CN102344395A - Synthesis method for bifenazate - Google Patents
Synthesis method for bifenazate Download PDFInfo
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- CN102344395A CN102344395A CN2011102128824A CN201110212882A CN102344395A CN 102344395 A CN102344395 A CN 102344395A CN 2011102128824 A CN2011102128824 A CN 2011102128824A CN 201110212882 A CN201110212882 A CN 201110212882A CN 102344395 A CN102344395 A CN 102344395A
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Abstract
The invention belongs to the technical field of pesticide and midbody synthesis, particularly relates to a synthesis method for bifenazate. In the synthesis method for the bifenazate, a target product is synthetized by taking para-hydroxydiphenyl as a raw material through nitration, methylation, hydrogenated reduction, diazotization, diazonium salt reduction and an acylation one-step method, wherein acylation reaction is directly performed on hydrazonium salt without treatment, thus, the experimental procedure is shortened, the yield is improved to above 65 percent from 50 percent, the conversion rate of a reaction product is high, and the purification treatment is easy to perform. The synthesis method for the bifenazate has the advantages that the operation is simple, the condition is mild, the yield is high, the cost is low, and the like, is easy to carry out industrial production and has a wide application prospect. The bifenazate synthetized by the invention can be used as a specific acaricide, is active in active stage of tetranychid, can also control pests, such as Tetranychus urticae, in the egg stage, and is used for cotton, hop and certain fruiter crops to effectively prevent all mites in the growth stage.
Description
Technical field
The invention belongs to agricultural chemicals and intermediate synthesis technical field, be specifically related to a kind of synthesis method of Bifenazate.
Background technology
Bifenazate (bifenazate) chemistry N ' by name-(the hydrazine carboxylic acid's isopropyl ester of 4-methoxyl biphenyl-3-) is a kind of novel hydrazine ester compound.It is narrow spectrum miticide, in the active period of tetranychid activity is arranged, and also can prevent and treat the ovum phase of insects such as Tetranychus urticae.Be used for cotton, hop and some fruit tree crop, the mite class of all growth phases of effectively preventing
[1]This medicine can provide to be killed and long residual selectivity preventive effect (harmless to beneficial mite and useful insect) fast, uses in the Mei Gezhou registration, and China is domestic does not at present also produce.
Take a broad view of the developing history of pesticide industry; The pesticide original medicine kind is increased to present more than 1000 by tens of the forties; Meanwhile; Some old kinds also constantly are being eliminated or are limiting the use of; To nineteen ninety-five, nearly more than 100 pesticide species are disabled, and it is individual that the pesticide species that is restricted at present or forbids has risen to hundreds of; Make decision again recently like European Union, eliminate 320 kinds of pesticide activity components from July 1st, 2003.From absolute number, it is over and done with that the agricultural chemicals recruit registers many 10 years of quantity, and the crop protection products recruit who emerges in recent years is less.This mainly is because after the execution of food quality protection rules; Environmental Protection Agency has slowed down the speed of agriculture chemical registration; And some are engaged in more energy being concentrated on through on the reliable product of check with the production firm of crossing patent phase agricultural chemicals of basic agricultural chemicals; Continuous upgrading product innovation; They are transformed into new preparation and pre-composition and form due to a kind of tendency; The input of research and development novel molecular has more commercial value relatively.Reduced though develop agricultural chemicals recruit's quantity at present, wherein also be no lack of very potential " blockbuster "
[2,3]The Bifenazate that Uniroyal company produces is exactly one of them, and its commodity are called Acramite.
Bifenazate has a lot of synthesis methods at present as a kind of known synthetic pesticide, and what report was once arranged is starting raw material with 3-bromo-4-methoxyl biphenyl, 5-bromo-2-anisidine respectively, through the transition metal-catalyzed target product that obtains respectively
[4-7], be raw material with the parazon through with the amination reaction of diisopropyl azodiformate and then obtain product
[8,9]But cost is all too high, and difficulty is carried out industrial production.The difficulty that how to reduce production costs and operate obtains target product and has great importance.The present invention is raw material with the parazon, through nitrated, methylate, hydrogenating reduction, diazotization, diazonium salt reduction and acidylate single stage method synthesize target product.Advantage such as that the inventive method has is simple to operate, mild condition, yield are high, with low cost is easy to suitability for industrialized production, has broad prospect of application.Wherein hydrazonium salt is not handled and is directly carried out acylation reaction and shortened experimental procedure, has obviously improved yield, bring up to more than 65% from 50%, and reaction conversion ratio is high, is prone to carry out purification process.
Reference:
[1] scientific and technological development. agricultural, commodities market news on the ten.
2006, 435,18-19.
[2]?Bautista?F.?M.，
et?a1．
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[4]?Park?S.?B.，
et?a1．?US?6,706，895?(?
2004).
[5]?Wang?Z.?R.，
et?a1．
Tetrahedron?Lett．
1999，40,?3543-3546.
[6]?Yoshiaki?Kitamura，
et?a1．
Tetrahedron．
2007，63：10596-10602.
[7]?Deng?C.?L.，
et?a1．
Eur．J．Org．Chem．
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[8]?Chee?G.?L.，
et?a1．US?6,093，843?(
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[9]?Gaik?L.，
et?a1．
Synthetic?Commun．
2006，36,?2151-2156。
Summary of the invention
The object of the invention is to provide a kind of synthesis method of novel agrochemical Bifenazate.
The synthesis method of the Bifenazate that the present invention proposes, its synthetic route is following:
Concrete steps are following:
(1) 3-nitro-4-methoxyl biphenyl (III) is synthetic
Parazon is dissolved in methyl tertiary butyl ether (MTBE), and mixing and stirring splashes into nitric acid in the gained mixing solutions, drips off continued and stirs 1-3h, and whole process temperature is controlled at 20-40 ℃; TLC detects, and reaction finishes.System is poured in the frozen water, separated out a large amount of solids, suction filtration, drying obtains xanchromatic solid chemical compound 3-nitro-4-xenol (II).Wherein, the mol ratio of parazon and nitric acid is 1: (1-2).
3-nitro-4-xenol, methylcarbonate, Tetrabutyl amonium bromide (TBAB) and salt of wormwood are joined in the reaction flask, be warming up to 80-100 ℃, reacted 40-50 hour; TLC detects, and reaction finishes.System is cooled to room temperature, in system, drips HCl solution, adjustings PH is 4-6, and system does not have bubble and emerges at this moment.System is poured in the frozen water, separated out a large amount of solids, suction filtration, drying obtains tawny solid chemical compound 3-nitro-4-methoxyl biphenyl (III).Wherein the mol ratio of 3-nitro-4-xenol and methylcarbonate is 1: (2-10), the mol ratio of 3-nitro-4-xenol and Tetrabutyl amonium bromide is 1: (1-3), the mol ratio of 3-nitro-4-xenol and salt of wormwood is 1: (2-5).
(2) 3-amino-4-methoxyl biphenyl (IV) is synthetic
3-nitro-4-methoxyl biphenyl that step (1) is obtained joins in the reaction flask; With methyl alcohol is solvent; Raney's nickel is a catalyzer; At pressure is 1.5MPa; Temperature is to react 1-3h under the 50-100 ℃ of condition; After TLC detected and shows that reaction is accomplished, rotary evaporation in vacuo was removed methyl alcohol, promptly gets 3-amino-4-methoxyl biphenyl.Wherein, the mol ratio of 3-nitro-4-methoxyl biphenyl and Raney's nickel is 1: (0.01-0.05).
(3) N '-(the 4-methoxyl biphenyl-3-) hydrazine carboxylic acid's isopropyl ester (I) is synthetic
3-amino-4-methoxyl biphenyl and HCl-H that step (2) is obtained
2O solution, mixing and stirring under the room temperature, ice-water bath is cooled to 0 ℃ then.With NaNO
2The aqueous solution slowly be added drop-wise in the system, behind the reaction 0.5-2h, obtain diazonium salt solution, remain through detecting no raw material.Tin protochloride is dissolved in the concentrated hydrochloric acid, is cooled to-20 ℃, slowly be added drop-wise in the diazonium salt solution and go, this moment, solution temperature rose, and thickness constantly drips tin chloride solution gradually, was yellow muddy, behind the stirring 0.5-2h, was the canescence muddiness.With solid filtering, vacuum-drying obtains 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride.Wherein, the mol ratio of 3-amino-4-methoxyl biphenyl and Sodium Nitrite is 1: (1-2), the mol ratio of 3-amino-4-methoxyl biphenyl and tin protochloride is 1: (2-8).
Mix under 3-(4-methoxyl biphenyl base-3-yl) the diazanyl hydrochloride solid that obtains and the toluene ice bath, add pyridine, the mixing solutions of isopropyl chlorocarbonate and toluene is joined in the system.0 ℃ is reacted 1h down, and TLC detects, and reaction finishes.System washing twice then, the water extracted in toluene, extraction liquid mixes with original toluene mutually, and vacuum rotary steam obtains hazel target product I, i.e. Bifenazate.Wherein, the mol ratio of 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride and pyridine is 1: (1-3), the mol ratio of 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride and isopropyl chlorocarbonate is 1: (1-3).
Among the present invention, HCl-H described in the step (3)
2HCl and H in the O solution
2The volume ratio of O is 1:1, and HCl adopts the concentrated hydrochloric acid of massfraction 37.5%.
The invention has the advantages that:
Diazonium salt reduzate-hydrazonium salt of the present invention is not handled and is directly carried out acylation reaction and shortened experimental procedure, has obviously improved yield, bring up to more than 65% from 50%, and reaction system is assorted, is prone to carry out aftertreatment.
Embodiment
Followingly further specify the present invention, but can not limit content of the present invention through embodiment.
Embodiment 1: the preparation of compound Bifenazate (I)
In the there-necked flask of 250ml, the parazon of 5g (29.4mmol) is dissolved in the methyl tertiary butyl ether (MTBE) of 25ml, mixes and stir 5min, temperature is controlled at 30 ℃.(58.8mmol, 2eq.) nitric acid and 10mlMTBE are miscible pours in the dropping funnel, dropwises in the 1h, continues to stir 3h to get 4ml.TLC detects, and reaction finishes.System is poured in the 300ml frozen water, stirred 5min, this moment, the liquid level top layer did not have darkorange liquid, separated out a large amount of solids, suction filtration, and drying obtains yellow solid 3-nitro-4-xenol (II) 5.9g, and yield is 93%.
With the 3-nitro-4-xenol solid 5g (23.2mmol) and 40ml methylcarbonate that obtain, 8.2g (1.1eq.) Tetrabutyl amonium bromide (TBAB) and 3.2g (1eq.) salt of wormwood stirring and evenly mixing are warming up to 100 ℃ of backflows.TLC detects behind the 48h, and reaction finishes.System is cooled to room temperature, in system, drips HCl solution, transfer to PH4-6, system did not have bubble and emerged this moment.System is poured in the 200ml frozen water, separated out a large amount of solids, suction filtration, drying obtains tawny solid 3-nitro-4-methoxyl biphenyl (III) 5.253g, and yield is 98.7%.
5g3-nitro-4-the methoxyl biphenyl (III) of gained is joined in the reaction flask; Add 20ml methyl alcohol; With 5% Raney's nickel is catalyzer; React down 3h at 60 ℃ with 1.5MPa; After TLC detects and shows that reaction is accomplished; Rotary evaporation in vacuo is removed methyl alcohol, promptly gets desired product compound 3-amino-4-methoxyl biphenyl (IV) 4.0g, and yield is 93%.
With 3g 3-amino-4-methoxyl biphenyl (IV) and HCl-H
2Mixing and stirring under O (30+30ml, hydrochloric acid are the concentrated hydrochloric acid of the massfraction 37.5%) room temperature, ice-water bath is cooled to 0 ℃ then.With 1.35g NaNO
2The aqueous solution slowly be added drop-wise in the system, detect no raw material behind the 0.5h and remain.With the tin protochloride of 13.56g, be dissolved in the 30ml concentrated hydrochloric acid, be cooled to-20 ℃, slowly be added drop-wise in the diazonium salt solution and go; This moment, solution temperature rose, and thickness constantly drips tin chloride solution gradually; Be yellow muddy, constantly stir lh after, be the canescence muddiness.With solid filtering, vacuum-drying obtains 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride.
Mix under 3-(4-methoxyl biphenyl base-3-yl) the diazanyl hydrochloride solid that obtains and the 20ml toluene ice bath, add the 1.78g pyridine, the system flavescence joins the mixing solutions of 2.75g isopropyl chlorocarbonate and 5ml toluene in the system.0 ℃ is reacted 1h down, and TLC detects, and reaction finishes.System washing twice then, the water extracted in toluene, extraction liquid mixes with original toluene mutually, and vacuum rotary steam obtains hazel solid Bifenazate (I) 2.97g, and yield is 66%.
Characterization data is following:
1H?NMR(300?MHz，CDCl
3，TMS)，6：1．25(d，6H，2-CH
3)，3．89(s，3H，-CH
3)，4．97(m，1?H)，6．40(S，1H，-NH-)，6．88(d，1H)，7．07(d，2H)，7．28(t，1H)，7．39(t，2H)，7．52(d，2H)。
Embodiment 2: the preparation of compound Bifenazate (I)
In the there-necked flask of 250ml, the parazon of 5g (29.4mmol) is dissolved in the methyl tertiary butyl ether (MTBE) of 25ml, mixes and stir 5min, temperature is controlled at 20 ℃.(29.4mmol, 1eq.) nitric acid and 10mlMTBE are miscible pours in the dropping funnel, dropwises in the 1h, continues to stir 3h to get 2ml.TLC detects, and reaction finishes.System is poured in the 300ml frozen water, stirred 5min, this moment, the liquid level top layer did not have darkorange liquid, separated out a large amount of solids, suction filtration, and drying obtains yellow solid 3-nitro-4-xenol (II) 5.9g, and yield is 80%.
With the 3-nitro-4-xenol solid 5g (23.2mmol) and 30ml methylcarbonate that obtain, 8.2g (1.1eq.) Tetrabutyl amonium bromide (TBAB) and 3.2g (1eq.) salt of wormwood stirring and evenly mixing are warming up to 90 ℃ of backflows.TLC detects behind the 48h, and reaction finishes.System is cooled to room temperature, in system, drips HCl solution, transfer to PH4-6, system did not have bubble and emerged this moment.System is poured in the 200ml frozen water, separated out a large amount of solids, suction filtration, drying obtains tawny solid 3-nitro-4-methoxyl biphenyl (III) 5.253g, and yield is 95%.
5g3-nitro-4-the methoxyl biphenyl (III) of gained is joined in the reaction flask; Add 20ml methyl alcohol; With 5% Raney's nickel is catalyzer; React down 3h at 70 ℃ with 1.5MPa; After TLC detects and shows that reaction is accomplished; Rotary evaporation in vacuo is removed methyl alcohol, promptly gets desired product compound 3-amino-4-methoxyl biphenyl (IV) 4.0g, and yield is 93%.
With 3g 3-amino-4-methoxyl biphenyl and HCl-H
2Mixing and stirring under O (30+30ml, hydrochloric acid are the concentrated hydrochloric acid of the massfraction 37.5%) room temperature, ice-water bath is cooled to 0 ℃ then.With 1.35g NaNO
2The aqueous solution slowly be added drop-wise in the system, detect no raw material behind the 1h and remain.With the tin protochloride of 16.95g, be dissolved in the 20ml concentrated hydrochloric acid, be cooled to-20 ℃, slowly be added drop-wise in the diazonium salt solution and go; This moment, solution temperature rose, and thickness constantly drips tin chloride solution gradually; Be yellow muddy, constantly stir lh after, be the canescence muddiness.With solid filtering, vacuum-drying obtains 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride solid.
Mix under 3-(4-methoxyl biphenyl base-3-yl) the diazanyl hydrochloride solid that obtains and the 20ml toluene ice bath, add the 1.78g pyridine, the system flavescence joins the mixing solutions of 3.12g isopropyl chlorocarbonate and 5ml toluene in the system.0 ℃ is reacted 2h down, and TLC detects, and reaction finishes.System washing twice then, the water extracted in toluene, extraction liquid mixes with original toluene mutually, and vacuum rotary steam obtains hazel solid Bifenazate (I) 3.1g, and yield is 69%.
Embodiment 3: the preparation of compound Bifenazate (I)
In the there-necked flask of 250ml, the parazon of 5g (29.4mmol) is dissolved in the methyl tertiary butyl ether (MTBE) of 25ml, mixes and stir 5min, temperature is controlled at 40 ℃.(58.8mmol, 2eq.) nitric acid and 10mlMTBE are miscible pours in the dropping funnel, dropwises in the 1h, continues to stir 3h to get 2ml.TLC detects, and reaction finishes.System is poured in the 300ml frozen water, stirred 5min, this moment, the liquid level top layer did not have darkorange liquid, separated out a large amount of solids, suction filtration, and drying obtains yellow solid 3-nitro-4-xenol (II) 5.9g, and yield is 85%.
With the 3-nitro-4-xenol solid 5g (23.2mmol) and 30ml methylcarbonate that obtain, 8.2g (1.1eq.) Tetrabutyl amonium bromide (TBAB) and 3.2g (1eq.) salt of wormwood stirring and evenly mixing are warming up to 100 ℃ of backflows.TLC detects behind the 48h, and reaction finishes.System is cooled to room temperature, in system, drips HCl solution, transfer to PH to 4-6, system did not have bubble and emerged this moment.System is poured in the 200ml frozen water, separated out a large amount of solids, suction filtration, drying obtains tawny solid 3-nitro-4-methoxyl biphenyl (III) 5.253g, and yield is 95%.
5g3-nitro-4-the methoxyl biphenyl (III) of gained is joined in the reaction flask; Add 20ml methyl alcohol; With 5% Raney's nickel is catalyzer; React down 3h at 70 ℃ with 1.5MPa; After TLC detects and shows that reaction is accomplished; Rotary evaporation in vacuo is removed methyl alcohol, promptly gets desired product compound 3-amino-4-methoxyl biphenyl (IV) 4.0g, and yield is 93%.
With 3g 3-amino-4-methoxyl biphenyl and HCl-H
2Mixing and stirring under O (30+30ml, hydrochloric acid are that massfraction is 37.5% the concentrated hydrochloric acid) room temperature, ice-water bath is cooled to 0 ℃ then.With 1.35g NaNO
2The aqueous solution slowly be added drop-wise in the system, detect no raw material behind the 0.5h and remain.With the tin protochloride of 16.95g, be dissolved in the 25ml concentrated hydrochloric acid, be cooled to-20 ℃, slowly be added drop-wise in the diazonium salt solution and go; This moment, solution temperature rose, and thickness constantly drips tin chloride solution gradually; Be yellow muddy, constantly stir lh after, be the canescence muddiness.With solid filtering, vacuum-drying obtains 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride.
Mix under 3-(4-methoxyl biphenyl base-3-yl) the diazanyl hydrochloride solid that obtains and the 20ml toluene ice bath, add the 3.55g pyridine, the system flavescence joins the mixing solutions of 5.12g isopropyl chlorocarbonate and 5ml toluene in the system.0 ℃ is reacted 1h down, and TLC detects, and reaction finishes.System washing twice then, the water extracted in toluene, extraction liquid mixes with original toluene mutually, and vacuum rotary steam obtains hazel solid Bifenazate (I) 3.15g, and yield is 70%.
Claims (2)
1. the synthesis method of a Bifenazate is characterized in that synthetic route is following:
Concrete steps are following:
(1) 3-nitro-4-methoxyl biphenyl (III) is synthetic
Parazon is dissolved in methyl tertiary butyl ether, and mixing and stirring splashes into nitric acid in the gained mixing solutions, drips off continued and stirs 1-3h, and whole process temperature is controlled at 20-40 ℃; TLC detects, and reaction finishes; System is poured in the frozen water, separated out a large amount of solids, suction filtration, drying obtains xanchromatic solid chemical compound 3-nitro-4-xenol (II); Wherein, the mol ratio of parazon and nitric acid is 1: (1-2);
3-nitro-4-xenol, methylcarbonate, Tetrabutyl amonium bromide and salt of wormwood are joined in the reaction flask, be warming up to 80-100 ℃, reacted 40-50 hour; TLC detects, and reaction finishes; System is cooled to room temperature, in system, drips HCl solution, adjustings PH is 4-6, and system does not have bubble and emerges at this moment; System is poured in the frozen water, separated out a large amount of solids, suction filtration, drying obtains tawny solid chemical compound 3-nitro-4-methoxyl biphenyl (III); Wherein the mol ratio of 3-nitro-4-xenol and methylcarbonate is 1: (2-10), the mol ratio of 3-nitro-4-xenol and Tetrabutyl amonium bromide is 1: (1-3), the mol ratio of 3-nitro-4-xenol and salt of wormwood is 1: (2-5);
(2) 3-amino-4-methoxyl biphenyl (IV) is synthetic
3-nitro-4-methoxyl biphenyl that step (1) is obtained joins in the reaction flask; With methyl alcohol is solvent; Raney's nickel is a catalyzer; At pressure is 1.5MPa; Temperature is to react 1-3h under the 50-100 ℃ of condition; After TLC detected and shows that reaction is accomplished, rotary evaporation in vacuo was removed methyl alcohol, promptly gets 3-amino-4-methoxyl biphenyl; Wherein, the mol ratio of 3-nitro-4-methoxyl biphenyl and Raney's nickel is 1: (0.01-0.05);
(3) N '-(the 4-methoxyl biphenyl-3-) hydrazine carboxylic acid's isopropyl ester (I) is synthetic
3-amino-4-methoxyl biphenyl and HCl-H that step (2) is obtained
2O solution, mixing and stirring under the room temperature, ice-water bath is cooled to 0 ℃ then; With NaNO
2The aqueous solution slowly be added drop-wise in the system, behind the reaction 0.5-2h, obtain diazonium salt solution, remain through detecting no raw material; Tin protochloride is dissolved in the concentrated hydrochloric acid, is cooled to-20 ℃, slowly be added drop-wise in the diazonium salt solution and go, this moment, solution temperature rose, and thickness constantly drips tin chloride solution gradually, was yellow muddy, behind the stirring 0.5-2h, was the canescence muddiness; With solid filtering, vacuum-drying obtains 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride; Wherein, the mol ratio of 3-amino-4-methoxyl biphenyl and Sodium Nitrite is 1: (1-2), the mol ratio of 3-amino-4-methoxyl biphenyl and tin protochloride is 1: (2-8);
Mix under 3-(4-methoxyl biphenyl base-3-yl) the diazanyl hydrochloride solid that obtains and the toluene ice bath, add pyridine, the mixing solutions of isopropyl chlorocarbonate and toluene is joined in the system; 0 ℃ is reacted 1h down, and TLC detects, and reaction finishes; System washing twice then, the water extracted in toluene, extraction liquid mixes with original toluene mutually, and vacuum rotary steam obtains hazel target product I, i.e. Bifenazate; Wherein, the mol ratio of 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride and pyridine is 1: (1-3), the mol ratio of 3-(4-methoxyl biphenyl base-3-yl) diazanyl hydrochloride and isopropyl chlorocarbonate is 1: (1-3).
2. method according to claim 1 is characterized in that HCl-H described in the step (3)
2HCl and H in the O solution
2The volume ratio of O is 1:1, and HCl adopts the concentrated hydrochloric acid of massfraction 37.5%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400042A (en) * | 2017-08-11 | 2017-11-28 | 盐城师范学院 | A kind of process for cleanly preparing of the methoxyl biphenyl of 3 nitro 2 |
| CN107513027A (en) * | 2017-08-30 | 2017-12-26 | 上海开荣化工科技有限公司 | The production technology of Bifenazate |
| CN109265350A (en) * | 2018-10-16 | 2019-01-25 | 山东省农药科学研究院 | The synthetic method of acaricide Bifenazate intermediate 3- nitro -4- methoxyl biphenyl |
| CN109988084A (en) * | 2019-04-23 | 2019-07-09 | 绍兴上虞新银邦生化有限公司 | A kind of Bifenazate synthetic method |
| CN113912511A (en) * | 2021-11-29 | 2022-01-11 | 广东广康生化科技股份有限公司 | Synthesis method of bifenazate intermediate |
| CN114878736A (en) * | 2022-06-07 | 2022-08-09 | 江苏恒生检测有限公司 | Method for determining impurities in bifenazate |
| WO2023000616A1 (en) * | 2021-07-23 | 2023-01-26 | 帕潘纳(北京)科技有限公司 | Method for preparing bifenazate |
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