CN103396366A - Production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole - Google Patents
Production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- QPZYPAMYHBOUTC-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazole-3-carbonitrile Chemical compound NC1=CC(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl QPZYPAMYHBOUTC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 30
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000012954 diazonium Substances 0.000 claims abstract description 8
- ITNMAZSPBLRJLU-UHFFFAOYSA-N 2,6-dichloro-4-(trifluoromethyl)aniline Chemical compound NC1=C(Cl)C=C(C(F)(F)F)C=C1Cl ITNMAZSPBLRJLU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001989 diazonium salts Chemical class 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000013517 stratification Methods 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000284 extract Substances 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 239000004304 potassium nitrite Substances 0.000 claims description 2
- 235000010289 potassium nitrite Nutrition 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 238000006193 diazotization reaction Methods 0.000 abstract description 2
- 150000007857 hydrazones Chemical class 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- HHNXOWUQVSCKQY-UHFFFAOYSA-N 2,3-dicyanopropanoic acid Chemical compound OC(=O)C(C#N)CC#N HHNXOWUQVSCKQY-UHFFFAOYSA-N 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FNELVJVBIYMIMC-UHFFFAOYSA-N Ethiprole Chemical compound N1=C(C#N)C(S(=O)CC)=C(N)N1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl FNELVJVBIYMIMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- -1 2,6-dichloro p-trifluoromethylaniline acetic acid Chemical compound 0.000 description 1
- ZOCSXAVNDGMNBV-UHFFFAOYSA-N 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile Chemical compound NC1=C(S(=O)C(F)(F)F)C(C#N)=NN1C1=C(Cl)C=C(C(F)(F)F)C=C1Cl ZOCSXAVNDGMNBV-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 239000005899 Fipronil Substances 0.000 description 1
- 241000258937 Hemiptera Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000000073 carbamate insecticide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229940013764 fipronil Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention discloses a production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole. The production method is characterized in that in an acid solution, an acid and 2,6-dichloro-4-trifluoromethyl phenylamine undergo a reaction to produce a salt; 2,3-dicyanopropionate is fast added into the salt and sodium nitrite is added into the reaction system at a normal temperature; the reaction product is filled with water with stirring for layering; and the reaction system undergoes a cyclization reaction in an ammonia water medium. The production method greatly reduces reaction time. Through immediate condensation of the produced diazonium salt and 2,3-dicyanopropionate, a hydrazone synthesis reaction in diazotization is effectively avoided so that product content is more than 96% and a yield is more than 83%.
Description
Technical field
The invention belongs to chemical material field, be specifically related to the production method of a kind of 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles.
Background technology
5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles is the important intermediate of synthesizing efficient sterilant " ethiprole " (English popular name: fipronil, trade(brand)name: Frontline, Regent etc.), its molecular formula H
5Cl
2F
3N
4, MP:132-141 ℃, another name arylpyrazole nitrile, No. CAS: 120068-79-63, high purity product (content>=95%) is faint yellow or white crystal shape.
5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles structural formula
Ethiprole is researched and developed and goes into operation in 1987～1989 years by Rhone-Poulenc Company at first, in China, registers in 1992, with trade(brand)name Goliath etc., in Europe, goes on the market in 1996.This medicine novel structure uniqueness, active high, various pests is had to excellent prevention effect, especially to insects such as Hemiptera, lepidopteran, Thysanoptera, Coleopteras and to the insect that cyclopentadiene, chrysanthemum ester class, carbamate insecticides have produced resistance, all demonstrate high susceptibility, per hectare only needs tens gram effective constituents just can control pierce-suck type and pests with chewing mouthparts.Through developing application for many years, ethiprole has developed into a quite concerned efficient pesticides, and its prospect of production is very optimistic.
5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles synthetic route is a lot, yet most synthetic route exists raw material sources to be difficult for, reactions steps is various, and the spent acid discharging of waste liquid is many, is difficult for processing, use reagent toxicity larger, industrial protection requires the shortcomings such as high.Therefore, select that synthesis step is simple, the excellent good reasonably synthetic route cheaply of technological process environmental protection, quality product, realize large-scale industrial production, have very great meaning.
Present 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles manufacture method is mainly: under the chilled brine condition (lower than 10 ℃), (vitriol oil and glacial acetic acid) slowly adds Sodium Nitrite in nitration mixture, carried out diazotization reaction 1 hour, obtain light yellow scattered paste shape thing, at ambient temperature, stir slowly and drip 2,6-dichloro p-trifluoromethylaniline acetic acid solution, be warming up to slowly 50 ℃ of reactions and obtained diazonium salt in 4 hours; Under lower than 15 ℃ of conditions, splash into 2,3-dicyano ethyl propanoate, insulation reaction 2 hours, add 2-3 water doubly, then stir 1-2 hour, product is carried out to cooling, stratification, upper strata liquid adds ethylene dichloride and divides three extractions, must extract material, merges layered material under condenses; At ambient temperature, in condenses, add strong aqua, carried out ring-closure reaction 3 hours, after washing 2-3 time with water, ethylene dichloride is reclaimed in underpressure distillation, then with solvent, product is carried out to recrystallization, after filtering drying, obtain final product 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles.This method reactions steps complexity, need to use a large amount of vitriol oils, and want low-temp reaction, and reaction yield is only 75%, and production cost is high, and environmental pollution is large.
Summary of the invention
The purpose of this invention is to provide 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles production method that a kind of reaction conditions is gentle, productive rate is high.In order to realize purpose of the present invention, intend adopting following technical scheme:
One aspect of the present invention relates to the production method of a kind of 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles, it is characterized in that comprising the steps:
At normal temperatures, 2, the 6-dichlor-4-trifluoromethyl aniline mixes with acid, add 2, the 3-dicyano ethyl propanoate, add Sodium Nitrite or potassium nitrite under 5-15 ℃ of condition, under 20～25 ℃ of conditions, stir 2-4 hour, then under 15-25 ℃ of condition, add water, stir and after 0.2-1 hour, add water and carry out stratification, minute take off a layer oily matter, upper aqueous layer extracts with toluene, extraction liquid merges in oily matter, with strong aqua, regulates pH >=11, after stirring at normal temperature 2-4 hour, through washing, suction filtration, oven dry, obtain target product.
In a preferred embodiment of the present invention, described acid is the combination of a kind of in concentrated hydrochloric acid, Glacial acetic acid or two kinds.
In a preferred embodiment of the present invention, it is characterized in that the purity of products therefrom is more than 95%.
The present invention relates to the production method of a kind of 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles on the other hand, and its step comprises:
The concentrated hydrochloric acid that 1, will measure drops into the diazonium still, start stirring and cooling, the measured Glacial acetic acid of stalagmometer under normal temperature, add fast again measure 2, the 3-dicyano ethyl propanoate, add rear normal temperature and add 2,6-dichlor-4-trifluoromethyl aniline to stir 20-30 minute one-tenth hydrochloride, separate out and be suspended in Glacial acetic acid;
2, under 5-15 ℃ of condition, slowly add solid sodium nitrite, cooling, remain normal temperature, the joining day is 1-2 hour, adds rear normal temperature and stirs 4-6 hour;
3, sampling analysis 2, and 6-dichlor-4-trifluoromethyl aniline content, less than 0.8%, without diazonium salt, adds the water that measures, after stirring half an hour, and stratification, layer oily matter is standby, and upper aqueous layer, with after quantitative toluene extraction, merges oily matter;
4, material is added to the cyclisation still, with strong aqua, be adjusted to PH greater than 11, stirring at normal temperature 2-4 hour, washing, centrifugal, recrystallization, dry to obtain the off-white color solid.
Method of the present invention, in acid solution, with 2,6-dichlor-4-trifluoromethyl aniline salify, and then adds 2,3-dicyano ethyl propanoate fast, under normal temperature, adds Sodium Nitrite, then stirs and to add water stratification, and finally ring-closure reaction in aqueous ammonia medium, get product.Reaction times of the present invention is saved greatly, and the diazonium salt of generation and the condensation immediately of 2,3-dicyano ethyl propanoate, prevent the one-tenth hydrazone reaction in the diazonium process most effectively, makes product content reach 96%, and yield reaches more than 83%.
The present invention has following advantage:
1, do not use the vitriol oil, aftertreatment is simple, and cost is low;
2, the reaction times short, the step simplified control;
3, reaction conditions simple, without low temperature, institute responds and is all normal-temperature reaction;
4, reaction yield, up to more than 83%, is produced 75% yield far above normal process.
The accompanying drawing explanation
The product HPLC detected result of Fig. 1: embodiment 1.
Embodiment
The present invention is further illustrated below in conjunction with embodiment:
Embodiment 1
at one, electric mixer is housed, thermometer, in the 500ml there-necked flask of reflux exchanger and dropping funnel, add 30% hydrochloric acid 200g and 2, 6-dichlor-4-trifluoromethyl aniline 46g, at normal temperatures, add Sodium Nitrite 17g, stir after 3 hours, under 20～25 ℃ of conditions, add 2, 3-dicyano ethyl propanoate 30.5g, stirred 3 hours, then under cooling conditions, add water 200ml, stir and pour in the 1000m1 separating funnel after 0.5 hour, add water 300ml, stratification, divide and take off a layer oily matter, upper aqueous layer extracts with 50 * 2ml toluene, extraction liquid merges in oily matter, with strong aqua, regulate pH >=11, after stirring at normal temperature 3 hours, through washing, suction filtration (reclaiming the product in toluene), oven dry, high performance liquid chromatography (High performance Liquid Chromatography, HPLC), take methanol aqueous solution as moving phase, measure 5-Amino 3 cyano-1-(2, 6-dichlor-4-trifluoromethyl phenyl) purity (result is referring to Fig. 1) of pyrazoles product, obtaining purity is 96.5% product 55.3g, yield is 83.1%.
at one, electric mixer is housed, thermometer, in the 500ml there-necked flask of reflux exchanger and dropping funnel, add the acetic acid solution 200g and 2 that contains 10%HCl, 6-dichlor-4-trifluoromethyl aniline 46g, at normal temperatures, add Sodium Nitrite 17g, stir after 3 hours, under 20～25 ℃ of conditions, add 2, 3-dicyano ethyl propanoate 30.5g, stirred 3 hours, then under cooling conditions, add water 200ml, stir and pour in the 1000m1 separating funnel after 0.5 hour, add water 300ml, stratification, divide and take off a layer oily matter, upper aqueous layer extracts with 50 * 2ml toluene, extraction liquid merges in oily matter, with strong aqua, regulate PH >=11, after stirring at normal temperature 3 hours, through washing, suction filtration (reclaiming the product in toluene), oven dry, obtaining purity is 96.7% product 55.8g, yield is 84.0%.
Embodiment 3
at one, electric mixer is housed, thermometer, in the 500ml there-necked flask of reflux exchanger and dropping funnel, add 30% hydrochloric acid 200g, 2, 3-dicyano ethyl propanoate 30.5g and 2, 6-dichlor-4-trifluoromethyl aniline 46g, at normal temperatures, slowly add Sodium Nitrite 17g, under 20～25 ℃ of conditions, add and stirred 5 hours, then under cooling conditions, add water 200ml, stir and pour in the 1000m1 separating funnel after 0.5 hour, add water 300ml, stratification, divide and take off a layer oily matter, upper aqueous layer extracts with 50 * 2ml toluene, extraction liquid merges in oily matter, with strong aqua, regulate PH >=11, after stirring at normal temperature 3 hours, through washing, suction filtration (reclaiming the product in toluene), oven dry, obtaining purity is 95.8% product 58.9g, yield is 87.9%.
Embodiment 4
at one, electric mixer is housed, thermometer, in the 500ml there-necked flask of reflux exchanger and dropping funnel, add the acetic acid solution 200g that contains 10%HCl, 2, 3-dicyano ethyl propanoate 30.5g and 2, 6-dichlor-4-trifluoromethyl aniline 46g, at normal temperatures, slowly add Sodium Nitrite 17g, under 20～25 ℃ of conditions, add and stirred 5 hours, then under cooling conditions, add water 200ml, stir and pour in the 1000m1 separating funnel after 0.5 hour, add water 300ml, stratification, divide and take off a layer oily matter, upper aqueous layer extracts with 50 * 2ml toluene, extraction liquid merges in oily matter, with strong aqua, regulate PH >=11, after stirring at normal temperature 3 hours, through washing, suction filtration (reclaiming the product in toluene), oven dry, obtaining purity is 96.1% product 59.2g, yield is 88.6%.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, and any variation or replacement of expecting without creative work, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (4)
1. the production method of a 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles, is characterized in that comprising the steps:
At normal temperatures, 2, the 6-dichlor-4-trifluoromethyl aniline mixes with acid, add 2, the 3-dicyano ethyl propanoate, add Sodium Nitrite or potassium nitrite under 5-15 ℃ of condition, under 20～25 ℃ of conditions, stir 2-4 hour, then under 15-25 ℃ of condition, add water, stir and after 0.2-1 hour, add water and carry out stratification, minute take off a layer oily matter, upper aqueous layer extracts with toluene, extraction liquid merges in oily matter, with strong aqua, regulates pH >=11, after stirring at normal temperature 2-4 hour, through washing, suction filtration, oven dry, obtain target product.
2. production method according to claim 1, is characterized in that described acid is the combination of a kind of in concentrated hydrochloric acid, Glacial acetic acid or two kinds.
3. production method according to claim 1 and 2, is characterized in that the purity of products therefrom is more than 95%.
4. the production method of a 5-Amino 3 cyano-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles, its step comprises:
(1) concentrated hydrochloric acid that will measure drops into the diazonium still, start stirring and cooling, the measured Glacial acetic acid of stalagmometer under normal temperature, add fast again measure 2, the 3-dicyano ethyl propanoate, add rear normal temperature and add 2,6-dichlor-4-trifluoromethyl aniline to stir 20-30 minute one-tenth hydrochloride, separate out and be suspended in Glacial acetic acid;
(2) under 5-15 ℃ of condition, slowly add solid sodium nitrite, cooling, remain normal temperature, the joining day is 1-2 hour, adds rear normal temperature and stirs 4-6 hour;
(3) sampling analysis 2, and 6-dichlor-4-trifluoromethyl aniline content, less than 0.8%, without diazonium salt, adds the water that measures, after stirring half an hour, and stratification, layer oily matter is standby, and upper aqueous layer, with after quantitative toluene extraction, merges oily matter;
(4) material is added to the cyclisation still, with strong aqua, be adjusted to PH greater than 11, stirring at normal temperature 2-4 hour, washing, centrifugal, recrystallization, dry to obtain the off-white color solid.
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| CN106220565A (en) * | 2016-08-17 | 2016-12-14 | 江苏托球农化股份有限公司 | A kind of synthesis technique of 5 amino 3 cyano group 1 (2,6 dichloro-4,4 trifluoromethyl) pyrazoles |
| CN107353251A (en) * | 2017-07-24 | 2017-11-17 | 连云港埃森化学有限公司 | A kind of ethiprole production technology |
| CN110483480A (en) * | 2019-09-11 | 2019-11-22 | 江苏优普生物化学科技股份有限公司 | The synthetic method of 2- (3- chloropyridine -2- base) -5- hydroxyl -3- pyrazolidinecarboxylate |
| CN110981806A (en) * | 2019-12-06 | 2020-04-10 | 江苏优普生物化学科技股份有限公司 | Method for synthesizing aryl pyrazole nitrile and byproduct carbonic acid diester |
| CN111018786A (en) * | 2019-12-06 | 2020-04-17 | 江苏优普生物化学科技股份有限公司 | Production method of aryl pyrazole nitrile |
| CN112094235A (en) * | 2020-11-11 | 2020-12-18 | 苏州开元民生科技股份有限公司 | Preparation method of 5-amino-3-cyano-1- (2, 6-dichloro-4-trifluoromethylphenyl) pyrazole |
| CN112480010A (en) * | 2020-12-02 | 2021-03-12 | 江苏优普生物化学科技股份有限公司 | Method for preparing urethane and diethyl carbonate |
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