CN108991003B - Application of amide derivative containing pyrazole ring in preparation of herbicide - Google Patents
Application of amide derivative containing pyrazole ring in preparation of herbicide Download PDFInfo
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- CN108991003B CN108991003B CN201810995075.6A CN201810995075A CN108991003B CN 108991003 B CN108991003 B CN 108991003B CN 201810995075 A CN201810995075 A CN 201810995075A CN 108991003 B CN108991003 B CN 108991003B
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- pyrazole
- trifluoromethyl
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
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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
Abstract
The invention relates to application of an amide derivative containing a pyrazole ring in preparation of a herbicide. It was tested on Lettuce (Lettuce), glume-cut (Agrostis) seeds, which were surface sterilized for 10 minutes using 5-10% Chlorox solution before bioassay, followed by thorough rinsing with deionized water of 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 compound obtained through biological assay has good herbicidal activity, so that a foundation is provided for the research and development of new pesticides.
Description
Technical Field
The invention relates to application of a novel amide derivative containing a pyrazole ring, namely the amide derivative containing the pyrazole ring in preparation of herbicides.
Background
In recent decades, the pesticide industry has entered the rapid development age, and the most prominent feature is the application of a large amount of heterocyclic compounds, so that the pesticide is shifted from the old age of high toxicity, high side effect and high residue to a new age of ultra-efficient, pollution-free and environment-friendly pesticide application, and the heterocyclic compounds are wide in variety, including various series containing nitrogen, oxygen, sulfur and the like, but the heterocyclic compounds also belong to nitrogen-containing heterocycles with higher application weight in the pesticide. Until now, at the end of the last century, the newly marketed heterocyclic compounds all contain nitrogen elements, such as the sulfonylurea herbicides Tribenuron methyl (Tribenuron methyl), the azole fungicides Triadimefon (triadimifon), the miticide Fenpyroximate (Fenpyroximate), the neonicotinoid insecticides Thiamethoxam (Thiamethoxam), and the like, and thus, the heterocyclic compounds have excellent effects in both weeding, sterilization, and insecticidal and acaricidal properties, and nitrogen-containing heterocyclic compounds are most prominent.
When the development of new heterocyclic compounds is the focus of research on new compounds, pyrazole derivatives have an important position in the field of new drug development as an important class of heterocyclic compounds. Due to the characteristics of high efficiency, low toxicity and structural diversity of pyrazole compounds, a plurality of novel, high-efficiency and environment-friendly pyrazole derivative pesticide varieties also come into play, but with the wide use of the pyrazole compounds, the resistance problem is increasingly prominent due to single action site, and germs and insect pests have gradually generated resistance to the pyrazole derivatives with different degrees, so that the development of the pyrazole pesticide varieties with novel structures increasingly shows the necessity and urgency, and is one of the hotspots of the current research.
Disclosure of Invention
The invention aims to provide application of an amide derivative containing a pyrazole ring in preparation of herbicides.
The application of the amide derivative containing the pyrazole ring in the preparation of the herbicide is characterized in that the structural formula is shown as the formula (I):
in formula (I): r is phenyl or substituted phenyl, and the substituent of the substituted phenyl is halogen, 2-perfluoropropyl, ethoxy, trifluoromethyl, trifluoromethoxy, trimethylureido, methyl and methoxy.
The application of the amide derivative containing the pyrazole ring in the preparation of the herbicide for preventing and controlling lettuce and glume cutting is characterized in that the structural formula is shown as the formula (I):
in formula (I): r is phenyl or substituted phenyl, and the substituent of the substituted phenyl is halogen, 2-perfluoropropyl, ethoxy, trifluoromethyl, trifluoromethoxy, trimethylureido, methyl and methoxy.
The application is characterized in that R in the formula (I) is one of the following: phenyl, 4- (2-perfluoropropane) phenyl, 4-ethoxyphenyl, 3, 4-difluorophenyl, 2- (trifluoromethyl) phenyl, 3-fluorophenyl, 2- (trifluoromethoxy) phenyl, trimethylureido, 3, 5-dimethylphenyl, 2-methoxyphenyl, 2-chlorophenyl.
Compared with the prior art, the invention has the following beneficial effects: the 1-methyl-N- (2- (3-phenylureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-formamide derivative provided by the invention has good herbicidal activity, particularly has good inhibition on lettuce and strawberries, and provides a foundation for 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 11 preparation of methyl-N- (2- (3-phenylureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-carboxamide
(1) Synthesis of tert-butyl (2- (1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamido) ethyl) carbamate (II):
1-methyl-3-trifluoromethyl-1H-pyrazole-4-carbonyl chloride (1.06g,5mmol) was added to dichloromethane (20ml), stirred and N-Boc-ethylenediamine (0.88g,5.5mmol) was slowly added dropwise, followed by triethylamine (2.02g,20mmol), stirred at room temperature for 2H, TLC (EA/PE ═ 2/1(V)) followed by DCM/H after completion of the reaction2And extracting the O-1/1 (V) system for three times, and distilling under reduced pressure to remove the solvent to obtain the tert-butyl (2- (1-methyl-3-trifluoromethyl-1H-pyrazole-4-formylamino) ethyl) carbamate shown in the formula (II).
(2) Synthesis of N- (2-aminoethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide (iii):
adding 1.68g and 5mmol of tert-butyl (2- (1-methyl-3-trifluoromethyl-1H-pyrazole-4-formylamino) ethyl) carbamate shown in formula (II) into 20ml of dichloromethane, adding 1.71g and 15mmol of trifluoroacetic acid, stirring at room temperature for 2H, continuing stirring for 1H when no gas is discharged from the reaction system (no bubbling occurs), and removing the solvent and the redundant trifluoroacetic acid by reduced pressure distillation after the reaction is finished to obtain the N- (2-aminoethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-formamide shown in formula (III).
(3) Synthesis of 1-methyl-N- (2- ((1- (methylamino) vinyl) amino) ethyl) -3-trifluoromethyl-1H-pyrazole-4-carboxamide derivative formula:
adding N- (2-aminoethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-formamide shown in formula (III) into dichloromethane, feeding the dichloromethane and phenyl isocyanate according to a molar ratio of 1:1.1, stirring at room temperature, reacting overnight, tracking by TLC (EA/PE ═ 2/1(V)), distilling under reduced pressure to remove the solvent after the reaction is completed, leaching with petroleum ether, recrystallizing with 75% ethanol, and purifying by column chromatography to obtain the target compound, namely 1-methyl-N- (2- (3-phenylureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-formamide shown in formula (I-1), wherein the yield is 20%, m.p.177-178 ℃, and 1-methyl-N- (2- (3-phenylureido) ethyl) -3-one shown in formula (I-1) trifluoromethyl-1H-pyrazole-4-carboxamide has the following structural formula:
1-methyl-N- (2- (3-phenylureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:3.49(t,J＝6.0Hz,2H,CH2),3.52(t,J＝5.0Hz,2H,CH2),3.85(s,3H,CH3),5.65(s,1H,NH),7.08～7.10(m,3H,Ph+NH),7.31(d,J＝4.0Hz,4H,Ph),7.87(s,1H,CH).
EXAMPLE 21 preparation of methyl-N- (2- (3- (4- (2-perfluoropropyl) phenyl) ureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-carboxamide
(1) Synthesis of tert-butyl (2- (1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamido) ethyl) carbamate (II):
1-methyl-3-trifluoromethyl-1H-pyrazole-4-carbonyl chloride (1.06g,5mmol) was added to dichloromethane (20ml), stirred and N-Boc-ethylenediamine (0.88g,5.5mmol) was slowly added dropwise, followed by triethylamine (2.02g,20mmol), stirred at room temperature for 2H, TLC (EA/PE ═ 2/1(V)) followed by DCM/H after completion of the reaction2Extracting for three times with O-1/1 (V) system, distilling under reduced pressure to remove solvent to obtain (2- (1-methyl-3-trifluoromethyl-1H-pyrazole) shown in formula (II)-4-carboxamido) ethyl) carbamic acid tert-butyl ester.
(2) Synthesis of N-2-aminoethyl-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide (iii):
adding 1.68g and 5mmol of tert-butyl (2- (1-methyl-3-trifluoromethyl-1H-pyrazole-4-formylamino) ethyl) carbamate shown in a formula (II) into 20ml of dichloromethane, adding 1.71g and 15mmol of trifluoroacetic acid, stirring at room temperature for 2H, continuing stirring for 1H when no gas is discharged from a reaction system (no bubbling occurs), and after the reaction is finished, removing the solvent and the redundant trifluoroacetic acid by reduced pressure distillation to obtain the N-2-aminoethyl-1-methyl-3-trifluoromethyl-1H-pyrazole-4-formamide shown in a formula (III).
(3) Synthesis of 1-methyl-N- (2- ((1- (methylamino) vinyl) amino) ethyl) -3-trifluoromethyl-1H-pyrazole-4-carboxamide derivative formula:
adding N- (2-aminoethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-formamide shown in formula (III) into dichloromethane, feeding the dichloromethane and 4- (2-perfluoropropyl) phenyl isocyanate according to a molar ratio of 1:1.1, stirring at room temperature, reacting overnight, tracking by TLC (EA/PE ═ 2/1(V)), distilling under reduced pressure to remove a solvent after the reaction is completed, eluting by petroleum ether, recrystallizing by 75% of ethanol, and purifying by a column to obtain the target compound, namely 1-methyl-N- (2- (3- (4- (2-perfluoropropyl) phenyl) ureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-formamide shown in formula (I-2), yield 35.5%, m.p.165-167 ℃, 1-methyl-N- (2- (3- (4- (2-perfluoropropyl) phenyl) ureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-carboxamide of formula (i-2) having the following structural formula:
1-methyl-N- (2- (3- (4- (2-perfluoropropyl) phenyl) ureido) ethyl) -3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:3.47～3.51(m,4H,2CH2),3.75(s,3H,CH3),6.32(t,J＝5.5Hz,1H,NH),7.02(t,J＝7.5Hz,1H,NH),7.24(t,J＝8.0Hz,2H,Ph),7.29(d,J＝8.5Hz,2H,Ph),7.94(s,1H,NH),7.59(s,1H,CH).
EXAMPLE 3 preparation of N- (2- (3- (4-ethoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in step (3) of example 1 was replaced with 4-ethoxyphenyl isocyanate, and the other operation was the same as in example 1 to obtain N- (2- (3- (4-ethoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide in 77.5% yield, m.p.40 ℃ and N- (2- (3- (4-ethoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide of formula (I-3) having the following structural formula:
n- (2- (3- (4-ethoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:1.42(t,J＝7.0Hz,3H,CH3),3.43～3.46(m,2H,CH2),3.48～3.51(m,2H,CH2),3.89(s,3H,CH3),3.99～4.03(m,2H,CH2),5.49(s,1H,NH),6.72(s,1H,NH),6.85(d,J＝8.5Hz,2H,Ph),7.17(d,J＝9.0Hz,2H,Ph),7.21(s,1H,NH),7.90(s,1H,CH).
EXAMPLE 4 preparation of N- (2- (3- (3, 4-difluorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in step (3) of example 1 was replaced with 3, 4-difluorophenyl isocyanate and the same procedure as in example 1 was repeated to obtain N- (2- (3- (3, 4-difluorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide in 64.1% yield, m.p.70-71 ℃ and N- (2- (3- (3, 4-difluorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide of formula (I-4) was represented by the following structural formula:
n- (2- (3- (3, 4-difluorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:3.20～3.24(m,2H,CH2),3.26～3.30(m,2H,CH2),3.93(s,3H,CH3),6.31(t,J＝5.5Hz,1H,NH),7.03(t,J＝5.0Hz,1H,Ph),7.25～7.31(m,1H,Ph),7.61～7.65(m,1H,Ph),8.29(s,1H,CH),8.31(t,J＝5.5Hz,1H,NH),8.81(s,1H,NH).
EXAMPLE 5 preparation of N- (2- (3- (2-trifluoromethylphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in step (3) of example 1 was replaced with 2-trifluoromethylphenyl isocyanate, and the same operation as in example 1 was carried out to obtain N- (2- (3- (2-trifluoromethylphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide in 27.9% yield, m.p.169-17 ℃ and N- (2- (3- (2-trifluoromethylphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide of the formula (I-5) below:
n- (2- (3- (2-trifluoromethylphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:3.24～3.26(m,2H,CH2),3.27～3.39(m,2H,CH2),3.94(s,3H,CH3),7.12(t,J＝5.0Hz,1H,NH),7.19(t,J＝7.5Hz,1H,Ph),7.57(t,J＝7.5Hz,1H,Ph),7.62(d,J＝7.5Hz,1H,Ph),7.82(s,1H,CH),7.94(d,J＝8.5Hz,1H,Ph),8.30(s,1H,NH),8.32(t,J＝5.5Hz,1H,NH).
EXAMPLE 6 preparation of N- (2- (3- (3-fluorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in step (3) of example 1 was replaced with 3-fluorophenyl isocyanate, and the same procedures as in example 1 were repeated to obtain N- (2- (3- (3-fluorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide in 67.6% yield m.p.186-188 ℃.
N- (2- (3- (3-fluorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1HNMR(500MHz,CDCl3)δ:3.20～3.24(m,2H,CH2),3.26～3.30(m,2H,CH2),3.93(s,3H,CH3),6.57(t,J＝5.0Hz,1H,NH),6.67～6.71(m,1H,Ph),7.04(d,J＝8.0Hz,1H,Ph),7.21～7.25(m,1H,Ph),7.45～7.48(m,1H,Ph),8.32(s,1H,CH),8.33(t,J＝5.0Hz,1H,NH),9.04(s,1H,NH).
EXAMPLE 7 preparation of N- (2- (3- (2-trifluoromethoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in step (3) of example 1 was replaced with 2-trifluoromethoxyphenyl isocyanate, and the same operation as in example 1 was carried out to obtain N- (2- (3- (2-trifluoromethoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide in a yield of 36.4% and m.p.187-189 ℃.
N- (2- (3- (2-trifluoromethoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:3.50～3.53(m,2H,CH2),3.57～3.60(m,2H,CH2),3.91(s,3H,CH3),5.75(s,1H,NH),6.76(s,1H,NH),6.95(s,1H,NH),7.05(t,J＝8.0Hz,1H,Ph),7.23～7.25(m,1H,Ph),7.87(s,1H,CH),8.10(d,J＝7.5Hz,1H,Ph).
EXAMPLE 8 preparation of N- (2- (trimethylureido) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in step (3) of example 1 was replaced with trimethylurea and the procedure was otherwise as in example 1 to give N- (2- (trimethylureido) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide in 56.7% yield, m.p.174-175 ℃.
N- (2- (trimethylureido) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:2.19(s,6H,CH3),2.29(s,3H,CH3),3.42～3.46(m,4H,2CH2),3.95(s,3H,CH3),5.82(s,1H,NH),6.93(s,2H,Ph),7.18(s,1H,NH),7.71(s,1H,CH).
EXAMPLE 9 preparation of N- (2- (3- (3, 5-dimethylphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in the step (3) of example 1 was replaced with 3, 5-dimethylphenyl isocyanate and the same operations as in example 1 were carried out to obtain N- (2- (3- (3, 5-dimethylphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide represented by the formula (I-9) in a yield of 59.6% and m.p.103-104 ℃.
N- (2- (3- (3,5 dimethylphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:2.25(s,6H,2CH3),3.44～3.49(m,4H,2CH2),3.82(s,3H,CH3),5.95(t,J＝5.0Hz,1H,NH),6.71(s,1H,NH),6.90(s,2H,Ph),7.11(s,1H,NH),7.34(s,1H,NH),7.92(s,1H,CH).
EXAMPLE 10 preparation of N- (2- (3- (2-methoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate obtained in the step (3) of example 1 was replaced with 2-methoxyphenyl isocyanate, and the same operation as in example 1 was carried out to obtain N- (2- (3- (2-methoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide represented by the formula (I-10) in a yield of 76.7% and m.p.166-167 ℃.
N- (2- (3- (2-methoxyphenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:3.49～3.53(m,2H,CH2),3.55～3.58(m,2H,CH2),3.83(s,3H,CH3),3.87(s,3H,CH3),5.39(t,J＝5.0Hz,1H,NH),6.86～6.89(m,1H,Ph),6.91(s,1H,NH),6.95～7.04(m,3H,Ph+NH),7.85(s,1H,CH),7.95(d,J＝8.0Hz,1H,Ph).
EXAMPLE 11 preparation of N- (2- (3- (2-chlorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide
The phenyl isocyanate in the step (3) of example 1 was replaced with 2-chlorophenyl isocyanate and the same operation as in example 1 was carried out to obtain N- (2- (3- (2-chlorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide represented by the formula (I-11) in 52.2% yield m.p.155-156 ℃.
N- (2- (3- (2-chlorophenyl) ureido) ethyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide:1H NMR(500MHz,CDCl3)δ:3.50～3.52(m,2H CH2),3.55～3.57(m,2H,CH2),3.87(s,3H,CH3),6.03(s,1H,NH),6.99(t,J＝8.0Hz,1H,Ph),7.10(s,1H,NH),7.19(t,J＝5.0Hz,1H,NH),7.24(t,J＝8.0Hz,1H,Ph),7.34(d,J＝7.5Hz,1H,Ph),7.87(s,1H,CH),8.03(d,J＝8.0Hz,1H,Ph).
example 12 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 Grade 1,1.5cm) was placed in each well to be used. All control wellsThere was 200. mu.L of water, 180. mu.L of water and 20. mu.L of solvent in the control + solvent wells, and 180. mu.L of water and 20. mu.L of suitably diluted sample in all sample wells. 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 shown in Table 1, the compounds of the present invention showed good inhibition to lettuce at 1mm, especially the compounds (1) and (11).
Claims (2)
1. The application of amide derivatives containing pyrazole rings in the preparation of herbicides for controlling lettuce is characterized in that the structural formula is shown as the formula (I):
in formula (I): r is one of the following: phenyl, 4- (2-perfluoropropane) phenyl, 3, 4-difluorophenyl, 2- (trifluoromethyl) phenyl, 3-fluorophenyl, 2-methoxyphenyl, or 2-chlorophenyl.
2. The application of the amide derivative containing the pyrazole ring in the preparation of the herbicide for preventing and controlling glume cutting is characterized in that the structural formula is shown as the formula (I):
in formula (I): r is one of the following: 2- (trifluoromethyl) phenyl, 3-fluorophenyl, 3, 5-dimethylphenyl or 2-chlorophenyl.
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Citations (4)
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| 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 |
| CN108383790A (en) * | 2017-12-01 | 2018-08-10 | 浙江工业大学 | A kind of amides compound and the preparation method and application thereof containing pyrazole ring |
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2018
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| 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 |
| CN108383790A (en) * | 2017-12-01 | 2018-08-10 | 浙江工业大学 | A kind of amides compound and the preparation method and application thereof containing pyrazole ring |
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