CN103204775A - Oxidation method of acetophenone - Google Patents
Oxidation method of acetophenone Download PDFInfo
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Abstract
The invention discloses an oxidation method of acetophenone. According to the method, under oxidation reaction conditions, acetophenone, an oxidant, a solvent and a catalyst are mixed and subjected to a contact reaction. The method is characterized in that the catalyst is a soluble zinc salt modified heteroatom molecular sieve.
Description
Technical field
The invention relates to a kind of method for oxidation of methyl phenyl ketone, further saying so prepares the method for phenylacetate about a kind of catalyzed oxidation methyl phenyl ketone.
Background technology
Phenylacetate is colourless liquid, 195.7 ℃ of boiling points, relative density 1.0780, refractive index 1.5033,76 ℃ of flash-points.Can be miscible with ethanol, ether, chloroform and acetic acid, be slightly soluble in water.Strong refractivity is arranged, the phenol smell is arranged.Main intermediate as solvent and organic synthesis, phenylacetate also can obtain hydroxyacetophenonum through translocation reaction, is used for the treatment of diseases such as acute or chronic icteric hepatitis, cholecystitis.
At present, industrial production phenylacetate is mainly reacted by sodium phenylate and acetic anhydride and gets.A kind of working method is that phenol is joined in the sodium hydroxide solution, and stirring and dissolving is mixed with the phenol sodium solution, adds acetic anhydride, in 30～40 ℃ of reactions.The reaction product of gained is water, diluted sodium hydroxide solution, water washing successively, after the calcium chloride drying, the distillation and finished product.Another kind of working method is phenol and acetic anhydride to be heated to together boil, and refluxes, and washes successively after the cooling, alkali cleaning, washing, and behind anhydrous sodium sulfate drying, it is phenylacetate that 190～195 ℃ of cuts are collected in distillation.As seen, no matter all there is complicated operation in which kind of working method, the product treatment step is many or reaction conditions is harsh relatively, problem of environment pollution caused such as soda acid are used in reaction.
Therefore, exploring a kind of is good, the method for environmental friendliness and simple new catalyzed oxidation methyl phenyl ketone particularly of initial feed and transformation efficiency height, phenylacetate selectivity with the methyl phenyl ketone, is of great practical significance.In today that environmental problem comes into one's own day by day, more seem very necessary.
Titanium-silicon molecular sieve TS-1 is the desirable oxide catalyst when being oxygenant with the hydrogen peroxide, and reaction conditions is extremely gentle, even can react at normal temperatures and pressures.It is report [the Baeyer-Villiger rearrangement catalysed bytitanium silicate molecular sieve (TS-1)/H that catalyzer carries out methyl phenyl ketone oxidation research aspect that document also has with the HTS
2O
2System, Catalysis Letters, Volume 40, Numbers1-2,47～50], but the leeway that acetophenone conversion and phenylacetate selectivity still improve a lot.
Summary of the invention
Therefore, the present invention seeks to the deficiency at existing technology, provide a kind of environmentally friendly and technology is simple, is oxidizer catalytic Oxybenzene ethyl ketone and with the method for higher selectively producing acetic acid phenyl ester with the hydrogen peroxide.
Oxybenzene ethyl ketone provided by the invention prepares the method for phenylacetate, it is characterized in that the hetero-atom molecular-sieve with the soluble zinc salt modification is catalyzer, being 20～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with methyl phenyl ketone, oxygenant, solvent and catalyst mix contact reacts, wherein the mol ratio of methyl phenyl ketone and oxygenant is 1: 2～20, the mass ratio of solvent and catalyzer is 1～200: 1, in the hetero-atom molecular-sieve of described soluble zinc salt modification, hetero-atom molecular-sieve (in heteroatoms) is 0.05～10: 1 with the mol ratio of soluble zinc salt (in zinc).
Method provided by the invention, with respect to traditional method, problems such as traditional processing technology complexity, equipment corrosion and noxious emission have been overcome, adopt the hetero-atom molecular-sieve of soluble zinc salt modification as the oxidation activity component, in raw material, need not to add any inhibitor or initiator, be green synthesis process.Has the simple and high advantage of phenylacetate yield of production process.
Embodiment
In the method for catalyzed oxidation methyl phenyl ketone provided by the invention, described catalyzer is the hetero-atom molecular-sieve of soluble zinc salt modification.Hetero-atom molecular-sieve is one or more the molecular sieve that contains in the framework of molecular sieve structure in the heteroatomss such as being selected from titanium, vanadium, iron, cobalt, tin, cerium, as HTS, V-Si molecular sieve, iron si molecular sieves, cobalt si molecular sieves, tin si molecular sieves, cerium si molecular sieves etc., preferred HTS wherein.Described HTS is one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48, and preferred hetero-atom molecular-sieve is titanium-silicon molecular sieve TS-1.Most preferred hetero-atom molecular-sieve is the HTS of the MFI structure of hollow structure crystal grain, and the radical length of the cavity part of its hollow structure is 5～300 nanometers, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm.
Method provided by the invention, described catalyzer is in the hetero-atom molecular-sieve of soluble zinc salt modification, and soluble zinc salt is selected from one or more in zinc phosphate, zinc nitrate, zinc chloride, zinc sulfate, Zinc Gluconate, zinc acetate, zinc bromide, zinc fluoride or the zinc hydrogen phosphate.
In the hetero-atom molecular-sieve of described soluble zinc salt modification, hetero-atom molecular-sieve (in heteroatoms) is 0.05～10: 1 with the mol ratio of soluble zinc salt (in zinc), preferred 0.1～5: 1.The hetero-atom molecular-sieve of soluble zinc salt modification, be by soluble Zn salt brine solution and hetero-atom molecular-sieve mix that the back is dry, roasting and getting, wherein dry, roasting condition is well known to those skilled in the art, at this and have no special requirements, drying generally is in air atmosphere, handles 1～8h in ℃ scope of room temperature～200; Usually, the temperature of described roasting can be 200～800 ℃, and the time can be 1～12 hour.Described roasting can be carried out under air or oxygen atmosphere.
In the method provided by the invention, described oxygenant is hydrogen peroxide, can be pure product, but considers the preferably aqueous solution of hydrogen peroxide from angle economic and safety, and the quality percentage composition of hydrogen peroxide is selected from 5%～90%, preferred 10%～70%.
In the method provided by the invention, the raw material optimum ratio is as follows: the mol ratio of methyl phenyl ketone and oxygenant is preferably 1: 5～and 15, the mass ratio of solvent and catalyzer is preferably 5～150: 1.Amount between benzene feedstock ethyl ketone and the catalyzer does not have clear and definite restriction, can realize that the present invention gets final product, and the mass ratio of general methyl phenyl ketone and catalyzer is 0.5～100: 1.
In method provided by the invention, temperature of reaction is preferably 40～120 ℃, and reaction pressure is preferably 0.1～2.5MPa.
In method provided by the invention, described solvent is selected from nitrile or their mixing such as alcohols such as water or methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or ketone such as acetone, butanone or acetonitrile, propionitrile, benzyl cyanide, be preferably acetonitrile, propionitrile, benzyl cyanide, acetone, water or their mixing, more preferably benzyl cyanide, acetone, acetonitrile.
In preparation method provided by the invention, reinforced order does not have special requirement yet, can add methyl phenyl ketone earlier, can add oxygenant and/or solvent earlier yet.
Be further described below by the present invention of embodiment, but therefore do not limit content of the present invention.
In embodiment and the Comparative Examples, agents useful for same is commercially available chemically pure reagent, and wherein hydrogen peroxide is the aqueous solution of mass concentration 30%.Used HTS is the HTS Industrial products of the described embodiment 6 of Chinese patent CN1301599A, this HTS is the MFI structure, have hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This HTS sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 milligrams/gram.
Its preparation process of HTS of catalyzer soluble zinc salt modification among the embodiment is as follows: at normal temperatures and pressures, as required a certain amount of soluble Zn salt brine solution and HTS are mixed, then under air atmosphere, change 120 ℃ of dry 5h in the baking oven over to, at last at 550 ℃ of roasting 5h of retort furnace.The mol ratio of HTS in the catalyst preparation process (in titanium) and soluble zinc salt (in zinc) sees the explanation among each embodiment for details.
In Comparative Examples and embodiment:
Comparative Examples 1
This Comparative Examples illustrates under the situation that does not have catalyzer to exist, the reaction process of methyl phenyl ketone and hydrogen peroxide and result.
Be 1: 5 with methyl phenyl ketone, hydrogen peroxide and solvent according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, wherein the solvent methanol quality is 20g, is that 60 ℃ of pressure are to react under the 1.5MPa in temperature.Behind the reaction 2h, the transformation efficiency of methyl phenyl ketone, phenylacetate selectivity are 0%.
Comparative Examples 2
This Comparative Examples illustrates under the situation of catalyst Ti-si molecular sieves Individual existence, the reaction process of methyl phenyl ketone and hydrogen peroxide and result.
Be 1: 7 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyst Ti-si molecular sieves according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent methanol and catalyzer is 20: 1, the mass ratio of methyl phenyl ketone and catalyzer is 10: 1, is that 80 ℃ of pressure are to react under the 1.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 35%; The phenylacetate selectivity is 48%.
Comparative Examples 3
This Comparative Examples illustrates under the situation of catalyzer soluble zinc salt (zinc phosphate) Individual existence, the reaction process of methyl phenyl ketone and hydrogen peroxide and result.
Be 1: 5 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (zinc phosphate) according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent acetone and catalyzer is 40: 1, the mass ratio of methyl phenyl ketone and catalyzer is 10: 1, is that 60 ℃ of pressure are to react under the 2.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 6%; The phenylacetate selectivity is 21%.
Embodiment 1
Be 1: 10 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc nitrate and HTS 0.2: 1) according to methyl phenyl ketone and hydrogen peroxide mol ratio, solvent acetonitrile is 20: 1 with the catalyst quality ratio, methyl phenyl ketone is 10: 1 with the catalyst quality ratio, is that 50 ℃ of pressure are to react under the 1.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 83%; The phenylacetate selectivity is 66%.
Embodiment 2
Be 1: 6 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc phosphate and HTS 1: 1) according to methyl phenyl ketone and hydrogen peroxide mol ratio, solvent acetone is 50: 1 with the catalyst quality ratio, methyl phenyl ketone is 20: 1 with the catalyst quality ratio, is that 60 ℃ of pressure are to react under the 2.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 59%; The phenylacetate selectivity is 68%.
Embodiment 3
Be 2: 11 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc sulfate and HTS 0.1: 1) according to methyl phenyl ketone and hydrogen peroxide mol ratio, solvent acetic acid is 60: 1 with the catalyst quality ratio, methyl phenyl ketone is 1: 1 with the catalyst quality ratio, is that 100 ℃ of pressure are to react under the 0.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 56%; The phenylacetate selectivity is 70%.
Embodiment 4
Be 1: 8 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc hydrogen phosphate and HTS 2: 1) according to methyl phenyl ketone and hydrogen peroxide mol ratio, solvent methanol is 35: 1 with the catalyst quality ratio, methyl phenyl ketone is 50: 1 with the catalyst quality ratio, is that 40 ℃ of pressure are to react under the 0.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 54%; The phenylacetate selectivity is 67%.
Embodiment 5
Be 1: 12 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc chloride and HTS 5: 1) according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 5: 1, the mass ratio of methyl phenyl ketone and catalyzer is 70: 1, is that 80 ℃ of pressure are to react under the 0.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 63%; The phenylacetate selectivity is 66%.
Embodiment 6
Be 3: 17 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc acetate and HTS 0.2: 1) according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent benzol acetonitrile and catalyzer is 120: 1, the mass ratio of methyl phenyl ketone and catalyzer is 100: 1, is that 90 ℃ of pressure are to react under the 1.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 72%; The phenylacetate selectivity is 61%.
Embodiment 7
Be 1: 5 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc bromide and HTS 0.3: 1) according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, solvent (equal-volume is than acetonitrile and acetone) is 200: 1 with the mass ratio of catalyzer, the mass ratio of methyl phenyl ketone and catalyzer is 0.5: 1, is that 60 ℃ of pressure are to react under the 0.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 70%; The phenylacetate selectivity is 68%.
Embodiment 8
Be 1: 10 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of Zinc Gluconate and HTS 0.5: 1) according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent propionitrile and catalyzer is 10: 1, the mass ratio of methyl phenyl ketone and catalyzer is 30: 1, is that 70 ℃ of pressure are to react under the 1.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 91%; The phenylacetate selectivity is 64%.
Embodiment 9
Be 1: 15 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc fluoride and HTS 0.8: 1) according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 80: 1, the mass ratio of methyl phenyl ketone and catalyzer is 90: 1, is that 120 ℃ of pressure are to react under the 0.1MPa in temperature.Behind the reaction 2h, acetophenone conversion is 95%; The phenylacetate selectivity is 61%.
Embodiment 10
Be 1: 9 with methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (mol ratio of zinc sulfate and HTS 0.3: 1) according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent tertiary butanol and catalyzer is 100: 1, the mass ratio of methyl phenyl ketone and catalyzer is 60: 1, is that 110 ℃ of pressure are to react under the 0.2MPa in temperature.Behind the reaction 2h, acetophenone conversion is 86%; The phenylacetate selectivity is 66%.
Embodiment 11
Method Oxybenzene ethyl ketone according to embodiment 1 prepares phenylacetate.Different is that methyl phenyl ketone and hydrogen peroxide mol ratio become 1: 4.Behind the reaction 2h, acetophenone conversion is 15%; The phenylacetate selectivity is 47%.
Embodiment 12
Method Oxybenzene ethyl ketone according to embodiment 5 prepares phenylacetate.The mol ratio of HTS that different is in the catalyzer and zinc chloride becomes 12: 1.Behind the reaction 2h, acetophenone conversion is 46%; The phenylacetate selectivity is 52%.
Embodiment 13
Method Oxybenzene ethyl ketone according to embodiment 6 prepares phenylacetate.Different is that zinc acetate is replaced by equimolar zinc chloride.Behind the reaction 2h, acetophenone conversion is 85%; The phenylacetate selectivity is 67%.
Embodiment 14
Method Oxybenzene ethyl ketone according to embodiment 10 prepares phenylacetate.Different is that solvent tertiary butanol is replaced by benzyl cyanide.Behind the reaction 2h, acetophenone conversion is 89%; The phenylacetate selectivity is 71%.
Embodiment 15
With methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (Zinc Gluconate and according to the mol ratio of the V-Si molecular sieve of the method preparation of describing among the Chinese patent CN1840477A embodiment 12: 1, wherein Si/ heteroatoms mol ratio is 80: 1 in the V-Si molecular sieve) be 2: 11 according to methyl phenyl ketone and hydrogen peroxide mol ratio, solvent acetic acid is 50: 1 with the catalyst quality ratio, methyl phenyl ketone is 0.5: 1 with the catalyst quality ratio, is that 100 ℃ of pressure are to react under the 0.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 65%; The phenylacetate selectivity is 76%.
Embodiment 16
With methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (primary zinc phosphate and according to J.Mol.Catal.A:Chem., 1996, the mol ratio of the tin si molecular sieves of the method preparation of describing in 105:149～158 5: 1, wherein Si/ heteroatoms mol ratio is 60: 1 in the tin si molecular sieves) be 1: 6 according to methyl phenyl ketone and hydrogen peroxide mol ratio, solvent methanol is 25: 1 with the catalyst quality ratio, methyl phenyl ketone is 10: 1 with the catalyst quality ratio, is that 60 ℃ of pressure are to react under the 0.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 45%; The phenylacetate selectivity is 69%.
Embodiment 17
With methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (zinc bromide and according to J.Chem.Soc.Chem.Commun., 1997, the mol ratio of the HTS Ti-Beta of the method preparation described in 677～678 0.2: 1, wherein Si/ heteroatoms mol ratio is 30: 1 in the HTS) be 1: 12 according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent acetonitrile and catalyzer is 5: 1, the mass ratio of methyl phenyl ketone and catalyzer is 20: 1, is that 80 ℃ of pressure are to react under the 0.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 46%; The phenylacetate selectivity is 71%.
Embodiment 18
With methyl phenyl ketone, hydrogen peroxide, solvent and catalyzer (zinc acetate and according to Chem.Commun., 1994, the mol ratio of the HTS Ti-MCM-41 of the method preparation described in 147～148 0.3: 1, wherein Si/ heteroatoms mol ratio is 40: 1 in the HTS) be 3: 17 according to the mol ratio of methyl phenyl ketone and hydrogen peroxide, the mass ratio of solvent benzol acetonitrile and catalyzer is 30: 1, the mass ratio of methyl phenyl ketone and catalyzer is 50: 1, is that 90 ℃ of pressure are to react under the 1.5MPa in temperature.Behind the reaction 2h, acetophenone conversion is 62%; The phenylacetate selectivity is 66%.
From embodiment 1～18 and Comparative Examples 1～3 as can be seen: method provided by the invention, adopting the HTS of soluble zinc salt modification is catalyzer, its acetophenone conversion and phenylacetate selectivity are apparently higher than comparative sample such as unmodified HTS.
Claims (11)
1. the method for oxidation of a methyl phenyl ketone is under oxidation reaction condition, with methyl phenyl ketone, oxygenant, solvent and catalyst mix contact reacts, it is characterized in that described catalyzer is the hetero-atom molecular-sieve with the soluble zinc salt modification.
2. according to the method for claim 1, it is characterized in that this method is that 20～180 ℃ and pressure are to carry out under the condition of 0.1～3MPa in temperature, wherein, the mol ratio of methyl phenyl ketone and oxygenant is 1: 2～20, the mass ratio of solvent and catalyzer is 1～200: 1, and in the hetero-atom molecular-sieve of described soluble zinc salt modification, the mol ratio of hetero-atom molecular-sieve and soluble zinc salt is 0.05～10: 1, hetero-atom molecular-sieve is in heteroatoms, and soluble zinc salt is in zinc.
3. according to the method for claim 1 or 2, wherein, described hetero-atom molecular-sieve is selected from HTS, V-Si molecular sieve, iron si molecular sieves, tin si molecular sieves or cerium si molecular sieves.
4. according to the method for claim 3, wherein, described HTS is selected from one or more among TS-1, TS-2, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, the Ti-ZSM-48.
5. according to the process of claim 1 wherein, described hetero-atom molecular-sieve is the HTS of the MFI structure of hollow structure crystal grain, and the radical length of the cavity part of its hollow structure is 5～300 nanometers, and described HTS is at 25 ℃, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under 1 hour the condition is at least 70 milligrams/gram, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this HTS and the desorption isotherm.
6. according to the process of claim 1 wherein, described soluble zinc salt is selected from one or more in zinc phosphate, zinc nitrate, zinc chloride, zinc sulfate, Zinc Gluconate, zinc acetate, zinc bromide, zinc fluoride and the zinc hydrogen phosphate.
7. according to the process of claim 1 wherein, the mol ratio of methyl phenyl ketone and oxygenant is 1: 5～15, and the mass ratio of solvent and catalyzer is 5～150: 1, and the mass ratio of methyl phenyl ketone and catalyzer is 0.5～100: 1.
8. according to the method for claim 1, it is characterized in that the hetero-atom molecular-sieve with the soluble zinc salt modification is catalyzer, being 40～120 ℃ in temperature is under the condition of 0.1～2.5MPa with pressure, and methyl phenyl ketone, oxygenant, solvent and catalyst mix are contacted.
9. according to the process of claim 1 wherein, described catalyzer is the HTS of soluble zinc salt modification, and the mol ratio of HTS and soluble zinc salt is 0.1～5: 1, and HTS is in titanium, and soluble zinc salt is in zinc.
10. according to the process of claim 1 wherein, the hetero-atom molecular-sieve of soluble zinc salt modification, be by soluble Zn salt brine solution and hetero-atom molecular-sieve mix that the back is dry, roasting and getting.
11. according to claim 1,2,7, one of 8 method, wherein, described oxygenant is hydrogen peroxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110015956A (en) * | 2019-05-08 | 2019-07-16 | 葫芦岛市载大瀛嘉化工有限公司 | A kind of 4-(2,2- dichloro cyclopropyl) phenoxyacetic acid ester preparation method |
| CN111482197A (en) * | 2019-01-28 | 2020-08-04 | 中国石油化工股份有限公司 | Iron-vanadium molecular sieve, preparation method and application thereof, and method for preparing benzenediol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111482197A (en) * | 2019-01-28 | 2020-08-04 | 中国石油化工股份有限公司 | Iron-vanadium molecular sieve, preparation method and application thereof, and method for preparing benzenediol |
| CN110015956A (en) * | 2019-05-08 | 2019-07-16 | 葫芦岛市载大瀛嘉化工有限公司 | A kind of 4-(2,2- dichloro cyclopropyl) phenoxyacetic acid ester preparation method |
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