CN108863934B - Application of 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivative in preparation of herbicide - Google Patents
Application of 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivative in preparation of herbicide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
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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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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Abstract
The invention discloses 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivatives for use in the preparation of herbicides. It was tested on Lettuce (Lettuce) and glume-cut (Agrostis) seeds, which were surface sterilized for 10 minutes using 5-10% Chlorox solution prior to bioassay, followed by thorough rinsing with deionized water from Millipore system, followed by air drying in sterile environment. Sample treatment: all samples use acetone as a solvent, a solution with the concentration of 1mM is prepared, and then the tested compound shows good inhibition on lettuce and glume cutting through biological assay; the compound provided by the invention is a new compound with herbicidal activity, and provides a foundation for the research and development of new pesticides.
Description
Technical Field
The invention relates to application of a novel pyrazole compound containing amide, namely 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivative in preparation of herbicides.
Background
Nowadays, pyrazole amide and urea compounds usually have excellent and wide biological activity such as low toxicity, high efficiency and the like due to containing high-activity structural groups such as pyrazole, amide and urea bridges, thiourea compounds also have wide biological activity such as antiallergic, anti-inflammatory, antibacterial, insecticidal and herbicidal and the like, the research on the bactericidal activity of thiourea derivatives is more advanced by the wide use of high-efficiency and low-toxicity bactericides of the thiourea compounds thiophanate and thiophanate methyl in the last 60 th century, and dozens of new varieties of the thiourea bactericides, insecticides, plant growth regulators, rodenticides and the like, such as bactericide prodigiosin, insecticide phlebofenobucin, acaricide, plant growth regulators furbenuron and rodenticide and the like, are successfully developed by some pharmaceutical companies abroad until now. The compound has the advantages of low residue on plants, small phytotoxicity, low acute toxicity on mammals and the like.
Disclosure of Invention
The invention aims to provide application of a 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivative in preparation of herbicides.
The application of the 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivative in preparing herbicides is characterized in that the structural formula is shown as the formula (I):
in formula (I): r0Is hydrogen or methyl, R1Is phenyl or substituted phenyl, and the substituent of the substituted phenyl is halogen, methoxy, nitro, methyl, ethyl and butyl.
The application of the 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivative in preparing herbicides for controlling lettuce and glume cutting is characterized in that the structural formula is shown as the formula (I):
in formula (I): r0Is hydrogen or methyl, R1Is phenyl or substituted phenyl, and the substituent of the substituted phenyl is halogen, methoxy, nitro, methyl, ethyl and butyl.
The said use is characterized in that R in the formula (I)1Is one of the following: n-benzyl, (S) -N- (1-phenylethyl), (R) -N- (1-phenylethyl), N- (1- (4-chlorophenyl) ethyl), N- (4-butylbenzene-2 butyl), N-phenylethyl, N- (naphthalene-1-methylene), N- (pyridine-3-methylene).
Compared with the prior art, the invention has the following beneficial effects: the invention provides a 1-methyl-3-difluoromethyl-1H-pyrazole-4-amide derivative, a preparation method thereof and application thereof in preparation of herbicides, wherein the preparation method is simple and convenient to operate, and the obtained compound shows good inhibition on lettuce and glume cutting; the compound provided by the invention is a new compound with herbicidal activity, and provides a foundation for the research and development of new pesticides.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
EXAMPLE 1 preparation of N-benzyl-1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide
(1) Synthesis of ethyl 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylate (II):
carrying out reflux reaction on ethyl difluoroacetoacetate (7.36g,40mmol) and triethyl orthoformate (8.88g, 60mmol) in acetic anhydride (12.24g,0.12mol) for 8 hours, tracing the reactants in a gas phase until the reaction is complete, and carrying out reduced pressure distillation after the reaction is finished to remove redundant triethyl orthoformate to obtain a crude product shown in a formula 1; dropwise adding formula 1(9.6g,40mmol) into a mixed solution of 40% methylhydrazine (6.9g,60mmol) and ethanol (20ml) under ice bath, refluxing for 6 hours, tracking the reaction by TLC (EA/PE ═ 1/1(V)), distilling under reduced pressure after the reaction is finished, adding ethyl acetate (20ml) and saturated saline water for extraction three times, dehydrating the organic layer with anhydrous sodium sulfate, and then suspending and steaming to obtain 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid ethyl ester represented by formula (II);
(2) synthesis of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid type (III):
adding 1-methyl-3-difluoromethyl-1H-pyrazole-4-ethyl formate (8.88g, 40mmol) shown in formula (II) into a 5% sodium hydroxide aqueous solution (100ml), reacting at 60 ℃ for 3 hours until a reaction system is transparent, then adding hydrochloric acid to neutralize the reaction system to adjust the pH to be weakly acidic, precipitating a solid, stopping the reaction, and performing suction filtration to obtain 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid shown in formula (III).
(3) Synthesis of N-benzyl-1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide formula (K1):
refluxing 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid (7.76g, 40mmol) shown in formula (III) and thionyl chloride (47.6g,0.4mol) for 4 hours, continuing to react for 30min when the reaction system becomes a light yellow transparent liquid, stopping the reaction, cooling to room temperature, distilling under reduced pressure to obtain 1-methyl-3-difluoromethyl-1H-pyrazole-4-acyl chloride, adding 1-methyl-3-difluoromethyl-1H-pyrazole-4-acyl chloride (2mmol) into 15ml of dichloromethane, adding phenylmethylamine (2.1mmol), slowly dropwise adding triethylamine (0.3g,3mmol) and stirring at room temperature overnight; TLC (EA: PE ═ 2:1(V)) was followed, and after completion of the reaction, extraction was performed three times using a dichloromethane/water ═ 1:1(V) system, the organic layer was concentrated, extracted with toluene or 75% ethanol, and column chromatography was performed (EA: PE ═ 2:1(V)) to obtain N-benzyl-1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide represented by (K11)
The structural formula of the N-benzyl-1-methyl-3- (difluoromethyl) -1H-pyrazole-4-formamide shown in the formula (K11) is as follows:
n-benzyl-1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide: light yellow solid, yield: 52.1%, melting point: 88 to 89 ℃,1H NMR(400MHz,CDCl3):3.94 (s,3H,CH3),4.63(d,J＝5.6Hz,2H,CH2),6.67(s,1H,NH), 6.86(t,J＝54.4Hz,1H,HCF2),7.29(s,1H,CH),7.29～7.32 (m,1H,Ph),7.34～7.39(m,3H,Ph),7.95(s,1H,CH).
EXAMPLE 2 preparation of (S) -1-methyl-N- (1-phenylethyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide
The phenylmethylamine in step 3) of example 1 was changed to (S) -1-phenethyl-1-amine, the ratio of the amounts of ethyl difluoroacetoacetate to triethyl orthoformate was 1:2, the ratio of the amounts of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to the amounts of thionyl chloride species was 1:1, 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to the amounts of (S) -1-phenethyl-1-amine was 1:1, the organic solvent was dioxane, otherwise, the procedure of example 1 was repeated to give the objective compound 1-methyl- (S) -N- (1-phenylethyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide represented by the formula (K12).
(S) -1-methyl-N- (1-phenylethyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide: light yellow solid, yield: 60.4%, melting point: the temperature of 90-91 ℃,1H NMR(500MHz, CDCl3):1.55(d,J＝5Hz,3H,CH3),3.91(s,3H,CH3), 5.21～5.27(m,1H,CH),6.66(s,1H,NH),6.83(t,J＝54.5 Hz,1H,HCF2),7.25～7.28(m,1H,Ph),7.32～7.35(m,4H,Ph), 7.90(s,1H,CH).
EXAMPLE 3 preparation of (R) -1-methyl-N- (1-phenylethyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide
The phenylmethylamine in step 3) of example 1 was changed to (R) -1-phenethyl-1-amine, the ratio of the amounts of ethyl difluoroacetoacetate to triethyl orthoformate was 1:5, the ratio of the amounts of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to the amounts of thionyl chloride was 1:190, the ratio of the amounts of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to the amounts of (R) -1-phenethyl-1-amine was 1:3, the organic solvent was toluene, otherwise, example 1 was followed to obtain (R) -1-methyl-N- (1-phenylethyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide represented by the formula (K13).
(R) -1-methyl-N- (1-phenylethyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide: light yellow solid, yield: 44.5%, melting point: the temperature is 83-84 ℃,1H NMR(400MHz, CDCl3):1.57(d,J＝6.8Hz,3H,CH3),3.92(s,3H,CH3), 5.22～5.29(m,1H,CH),6.69(s,1H,NH),6.86(t,J＝54.5 Hz,1H,HCF2),7.26～7.31(m,2H,Ph),7.34～7.37(m,3H,Ph), 7.91(s,1H,CH).
EXAMPLE 4 preparation of N- (1- (4-chlorophenyl) ethyl) -1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide
The phenylmethylamine in step 3) of example 1 was changed to 1- (4-chlorophenyl) ethyl-1-amine, and the same procedure as in example 1 was repeated to obtain N- (1- (4-chlorophenyl) ethyl) -1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide represented by the formula (K14)
N- (1- (4-chlorophenyl) ethyl) -1-methyl-3- (difluoromethyl) -1H-pyraneOxazole-4-carboxamide: light yellow solid, yield: 53%, melting point: 114 to 115 ℃ of the reaction kettle,1H NMR(400MHz, CDCl3):1.54(d,J＝7.2Hz,3H,CH3),3.92(s,3H,CH3), 5.18～5.22(m,1H,CH),6.71(s,1H,NH),6.85(t,J＝54.4 Hz,1H,HCF2),7.29～7.33(m,4H,Ph),7.91(s,1H,CH).
EXAMPLE 5 preparation of N- (1- (4- (sec-butyl) phenyl) ethyl) -1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide
The phenylmethylamine in step 3) of example 1 was changed to 4- (sec-butyl) aniline, the ratio of the amounts of ethyl difluoroacetoacetate to triethyl orthoformate was 1:4, the ratio of the amounts of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to thionyl chloride was 1:100, the ratio of the amounts of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to 4- (sec-butyl) aniline was 1:2, dioxane was used as an organic solvent, otherwise, in the same manner as in example 1, N- (1- (4- (sec-butyl) phenyl) ethyl) -1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide represented by the formula (K15) was obtained.
N- (1- (4- (sec-butyl) phenyl) ethyl) -1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide: light yellow solid, yield: 39.8%, melting point: at the temperature of 74-75 ℃,1H NMR (500MHz,CDCl3):1.25(d,J＝6.5Hz,3H,CH3),1.81～1.86 (m,2H,CH2),2.67～2.72(m,2H,CH2),3.91(s,3H,CH3), 4.17～4.22(m,1H,CH),6.22(s,1H,NH),6.83(t,J＝54.5 Hz,1H,HCF2),7.16～7.20(m,3H,Ph),7.26～7.29(m,2H,Ph), 7.88(s,1H,CH).
EXAMPLE 61 preparation of methyl-N-phenethyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide
The phenylmethylamine in step 3) of example 1 was changed to 2-phenyl-1-amine, the ratio of the amounts of ethyl difluoroacetoacetate to triethyl orthoformate was 1:3, the ratio of the amounts of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to the amounts of thionyl chloride was 1:5, the ratio of 1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxylic acid to the amounts of 2-phenyl-1-amine was 1:1.5, and tetrahydrofuran was used as an organic solvent in the same manner as in example 1 to obtain 1-methyl-N-phenethyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide represented by the formula (K16)
1-methyl-N-phenethyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide: light yellow solid, yield: 62.1%, melting point: the temperature of 55-56 ℃,1H NMR(500MHz,CDCl3):2.91 (d,J＝7.0Hz,2H,CH2),3.66～3.70(m,2H,CH2),3.91(s, 3H,CH3),6.38(s,1H,NH),6.79(t,J＝54.5Hz,1H,HCF2), 7.23～7.26(m,3H,Ph),7.32(t,J＝7.5Hz,2H,Ph),7.34(s, 1H,CH).
EXAMPLE 7 preparation of N, 1-dimethyl-N- (naphthalene-1-methyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide
The phenylmethylamine in step 3) of example 1 was changed to N-methyl-1- (naphthalen-1-yl) methylamine, and the other procedures were the same as in example 1 to obtain N, 1-dimethyl-N- (naphthalen-1-methyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide represented by the formula (K17)
N, 1-dimethyl-N- (naphthalene-1-methyl) -3- (difluoromethyl) -1H-pyrazole-4-carboxamide: light yellow solid, yield: 51.5%, melting point: at the temperature of 94-95 ℃,1H NMR(500 MHz,CDCl3):2.43(s,3H,CH3),3.98(s,3H,CH3),5.16 (s,2H,CH2),7.12(t,J＝54Hz,1H,HCF2),7.40(s,1H,Ph), 7.47～7.55(m,4H,Ph),7.84～7.91(m,2H,Ph),7.93(s,1H, CH).
example 8 herbicidal Activity test
Test subjects: lettuce (Lettuce) and seeds of Agrostis stipulata (Agrostis).
And (3) test treatment: seed treatment: prior to bioassay, seeds were surface sterilized using 5-10% Chlorox solution for 10 minutes, followed by thorough rinsing with deionized water from Millipore system, followed by air drying in sterile environment. Sample treatment: all samples were prepared in a 1mM solution using acetone as a solvent and left to stand until use.
And (3) biological determination: all bioassays were performed in duplicate and were performed in sterile pyrogen-free polystyrene 24-well cell culture plates (CoStar 3524, Corning Incorporated). A filter paper disc (Whatman Grade1,1.5cm) was placed in each well to be used. All control wells contained 200. mu.L of water, control + solvent wells contained 180. mu.L of water and 20. mu.L of solvent, and all sample wells contained 180. mu.L of water and 20. mu.L of appropriately diluted sample. Before adding the sample, 180. mu.L of water was first pipetted into the wells. All plates were placed in a sterile environment and the chance of contamination was minimized. All wells were filled with 5 seeds and sealed with a lid. Placing the plate in a CU-36L5 incubator at 26 deg.C and light intensity of 120.1 umols-1m-2And incubating the plates for at least 7 days to obtain a relatively subjective plant ranking. The ranking is divided into 5 levels: 0-5. A rating of 0 indicates no significant inhibition (sample well plants are identical to control + solvent well plants) and a rating of 5 indicates complete inhibition, i.e. all seeds in the wells did not germinate at all.
The results of the herbicidal activity test are shown in table 1.
Herbicidal Activity of Compounds at Table 11 mm
As can be seen from Table 1, the compound of the present invention shows a good inhibitory effect on lettuce at 1mm, especially the (K-14) compound; the compound shows better inhibition to glume-cutting, especially to (K-14) and (K-15) compounds; other compounds also show good inhibition on lettuce and glume cutting.
Claims (1)
1. 1-methyl-3-difluoromethyl-1HApplication of-pyrazole-4-amide derivative in preparation of herbicide for controlling lettuce and glume branches, and is characterized in that the structural formula is shown as formula (I)Shown in the figure:
in formula (I): r0Is hydrogen, R1Is (S) -N- (1-phenylethyl),
Or R0Is hydrogen, R1Is (R) -N- (1-phenethyl),
Or R0Is hydrogen, R1Is N- (1- (4-chlorophenyl) ethyl),
Or R0Is hydrogen, R1Is N-phenethyl.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104636A (en) * | 1992-06-11 | 1995-07-05 | 罗纳-普朗克农业有限公司 | New compositions of matter |
| WO2004035545A2 (en) * | 2002-10-18 | 2004-04-29 | E.I. Du Pont De Nemours And Company | Azolecarboxamide herbicides |
| WO2005070889A1 (en) * | 2004-01-23 | 2005-08-04 | E.I. Dupont De Nemours And Company | Herbicidal amides |
| WO2009024342A2 (en) * | 2007-08-23 | 2009-02-26 | Syngenta Participations Ag | Novel microbiocides |
| CN107935930A (en) * | 2017-12-01 | 2018-04-20 | 浙江工业大学 | 3 difluoromethyl 1H pyrazoles of a kind of 1 methyl, 4 amide derivatives and preparation method and application |
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- 2018-08-29 CN CN201810996537.6A patent/CN108863934B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1104636A (en) * | 1992-06-11 | 1995-07-05 | 罗纳-普朗克农业有限公司 | New compositions of matter |
| WO2004035545A2 (en) * | 2002-10-18 | 2004-04-29 | E.I. Du Pont De Nemours And Company | Azolecarboxamide herbicides |
| WO2005070889A1 (en) * | 2004-01-23 | 2005-08-04 | E.I. Dupont De Nemours And Company | Herbicidal amides |
| WO2009024342A2 (en) * | 2007-08-23 | 2009-02-26 | Syngenta Participations Ag | Novel microbiocides |
| CN107935930A (en) * | 2017-12-01 | 2018-04-20 | 浙江工业大学 | 3 difluoromethyl 1H pyrazoles of a kind of 1 methyl, 4 amide derivatives and preparation method and application |
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