports changing amides to sulfonamides, WO 2007043677 changes amides to sulfamides, and WO 2007024833 reports inserting a carbonyl group in the amide bond to give a structure similar to the carbonyl amide group. The modified compounds all show certainThe pesticidal activity of (a); at R3In the change, CN 102093335A reports that the amide is modified into hydrazone, and shows better activity on the diamond back moth; WO 2006040113A 2 reports that amino groups are modified with fatty alkyl, alkylamine and the like, and the modified amino groups have good activity on diamondback moth and armyworm.
Disclosure of Invention
The invention aims to synthesize a pyridine pyrazole-4-formamide compound with a brand-new structure and a sulfur-containing functional group, which can be used for preparing pesticides for preventing and treating agricultural insect pests. The specific technical scheme is as follows:
fatty amide in a benzamide structure is respectively hidden in 1,3, 4-oxadiazole and dihydrazide, a sulfur-containing functional group is connected by an active substructure splicing method, a lead is structurally modified, and a series of pyridine pyrazole-4-formamide compounds based on the sulfur-containing functional group and represented by general formulas (I) and (II) which are not reported in documents are synthesized,
in the general formulas (I) and (II),
X1or X2Each independently is chlorine, bromine or hydrogen;
R1is methylsulfinyl, methylsulfonyl, dimethylsulfide, dimethylsulfoxide or dimethylsulfone;
R2is methylthio, methylsulfinyl or methylsulfonyl.
The specific chemical formulas of the above general formulas (I) and (II) are:
3-bromo-N- (4-chloro-2-methyl-6- (5- (methylsulfinyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (5- (methylsulfonyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-bromo-2-methyl-6- (5- (methylsulfinyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-bromo-2-methyl-6- (5- (methylsulfonyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylthio) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-bromo-2-methyl-6- (5- ((methylsulfinyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-bromo-2-methyl-6- (5- ((methylsulfonyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-6- (5- ((methylsulfonyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1H-pyrazole-5-carboxamide,
3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-6- (5- ((methylsulfinyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1H-pyrazole-5-carboxamide,
3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-6- (5- ((methylthio) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylthio) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylsulfinyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylsulfonyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylthio) acetyl) hydrazinocarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylsulfinyl) acetyl) hydrazinecarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-bromo-2-methyl-6- (2- (2- (methylthio) acetyl) hydrazinecarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-bromo-2-methyl-6- (2- (2- (methylsulfinyl) acetyl) hydrazinecarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylsulfonyl) acetyl) hydrazinecarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide,
3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-6- (2- (2- (methylsulfinyl) acetyl) hydrazinecarbonyl) phenyl) -1H-pyrazole-5-carboxamide,
3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-6- (2- (2- (methylsulfonyl) acetyl) hydrazinecarbonyl) phenyl) -1H-pyrazole-5-carboxamide
And/or 3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-6- (2- (2- (methylthio) acetyl) hydrazinecarbonyl) phenyl) -1H-pyrazole-5-carboxamide.
The preparation method of the pyridine pyrazole-4-carboxamide compound based on the sulfur-containing functional group comprises the following steps:
the preparation method of the pyridine pyrazole-4-formamide compound containing the sulfur functional group represented by the general formula (I) comprises the following steps:
s1-1: intermediate M1 was reacted with CS in methanol solvent2The MeONa is refluxed and reacted under the alkaline condition to obtain an intermediate M2;
s1-2: reacting the intermediate M2 obtained in the step S1-1 with methyl iodide in an inert solution, and oxidizing with MCPBA to obtain a pyridine pyrazole-4-formamide compound based on a sulfur-containing functional group, which is shown as a general formula (I-1); the specific reaction route is as follows:
the compound based on a pyridinylpyrazole-4-carboxamide having a sulfur-containing functional group represented by the general formula (I-1) includes the following:
the preparation method of the pyridine pyrazole-4-formamide compound containing the sulfur functional group represented by the general formula (II) comprises the following steps:
s2-1: reacting the intermediate M1 with methylthio acetic acid under the condition of DMF to obtain a compound shown as a general formula (II-1);
s2-2: oxidizing the compound with the general formula (II-1) obtained in the step S2-1 in an inert solvent by using MCPBA to obtain a pyridylpyrazole-4-formamide compound with a structure containing thioether and derivatives thereof shown in the general formula (II-2); the reaction route is as follows:
the compound represented by the general formula (II-2) based on a pyridinylpyrazole-4-carboxamide compound having a sulfur-containing functional group includes the following substances:
the invention also provides another preparation method of the pyridine pyrazole-4-formamide compound containing the sulfur functional group represented by the general formula (I), which comprises the following specific steps:
s3-1: dehydrating and condensing the compound represented by the general formula (II-1) obtained in step S2-1 of claim 6 with PTSC to obtain a compound represented by the general formula (I-2').
S3-2: oxidizing the compound of the formula ((I-2') obtained in the step S3-1 with MCPBA in an inert solvent to obtain a pyridylpyrazole-4-carboxamide compound based on a sulfur-containing functional group represented by the formula (I-2), wherein the reaction scheme is as follows:
the compound represented by the general formula (I-2) based on a pyridine-pyrazole-4-carboxamide compound having a sulfur-containing functional group comprises the following substances:
in the preparation method of the pyridine pyrazole-4-carboxamide compound containing sulfur functional groups, the used alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate; the inert solvent is one of N, N-dimethylformamide, N-dimethylacetamide, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, diethyl ether, methyl tert-butyl ether, benzene, chlorobenzene, toluene or 1, 4-dioxane.
The invention also provides an agricultural and horticultural insecticide which is the pyridine pyrazole-4-carboxamide compound based on sulfur-containing functional groups prepared by the method of the invention as an active ingredient.
The invention has the beneficial effects that:
according to the invention, starting from the development direction of new pesticides, the benzamide compounds are further structurally modified, fatty amide is latent in 1,3, 4-oxadiazole and dihydrazide, and the sulfur-containing functional groups are connected by an active substructure splicing method, so that a series of pyridine pyrazole-4-carboxamide compounds with the sulfur-containing functional groups, which are not reported in documents, are obtained.
The method is simple and convenient to operate, and the obtained pyridine pyrazole-4-formamide compound with the sulfur-containing functional group has larger change compared with the lead chlorantraniliprole, but has better insecticidal activity by performing a biological activity test on the compound; the pyridine pyrazole-4-carboxamide compound with the sulfur-containing functional group is used as an active ingredient of agricultural and horticultural insecticides and has excellent prevention effect on harmful insects such as lepidoptera, hemiptera, coleopteran and the like; and the pesticide also has the advantages of high efficiency, low toxicity and environmental friendliness.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the following specific embodiments:
example 1: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylthio) acetyl) hydrazinocarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
In a 100mL single-neck flask, intermediate 3-bromo-N- (4-chloro-2- (hydrazinocarbonyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.48g,1mmol), methylthioacetic acid (0.10g, 1.0mmol) and TBTU (0.35g, 1.1mmol) were dissolved in 20mL of N, N-Dimethylformamide (DMF), stirred at room temperature for 15min, then TEA (0.30g, 3.0mmol) was added and stirred continuously, the reaction was allowed to react for 3H, TLC point plate tracking was performed, after the starting material point disappeared, the reaction solution was poured into 500mL of saturated sodium chloride solution and stirred for 0.5H, the solid was filtered, dried, and purified by column chromatography.
Example 2: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylsulfinyl) acetyl) hydrazinecarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
In a 100mL single-neck flask, intermediate 3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylthio) acetyl) hydrazinocarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.57g,1mmol), m-chloroperoxybenzoic acid (MCPBA) (0.21g, 1.O mmol) were dissolved in 20mL Dichloromethane (DCM), stirred for 15min under ice bath, then added and sodium bicarbonate (0.25g, 3mmol) were stirred continuously, reacted for 3H, followed by TCL point plate, after the starting material point disappeared, the reaction was dried under reduced pressure, and purified by column chromatography.
Example 3: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylsulfonyl) acetyl) hydrazinecarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
In a 100mL single-neck flask, intermediate 3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylthio) acetyl) hydrazinocarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.57g,1mmol) and m-chloroperoxybenzoic acid (MCPBA) (0.51g, 2.5mmol) were dissolved in 20mL Dichloromethane (DCM), stirred at room temperature for 15min, then added and sodium bicarbonate (0.25g, 3mmol) were stirred continuously, reacted for 3H, followed by a TCL point plate, after the starting material point disappeared, the reaction was dried under reduced pressure and purified by column chromatography.
Example 4: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylthio) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
In a 100mL single-neck flask, intermediate 3-bromo-N- (4-chloro-2-methyl-6- (2- (2- (methylthio) acetyl) hydrazinocarbonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.57g,1mmol), p-toluenesulfonyl chloride (PTSC) (0.38g, 2.0mmol) were dissolved in 20mL N, N-Dimethylformamide (DMF), stirred at room temperature for 15min, then Triethylamine (TEA) (0.30g, 3.0mmol) was added and stirring continued, the reaction was carried out for 4H, the TCL point plate was followed, after the starting point had disappeared, the reaction solution was poured into 500mL saturated sodium chloride solution, stirred for 0.5H, the solid was filtered, dried, and purified by column chromatography.
Example 5: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylsulfinyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
In a 100mL single-neck flask, intermediate 3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylthio) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.55g,1mmol), m-chloroperoxybenzoic acid (MCPBA) (0.21g, 1.O mmol) were dissolved in 20mL Dichloromethane (DCM), stirred for 15min under ice bath, then added and sodium bicarbonate (0.25g, 3mmol) were stirred continuously, the reaction was allowed to react for 3H, the TCL point plate was followed, after the starting material point disappeared, the reaction was dried under reduced pressure, and purified by column chromatography.
Example 6: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylsulfonyl) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
In a 100mL single-neck flask, intermediate 3-bromo-N- (4-chloro-2-methyl-6- (5- ((methylthio) methyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.55g,1mmol), m-chloroperoxybenzoic acid (MCPBA) (0.51g, 2.5mmol) were dissolved in 20mL Dichloromethane (DCM), stirred at normal temperature for 15min, then added and sodium bicarbonate (0.25g, 3mmol) were stirred continuously, the reaction was carried out for 3H, the TCL point plate was followed, after the starting material point disappeared, the reaction solution was dried under reduced pressure, and purified by column chromatography.
Example 7: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (5- (methylsulfonyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
i. In a 100mL single-necked flask, intermediate 3-bromo-N- (4-chloro-2- (hydrazinocarbonyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.48g,1mmol), carbon disulfide (CS)2) (0.26g, 3.4mmol) is dissolved in 20mL ethanol, stirred for 15min at normal temperature, then added with potassium hydroxide (0.06g, 1mmol) and stirred continuously, reacted for 8h at reflux temperature, followed by TCL dot plate, after the raw material dot disappears, the reaction solution is decompressed and dried, diluted hydrochloric acid is added to adjust the pH value<And 7, filtering, drying a filter cake, and purifying by column chromatography to obtain an intermediate 3-bromo-N- (4-chloro-2- (5-mercapto-1, 3, 4-oxadiazol-2-yl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-formamide.
ii, in a 100mL single-neck bottle, dissolving the intermediate 3-bromo-N- (4-chloro-2- (5-mercapto-1, 3, 4-oxadiazol-2-yl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.53g,1mmol) and iodomethane (0.14g, 1.0mmol) in 20mL methanol, stirring at normal temperature for 15min, adding sodium methoxide (0.05g, 1.0mmol), continuing stirring, reacting for 3H, tracking a TLC point plate, drying the reaction solution under reduced pressure after the raw material point disappears, purifying by column chromatography to obtain the intermediate 3-bromo-N- (4-chloro-2-methyl-6- (5- (methylthio) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide.
iii, dissolving intermediate 3-bromo-N- (4-chloro-2-methyl-6- (5- (methylthio) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.55g,1mmol) and M-chloroperoxybenzoic acid (M-CPBA) (0.51g, 2.5mmol) in 20mL dichloromethane in a 100mL single-neck flask, stirring at normal temperature for 15min, adding sodium bicarbonate (0.25g, 3.0mmol), continuing stirring, reacting for 3H, tracing by TLC point plate, drying the reaction solution under reduced pressure after the raw material point disappears, and purifying by column chromatography.
Example 8: preparation of 3-bromo-N- (4-chloro-2-methyl-6- (5- (methylsulfinyl) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide
In a 100mL single-neck flask, intermediate 3-bromo-N- (4-chloro-2-methyl-6- (5- (methylthio) -1,3, 4-oxadiazol-2-yl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (0.56g,1.0mmol), m-chloroperoxybenzoic acid (MCPBA) (0.21g, 1.O mmol) were dissolved in 20mL Dichloromethane (DCM), stirred for 15min in ice bath, then added and sodium bicarbonate (0.25g, 3mmol) were stirred continuously, the reaction was allowed to react for 3H, the TCL point plate was followed, after the starting material point disappeared, the reaction was dried under reduced pressure, and purified by column chromatography.
Example 9: the compounds prepared in the examples are shown in Table 1
TABLE 1 physical Properties of the Compounds prepared in the examples
Example 10: and (3) biological activity test: has insecticidal effect on diamondback moth.
Selecting 3-instar larvae, and performing insecticidal activity test by a leaf-dipping disc feeding method. 20mg of the original drug is weighed and dissolved by acetone, and the mother liquor of 2000ppm is prepared by tween water. Diluting the mother liquor with 0.05% Tween water to obtain the medicinal liquid with desired concentration. Each treatment 3 was repeated with a blank control. Soaking the prepared fresh bracteal dish in the liquid medicine for 10 seconds, taking out and naturally drying. 3 leaf discs are placed in each culture dish, and 7 third-instar larvae are inoculated and sealed. The number of dead and live insects was examined at 1d, 2d, and 3d, and statistical analysis was performed.
Corrected mortality (%). Pest death number ÷ Pest Total number × 100%
The results are shown in Table 2:
TABLE 2 insecticidal Effect of the Compounds obtained in the examples on Plutella xylostella
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. Furthermore, it should be understood that although the present specification describes embodiments, this does not include only one embodiment, and such description is for clarity only, and those skilled in the art should be able to make the specification as a whole, and the embodiments may be appropriately combined to form other embodiments understood by those skilled in the art.
Claims (2)
1. An agricultural and horticultural insecticide characterized by: the pyridine pyrazole-4-carboxamide compound prepared by the following preparation method is used as an active ingredient,
the preparation method of the pyridine pyrazole-4-carboxamide compound comprises the following steps:
s1-1: intermediate M1 was reacted with CS in methanol solvent2Carrying out reflux reaction under an alkaline condition to obtain an intermediate M2;
s1-2: reacting the intermediate M2 obtained in the step S1-1 with methyl iodide in an inert solution, and oxidizing with MCPBA to obtain a pyridine pyrazole-4-formamide compound based on a sulfur-containing functional group, which is shown as a general formula (I-1); the reaction route is as follows:
the pyridine pyrazole-4-formamide compound based on the sulfur-containing functional group and shown in the general formula (I-1) has the specific structure of the chemical formula:
2. An agricultural and horticultural insecticide according to claim 1, wherein: the alkali used in the preparation method of the pyridine pyrazole-4-formamide compound is selected from one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate; the inert solvent is one of N, N-dimethylformamide, N-dimethylacetamide, acetone, acetonitrile, tetrahydrofuran, chloroform, dichloromethane, diethyl ether, methyl tert-butyl ether, benzene, chlorobenzene, toluene or 1, 4-dioxane.
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| CN101287721A (en) * | 2005-10-14 | 2008-10-15 | 住友化学株式会社 | Hydrazide compound and pesticidal use of the same |
| CN101747325A (en) * | 2010-01-15 | 2010-06-23 | 江苏省农药研究所股份有限公司 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
| CN108752330A (en) * | 2018-06-22 | 2018-11-06 | 南京工业大学 | A kind of pyridine of the oxadiazole rings containing 1,2,4- connects pyrazole-4-carboxamide class compound and the preparation method and application thereof |
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| CN101287721A (en) * | 2005-10-14 | 2008-10-15 | 住友化学株式会社 | Hydrazide compound and pesticidal use of the same |
| CN101747325A (en) * | 2010-01-15 | 2010-06-23 | 江苏省农药研究所股份有限公司 | Neighboring Heterocyclic formanilide compound and synthesis method and application thereof |
| CN108752330A (en) * | 2018-06-22 | 2018-11-06 | 南京工业大学 | A kind of pyridine of the oxadiazole rings containing 1,2,4- connects pyrazole-4-carboxamide class compound and the preparation method and application thereof |
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