CN103193611A - Method for synthesizing m-trifluoromethyl acetophenone - Google Patents
Method for synthesizing m-trifluoromethyl acetophenone Download PDFInfo
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- CN103193611A CN103193611A CN2013100990115A CN201310099011A CN103193611A CN 103193611 A CN103193611 A CN 103193611A CN 2013100990115 A CN2013100990115 A CN 2013100990115A CN 201310099011 A CN201310099011 A CN 201310099011A CN 103193611 A CN103193611 A CN 103193611A
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Abstract
The invention discloses a method for synthesizing m-trifluoromethyl acetophenone which is an important intermediate for medicine, pesticide and pigment. According to the method, m-trifluoromethylaniline as the initial raw material is diazotized to prepare a diazonium salt which is coupled with acetaldoxime under the catalysis of a copper salt by controlling the pH value at 4-4.5 and the temperature at 0-5 DEG C, and the coupling compound is extracted by an organic solvent and then hydrolyzed by using hydrochloric acid to obtain the m-trifluoromethyl acetophenone. The total yield of the m-trifluoromethyl acetophenone produced according to the method is more than 70 percent; and the reaction conditions of the method are simple, the yield is high, the pollution is small, and the method is applied to industrial production.
Description
Technical field
The invention belongs to the field of chemical synthesis, specifically is a kind of synthetic method of (TrifluoroMethyl)acetophenone.
Background technology
(TrifluoroMethyl)acetophenone (3'-(Trifluoromethyl) acetophenone) is called for short TFAP, and weak yellow liquid is mainly used in fields such as medicine, agricultural chemicals and dyestuff.It is the key intermediate of synthesizing methoxy propylene ester compound oxime bacterium ester (Trifloxystrobin, trade(brand)name Flint), also is simultaneously the important source material of synthetic medicine, dyestuff.Its crucial derived product oxime bacterium ester is the sterilant of a kind of new and effective, safety, wide spectrum, Powdery Mildew, leaf spot there is special efficacy, also rust, oidium, damping-off, scab of apple etc. there is good active, to low toxicities such as Mammals and honeybee, bird, fish, worms, the environment metabolism is fast, therefore environmentally safe, no teratogenesis, carcinogenic, mutagenesis also have no adverse effects to heredity.The method of the synthetic (TrifluoroMethyl)acetophenone of report has both at home and abroad: hydrolysis again behind the grignard reaction of m-trifluoromethyl benzene first cyanogen and methyl iodide; M-trifluoromethylbenzoic acid is after chloride and the reaction of the cadion of methyl iodide; M-trifluoromethyl phenyl aldehyde and diazomethane reaction; The Grignard reagent of m-trifluoromethyl phenyl-bromide and acetic anhydride reaction.First three methods raw material sources difficulty, dangerous big is difficult for industrialization; The easily industrialization of last a kind of method, but used cost of material is very high, does not have competitive capacity.
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Summary of the invention
The object of the present invention is to provide a kind of method of synthetic (TrifluoroMethyl)acetophenone.This method adopts the technology of classical diazotization, coupling addition and hydrolysis to synthesize the target product (TrifluoroMethyl)acetophenone, and the temperature of reaction that this method relates to is moderate, and reaction is all carried out under normal pressure, and all reactions all safety are controlled.The content of (TrifluoroMethyl)acetophenone reaches more than 99.5% in the finished product that make, and dopant species is few, and product quality and performances are stable.
Reaction mechanism of the present invention is as follows:
The invention provides a kind of synthetic method of (TrifluoroMethyl)acetophenone, is starting raw material with the 3-Aminotrifluorotoluene, and concrete steps comprise:
(1), diazotization reaction
3-Aminotrifluorotoluene slowly adds and is equipped with in the four-hole bottle of sulphuric acid soln, be cooled to then 0 ℃ and begin to drip the 30%(mass concentration) NaNO
2The aqueous solution, the control temperature is not higher than 5 ℃, drips off back insulated and stirred 1 hour, is prepared into faint yellow diazonium salt clear liquor, heat preservation for standby use.
(2), coupled reaction
Add catalyzer mantoquita, acetic acid, the 50% ethylidenehydroxylamine aqueous solution and organic solvent in the four-hole bottle, stir and cooling.Begin to drip above-mentioned diazonium salt clear liquid after being cooled to below 5 ℃, and drip 30% liquid caustic soda simultaneously, pH is 4 ~ 4.5 in control, and temperature is at 0 ~ 5 ℃.Be warming up to 15 ℃ after adding, and stirred 1 ~ 2 hour, standing demix, upper organic phase is washed till neutrality with 5% ammoniacal liquor.
(3) hydrolysis reaction
Certain density hydrochloric acid is joined in the above-mentioned organic phase, and heated and stirred refluxed 3 ~ 5 hours, the cooling standing demix, upper organic phase is extremely neutral with the sodium bicarbonate aqueous solution alkali cleaning, anhydrous sodium sulfate drying, behind the precipitation again underpressure distillation get weak yellow liquid, be target product.
In the described step (1) in the used sulphuric acid soln mol ratio of sulfuric acid and 3-Aminotrifluorotoluene be 2.0 ~ 3.0:1.The general action of mineral acid has the dissolving arylamine, produces HNO in the diazotization reaction
2With keep the reaction medium strongly-acid.When mol ratio is lower than 2.0:1, sour quantity not sufficient, the easy and unreacted arylamine of the diazonium salt of generation takes place to generate a large amount of diazoamino compounds from coupled reaction.And when mol ratio during greater than 3.0:1, excessive acid causes waste.When mol ratio was 2.0 ~ 3.0:1, its reaction preference and yield were very nearly the same.
The mass concentration of used sulphuric acid soln is 20% ~ 25% in the described step (1).When all sulphuric acid soln concentration less than 20% the time because the concentration of acid is lower, it is less that arylamine and effect of sulfuric acid are converted into the speed of ammonium salt, the diazotization reaction time is longer.When all sulphuric acid soln concentration greater than 25% the time because the concentration of acid is higher, become free arylamine then unfavorable for ammonium salt hydrolysis, make the free arylamine concentration that participates in diazotization reaction obviously descend, cause diazotization reaction speed to reduce, the reaction times increases.
The mol ratio of used Sodium Nitrite and 3-Aminotrifluorotoluene is 1.05 ~ 1.1:1 in the described step (1).Work as NaNO
2Usefulness quantity not sufficient 1.0 equivalents the time, easily take place to produce diazoamino compound from coupled reaction.But the NaNO of too excessive
2Because energy oxidation and nitrosylation etc. cause a series of side reactions, cause next step coupled reaction yield to reduce.The rate of addition of sodium nitrite solution is also very important in addition, NaNO
2Feed rate, depend on that the speed of diazotization reaction speed, main purpose are to guarantee not lack Sodium Nitrite from start to finish in the entire reaction course.It is slow to feed intake, the yellow mercury oxide that the arylamine meeting that has little time to act on and diazonium salt effect produce the diazoamino thing; Too fast if feed intake, can cause the locality Sodium Nitrite excessive, heat release is too fast, be difficult to control, the nitrous acid throughput rate surpasses diazotization to its wear rate simultaneously, then makes this part nitrous acid decompose loss, so not only waste raw material, and produce poisonous, irritant gas NO
xTherefore, must control well to the Sodium Nitrite feed rate.
Temperature of reaction can not be higher than 5 ℃ in the described step (1), because general diazonium salt is very unstable when temperature is higher than 5 ℃, decomposes easily.
The catalyzer mantoquita is generally mantoquitas such as cuprous chloride, cupric chloride, copper sulfate and venus crystals in the described step (2), and the mol ratio of catalyzer mantoquita and 3-Aminotrifluorotoluene is 0.05 ~ 0.15:1.The coupled reaction of diazonium salt and aldoxime is generally made catalyzer with mantoquita.
The mol ratio of acetic acid and 3-Aminotrifluorotoluene is 0.2 ~ 0.6:1 in the described step (2).The effect of acetic acid is to generate sodium acetate and as the buffer reagent of reaction system in reaction process.
In the described step (2) in the 50% ethylidenehydroxylamine aqueous solution mol ratio of ethylidenehydroxylamine and 3-Aminotrifluorotoluene be 1.2 ~ 1.5:1.
Used organic solvent is high boiling point in the described step (2), density less than water and with the immiscible inert organic solvents of water, for example: toluene, Mixed XYLENE etc.The effect that adds this organic solvent is the (TrifluoroMethyl)acetophenone oxime intermediate that extraction in time generates, and prevents that it from continuing to take place other side reaction.
Described step (2) is controlled pH value of reaction system 4 ~ 4.5 by dripping 30% liquid caustic soda in dripping the diazonium salt reaction process.PH value of reaction system is below or above 4 ~ 4.5 scopes reaction yield is obviously descended in the coupled reaction process.
Described step (2) is bathed the control temperature of reaction system by cryosel and is no more than 5 ℃ in reaction process, and general temperature control is at 0 ~ 5 ℃.
The concentration of the used hydrochloric acid of hydrolysis is generally 15% ~ 20% in the described step (3).The too low then hydrolysis time of concentration of hydrochloric acid is longer, and the too high then reaction yield of concentration can descend.
The method of synthetic (TrifluoroMethyl)acetophenone provided by the present invention safety is controlled, and the finished product foreign matter content that makes is low, quality and stable performance.
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Embodiment
Embodiment 1
A kind of synthetic method of (TrifluoroMethyl)acetophenone is starting raw material with the 3-Aminotrifluorotoluene, and concrete steps comprise:
(1), diazotization reaction
46 g 3-Aminotrifluorotoluenes slowly add and are equipped with in the four-hole bottle of 280 g sulphuric acid solns (mass concentration 20%), are cooled to 0 ℃ and begin to drip 30%NaNO then
2The aqueous solution 72 g, 0 ~ 5 ℃ of control temperature drips off back insulated and stirred 1 hour, makes faint yellow diazonium salt clear liquor, heat preservation for standby use.
(2), coupled reaction
Add 4.2 g cuprous chlorides in the four-hole bottle, 10.2 g acetic acid, the 50% ethylidenehydroxylamine aqueous solution, 50.5 g and 100 mL toluene stir and cooling.Begin to drip above-mentioned diazonium salt clear liquid after being cooled to below 5 ℃, and drip 30% liquid caustic soda simultaneously, pH is 4 ~ 4.5 in control, and temperature is at 0 ~ 5 ℃.Be warming up to 15 ℃ and stirring after adding, the GC trace analysis, standing demix after reaction finishes, upper organic phase is washed till neutrality with 5% ammoniacal liquor.
(3) hydrolysis reaction
Be that 20% hydrochloric acid joins in the above-mentioned organic phase with 90 mL concentration, heated and stirred refluxes, the reaction of GC trace analysis, standing demix after hydrolysis reaction finishes, upper organic phase is extremely neutral with the sodium bicarbonate aqueous solution alkali cleaning, anhydrous sodium sulfate drying, behind the precipitation again underpressure distillation get weak yellow liquid 37.7 g, be (TrifluoroMethyl)acetophenone, GC analyzes, content 99.7%, yield 70%.
Embodiment 2
(1), diazotization reaction
46 g 3-Aminotrifluorotoluenes slowly add and are equipped with in the four-hole bottle of 280 g sulphuric acid solns (mass concentration 25%), are cooled to 0 ℃ and begin to drip 30%NaNO then
2The aqueous solution 71 g, 0 ~ 5 ℃ of control temperature drips off back insulated and stirred 1 hour, makes faint yellow diazonium salt clear liquor, heat preservation for standby use.
(2), coupled reaction
Add 8.6 g venus crystalss in the four-hole bottle, 5.2 g acetic acid, the 50% ethylidenehydroxylamine aqueous solution, 45.5 g and 100 mL toluene stir and cooling.Begin to drip above-mentioned diazonium salt clear liquid after being cooled to below 5 ℃, and drip 30% liquid caustic soda simultaneously, pH is 4 ~ 4.5 in control, and temperature is at 0 ~ 5 ℃.Be warming up to 15 ℃ and stirring after adding, the GC trace analysis, standing demix after reaction finishes, upper organic phase is washed till neutrality with 5% ammoniacal liquor.
(3) hydrolysis reaction
Be that 20% hydrochloric acid joins in the above-mentioned organic phase with 90 mL concentration, heated and stirred refluxes, the reaction of GC trace analysis, standing demix after hydrolysis reaction finishes, upper organic phase is extremely neutral with the sodium bicarbonate aqueous solution alkali cleaning, anhydrous sodium sulfate drying, behind the precipitation again underpressure distillation get weak yellow liquid 39.3 g, be (TrifluoroMethyl)acetophenone, GC analyzes, content 99.6%, yield 73%.
Embodiment 3
A kind of synthetic method of (TrifluoroMethyl)acetophenone is starting raw material with the 3-Aminotrifluorotoluene, and concrete steps comprise:
(1), diazotization reaction
46 g 3-Aminotrifluorotoluenes slowly add and are equipped with in the four-hole bottle of 280 g sulphuric acid solns (mass concentration 25%), are cooled to 0 ℃ and begin to drip 30%NaNO then
2The aqueous solution 72 g, 0 ~ 5 ℃ of control temperature drips off back insulated and stirred 1 hour, makes faint yellow diazonium salt clear liquor, heat preservation for standby use.
(2), coupled reaction
Add 3.9 g cupric chlorides in the four-hole bottle, 8.0 g acetic acid, the 50% ethylidenehydroxylamine aqueous solution, 48.5 g and 100 mL toluene stir and cooling.Begin to drip above-mentioned diazonium salt clear liquid after being cooled to below 5 ℃, and drip 30% liquid caustic soda simultaneously, pH is 4 ~ 4.5 in control, and temperature is at 0 ~ 5 ℃.Be warming up to 15 ℃ and stirring after adding, the GC trace analysis, standing demix after reaction finishes, upper organic phase is washed till neutrality with 5% ammoniacal liquor.
(3) hydrolysis reaction
Be that 20% hydrochloric acid joins in the above-mentioned organic phase with 90 mL concentration, heated and stirred refluxes, the reaction of GC trace analysis, standing demix after hydrolysis reaction finishes, upper organic phase is extremely neutral with the sodium bicarbonate aqueous solution alkali cleaning, anhydrous sodium sulfate drying, behind the precipitation again underpressure distillation get weak yellow liquid 40.2 g, be (TrifluoroMethyl)acetophenone, GC analyzes, content 99.6%, yield 75%.
Embodiment 4
A kind of synthetic method of (TrifluoroMethyl)acetophenone is starting raw material with the 3-Aminotrifluorotoluene, and concrete steps comprise:
(1), diazotization reaction
46 g 3-Aminotrifluorotoluenes slowly add and are equipped with in the four-hole bottle of 280 g sulphuric acid solns (mass concentration 25%), are cooled to 0 ℃ and begin to drip 30%NaNO then
2The aqueous solution 72 g, 0 ~ 5 ℃ of control temperature drips off back insulated and stirred 1 hour, makes faint yellow diazonium salt clear liquor, heat preservation for standby use.
(2), coupled reaction
Add 4.6 g copper sulfate in the four-hole bottle, 8.0 g acetic acid, the 50% ethylidenehydroxylamine aqueous solution, 50.0 g and 100 mL toluene stir and cooling.Begin to drip above-mentioned diazonium salt clear liquid after being cooled to below 5 ℃, and drip 30% liquid caustic soda simultaneously, pH is 4 ~ 4.5 in control, and temperature is at 0 ~ 5 ℃.Be warming up to 15 ℃ and stirring after adding, the GC trace analysis, standing demix after reaction finishes, upper organic phase is washed till neutrality with 5% ammoniacal liquor.
(3) hydrolysis reaction
Be that 20% hydrochloric acid joins in the above-mentioned organic phase with 90 mL concentration, heated and stirred refluxes, the reaction of GC trace analysis, standing demix after hydrolysis reaction finishes, upper organic phase is extremely neutral with the sodium bicarbonate aqueous solution alkali cleaning, anhydrous sodium sulfate drying, behind the precipitation again underpressure distillation get weak yellow liquid 42.0 g, be (TrifluoroMethyl)acetophenone, GC analyzes, content 99.9%, yield 78%.
Embodiment 5
A kind of synthetic method of (TrifluoroMethyl)acetophenone is starting raw material with the 3-Aminotrifluorotoluene, and concrete steps comprise:
(1), diazotization reaction
200 L water are put into the diazotization still, and it is freezing to open stirring and chuck, slowly puts into the 60 Kg vitriol oils then.When treating that the still temperature is lower than 30 ℃ toward wherein slowly adding 3-Aminotrifluorotoluene 31 Kg.Add the back and continue to stir, treat that temperature of charge is lower than under 5 ℃ the condition to drip 30% sodium nitrite solution, 44.5 Kg, drip off back insulated and stirred 1 hour, stand-by.
(2), coupled reaction
3.1 Kg copper sulfate, 5.4 Kg acetic acid, the 50% ethylidenehydroxylamine aqueous solution, 33.7 Kg and 100 L Mixed XYLENEs are put into the coupling still, it is freezing to open stirring and chuck, treat that temperature of charge drips above-mentioned diazonium liquid between 0 ~ 5 ℃, and drip 30% liquid caustic soda simultaneously that pH is between 4 ~ 4.5 in control.Added insulated and stirred 10 minutes.It is freezing to close chuck, opens the chuck heating, makes temperature rise between 15 ℃ ~ 20 ℃ insulated and stirred 1 hour.GC trace analysis, the reaction back standing demix that finishes, lower floor's water divide to extraction kettle and with 50 L Mixed XYLENEs extractions, with the organic phase merging and divide to the alkali cleaning still.30 L put into the alkali cleaning still with 5% ammoniacal liquor, stir standing demix after 1 hour, and upper organic phase is divided to hydrolysis kettle.
(3) hydrolysis reaction
Be that 20% hydrochloric acid is put into hydrolysis kettle with 60 L concentration, open stir, jacket steam, temperature control between 90 ℃ ~ 95 ℃, the GC trace analysis reacts.Hydrolysis reaction finishes, and cool off the back, standing demix, and upper organic phase is divided to the alkali cleaning still.Open and stir, sodium hydrogen carbonate solution 30 L with 10% add the alkali cleaning still, add to stir standing demix after 30 minutes, upper organic phase precipitation, underpressure distillation are got weak yellow liquid 27.6 Kg, be (TrifluoroMethyl)acetophenone, GC analyzes, content 99.8%, yield 76%.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all is included within protection scope of the present invention.
Claims (8)
1. the synthetic method of a (TrifluoroMethyl)acetophenone is characterized in that: be starting raw material with the 3-Aminotrifluorotoluene, concrete steps comprise:
(1) diazotization reaction
3-Aminotrifluorotoluene slowly adds and is equipped with in the four-hole bottle of sulphuric acid soln, is cooled to 0 ℃ and begin to drip the NaNO of 30% mass concentration then
2The aqueous solution, the control temperature is not higher than 5 ℃, drips the back insulated and stirred 1 hour, is prepared into faint yellow diazonium salt clear liquor, heat preservation for standby use;
(2) coupled reaction
Add the catalyzer mantoquita in the four-hole bottle, acetic acid, the 50% ethylidenehydroxylamine aqueous solution and organic solvent stirs and cooling, begin to drip above-mentioned diazonium salt clear liquid after being cooled to below 5 ℃, and drip 30% liquid caustic soda simultaneously, and pH is 4 ~ 4.5 in control, and temperature is at 0 ~ 5 ℃, be warming up to 15 ℃ after adding, and stirred 1 ~ 2 hour, standing demix, upper organic phase is washed till neutrality with 5% ammoniacal liquor;
(3) hydrolysis reaction
Certain density hydrochloric acid is joined in the above-mentioned organic phase, and heated and stirred refluxed 3 ~ 5 hours, the cooling standing demix, upper organic phase is extremely neutral with the sodium bicarbonate aqueous solution alkali cleaning, anhydrous sodium sulfate drying, behind the precipitation again underpressure distillation get weak yellow liquid, be target product.
2. the synthetic method of a kind of (TrifluoroMethyl)acetophenone according to claim 1, it is characterized in that: the mass concentration of sulphuric acid soln is 20% ~ 25% in the described step (1), and the mol ratio of sulfuric acid, Sodium Nitrite and 3-Aminotrifluorotoluene is 2.0 ~ 3.0:1.05 ~ 1.1:1.
3. the synthetic method of a kind of (TrifluoroMethyl)acetophenone according to claim 1, it is characterized in that: the catalyzer mantoquita is any in the following compounds in the described step (2): cuprous chloride, cupric chloride, copper sulfate, venus crystals etc., and the mol ratio of catalyzer mantoquita and 3-Aminotrifluorotoluene is 0.05 ~ 0.15:1.
4. the synthetic method of a kind of (TrifluoroMethyl)acetophenone according to claim 1 is characterized in that: the mol ratio of acetic acid and 3-Aminotrifluorotoluene is 0.2 ~ 0.6:1 in the described step (2).
5. the synthetic method of a kind of (TrifluoroMethyl)acetophenone according to claim 1 is characterized in that: in the described step (2) in the 50% ethylidenehydroxylamine aqueous solution mol ratio of ethylidenehydroxylamine and 3-Aminotrifluorotoluene be 1.2 ~ 1.5:1.
6. the synthetic method of a kind of (TrifluoroMethyl)acetophenone according to claim 1, it is characterized in that: used organic solvent is high boiling point in the described step (2), density less than water and with the immiscible inert organic solvents of water, for example: toluene, Mixed XYLENE etc.
7. the synthetic method of a kind of (TrifluoroMethyl)acetophenone according to claim 1, it is characterized in that: in the described step (2) in dripping the diazonium salt reaction process, control pH value of reaction system 4 ~ 4.5 by dripping 30% liquid caustic soda, and bathe the control temperature of reaction system by cryosel and be no more than 5 ℃, temperature is controlled at 0 ~ 5 ℃.
8. the synthetic method of a kind of (TrifluoroMethyl)acetophenone according to claim 1 is characterized in that: the mass concentration of the used hydrochloric acid of hydrolysis is 15% ~ 20% in the described step (3).
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Cited By (5)
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| CN112778109A (en) * | 2021-01-15 | 2021-05-11 | 杭州臻挚生物科技有限公司 | Preparation method of 1- [ 3-chloro-5- (trifluoromethyl) phenyl ] -2,2, 2-trifluoroacetone and derivatives thereof |
| CN113461503A (en) * | 2021-08-18 | 2021-10-01 | 杭州臻挚生物科技有限公司 | Preparation method of trifluoro acetophenone derivatives |
| CN114507155A (en) * | 2022-02-16 | 2022-05-17 | 浙江欣禾生物股份有限公司 | Preparation method of m-trifluoromethyl acetophenone oxime |
| CN116693375A (en) * | 2023-08-08 | 2023-09-05 | 山东国邦药业有限公司 | Synthesis method of 2, 4-dichloro-5-fluoro acetophenone |
| WO2023223105A1 (en) * | 2022-05-18 | 2023-11-23 | Deepak Nitrite Limited | A process of preparation of 3'-(trifluoromethyl)acetophenone (tfmap) |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112778109A (en) * | 2021-01-15 | 2021-05-11 | 杭州臻挚生物科技有限公司 | Preparation method of 1- [ 3-chloro-5- (trifluoromethyl) phenyl ] -2,2, 2-trifluoroacetone and derivatives thereof |
| CN113461503A (en) * | 2021-08-18 | 2021-10-01 | 杭州臻挚生物科技有限公司 | Preparation method of trifluoro acetophenone derivatives |
| CN114507155A (en) * | 2022-02-16 | 2022-05-17 | 浙江欣禾生物股份有限公司 | Preparation method of m-trifluoromethyl acetophenone oxime |
| WO2023223105A1 (en) * | 2022-05-18 | 2023-11-23 | Deepak Nitrite Limited | A process of preparation of 3'-(trifluoromethyl)acetophenone (tfmap) |
| CN116693375A (en) * | 2023-08-08 | 2023-09-05 | 山东国邦药业有限公司 | Synthesis method of 2, 4-dichloro-5-fluoro acetophenone |
| CN116693375B (en) * | 2023-08-08 | 2023-11-24 | 山东国邦药业有限公司 | Synthesis method of 2, 4-dichloro-5-fluoro acetophenone |
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| CN103193611B (en) | 2015-09-09 |
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