CN103304480A - Benzoyl parazole compound as well as synthesis method thereof and application of same as herbicide - Google Patents
Benzoyl parazole compound as well as synthesis method thereof and application of same as herbicide Download PDFInfo
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Abstract
The invention discloses a benzoyl parazole compound as well as a synthesis method of the benzoyl parazole compound and an application of the benzoyl parazole compound as herbicide, relates to the benzoyl parazole compound as the herbicide and a synthesis method of the benzoyl parazole compound, and mainly solves the problem that the conventional benzoyl parazole compound as the herbicide is low in herbicide activity. According to the formula of the benzoyl parazole compound, the synthesis method comprises the following steps of: firstly, mixing a pyrazolone compound, acetonitrile and triethylamine, further dropping an acetonitrile-dissolved benzoyl chloride compound, thus obtaining a benzoyl pyrazol ester compound through reduced pressure distillation; and secondly, mixing the acetonitrile, acetone cyanogens alcohol and the benzoyl pyrazol ester compound, adding triethylamine, raising the reaction temperature, thus obtaining the benzoyl parazole compound through liquid separation and solvent evaporation. The seven benzoyl parazole compounds disclosed by the invention are excellent in herbicide activity and are mainly applied to herbicide as active components.
Description
Technical field
The present invention relates to can be used as benzoylpyrazole compounds and the synthetic method thereof of weedicide.
Background technology
P _ Hydroxyphenyl pyruvic acid dual oxide enzyme (HPPD) is the new weedicide target enzyme of a class of finding the nineties in 20th century.HPPD inhibitor take this enzyme as target has behind active high, broad weed-killing spectrum, the front bud of bud all available, residual low, characteristics such as Environmental compatibility good, uses is safe, and becomes the focus that chemical pesticide is studied because of the report about its resistance not yet.The benzoylpyrazole compounds is the Typical Representative of HPPD inhibitor, they have special weeding activity, now developed a large amount of benzoylpyrazole compounds, wherein commercial kind comprises pyrazolate (Pyrazolate), benzofenap (Benzofenap), pyrazoxyfen (Pyazoxyfen) ， isoxazole humulone (Isoxaflutole) and Pyrasulfotole etc.But to the weeds of some kind, remain further to be improved such as the weeding activity of the weeds such as piemarker, Amaranthus retroflexus.
Summary of the invention
The objective of the invention is in order to solve existing benzoylpyrazole compounds as the lower problem of weedicide weeding activity, and provide benzoylpyrazole compounds and synthetic method thereof and with the application of this compounds as weedicide.
(IV) is as follows for the general formula of benzoylpyrazole compounds of the present invention:
(IV)
Seven kinds of benzoylpyrazole compounds are as follows respectively:
(1) works as R
1Be NO
2Base, R
2Be SO
2CH
3Base, R
3Be CH
3During base, compound is 1,3-dimethyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols, and its structural formula (4a) is:
(2) work as R
1Be NO
2Base, R
2Be SO
2CH
3Base, R
3Be CF
3During base, compound is 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols, and its structural formula (4b) is:
(3) work as R
1Be NO
2Base, R
2Be SO
2CH
3Base, R
3During for cyclopropyl, compound is 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols, and its structural formula (4c) is:
(4) work as R
1Be NO
2Base, R
2Be CF
3Base, R
3Be CH
3During base, compound is 1,3-dimethyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols, and its structural formula (4d) is:
(5) work as R
1Be NO
2Base, R
2Be CF
3Base, R
3Be CF
3During base, compound is 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols, and its structural formula (4e) is:
(6) work as R
1Be NO
2Base, R
2Be CF
3Base, R
3During for cyclopropyl, compound is 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols, and its structural formula (4f) is:
(7) work as R
1Be SO
2CH
3Base, R
2Be CF
3Base, R
3Be CF
3During base, compound is 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-methylsulfonyl-4-trifluoromethyl) Benzoylpyrazols, and its structural formula (4g) is:
The synthetic method of benzoylpyrazole compounds of the present invention follows these steps to realize:
One, adding pyrazolone compound (II), acetonitrile and triethylamine in the four-hole bottle stirs, water-bath control temperature of reaction is 15～20 ℃, drip again the Benzoyl chloride compounds (I) with the acetonitrile dissolving, under the room temperature behind stirring reaction 1～5h, remove solvent under reduced pressure and obtain solid product, solid product uses the methylene dichloride dissolving, removes solvent under reduced pressure again and obtain benzoylpyrazole ester compound (III) behind washing, separatory;
Two, add acetonitrile and acetone cyanohydrin in the reaction vessel, add again the benzoylpyrazole ester compound (III) that step 1 obtains, water-bath control temperature of reaction is 23～28 ℃, drip triethylamine, then the temperature of reaction to 60 that raises ℃ is steamed to desolventize behind reaction 5.5～6.5h and is obtained solid formation, and solid formation uses the methylene dichloride dissolving, add separatory behind the pH=2 of deionized water regulation system, steam at last and obtain the benzoylpyrazole compounds after desolventizing;
Wherein when Benzoyl chloride compounds (I) was 2-nitro-4-methylsulfonyl Benzoyl chloride, pyrazolone compound (II) was 1-methyl-3-cyclopropyl-5-pyrazolone, 1-methyl-3-trifluoromethyl-5-pyrazolone or 1,3-dimethyl-5-pyrazolone;
When Benzoyl chloride compounds (I) was 2-nitro-4-trifluoromethyl benzoyl chloride, pyrazolone compound (II) was 1-methyl-3-cyclopropyl-5-pyrazolone, 1-methyl-3-trifluoromethyl-5-pyrazolone or 1,3-dimethyl-5-pyrazolone;
When Benzoyl chloride compounds (I) was 2-methylsulfonyl-4-trifluoromethyl benzoyl chloride, pyrazolone compound (II) was 1-methyl-3-trifluoromethyl-5-pyrazolone.
To sum up the synthetic method of benzoylpyrazole compounds of the present invention realizes by following reaction scheme:
Be applied in the weedicide as activeconstituents with seven kinds of benzoylpyrazole compounds that meet general formula of the present invention (IV).
The present invention at first synthesizes the benzoylpyrazole ester compound by the ester reaction that becomes of Benzoyl chloride compounds and pyrazolone compound, again the benzoylpyrazole ester compound is carried out the synthetic 7 kinds of benzoylpyrazole compounds of translocation reaction.And adopt the method for " the initiative pesticide bioactivity is estimated SOP weedicide volume " to carry out weeding activity to 7 kinds of benzoylpyrazole compounds and screen, test result demonstrates benzoylpyrazole compounds of the present invention piemarker, lady's-grass, Amaranthus retroflexus, barnyard grass, Eclipta prostrata, Herba Setariae Viridis are all had weeding activity, and is obvious to the herbicidal effect of piemarker and Amaranthus retroflexus.
Embodiment
Embodiment one: present embodiment 1, the synthetic method of 3-dimethyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols follow these steps to realize:
One, in four-hole bottle, adds 1 of 0.1mol, acetonitrile and the 0.125mol triethylamine of 3-dimethyl-5-pyrazolone, 80mL stir, water-bath control temperature of reaction is 20 ℃, the 2-nitro of the 0.105mol of again dropping usefulness 40ml acetonitrile dissolving-4-methylsulfonyl Benzoyl chloride, under the room temperature behind the stirring reaction 4h, remove solvent under reduced pressure and obtain solid product, solid product uses the dissolving of 50mL methylene dichloride, behind 100mL washing, separatory, remove again solvent under reduced pressure and obtain 2-nitryl-4-thiamphenicol benzoic acid-[1,3-dimethyl-pyrazoles-5-yl]-ester;
Two; adding 150mL acetonitrile and 0.2ml purity are 98.5% acetone cyanohydrin in the reaction vessel; add again the 0.1mol2-nitryl-4-thiamphenicol benzoic acid-[1 that step 1 obtains; 3-dimethyl-pyrazoles-5-yl]-ester; water-bath control temperature of reaction is 25 ℃; drip again the 0.21mol triethylamine; then the temperature of reaction to 60 that raises ℃; steam to desolventize behind the reaction 6h and obtain solid formation; solid formation uses the dissolving of 50mL methylene dichloride; add separatory behind the pH=2 of deionized water regulation system; obtain 1,3-dimethyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols after steaming desolventizes at last.
Wherein step 1 drips 2-nitro with the 0.105mol of 40ml acetonitrile dissolving-4-methylsulfonyl Benzoyl chloride, and its time for adding is 10min.
The 2-nitryl-4-thiamphenicol benzoic acid-[1 that the present embodiment step 1 obtains; 3-dimethyl-pyrazoles-5-yl]-yield of ester is 89.8%; purity is 95.3%; finally obtain 1; the yield of 3-dimethyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols is 89.8%, and purity is 95.3%.
Wherein the preparation method of 2-nitro-4-methylsulfonyl Benzoyl chloride follows these steps to realize:
The thionyl chloride that adds 320mL in the four-hole bottle, 0.4mol the 2-nitryl-4-thiamphenicol benzoic acid and the catalyzer DMF of 0.5g, 2h is heated to reflux temperature, reflux 4h, air distillation goes out the 250mL thionyl chloride after being cooled to 60 ℃, add again the 200mL ethylene dichloride and continue air distillation, stop distillation after steaming 150mL, cool to 0 ℃ and separate out 2-nitro-4-methylsulfonyl Benzoyl chloride.Its proton nmr spectra data are: 1H-NMR (400MHz, DMSO) δ 8.53 (d, J=1.5Hz, 0H), 8.33 (dd, J=8.0,1.6Hz, 0H), 8.12 (d, J=8.0Hz, 0H), 3.39 (s, 1H).
To sum up the synthetic route of 2-nitro-4-methylsulfonyl Benzoyl chloride is:
Embodiment two: the synthetic method of present embodiment 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols follows these steps to realize:
One, the acetonitrile and the 0.125mol triethylamine that add the 1-methyl of 0.1mol-3-trifluoromethyl-5-pyrazolone, 80mL in the four-hole bottle stir, water-bath control temperature of reaction is 20 ℃, the 2-nitro of the 0.105mol of again dropping usefulness 40ml acetonitrile dissolving-4-methylsulfonyl Benzoyl chloride, under the room temperature behind the stirring reaction 4h, remove solvent under reduced pressure and obtain solid product, solid product uses the dissolving of 50mL methylene dichloride, removes solvent under reduced pressure again and obtain 2-nitryl-4-thiamphenicol benzoic acid-[1-methyl-3-trifluoromethyl-pyrazoles-5-yl]-ester behind 100mL washing, separatory;
Two; adding 150mL acetonitrile and 0.2ml purity are 98.5% acetone cyanohydrin in the reaction vessel; add again the 0.1mol2-nitryl-4-thiamphenicol benzoic acid that step 1 obtains-[1-methyl-3-trifluoromethyl-pyrazoles-5-yl]-ester; water-bath control temperature of reaction is 25 ℃; drip again the 0.21mol triethylamine; then the temperature of reaction to 60 that raises ℃; steam to desolventize behind the reaction 6h and obtain solid formation; solid formation uses the dissolving of 50mL methylene dichloride; add separatory behind the pH=2 of deionized water regulation system, steam at last and obtain 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols after desolventizing.
Wherein step 1 drips 2-nitro with the 0.105mol of 40ml acetonitrile dissolving-4-methylsulfonyl Benzoyl chloride, and its time for adding is 10min.
The yield of the 2-nitryl-4-thiamphenicol benzoic acid that the present embodiment step 1 obtains-[1-methyl-3-trifluoromethyl-pyrazoles-5-yl]-ester is 91.7%; purity is 95.9%; the yield of the 1-methyl that finally obtains-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols is 90.1%, and purity is 93.8%.
Wherein the preparation method of 1-methyl-3-trifluoromethyl-5-pyrazolone follows these steps to realize:
Add the ethanol of 100mL and the trifluoroacetic ethyl acetoacetate of 0.2mol in the four-hole bottle, stirring lower water-bath control temperature of reaction is 20 ℃, 0.5h interior dropping 27mL mass concentration is 40% the methyl hydrazine aqueous solution, reflux 2h, underpressure distillation goes out ethanol, with obtaining 1-methyl-3-trifluoromethyl-5-pyrazolone behind the toluene recrystallization.Its proton nmr spectra data are: 1H-NMR (400MHz, CDCl3) δ 7.02 (s, 1H), 6.01 (s, 1H), 3.82 (s, 3H).
To sum up the synthetic route of 1-methyl-3-trifluoromethyl-5-pyrazolone is:
Embodiment three: the synthetic method of present embodiment 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols follows these steps to realize:
One, the acetonitrile and the 0.125mol triethylamine that add the 1-methyl of 0.1mol-3-cyclopropyl-5-pyrazolone, 80mL in the four-hole bottle stir, water-bath control temperature of reaction is 20 ℃, the 2-nitro of the 0.105mol of again dropping usefulness 40ml acetonitrile dissolving-4-methylsulfonyl Benzoyl chloride, under the room temperature behind the stirring reaction 4h, remove solvent under reduced pressure and obtain solid product, solid product uses the dissolving of 50mL methylene dichloride, removes solvent under reduced pressure again and obtain 2-nitryl-4-thiamphenicol benzoic acid-[1-methyl-3-cyclopropyl-pyrazoles-5-yl]-ester behind 100mL washing, separatory;
Two; adding 150mL acetonitrile and 0.2ml purity are 98.5% acetone cyanohydrin in the reaction vessel; add again the 0.1mol2-nitryl-4-thiamphenicol benzoic acid that step 1 obtains-[1-methyl-3-cyclopropyl-pyrazoles-5-yl]-ester; water-bath control temperature of reaction is 25 ℃; drip again the 0.21mol triethylamine; then the temperature of reaction to 60 that raises ℃; steam to desolventize behind the reaction 6h and obtain solid formation; solid formation uses the dissolving of 50mL methylene dichloride; add separatory behind the pH=2 of deionized water regulation system, steam at last and obtain 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols after desolventizing.
Wherein step 1 drips 2-nitro with the 0.105mol of 40ml acetonitrile dissolving-4-methylsulfonyl Benzoyl chloride, and its time for adding is 10min.
The yield that the present embodiment step 1 obtains 2-nitryl-4-thiamphenicol benzoic acid-[1-methyl-3-cyclopropyl-pyrazoles-5-yl]-ester is 90.3%; purity is 96.4%; the yield of the 1-methyl that finally obtains-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols is 90.7%, and purity is 93.4%.
Wherein the preparation method of 1-methyl-3-cyclopropyl-5-pyrazolone follows these steps to realize:
Add the ethanol of 100mL and the cyclopropane carbonyl ethyl acetate of 0.2mol in the four-hole bottle; stirring lower water-bath control temperature of reaction is 20 ℃; 0.5h interior dropping 27mL mass concentration is 40% the methyl hydrazine aqueous solution; at 40 ℃ of lower insulation 2h; remove etoh solvent under reduced pressure, obtain 1-methyl-3-cyclopropyl-5-pyrazolone.Its proton nmr spectra data are: 1H-NMR (400MHz, DMSO) δ 5.03 (d, J=16.6Hz, 1H), 3.38 (s, 3H), 1.73 – 1.57 (m, 1H), 0.77 (t, J=8.9Hz, 2H), 0.55 (d, J=2.6Hz, 2H).
To sum up the synthetic route of 1-methyl-3-cyclopropyl-5-pyrazolone is:
Embodiment four: present embodiment 1, the synthetic method of 3-dimethyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols follow these steps to realize:
One, in four-hole bottle, adds 1 of 0.1mol, acetonitrile and the 0.125mol triethylamine of 3-dimethyl-5-pyrazolone, 80mL stir, water-bath control temperature of reaction is 20 ℃, the 2-nitro of the 0.105mol of again dropping usefulness 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, under the room temperature behind the stirring reaction 4h, remove solvent under reduced pressure and obtain solid product, solid product uses the dissolving of 50mL methylene dichloride, behind 100mL washing, separatory, remove again solvent under reduced pressure and obtain 2-nitryl-4-thiamphenicol benzoic acid-[1,3-dimethyl pyrazole-5-yl]-ester;
Two; adding 150mL acetonitrile and 0.2ml purity are 98.5% acetone cyanohydrin in the reaction vessel; add again the 0.1mol2-nitryl-4-thiamphenicol benzoic acid-[1 that step 1 obtains; 3-dimethyl pyrazole-5-yl]-ester; water-bath control temperature of reaction is 25 ℃; drip again the 0.21mol triethylamine; then the temperature of reaction to 60 that raises ℃; steam to desolventize behind the reaction 6h and obtain solid formation; solid formation uses the dissolving of 50mL methylene dichloride; add separatory behind the pH=2 of deionized water regulation system; obtain 1,3-dimethyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols after steaming desolventizes at last.
Wherein step 1 drips 2-nitro with the 0.105mol of 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, and its time for adding is 10min.
The present embodiment step 1 obtains 2-nitryl-4-thiamphenicol benzoic acid-[1; 3-dimethyl pyrazole-5-yl]-yield of ester is 90.1%; purity is 95.3%; finally obtain 1; the yield of 3-dimethyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols is 90.8%, and purity is 92.7%.
Wherein the preparation method of 2-nitro-4-trifluoromethyl benzoyl chloride realizes by following method:
One, adding the water of 160g and 300g mass concentration in the four-hole bottle is 65% the vitriol oil, the 2-nitro-4-trifluoromethyl Benzonitrile that adds 0.4mol, water-bath is cooled to room temperature behind the reflux 4h, then reaction solution is poured in 10min in the trash ice of 500g, under 80 ℃ temperature, dries after filtering and obtain 2-nitro-4-trifluoromethylbenzoic acid;
Two, the thionyl chloride that adds 300mL in the four-hole bottle, 0.4mol 2-nitro-4-trifluoromethylbenzoic acid and the catalyzer DMF of 0.5g, 2h is heated to reflux temperature, reheat backflow 4h, air distillation goes out the 180mL thionyl chloride after being cooled to 60 ℃, then add the 200mL ethylene dichloride and continue to cool to 60 ℃ after air distillation goes out the 150ml solvent again, underpressure distillation ethylene dichloride under the pressure of 20mmHg obtains 2-nitro-4-trifluoromethyl benzoyl chloride.Its proton nmr spectra data are: 1H-NMR (400MHz, DMSO) δ 8.36 (s, 1H), 8.15 (d, J=7.9Hz, 1H), 8.06 (d, J=8.0Hz, 1H).
To sum up the synthetic route of step 1 2-nitro-4-trifluoromethylbenzoic acid is:
The synthetic route of step 2 2-nitro-4-trifluoromethyl benzoyl chloride is:
Embodiment five: present embodiment 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-trifluoromethyl) synthetic method of Benzoylpyrazols follows these steps to realize:
One, the acetonitrile and the 0.125mol triethylamine that add the 1-methyl of 0.1mol-3-trifluoromethyl-5-pyrazolone, 80mL in the four-hole bottle stir, water-bath control temperature of reaction is 20 ℃, the 2-nitro of the 0.105mol of again dropping usefulness 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, under the room temperature behind the stirring reaction 4h, remove solvent under reduced pressure and obtain solid product, solid product uses the dissolving of 50mL methylene dichloride, removes solvent under reduced pressure again and obtain 2-nitro-4-trifluoromethylbenzoic acid-[1-methyl-3-trifluoromethyl pyrazol-5-yl]-ester behind 100mL washing, separatory;
Two; adding 150mL acetonitrile and 0.2ml purity are 98.5% acetone cyanohydrin in the reaction vessel; add again the 0.1mol2-nitro that step 1 obtains-4-trifluoromethylbenzoic acid-[1-methyl-3-trifluoromethyl pyrazol-5-yl]-ester; water-bath control temperature of reaction is 25 ℃; drip again the 0.21mol triethylamine; then the temperature of reaction to 60 that raises ℃; steam to desolventize behind the reaction 6h and obtain solid formation; solid formation uses the dissolving of 50mL methylene dichloride; add separatory behind the pH=2 of deionized water regulation system, steam at last and obtain 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols after desolventizing.
Wherein step 1 drips 2-nitro with the 0.105mol of 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, and its time for adding is 10min.
The yield that the present embodiment step 1 obtains 2-nitro-4-trifluoromethylbenzoic acid-[1-methyl-3-trifluoromethyl pyrazol-5-yl]-ester is 89.2%; purity is 92.5%; the yield of the 1-methyl that finally obtains-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols is 91.2%, and purity is 90.9%.
Embodiment six: the synthetic method of present embodiment 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols follows these steps to realize:
One, the acetonitrile and the 0.125mol triethylamine that add the 1-methyl of 0.1mol-3-cyclopropyl-5-pyrazolone, 80mL in the four-hole bottle stir, water-bath control temperature of reaction is 20 ℃, the 2-nitro of the 0.105mol of again dropping usefulness 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, under the room temperature behind the stirring reaction 4h, remove solvent under reduced pressure and obtain solid product, solid product uses the dissolving of 50mL methylene dichloride, removes solvent under reduced pressure again and obtain 2-nitro-4-trifluoromethylbenzoic acid-[1-methyl-3-cyclopropyl pyrazoles-5-yl]-ester behind 100mL washing, separatory;
Two; adding 150mL acetonitrile and 0.2ml purity are 98.5% acetone cyanohydrin in the reaction vessel; add again the 0.1mol2-nitro that step 1 obtains-4-trifluoromethylbenzoic acid-[1-methyl-3-cyclopropyl pyrazoles-5-yl]-ester; water-bath control temperature of reaction is 25 ℃; drip again the 0.21mol triethylamine; then the temperature of reaction to 60 that raises ℃; steam to desolventize behind the reaction 6h and obtain solid formation; solid formation uses the dissolving of 50mL methylene dichloride; add separatory behind the pH=2 of deionized water regulation system, steam at last and obtain 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols after desolventizing.
Wherein step 1 drips 2-nitro with the 0.105mol of 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, and its time for adding is 10min.
The yield that the present embodiment step 1 obtains 2-nitro-4-trifluoromethylbenzoic acid-[1-methyl-3-cyclopropyl pyrazoles-5-yl]-ester is 92.4%; purity is 95.1%; the yield of the 1-methyl that finally obtains-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols is 89.8%, and purity is 93.8%.
Embodiment seven: the synthetic method of present embodiment 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-methylsulfonyl-4-trifluoromethyl) Benzoylpyrazols follows these steps to realize:
One, the acetonitrile and the 0.125mol triethylamine that add the 1-methyl of 0.1mol-3-trifluoromethyl-5-pyrazolone, 80mL in the four-hole bottle stir, water-bath control temperature of reaction is 20 ℃, the 2-methylsulfonyl of the 0.105mol of again dropping usefulness 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, under the room temperature behind the stirring reaction 4h, remove solvent under reduced pressure and obtain solid product, solid product uses the dissolving of 50mL methylene dichloride, removes solvent under reduced pressure again and obtain 2-methylsulfonyl-4-trifluoromethylbenzoic acid-[1-methyl-3-trifluoromethyl pyrazol-5-yl]-ester behind 100mL washing, separatory;
Two; adding 150mL acetonitrile and 0.2ml purity are 98.5% acetone cyanohydrin in the reaction vessel; add again the 0.1mo2-methylsulfonyl that step 1 obtains-4-trifluoromethylbenzoic acid-[1-methyl-3-trifluoromethyl pyrazol-5-yl]-ester; water-bath control temperature of reaction is 25 ℃; drip again the 0.21mol triethylamine; then the temperature of reaction to 60 that raises ℃; steam to desolventize behind the reaction 6h and obtain solid formation; solid formation uses the dissolving of 50mL methylene dichloride; add separatory behind the pH=2 of deionized water regulation system, steam at last and obtain 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-methylsulfonyl-4-trifluoromethyl) Benzoylpyrazols after desolventizing.
Wherein step 1 drips 2-methylsulfonyl with the 0.105mol of 40ml acetonitrile dissolving-4-trifluoromethyl benzoyl chloride, and its time for adding is 10min.
The yield that the present embodiment step 1 obtains 2-methylsulfonyl-4-trifluoromethylbenzoic acid-[1-methyl-3-trifluoromethyl pyrazol-5-yl]-ester is 90.9%; purity is 95.2%; the yield of the 1-methyl that finally obtains-3-trifluoro methyl-5-hydroxy-4-(2-methylsulfonyl-4-trifluoromethyl) Benzoylpyrazols is 90.5%, and purity is 93.1%.
Adopt the method for " the initiative pesticide bioactivity is estimated SOP weedicide volume " to carry out the weeding activity shaker test 7 kinds of benzoylpyrazole compounds of the present invention.
Its process of the test is as follows:
One, takes by weighing respectively the benzoylpyrazole compounds that quality is 0.1g with analytical balance, with containing the DMF dissolving that mass concentration is 1% tween-80 emulsifying agent, be mixed with mass concentration and be 3.0% mother liquor, then use 10 times of distilled water dilutings, the mother liquor that obtains diluting is for subsequent use;
Two, pot-culture method: be respectively piemarker, lady's-grass, Amaranthus retroflexus, barnyard grass, Eclipta prostrata and Herba Setariae Viridis for the examination target, get internal diameter 6cm flowerpot, dress composite earth [vegetable garden soil: seedling medium=1:2, (v/v)] to 3/4 place, directly sow above-mentioned six kinds of weeds targets (bud rate 〉=85%), earthing 0.2cm treats that weeds grew to for 3 leaf phases for subsequent use.With the mother liquor of step 1 dilution according to 150ga.i./ha dosage after the dispenser of auto spraying tower, dry rear immigration hot-house culture until weeds blade face liquid, viewing test result after 15 days.
The test-results of 7 kinds of benzoylpyrazole compounds sees Table 1.
Table 1
Cauline leaf was sprayed when processing after the test-results of table 1 showed seedling, 150ga.i./ha 4h is higher to broadleaf weeds piemarker, Amaranthus retroflexus and Eclipta prostrata and gramineous weeds barnyard grass activity under the dosage, preventive effect is more than 80%, mainly cause weeds stem apex and lobus cardiacus albefaction, and then wilting and dried-up appears, it is dead that the whole strain of weeds finally appears.By table 1 as can be known 1; 3-dimethyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols and 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols are obvious to the herbicidal effect of piemarker and Amaranthus retroflexus, and can recover gradually green to the albefaction later stage that the dogstail blade causes.
Claims (5)
1. benzoylpyrazole compounds is characterized in that the general formula of benzoylpyrazole compounds is as follows:
Seven kinds of benzoylpyrazole compounds are as follows respectively:
(1) works as R
1Be NO
2Base, R
2Be SO
2CH
3Base, R
3Be CH
3During base, compound is 1,3-dimethyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols, and its structural formula is:
(2) work as R
1Be NO
2Base, R
2Be SO
2CH
3Base, R
3Be CF
3During base, compound is 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols, and its structural formula is:
(3) work as R
1Be NO
2Base, R
2Be SO
2CH
3Base, R
3During for cyclopropyl, compound is 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-methylsulfonyl) Benzoylpyrazols, and its structural formula is:
(4) work as R
1Be NO
2Base, R
2Be CF
3Base, R
3Be CH
3During base, compound is 1,3-dimethyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols, and its structural formula is:
(5) work as R
1Be NO
2Base, R
2Be CF
3Base, R
3Be CF
3During base, compound is 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols, and its structural formula is:
(6) work as R
1Be NO
2Base, R
2Be CF
3Base, R
3During for cyclopropyl, compound is 1-methyl-3-cyclopropyl-5-hydroxyl-4-(2-nitro-4-trifluoromethyl) Benzoylpyrazols, and its structural formula is:
(7) work as R
1Be SO
2CH
3Base, R
2Be CF
3Base, R
3Be CF
3During base, compound is 1-methyl-3-trifluoro methyl-5-hydroxy-4-(2-methylsulfonyl-4-trifluoromethyl) Benzoylpyrazols, and its structural formula is:
2. the method for synthesizing benzoylpyrazole compounds as claimed in claim 1 is characterized in that the synthetic method of benzoylpyrazole compounds follows these steps to realize:
One, adding pyrazolone compound II, acetonitrile and triethylamine in the four-hole bottle stirs, water-bath control temperature of reaction is 15～20 ℃, drip again the Benzoyl chloride compounds I with the acetonitrile dissolving, under the room temperature behind stirring reaction 1～5h, remove solvent under reduced pressure and obtain solid product, solid product uses the methylene dichloride dissolving, removes solvent under reduced pressure again and obtain benzoylpyrazole ester compound III behind washing, separatory;
Two, add acetonitrile and acetone cyanohydrin in the reaction vessel, add again the benzoylpyrazole ester compound III that step 1 obtains, water-bath control temperature of reaction is 23～28 ℃, drip triethylamine, then the temperature of reaction to 60 that raises ℃ is steamed to desolventize behind reaction 5.5～6.5h and is obtained solid formation, and solid formation uses the methylene dichloride dissolving, add separatory behind the pH=2 of deionized water regulation system, steam at last and obtain the benzoylpyrazole compounds after desolventizing;
Wherein when Benzoyl chloride compounds I was 2-nitro-4-methylsulfonyl Benzoyl chloride, pyrazolone compound II was 1-methyl-3-cyclopropyl-5-pyrazolone, 1-methyl-3-trifluoromethyl-5-pyrazolone or 1,3-dimethyl-5-pyrazolone;
When Benzoyl chloride compounds I was 2-nitro-4-trifluoromethyl benzoyl chloride, pyrazolone compound II was 1-methyl-3-cyclopropyl-5-pyrazolone, 1-methyl-3-trifluoromethyl-5-pyrazolone or 1,3-dimethyl-5-pyrazolone;
When Benzoyl chloride compounds I was 2-methylsulfonyl-4-trifluoromethyl benzoyl chloride, pyrazolone compound II was 1-methyl-3-trifluoromethyl-5-pyrazolone.
3. the synthetic method of benzoylpyrazole compounds according to claim 2 is characterized in that step 1 water-bath control temperature of reaction is 20 ℃.
4. the synthetic method of benzoylpyrazole compounds according to claim 2 is characterized in that step 2 water-bath control temperature of reaction is 25 ℃.
5. the application of benzoylpyrazole compounds as claimed in claim 1 is characterized in that the benzoylpyrazole compounds is applied in the weedicide as activeconstituents.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108191667A (en) * | 2018-01-04 | 2018-06-22 | 利尔化学股份有限公司 | The preparation method of 2- nitro -4- trifluoromethyl benzoic acid methyl esters |
| CN109006853A (en) * | 2018-07-30 | 2018-12-18 | 江苏常丰农化有限公司 | A kind of preparation process of the Herbicidal combinations Han 2,4-D |
| CN111808024A (en) * | 2019-04-11 | 2020-10-23 | 郑州手性药物研究院有限公司 | Phenylpyrazolone compound or salt thereof, preparation method and application |
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| CN101573035A (en) * | 2006-12-27 | 2009-11-04 | 石原产业株式会社 | Herbicide containing benzoylpyrazole compound |
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| JPS5643270A (en) * | 1979-09-13 | 1981-04-21 | Ishihara Sangyo Kaisha Ltd | Production of 4-benzoyl-5-hydroxypyrazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108191667A (en) * | 2018-01-04 | 2018-06-22 | 利尔化学股份有限公司 | The preparation method of 2- nitro -4- trifluoromethyl benzoic acid methyl esters |
| CN108191667B (en) * | 2018-01-04 | 2021-03-26 | 利尔化学股份有限公司 | Preparation method of 2-nitro-4-trifluoromethyl methyl benzoate |
| CN109006853A (en) * | 2018-07-30 | 2018-12-18 | 江苏常丰农化有限公司 | A kind of preparation process of the Herbicidal combinations Han 2,4-D |
| CN111808024A (en) * | 2019-04-11 | 2020-10-23 | 郑州手性药物研究院有限公司 | Phenylpyrazolone compound or salt thereof, preparation method and application |
| CN111808024B (en) * | 2019-04-11 | 2023-06-27 | 郑州手性药物研究院有限公司 | Phenyl pyrazolone compound or salt thereof, preparation method and application |
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