CN101284815B - Pyrazolyloxyacetic acid compounds, preparation method and application - Google Patents

Pyrazolyloxyacetic acid compounds, preparation method and application Download PDF

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CN101284815B
CN101284815B CN2008100248660A CN200810024866A CN101284815B CN 101284815 B CN101284815 B CN 101284815B CN 2008100248660 A CN2008100248660 A CN 2008100248660A CN 200810024866 A CN200810024866 A CN 200810024866A CN 101284815 B CN101284815 B CN 101284815B
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CN101284815A (en
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朱红军
施红
贾红圣
李玉峰
宋广亮
刘缓缓
孙永丰
王锦堂
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Nanjing Tech University
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Abstract

The invention discloses a pyrazolyloxyacetic acid compound, a preparation method and application thereof, wherein the compound has a structural general formula , X or Y is hydrogen or C1～4Alkyl radical, C1～4Alkoxy, substituted or unsubstituted phenoxy, halogen, nitro or trifluoromethyl; r is hydrogen or C1～4An alkyl group. The invention also discloses a preparation method of the compound and application of the compound in preparation of bactericides.

Description

Pyrazolyloxyacetic acid compounds, preparation method and application
Technical Field
The invention belongs to the field of organic chemistry, and particularly relates to a pyrazolyloxyacetic acid compound, a preparation method thereof, and application of the compound in the aspect of bactericides.
Background
Nitrogen-containing heterocycles are compounds with important application values and good biological activities, and a plurality of heterocycles are developed into new medicines and pesticide varieties and play important roles in human health and agricultural production. At present, many subject groups at home and abroad are engaged in research and development in the field. With the addition of WTO in China, the intellectual property protection is realized, the research in the field of reinforced heterocycles is urgently needed, and a new medicine with own intellectual property is sent out. Research on novel heterocycles is now active, pyrazole heterocycles have been regarded as important because of their broad biological activity, and many pyrazole fungicides, insecticides, herbicides, plant growth regulators, pharmaceuticals, and the like have been found.
Yoshioka Koichi reports that some pyrazolidinones have bactericidal properties [ Koichi Y, Norikazu T.preparation of 2- (3-oxo-2-pyrazolidinyl) -5-oxo-2-tetrahydrofurazacarboxylic acid derivatives antimicrobial agents [ P ]. JP 6221558, 1987, 09 ]. The compound shows good bactericidal activity, has contact and systemic activity in field tests, shows good protection and treatment activity, and especially has good activity on downy mildew, epidemic disease and the like caused by oomycetes. Most of plant diseases caused by oomycetes are difficult to control, and particularly downy mildew and epidemic diseases have short incubation period and more reinfection times, and can rapidly develop in one growing season of plants to cause epidemic diseases. The research on the sterilization action mechanism shows that: it is a novel mitochondrial respiration inhibitor which is of great interest due to its unique mode of action, broad bactericidal spectrum, and especially effective against resistant strains. Energy required by the bacterial cells is derived from oxidative decomposition of nutrients such as sugars, fats, proteins, etc. in the body to finally generate carbon dioxide and water, in which a series of redox reactions accompanied by dehydrogenation and electron transfer, i.e., respiration of the organism, are involved. The inhibitor has a bactericidal effect by inhibiting the mitochondrial respiration of the thallus so as to inhibit the energy generation, and is a unique action mechanism of the mitochondrial respiration inhibitor. Also, Zhao Yanlai et al reported some pyrazole compounds having bactericidal properties [ Zhao Yanlai, He Lin quan. heterocyclic chemistry introduction [ M ]. Beijing. higher education publishers, 1992: 229]. Meanwhile, the derivative of phenoxyacetic acid also has stronger antibacterial activity, is usually applied to herbicides, can also be used as a plant growth regulator, and is used as a lipid-lowering medicament in the field of medicine.
Disclosure of Invention
The invention aims to provide a pyrazolyloxyacetic acid compound with pharmacodynamic activity.
Another object of the present invention is to provide a process for the preparation of the above compound.
It is a further object of the present invention to provide a use of the above compound.
The object of the invention can be achieved by the following measures:
a compound of the general structural formula (I) or a salt thereof,
Figure S2008100248660D00021
wherein,
x or Y is independently hydrogen or C1～4Alkyl radical, C1～4Alkoxy, substituted or unsubstituted phenoxy, halogen, nitro or trifluoromethyl, preferably hydrogen, C1～4Alkyl, methoxy, phenoxy, fluoro, chloro, bromo, nitro or trifluoromethyl;
r is hydrogen or C1～4Alkyl, preferably hydrogen or ethyl.
The substituted or unsubstituted phenoxy group of the invention, wherein the substituent is C1～4Alkyl, nitro or halogen, preferably unsubstituted phenoxy.
A method for preparing a compound with a structural general formula (I) comprises the following synthetic route:
Figure S2008100248660D00022
reacting the substituted cinnamic acid with methanol or ethanol in the presence of p-toluenesulfonic acid to produce a substituted cinnamate; adding n-butyl alcohol and substituted cinnamate into a sodium methoxide solution, reacting for 1-24 h at 0-100 ℃, adding phenylhydrazine or substituted phenylhydrazine, and reacting for 0-24 h to obtain 1, 5-diaryl-3-pyrazolidinone; the preparation method comprises the following steps of (1), 5-diaryl-3-pyrazolidone is placed in an N, N-dimethylformamide solution, air is blown in, the reaction is carried out at the temperature of 0-100 ℃, and the 1, 5-diaryl-3-hydroxypyrazole is obtained after the cooling and filtering; then reacting with halogenated alkanoic acid or halogenated alkanoate to generate the compound (I). Wherein the concept of substituent X in the substituted cinnamic acid is as described above and the concept of substituent Y in the substituted phenylhydrazine is as described above.
Adding substituted cinnamic acid and p-toluenesulfonic acid into absolute ethyl alcohol and absolute methanol under stirring, and carrying out reflux reaction for 0-24 h to generate substituted cinnamate; adding n-butyl alcohol into a newly prepared sodium methoxide solution under stirring, then adding substituted cinnamate, carrying out reflux reaction for 0-24 h, then adding a proper amount of phenylhydrazine or substituted phenylhydrazine, continuing heating and reflux reaction for 0-24 h, cooling, and filtering to obtain the 1, 5-diaryl-3-pyrazolidone. Dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 10-100 ℃ for 0-24 h, cooling to room temperature, pouring into a beaker filled with water, cooling, and filtering to obtain 1, 5-diaryl-3-hydroxypyrazole; then reacting with bromoacetic acid, chloroacetic acid, sodium chloroacetate, ethyl bromoacetate and ethyl chloroacetate in solvents or aqueous solutions such as dioxane, acetonitrile, N-dimethylformamide, acetone, dichloromethane and chloroform under the alkaline conditions of triethylamine, potassium carbonate, sodium hydroxide and potassium hydroxide to obtain the (I) type 1, 5-diaryl-3-oxyacetic acid ethyl ester pyrazole with the structure of claim 1; then hydrolyzing in sodium hydroxide water solution to generate 1, 5-diaryl-3-oxyacetic acid pyrazole. .
The compound can be used for preparing bactericides and can be applied to various diseases caused by bacteria such as sclerotinia sclerotiorum sensitive strain sclerotiorum, vegetable gray mold sensitive strain Botryris cinerea, gibberellic disease sensitive strain Gibbrilazeae (Schw.) Petch, wheat sharp eyespot sensitive strain Rhizoctonia solani or rice blast fungus Pyricularia oryzae.
The novel pyrazolyloxyacetic acid bactericide can be used for preventing and treating diseases of various crops, and comprises medicinal plants of ginseng, American ginseng, pseudo-ginseng, bighead atractylodes rhizome, fritillaria, amomum villosum, chrysanthemum, medlar or lily; field plants of wheat, corn, rice, potato, sugar beet, peanut or cotton; vegetable crops of cabbage, tomato, cucumber, capsicum or lentil; horticultural crops of peach, pear, grape or strawberry; flowers of kaffir lily or aloe.
Detailed Description
Example 1
Adding 50ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 4-methoxycinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and then carrying out reduced pressure distillation to remove the methanol to obtain 8.82g of methyl 4-methoxycinnamate; adding methyl 4-methoxycinnamate and 50ml n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4h, then adding 8ml phenylhydrazine, continuing heating and refluxing for reaction for 24h, cooling, and filtering to obtain 10.11g of 1-phenyl-5- (4-methoxyphenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 8.92g of 1-phenyl-5- (4-methoxyphenyl) -3-hydroxypyrazole with the yield of 66.9%; 4.42g of hydroxypyrazole was added to 100ml of water, and the mixture was reacted with ethyl bromoacetate dropwise in an equal amount at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to give 4.91g of 1-phenyl-5- (4-methoxyphenyl) -3-oxoethyl acetate-based pyrazole (yield: 83.4%).1H NMRδ：1.30(t，3H)，3.79(s，3H)，4.27(q，2H)，4.86(s，2H)，5.98(s，1H)，6.80(d，2H)，7.13～7.29(m，7H)。
Example 2
Adding 100ml of anhydrous methanol and 0.5g of p-toluenesulfonic acid into 3, 4, 5-trimethoxy cinnamic acid (0.1mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 19.68g of methyl 4-methoxycinnamate; under stirring intoAdding 3, 4, 5-trimethoxy methyl cinnamate and 50ml of n-butanol into newly prepared 28% sodium methoxide solution, reacting for 4h at 100 ℃, then adding 10ml of phenylhydrazine, continuing heating and refluxing for reaction for 24h, cooling, and filtering to obtain 24.96g of 1-phenyl-5- (3, 4, 5-trimethoxyphenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 22.61g of 1-phenyl-5- (3, 4, 5-trimethoxyphenyl) -3-hydroxypyrazole with the yield of 69.3%; 11.31g of hydroxypyrazole was added to 100ml of water, an equal amount of bromoacetic acid was added dropwise thereto, and after a reaction at 100 ℃ for 2 hours, ethyl acetate was extracted, dried over anhydrous magnesium sulfate, filtered, and ethyl acetate was removed to obtain 10.50g of 1-phenyl-5- (3, 4, 5-trimethoxyphenyl) -3-oxyacetic acid-based pyrazole, with a yield of 79.0%.1H NMRδ：3.57(s，6H)，3.65(s，3H)，4.83(s，2H)，6.26(s，1H)，6.48(s，2H)，7.22～7.39(m，5H)，8.0(s，1H)。
Example 3
Adding 20ml of absolute ethanol and 0.3g of p-toluenesulfonic acid into 4-bromocinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 11.29g of ethyl 4-bromocinnamate; adding ethyl 4-bromocinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 6.55g of para-fluorohydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 12.1g of 1- (4-fluorophenyl) -5- (4-bromophenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 10.92g of 1- (4-fluorophenyl) -5- (4-bromophenyl) -3-hydroxypyrazole with the yield of 65.3%; 5.32g of hydroxypyrazole was added to 100ml of water, and an equal amount of chloroacetic acid was added dropwise to react at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to obtain 4.98g of 1- (4-fluorophenyl) -5- (4-bromophenyl) -3-oxyacetic acid ylpyrazole with a yield of 80.0%.1H NMRδ：4.88(s，2H)，6.26(s，1H)，6.88(d，2H)，7.02(d，2H)，7.22(d，2H)7.43(d，2H)，8.5(s，1H)。
Example 4
Adding 20ml of absolute ethanol and 0.3g of p-toluenesulfonic acid into 4-trifluoromethyl cinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 9.77g of ethyl 4-trifluoromethyl cinnamate; adding ethyl 4-trifluoromethyl cinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4h, then adding 8ml of phenylhydrazine, continuously heating and refluxing for reaction for 24h, cooling, and filtering to obtain 10.15g of 1-phenyl-5- (4-trifluoromethyl phenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 1-phenyl-5- (4-trifluoromethylphenyl) -3-hydroxypyrazole, wherein the yield is 9.40g and 70.2%; 5.40g of hydroxypyrazole was added to 100ml of water, an equal amount of sodium chloroacetate was added dropwise, reaction was carried out at 100 ℃ for 2 hours, then, ethyl acetate was extracted, the aqueous layer was neutralized with a 1N hydrochloric acid solution, and then, extraction was carried out with ethyl acetate, dried over anhydrous magnesium sulfate, filtered, and ethyl acetate was removed to obtain 5.40g of 1-phenyl-5- (4-trifluoromethylphenyl) -3-oxyacetopyrazole with a yield of 82.1%.1H NMRδ：4.83(s，2H)，6.16(s，1H)，7.10～7.31(m，9H)，8.5(s，1H)。
Example 5
Adding 20ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 4-fluorocinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 8.28g of methyl 4-fluorocinnamate; adding methyl 4-fluorocinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 9.4g of p-methylphenylhydrazine, continuing heating reflux reaction for 24 hours, cooling, and filtering to obtain 10.45g of 1- (4-methylphenyl) -5- (4-fluorophenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 8.20g of 1- (4-methylphenyl) -5- (4-fluorophenyl) -3-hydroxypyrazole with the yield of 61.2%; adding 4.00g hydroxypyrazole into 100ml water, dropwise adding equal amount of sodium chloroacetate, reacting at 100 deg.C for 2 hr, neutralizing with 1N hydrochloric acid solution, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, filteringAfter removal of ethyl acetate, 4.10g of 1- (4-methylphenyl) -5- (4-fluorophenyl) -3-oxoacetoxypyrazole was obtained in 84.2% yield.1H NMRδ：2.49(s，3H)，4.83(s，2H)，6.16(s，1H)，7.10～7.21(m，4H)，7.280～7.41(m，4H)，8.5(s，1H)。
Example 6
Adding 40ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 3, 4-dimethoxycinnamic acid (0.03mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 5.95g of methyl 3, 4-dimethoxycinnamate and 50ml of n-butanol; adding 3, 4-dimethoxy methyl cinnamate into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4h, then adding 3.75g of para-fluorophenylhydrazine, continuing heating reflux reaction for 24h, cooling, and filtering to obtain 7.28g of 1- (4-fluorophenyl) -5- (3, 4-dimethoxy phenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 6.50g of 1- (4-fluorophenyl) -5- (3, 4-dimethoxyphenyl) -3-hydroxypyrazole with the yield of 72.8%; 3.50g of hydroxypyrazole was added to 100ml of water, and the mixture was reacted with ethyl bromoacetate dropwise in an equal amount at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to give 3.40g of 1- (4-fluorophenyl) -5- (3, 4-dimethoxyphenyl) -3-oxoethyl acetate-pyrazole (yield: 74.8%).1H NMRδ：1.30(t，3H)，3.73(s，6H)，4.27(q，2H)，4.83(s，2H)，6.09(s，1H)，6.80～7.08(m，5H)，7.20～7.29(d，2H)
Example 7
Adding 50ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into cinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 7.85g of methyl cinnamate; adding methyl cinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 9.8g of p-tert-butyl phenylhydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 14.55g of 1- (4-tert-butylphenyl) -5-phenyl-3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, and bubbling airReacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 1- (4-tert-butylphenyl) -5-phenyl-3-hydroxypyrazole, 14.65g, yield 89.9%; 7.65g of hydroxypyrazole was added to 100ml of water, and the mixture was reacted with ethyl bromoacetate dropwise in an equal amount at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to give 9.1g of 1- (4-tert-butylphenyl) -5-phenyl-3-oxoethyl acetate-based pyrazole (yield: 94.0%).1H NMRδ：1.32(s，9H)，4.25(q，2H)，4.80(s，2H)，6.12(s，1H)，7.26～7.49(m，9H)。
Example 8
Adding 40ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 4-methyl cinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 8.00g of methyl 4-methyl cinnamate; adding methyl 4-methyl cinnamate and 50ml n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4h, then adding 9.8g of 2, 4-dichlorophenylhydrazine, continuously heating and refluxing for reaction for 24h, cooling, and filtering to obtain 10.95g of 1- (2, 4-dichlorophenyl) -5- (4-methylphenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 2 hours, cooling to room temperature, and filtering to obtain 1- (2, 4-dichlorophenyl) -5- (4-methylphenyl) -3-hydroxypyrazole, wherein the yield is 8.90g and 55.2%; 4.90g of hydroxypyrazole was added to 100ml of water, and the mixture was reacted with ethyl bromoacetate dropwise in an equal amount at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to give 5.20g of 1- (2, 4-dichlorophenyl) -5- (4-methylphenyl) -3-oxoethyl acetate pyrazole, which was obtained in 83.2% yield.1H NMRδ：1.30(t，3H)，2.35(s，3H)，4.12(q，2H)，4.90(s，2H)，6.12(s，1H)，7.12～7.36(m，7H)。
Example 9
Adding 80ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 3-phenoxycinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 10.50g of 4-phenoxycinnamic acid methyl ester; to a freshly prepared 28% sodium methoxide solution was added methyl 3-phenoxycinnamate with stirringReacting with 50ml of n-butanol at 100 ℃ for 4 hours, then adding 9.8g of 2, 4-dichlorophenylhydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 15.60g of 1- (2, 4-dichlorophenyl) -5- (3-phenoxyphenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 3 hours, cooling to room temperature, and filtering to obtain 11.90g of 1- (2, 4-dichlorophenyl) -5- (3-phenoxyphenyl) -3-hydroxypyrazole with the yield of 59.3%; 6.90g of hydroxypyrazole was taken out and put in a 100ml four-necked flask, 3.0g of potassium carbonate and 100ml of acetone were added, ethyl bromoacetate in an equal amount was slowly dropped, the mixture was refluxed for 2 hours, then acetone was removed, 100ml of water was added, extraction was performed with ethyl acetate, dried over anhydrous magnesium sulfate, and filtration was performed to remove ethyl acetate, whereby 6.10g of 1- (2, 4-dichlorophenyl) -5- (4-phenoxyphenyl) -3-oxoethyl acetate pyrazole was obtained, and the yield was 72.5%.1H NMRδ：1.32(t，3H)，4.25(q，2H)，4.80(s，2H)，6.12(s，1H)，6.86～7.20(m，10H)，7.40～7.47(d，2H)。
Example 10
Adding 50ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 4-chlorocinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 8.85g of methyl 4-chlorocinnamate; adding methyl 4-chlorocinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 11.0g of 2, 4-dinitrophenylhydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 12.0g of 1- (2, 4-dinitrophenyl) -5- (4-chlorophenyl) -3-pyrazolidinone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 4h, cooling to room temperature, and filtering to obtain 9.70g of 1- (2, 4-dinitrophenyl) -5- (4-chlorophenyl) -3-hydroxypyrazole with a yield of 53.5%; 6.70g of hydroxypyrazole was taken out and put in a 100ml four-necked flask, 0.8g of sodium hydroxide and 100ml of anhydrous methanol were added, ethyl bromoacetate in an equal amount was slowly dropped, the mixture was refluxed for 2 hours, then methanol was removed, 100ml of water was added, extraction was performed with ethyl acetate, drying was performed with anhydrous magnesium sulfate, filtration was performed, and ethyl acetate was removed to obtain 6.10g of 1- (2, 4-dinitrophenyl) -5- (4-chlorophenyl) -3-oxoethyl acetate-based pyrazole, with a yield of 73.1%.1H NMRδ：1.32(t，3H)，4.25(q，2H)，4.80(s，2H)，6.12(s，1H)，7.30～7.33(d，2H)，7.42～7.47(d，2H)，7.80(d，1H)，8.62(d，1H)，8.99(s，1H)。
Example 11
Adding 20ml of anhydrous methanol and 0.2g of p-toluenesulfonic acid into 4-chlorocinnamic acid (0.03mol) under stirring, carrying out reflux reaction for 2 hours, and then carrying out reduced pressure distillation to remove the methanol to obtain 5.55g of methyl 4-chlorocinnamate; adding methyl 4-chlorocinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 4.9g of p-tert-butylphenylhydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 8.10g of 1- (4-tert-butylphenyl) -5- (4-chlorophenyl) -3-pyrazolidinone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 6.18g of 1- (4-tert-butylphenyl) -5- (4-chlorophenyl) -3-hydroxypyrazole with the yield of 62.3%; 4.00g of hydroxypyrazole was added to 100ml of water, and an equal amount of ethyl chloroacetate was added dropwise to react at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to obtain 3.84g of 1- (4-tert-butylphenyl) -5- (4-chlorophenyl) -3-oxoethyl acetate pyrazole, with a yield of 75.8%.1H NMRδ：1.29(t，3H)，1.32(s，9H)，4.23(q，2H)，4.89(s，2H)，6.02(s，1H)，7.16～7.33(m，8H)。
Example 12
Adding 40ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 4-methyl cinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 8.10g of methyl 4-methyl cinnamate; adding methyl 4-methyl cinnamate and 50ml n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4h, then adding 6.5g of para-fluorophenylhydrazine, continuing heating reflux reaction for 24h, cooling, and filtering to obtain 10.65g of 1- (para-fluorophenyl) -5- (4-methylphenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 2h, cooling to room temperature, and filtering to obtain 1- (p-fluorophenyl) -5- (4-methylphenyl) -3-hydroxypyrazineOxazole, 9.50g, yield 70.4%; 5.50g of hydroxypyrazole was added to 100ml of water, and the mixture was reacted with ethyl bromoacetate dropwise in an equal amount at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to obtain 5.53g of 1- (p-fluorophenyl) -5- (4-methylphenyl) -3-oxoethyl acetate pyrazole (yield: 75.6%).1H NMRδ：1.29(t，3H)，2.45(s，3H)，4.26(q，2H)，4.83(s，2H)，6.12(s，1H)，7.16～7.33(m，8H)。
Example 13
Adding 50ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into cinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 7.55g of methyl cinnamate; adding methyl cinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 8.9g of 2, 4-dichlorophenylhydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 12.78g of 1- (2, 4-dichlorophenyl) -5-phenyl-3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 2 hours, cooling to room temperature, and filtering to obtain 1- (2, 4-dichlorophenyl) -5-phenyl-3-hydroxypyrazole, wherein the yield is 70.2%; 5.85g of hydroxypyrazole was added to 100ml of water, and an equal amount of chloroacetic acid was added dropwise to react at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to obtain 4.12g of 1- (2, 4-dichlorophenyl) -5-phenyl-3-oxoacetic acid pyrazole, with a yield of 60.0%.1H NMRδ：4.69(s，2H)，6.22(s，1H)，7.26～7.43(m，8H)，10.0(s，1H)。
Example 14
Under stirring, 20ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid were added to 4-methoxycinnamic acid (0.05mol), and after a reflux reaction for 2 hours, methanol was removed by distillation under reduced pressure to give 8.90g of methyl 4-methoxycinnamate; adding methyl 4-methoxycinnamate and 50ml n-butanol into new 28% sodium methoxide solution under stirring, reacting at 100 deg.C for 4h, adding 6.5g para-phenylhydrazine, heating and refluxing for 24h, cooling, and filtering to obtain 1- (4-fluorophenyl) -5- (4-methoxyphenyl) ion-substituted sodium methoxide solution11.38g of 3-pyrazolidinone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 9.42g of 1- (4-fluorophenyl) -5- (4-methoxyphenyl) -3-hydroxypyrazole with the yield of 65.9%; 5.00g of hydroxypyrazole was added to 100ml of water, and an equal amount of chloroacetic acid was added dropwise to react at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to obtain 4.81g of 1- (4-fluorophenyl) -5- (4-methoxyphenyl) -3-oxoacetoxypyrazole, with a yield of 80.1%.1H NMRδ：3.89(s，3H)，4.89(s，2H)，6.12(s，1H)，7.22～7.43(m，8H)，8.0(s，1H)。
Example 15
Adding 40ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 3, 4-dimethoxycinnamic acid (0.03mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 6.00g of methyl 3, 4-dimethoxycinnamate and 50ml of n-butanol; adding 3, 4-dimethoxy methyl cinnamate into a newly prepared 28 percent sodium methoxide solution under stirring, reacting for 4 hours at 100 ℃, then adding 4.9g of p-tert-butyl phenylhydrazine, continuing heating reflux reaction for 24 hours, cooling and filtering to obtain 8.55g of 1- (4-tert-butylphenyl) -5- (3, 4-dimethoxy phenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 7.70g of 1- (4-tert-butylphenyl) -5- (3, 4-dimethoxyphenyl) -3-hydroxypyrazole with a yield of 72.3%; 4.70g of hydroxypyrazole was added to 100ml of water, and an equal amount of chloroacetic acid was added dropwise to react at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to obtain 4.30g of 1- (4-tert-butylphenyl) -5- (4-trifluoromethylphenyl) -3-oxoacetic acid pyrazole, with a yield of 78.9%.1H NMRδ：1.32(s，9H)，4.89(s，2H)，6.12(s，1H)，7.02～7.23(m，4H)，7.32～7.48(m，4H)，8.0(s，1H)。
Example 16
To 3, 4, 5-trimethoxycinnamic acid (0.05mol) was added, with stirring, 40ml of anhydrous methanol and 0.5g of p-toluenesulfonic acid, and the mixture was refluxedAfter reacting for 2h, carrying out reduced pressure distillation to obtain 10.90g of methyl 4-methoxycinnamate; adding 3, 4, 5-trimethoxy methyl cinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4h, then adding 6.5g of p-methyl phenylhydrazine, continuing heating and refluxing for reaction for 24h, cooling, and filtering to obtain 13.80g of 1- (4-methylphenyl) -5- (3, 4, 5-trimethoxyphenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 10.75g of 1- (4-methylphenyl) -5- (3, 4, 5-trimethoxyphenyl) -3-hydroxypyrazole with the yield of 63.3%; 6.45g of hydroxypyrazole was added to 100ml of water, and the mixture was reacted with ethyl bromoacetate dropwise in an equal amount at 100 ℃ for 2 hours, followed by extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration and removal of ethyl acetate to give 6.63g of 1- (4-methylphenyl) -5- (3, 4, 5-trimethoxyphenyl) -3-oxoethyl acetate-based pyrazole (yield: 81.5%).1H NMRδ：1.30(t，3H)，2.32(s，3H)，3.56(s，6H)，3.65(s，3H)，4.26(q，2H)，4.89(s，2H)，6.11(s，1H)，7.12～7.23(m，4H)，7.48(d，2H)。
Example 17
Adding 40ml of absolute ethanol and 0.3g of p-toluenesulfonic acid into 4-bromocinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 11.10g of ethyl 4-bromocinnamate; adding ethyl 4-bromocinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 6.5g of p-methylphenylhydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 12.10g of 1- (4-methylphenyl) -5- (4-bromophenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 1h, cooling to room temperature, and filtering to obtain 10.87g of 1- (4-methylphenyl) -5- (4-bromophenyl) -3-hydroxypyrazole with the yield of 65.9%; adding 5.87g hydroxypyrazole into 100ml anhydrous acetone solution, dropwise adding equal amount of ethyl bromoacetate, refluxing for 2h, removing acetone, adding water, extracting with ethyl acetate, drying with anhydrous magnesium sulfate, filtering, and removing ethyl acetate to obtain 1- (4-methylphenyl) -5- (4-bromophenyl) -3-oxyethylEthyl acetate pyrazole 5.87g, yield 78.8%.1H NMRδ：1.30(t，3H)，2.32(s，3H)，4.26(t，2H)，4.89(s，2H)，6.08(s，1H)，6.82～7.03(d，2H)，7.08～7.23(m，4H)，7.32～7.43(d，2H)。
Example 18
Adding 50ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 4-chlorocinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and then carrying out reduced pressure distillation to remove the methanol to obtain 8.90g of methyl 4-chlorocinnamate; adding methyl 4-chlorocinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 8.9g of 2, 4-dichlorophenylhydrazine, continuing heating and refluxing for reaction for 24 hours, cooling, and filtering to obtain 13.30g of 1- (4-2, 4-dichlorophenyl) -5- (4-chlorophenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 5 hours, cooling to room temperature, and filtering to obtain 12.49g of 1- (4-2, 4-dichlorophenyl) -5- (4-chlorophenyl) -3-hydroxypyrazole with the yield of 72.7%; 6.00g of hydroxypyrazole is taken and added into 100ml of water, equal amount of sodium chloroacetate is added dropwise, reaction is carried out for 2h at 100 ℃, 6N hydrochloric acid solution is neutralized, ethyl acetate is extracted, anhydrous magnesium sulfate is dried, filtration is carried out, and ethyl acetate is removed to obtain 5.76g of 1- (4-2, 4-dichlorophenyl) -5- (4-chlorphenyl) -3-oxyacetic acid based pyrazole, wherein the yield is 82.2%.1H NMRδ：，4.86(s，2H)，6.18(s，1H)，6.89～7.23(m，4H)，7.38～7.43(m，2H)，7.52～7.53(s，1H)。
Example 19
Adding 40ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 4-fluorocinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 8.38g of methyl 4-fluorocinnamate; adding methyl 4-fluorocinnamate and 50ml of n-butanol into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4 hours, then adding 6.5g of para-fluorohydrazine, continuing heating reflux reaction for 24 hours, cooling, and filtering to obtain 11.25g of 1- (4-fluorophenyl) -5- (4-fluorophenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 deg.C for 1 hr, cooling to room temperature, and filteringTo obtain 9.91g of 1- (4-fluorophenyl) -5- (4-fluorophenyl) -3-hydroxypyrazole with a yield of 72.3%; 5.91g of hydroxypyrazole was added to 100ml of water, and an equal amount of sodium chloroacetate was added dropwise, followed by reaction at 100 ℃ for 2 hours, followed by neutralization with a 6N hydrochloric acid solution, extraction with ethyl acetate, drying over anhydrous magnesium sulfate, filtration, and removal of ethyl acetate to obtain 5.01g of 1- (4-fluorophenyl) -5- (4-fluorophenyl) -3-oxoacetoxypyrazole, with a yield of 70.0%.1H NMRδ：4.69(s，2H)，5.98(s，1H)，6.82(d，2H)，7.15～7.23(m，4H)，7.43(m，2H)。
Example 20
Adding 80ml of anhydrous methanol and 0.3g of p-toluenesulfonic acid into 3-phenoxycinnamic acid (0.05mol) under stirring, carrying out reflux reaction for 2 hours, and carrying out reduced pressure distillation to obtain 9.50g of 4-phenoxycinnamic acid methyl ester and 50ml of n-butanol; adding 3-phenoxycinnamic acid methyl ester into a newly prepared 28% sodium methoxide solution under stirring, reacting at 100 ℃ for 4h, then adding 6.5g of para-fluorohydrazine, continuing heating and refluxing for reaction for 24h, cooling, and filtering to obtain 13.60g of 1- (4-fluorophenyl) -5- (3-phenoxyphenyl) -3-pyrazolidone; dissolving the compound in N, N-dimethylformamide solution, blowing air, reacting at 100 ℃ for 3h, cooling to room temperature, and filtering to obtain 10.84g of 1- (4-fluorophenyl) -5- (3-phenoxyphenyl) -3-hydroxypyrazole with the yield of 62.1%; 5.84g of hydroxypyrazole was placed in a 100ml four-necked flask, 0.7g of sodium hydroxide and 100ml of acetone were added, ethyl bromoacetate in an equal amount was slowly dropped, the mixture was refluxed for 2 hours, then acetone was removed, 100ml of water was added, extraction was performed with ethyl acetate, dried over anhydrous magnesium sulfate, and filtration was performed to remove ethyl acetate, whereby 5.76g of 1- (4-fluorophenyl) -5- (4-phenoxyphenyl) -3-oxoacetic acid ethyl ester-based pyrazole was obtained in 78.6% yield.1H NMRδ：1.30(t，3H)，4.26(q，2H)，4.79(s，2H)，6.08(s，1H)，6.98～7.22(m，11H)，7.44(d，2H)。
Experiment for sterilizing 21 Pyrazolyloxyacetic acid fungicides
The final product obtained in example 1 was evaluated for bactericidal effect, and carbendazim and procymidone were selected as controls. Using Sclerotinia sclerotiorum sensitive strain sclerotiorum, vegetable gray mold sensitive strain Botryris cinerea Pers, gibberellic disease sensitive strain Gibbrella zeae (Schw.) Petch, wheat sharp blight sensitive strain Rhizoctonia solani and rice blast fungus Pyricularia oryzae Cav as targets, using cucumber seedlings in potted cotyledon period as test crops, and treating the dosage: in vitro: 10ug/ml live body: 1000ug/ml, bactericidal activity test was performed with clear water control.
1 in vitro assay methods:
1.1 preparation of a culture medium containing the medicine: dissolving the treating agent with acetone to prepare mother liquor; the reference medicament carbendazim is prepared into mother liquor by using 0.02mol/L diluted HCl. According to a certain concentration gradient, the test medicament and the control medicament are respectively added into a culture medium which is sterilized and cooled to about 45 ℃ to be mixed evenly, and then poured into a plate to prepare a medicament-containing plate.
1.2 virulence determination: the colony diameter method is adopted. A bacterial dish is connected to the center of the medicated plate with hypha facing downwards. The diameter of each treated colony was measured after incubation at 25 ℃ until the blank colonies were spread over the petri dish 2/3. Each colony was measured 2 times by the cross method, and the average thereof represents the size of the colony. Calculating the inhibition of the medicament on the growth rate of the thalli.
Figure S2008100248660D00111
2 in vivo test method:
2.1 crop culture: after accelerating germination, the cucumber is dibbled in a plastic basin with the length d equal to 6cm, the cucumber is sufficiently absorbed, and the cucumber is placed in a net room to be cultured until the cotyledon period for standby.
2.2 the application method comprises the following steps: the cucumber seedlings are uniformly applied to the whole cucumber seedlings by a throat sprayer in an indoor fume hood.
2.3 inoculation method: inoculating sclerotinia sclerotiorum and botrytis cinerea in advance, and taking three quarters of the containers for later use. After 24 hours of application, the edge of the colony was punched with a punch with a d of 5mm, and the hyphae of the cake were inoculated down onto the leaf surface.
2.4 culturing: and (3) placing the inoculated cucumber in a moisture preserving box for constant-temperature moisture preserving culture, wherein the culture temperature is 25 ℃, the humidity is 100%, and the light/dark ratio is 16/8:
ex vivo experiments colony diameters were measured when colonies grew above the 2/3 plate; the results of the in vivo test after 3 days of moist culture are shown in tables 1 and 2
TABLE 1 results of in vitro bactericidal Activity
Figure S2008100248660D00121
TABLE 2 list of bactericidal activity of living bodies
Figure S2008100248660D00131
Grading standard: a level: the inhibition rate is more than or equal to 90 percent; b stage: the inhibition rate is more than or equal to 70 percent by 90 percent; c level: the inhibition rate is more than 70 percent and is more than or equal to 50 percent; d stage: 50% inhibition.

Claims (5)

1. A compound or salt thereof selected from:
1-phenyl-5- (4-methoxyphenyl) -3-oxoethylacetate ethylpyrazole
1-phenyl-5- (3, 4, 5-trimethoxyphenyl) -3-oxyacetoxypyrazole
1- (4-fluorophenyl) -5- (4-bromophenyl) -3-oxyacetoxypyrazole
1-phenyl-5- (4-trifluoromethylphenyl) -3-oxyacetoxypyrazole
1- (4-methylphenyl) -5- (4-fluorophenyl) -3-oxyacetoxypyrazole
1- (4-fluorophenyl) -5- (3, 4-dimethoxyphenyl) -3-oxoethylacetate carbethoxypyrazole
1- (4-tert-butylphenyl) -5-phenyl-3-oxoethylacetate ethylpyrazole
1- (2, 4-dichlorophenyl) -5- (4-methylphenyl) -3-oxyacetic acid ethyl ester pyrazole
1- (2, 4-dinitrophenyl) -5- (4-chlorophenyl) -3-oxoethylacetate ethylpyrazole
1- (4-tert-butylphenyl) -5- (4-chlorophenyl) -3-oxoacetic acid ethyl ester pyrazole
1- (p-fluorophenyl) -5- (4-methylphenyl) -3-oxyacetic acid ethyl ester pyrazole
1- (2, 4-dichlorophenyl) -5-phenyl-3-oxyacetic acid pyrazole
1- (4-fluorophenyl) -5- (4-methoxyphenyl) -3-oxyacetic acid-based pyrazole
1- (4-methylphenyl) -5- (3, 4, 5-trimethoxyphenyl) -3-oxoacetoxyethylpyrazole
1- (4-methylphenyl) -5- (4-bromophenyl) -3-oxoacetic acid ethyl ester pyrazole
1- (2, 4-dichlorophenyl) -5- (4-chlorophenyl) -3-oxyacetic acid-based pyrazole
1- (4-fluorophenyl) -5- (4-fluorophenyl) -3-oxyacetoxypyrazole.
2. A preparation method of a compound with a structural general formula (I) comprises the following steps of reacting A with methanol or ethanol in the presence of p-toluenesulfonic acid to generate B; adding n-butyl alcohol and B into a sodium methoxide solution, reacting for 1-24 h at 0-100 ℃, then adding C, and reacting for 0-24 h to obtain D; d is placed in an N, N-dimethylformamide solution, air is blown into the solution, the reaction is carried out at the temperature of 0-100 ℃, and the E is obtained after cooling and filtering; then reacting with halogenated alkanoic acid or halogenated alkanoate to generate a compound (I), wherein the reaction formula is as follows:
Figure FSB00000396239200011
Figure FSB00000396239200021
wherein X or Y is hydrogen or C1～4Alkyl, methoxy, phenoxy, fluorine, chlorine, bromine, nitro or trifluoromethyl, and R is hydrogen or ethyl.
3. Process for the preparation of compounds of general structural formula (I) according to claim 2, characterized in that: when the bactericide (I) is prepared, E and halogenated alkanoic acid or halogenated alkanoate, the used organic solvent is dioxane, acetonitrile, N-dimethylformamide, acetone, dichloromethane or trichloromethane, and the used basic catalyst is triethylamine, potassium carbonate, sodium hydroxide or potassium hydroxide.
4. The use of a compound according to claim 1 for the preparation of a fungicide.
5. The use as claimed in claim 4, wherein the said bacterium is a sensitive strain of sclerotinia sclerotiorum, a sensitive strain of gray mold of vegetables, a sensitive strain of head blight of wheat, or rice blast fungus.
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