CN102766034A - Method for preparing methoxyacetophenone through heterogeneous catalytic reaction - Google Patents
Method for preparing methoxyacetophenone through heterogeneous catalytic reaction Download PDFInfo
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Abstract
A method for preparing methoxyacetophenone through heterogeneous catalytic reaction belongs to the technical field of fine chemical product preparation. The method comprises the steps as follows: taking a supported catalyst formed in such a way that zirconium oxides and heteropoly acid active components are supported on an MCM-41 mesoporous molecular sieve in a layer-to-layer manner to catalyze Friedel-Crafts acylation reaction of anisole and acetic anhydride so as to prepare methoxyacetophenone. The technical scheme adopted by the method contains two aspects: (1) a method of preparing a supported SiW/ZrO2/MCM-41 catalyst; (2), a method utilizing SiW/ZrO2/MCM-41 as a heterogeneous catalyst to catalyze Friedel-Crafts acylation reaction of anisole and acetic anhydride so as to prepare methoxyacetophenone. Compared with the method for preparing methoxyacetophenone in the prior art, the method has the advantages of mild reaction condition, simplicity in catalyst preparation, low loss probability of catalyst active component, high activity, high selectivity, simplicity in product follow-up processing, environment protection and the like.
Description
Technical field
The invention belongs to the fine chemical product preparing technical field, be specifically related to that a kind of reaction conditions is gentle, Preparation of Catalyst is simple and be prone to separate with reaction solution, product convenient post-treatment, heterogeneous catalytic reaction low in the pollution of the environment prepare the method for p-methoxy-acetophenone.
Background technology
P-methoxy-acetophenone (p-MOAP) is a kind of important spices and medicine intermediate.It has strong hawthorn fragrance, be bashfully, the indispensable raw material of flavor essence such as hawthorn.Be usually used in superior cosmetics and the soap compound very high stability being arranged in soap, also can make the fruit food flavor(ing).China GB 2760-86 is defined as the flavouring agent that allows use, is mainly used in spices such as preparation XIANGJIALANDOU, kernel, cream and tobacco.Also be used for sun-screening agent and organic synthesis, produce the midbody of homoanisic acid as puerarin, and the production of liquid crystal monomer.In recent years, be initial feed synthetic medicine intermediate with the p-methoxy-acetophenone, makeup especially fine chemical product such as sunscreen have good market outlook, and demand both domestic and external is all in continuous increase.
The Friedel-Crafts acylation reaction is one of important channel of synthetic p-methoxy-acetophenone.Its typical preparation method is to be raw material with the methyl-phenoxide, and Acetyl Chloride 98Min. or diacetyl oxide are acylating reagent, adopts catalyzer to make through the Friedel-Crafts acylation reaction.The investigator has carried out extensive studies to the catalyzer that is applied in the acylation reaction both at home and abroad, and the catalyzer that has adopted at present mainly contains metal halide (like AlCl
3, FeCl
3, TiCl
4Deng), clay, zeolite, solid acid, ionic liquid, heteropolyacid etc.
C. Kuroda people such as (Sei. Papers Inst. Phys. Chem. Res. 18, pp 51-60 (1932)) adopts excessive AlCl
3The aromatics and the Acetyl Chloride 98Min. that come catalysis to contain methoxyl group obtain p-methoxy-acetophenone.Yet there are a lot of drawbacks in this method, like AlCl
3Consumption greater than stoichiometric ratio, toxicity is big, severe corrosion equipment and contaminate environment, selectivity is lower, and there is irretrievable problem in homogeneous catalysis system.The employing AlCl that for example in patent (granted patent DE 000010331083A1), announces
3Catalysis methyl-phenoxide and Acetyl Chloride 98Min. prepare p-methoxy-acetophenone, and not only there is the defective of aforesaid method in this method, also need adopt toluene as solvent, have further increased the difficulty of isolating product.
(Journal of Chemical Society, Feb-952 pp-376-380) adopt TiCl to people such as Cullinane N. M.
4Prepare p-methoxy-acetophenone for catalyzer comes catalysis methyl-phenoxide and diacetyl oxide, after having reacted 4h, yield can reach 76%.The shortcoming of this kind method is that product is not easily separated, need carry out hydrolysis reaction earlier, isolates organic layer, and decompression is removed solvent and just can be obtained product then.
The Jasra of the U.S., people (granted patent US 6730814) such as Rakesh Vir adopt the polynite that exchanges with lanthanide element as heterogeneous catalyst, and catalysis methyl-phenoxide and diacetyl oxide prepare p-methoxy-acetophenone.The shortcoming of this method is that the polynite of adopting will be carried out loaded down with trivial details pre-treatment, is used for will using HCl, HNO earlier with the polynite of lanthanide element exchange
3The perhaps H in the organic acid
+Exchange part Na wherein
+And this kind method to have adopted Acetyl Chloride 98Min. be acylating reagent, in reaction process, can generate HCl, contaminate environment.
The people (granted patent DE 3809260) such as Botta A. of Germany adopt mordenite as catalyzer at 160 ℃, the N of 20 bar
2Make methyl-phenoxide and diacetyl oxide sustained reaction 3h under the pressure, can obtain 75% transformation efficiency and 98% selectivity.The defective of this method is that reaction conditions is comparatively harsh, needs to adopt HTHP, and also need add solvent in the reaction, is unfavorable for the product separation collection.
Also the someone adopts the HZSM-5 sieve peg-raking catalyst to come catalysis methyl-phenoxide and diacetyl oxide to carry out the synthetic p-methoxy-acetophenone of acylation reaction.It is catalyzer that this method adopts the 0.03g/mol methyl-phenoxide, and reactant methyl-phenoxide and diacetyl oxide mol ratio are 1:1, reacts 2h down at 100 ℃, and yield is merely about 23%.The HZSM-5 regenerating molecular sieve temperature that this method is used is high, and the recovery is low, and experimentation cost is high.Zeolite molecular sieve is made problem of acylation reaction catalyst ubiquity, and promptly easy carbon deposit and product are made the rapid deactivation that can cause catalyzer in the competitive adsorption of catalyst surface in the reaction process, and its application is restricted.
The people such as Zhao Zhenbo of institute should be changed in Chinese Academy of Sciences Changchun, adopt heteropolyacid-acetate strong solution catalysis methyl-phenoxide and diacetyl oxide, in the water bath with thermostatic control oscillator, prepare p-methoxy-acetophenone.The product yield of this method has only about 30%, and has the not segregative problem of product.
People such as the Xu Mei of petrochemical complex institute of Liaoming Petrochemical Univ are catalyzer with pure heteropolyacid; By methyl-phenoxide and the synthetic p-methoxy-acetophenone of acetic anhydride acylation reaction; Investigated different reaction conditions, when being catalyzer with phospho-wolframic acid (PW), the yield of product can reach 52.9%.But use pure phospho-wolframic acid to be catalyzer in this technology, phospho-wolframic acid is dissolved in the reaction solution fully, be difficult to reclaim, and very easily coking under reaction conditions, influence activity of such catalysts.
The old equality people of Northeastern University has studied under solvent-free condition; The heterogeneous Friedel-Crafts acylation reaction selectivity of H zeolite beta catalyst methyl-phenoxide and diacetyl oxide generates p-methoxy-acetophenone, and has inquired into the influence to product yield of reactant molar ratio, catalyst levels and temperature of reaction.At methyl-phenoxide 0.1 mol, AN/AA mol ratio 1:1.5, catalyst levels 1.0g, 95 ℃ of temperature of reaction, behind the reaction times 4h, the finished product yield is 73.25%.The shortcoming of this method is that H β prepare zeolite process is more loaded down with trivial details, need be with H β zeolite and NH
4NO
3Solution carries out IX 3 times, last longer, afterwards must be dry, roasting can be used.Old equality people has also studied with different carrying methods and has prepared SiO
2Load phosphotungstic acid (PW) catalyzer is used it for the acylation reaction of catalysis methyl-phenoxide and diacetyl oxide, synthetic p-methoxy-acetophenone.In the phospho-wolframic acid charge capacity is 40%, and when activation temperature was 150 ℃, catalytic performance was best; When methyl-phenoxide is 0.1mol, diacetyl oxide is 0.15mmol, and catalyst quality is 1.0g, 100 ℃ of reaction 4h down, and the yield of product can reach 68.5%.The shortcoming of this method is that catalyst levels is excessive, and reactant ratio remains to be investigated.Chen Ping also uses iodine as catalyzer, and catalysis methyl-phenoxide and diacetyl oxide prepare p-methoxy-acetophenone.Methyl-phenoxide is 0.1mol, and the mol ratio of methyl-phenoxide and diacetyl oxide is 1:1. 5, and the best in quality of catalyzer is 1.0g, and the reaction times is 1.5h, 100 ℃ of temperature of reaction, and product yield reaches 52. 9%.The maximum defective of this method is an iodine during as catalyzer, after reaction finishes, and must be through filtering; Use anhydrous magnesium sulfate drying after repeatedly washing organic layer; Elder generation's air distillation goes out lighting ends such as methyl-phenoxide, and underpressure distillation goes out the reaction product p-methoxy-acetophenone again, and this process is too loaded down with trivial details.
Zhao ground of Hebei University of Science and Technology has synthesized Lewis acid ion liquid [Bmim] Cl-AlCl along waiting people, is used for the synthetic p-methoxy-acetophenone of catalysis.At molar ratio of alcohol to acid 1:1. 5,60 ℃ of temperature of reaction, under reaction times 6 h, transformation efficiency reaches 78. 8%.Ionic liquid is after repeatedly using, and activity change is little, is a kind of effective, environment-friendly catalyst, but its preparation process is very loaded down with trivial details, and the product that reaction generates also is difficult for separating.
At present, the synthetic p-methoxy-acetophenone of method that also has other.Patent (publication number: CN 101270039A) a kind of method of utilizing the synthetic p-methoxy-acetophenone of phenol is provided for example.Mainly be in the presence of catalyzer, carry out acylation reaction with acylating reagent acetonitrile and phenol and generate phenylacetate; Phenylacetate is again through transformation, and Crystallization Separation obtains acetyl phenol afterwards; Acetyl phenol is finally generated p-methoxy-acetophenone through methoxylation.This method need be passed through polystep reaction, and wherein operational condition is extremely loaded down with trivial details, and needs in the acylation reaction to adopt protonic acid to make catalyzer; Rearrangement reaction need adopt alkylsulphonic acid to make catalyzer; Can generate the by product ammonium salt in the reaction process, and also have water in the reaction system, can be influential to molecular balance.
Heteropolyacid (HPAs) is one type of solid acid catalyst with special construction, and research at present mainly concentrates on the phospho-wolframic acid of Keggin structure.The assorted polygamy compound component of this structure is fairly simple, and structure is confirmed, with the principal character of complex compound and MOX.Heteropolyacid has been the optimum substituent of the classical acid catalyzer of generally acknowledging, and is simple because of its preparation, and very strong acidity is arranged, and environment friendly.But pure heteropolyacid is subject to its lower specific surface area during as homogeneous catalyst; Relatively poor thermostability and be soluble in shortcomings such as polar solvent; Need loaded by heteropoly acid be become heterogeneous catalyst on suitable carriers in the practical application,, improve its catalytic performance to improve its surface-area; Enhance mechanical strength and thermostability, and be easy to separate with reaction solution.
MCM-41 is the heteropolyacid carrier of being potential very much, and it has enough big specific surface area (> 1000m2/g), high thermostability (ca.900 ℃) and wide aperture (1.5 ~ 8nm); The heteropolyacid crowd has ~ and the aperture of 1.2nm can get in the MCM-41 duct easily.The catalyzer of the direct carried heteropoly acid of MCM-41 also can be used for the acylation reaction of methyl-phenoxide, but exists the problem that the active ingredient heteropolyacid runs off easily, causes active relatively low.
ZrO
2Surface hydroxyl has unique soda acid both sexes, utilizes ZrO
2Surface hydroxyl can and heteropolyacid and mesopore molecular sieve MCM-41 on the silicon hydroxyl between produce strong interaction; Through successively loaded zirconia, heteropolyacid on mesopore molecular sieve MCM-41; Wherein zirconium white plays the effect of a sticker; The firm degree of loaded by heteropoly acid is strengthened, and can effectively improve the activity and the anti-solution-off ability of heteropolyacid in the carried heteropoly acid catalyst.
Summary of the invention
To the problems referred to above that exist in the prior art, the object of the present invention is to provide that a kind of reaction conditions is gentle, Preparation of Catalyst is simple and be prone to separate with reaction solution, product convenient post-treatment, catalyzed reaction low in the pollution of the environment prepare the method for p-methoxy-acetophenone.It with on the MCM-41 mesopore molecular sieve successively the loaded catalyst of loaded zirconia and heteropolyacid active ingredient come the Friedel-Crafts acylation reaction of catalysis methyl-phenoxide and diacetyl oxide to generate the method for p-methoxy-acetophenone.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone; It is characterized in that with the methyl-phenoxide being substrate; Diacetyl oxide is an acylating reagent; Under the heterogeneous catalyst effect, carry out the Friedel-Crafts acylation reaction, obtain p-methoxy-acetophenone through aftertreatment, described heterogeneous catalyst is for the MCM-41 mesopore molecular sieve SiW/ZrO that obtains of loaded zirconia and heteropolyacid successively
2/ MCM-41 catalyzer.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, it is characterized in that: under the normal pressure, be substrate with the methyl-phenoxide, diacetyl oxide is an acylating reagent, at SiW/ZrO
2Be heated to 70 ~ 130 ℃ of reaction 1 ~ 8h under the/MCM-41 catalyst action, with the reaction solution rectification process, get 250 ~ 260 ℃ cut after reaction finishes, obtain p-methoxy-acetophenone.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, and the molar ratio that it is characterized in that methyl-phenoxide and diacetyl oxide is 1 ~ 30:1.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, and the molar ratio that it is characterized in that methyl-phenoxide and diacetyl oxide is 5 ~ 20:1.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, and the temperature of reaction that it is characterized in that the Friedel-Crafts acidylate is 90 ~ 130 ℃.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, and the reaction times that it is characterized in that the Friedel-Crafts acidylate is 2 ~ 6h.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, it is characterized in that described diacetyl oxide and SiW/ZrO
2The mass ratio of/MCM-41 catalyzer is 1:0.05 ~ 0.4.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, it is characterized in that described SiW/ZrO
2/ MCM-41 catalyzer obtains through immersion process for preparing, and concrete grammar is following:
1) preparation ZrO
2/ MCM-41: zirconium nitrate is dissolved in to process mass concentration in the deionized water be 0.5 ~ 25% zirconium metal nitrate aqueous solution; MCM-41 type mesopore molecular sieve carrier impregnation is gone in this nitrate aqueous solution; The oil bath evaporating water; Successively through 110 ℃ of oven drying 24h, 350 ℃ of roasting 4h in air atmosphere are for use more again; Described MCM-41 type mesopore molecular sieve can also can directly be bought through the hydrothermal synthesis method preparation of reporting in the document; Literature method is: with mass concentration is the 5% cetyl trimethylammonium bromide aqueous solution constantly stirring down, dropwise drips tetraethoxysilance, controls the pH value 11.0 of solution in the dropping process; Dropwise the aging 3h of back solution left standstill, the stainless steel crystallizing kettle of packing into then, 110 ℃ of crystallization 24h; After crystallization finishes, arrive neutrality, drying until solution with deionized water wash; 550 ℃ of roasting 6h in air atmosphere obtain MCM-41 type mesopore molecular sieve carrier;
2) preparation SiW/ZrO
2/ MCM-41: with silicotungstic acid water-soluble or pure in, process mass concentration and be 0.1～50% the aqueous solution or alcoholic solution, the ZrO that step 1) is obtained
2/ MCM-41 immerses in this silicon tungsten acid solution or the alcoholic solution, the oil bath evaporating water, and successively through 110 ℃ of oven dryings 24 hours, 110～800 ℃ of air atmosphere roastings 2～6 hours obtain SiW/ZrO
2/ MCM-41 catalyzer, described alcohol are ethanol or methyl alcohol, and described maturing temperature is preferably 110 ~ 300 ℃.
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, it is characterized in that the zirconium white charge capacity is 10 ~ 25% of a MCM-41 type mesopore molecular sieve weight in the step 1).
Described a kind of heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone, it is characterized in that step 2) in the silicotungstic acid charge capacity be ZrO
210 ~ 60 % of/MCM-41 weight.
Through adopting above-mentioned technology, with present compared with techniques, beneficial effect of the present invention is mainly reflected in:
1) the inventive method is carried out under normal pressure, and a reaction conditions gentleness and a step can accomplish, and reduce energy consumption of reaction, reduce the requirement of conversion unit;
2) originally be reflected under the condition of no solvent and carry out, methyl-phenoxide also is the solvent of acylation reaction as reactant the time, and reaction product is easy to separate;
3) the present invention is through using SiW/ZrO
2/ MCM-41 catalyzer is loaded to silicotungstic acid on the carrier, effectively improves its acidity and active, improves the situation of pure silicotungstic acid easy coking in reaction process simultaneously, has also solved it and very easily has been dissolved in the difficult and isolating problem of product of polar reaction liquid; Again at ZrO
2/ MCM-41 load silicotungstic acid has improved dispersity and the acidity of silicotungstic acid on the mesopore molecular sieve surface, has strengthened its firm degree at carrier surface; Effectively raise the activity of load type silicotungstic acid catalyst; Kept high selectivity simultaneously, the preparation method is simple, is easy to and reactants separate;
4) p-methoxy-acetophenone preparation method operational path provided by the invention is short, and reaction conditions is gentle, and Preparation of Catalyst is simple; The catalyst activity component is difficult for running off, having high reactivity, highly selective, and the product subsequent disposal is simple, and catalyzer can reuse; Economic benefit is high; Low in the pollution of the environment, environmentally friendly, be suitable for applying.
The practical implementation method
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1 ~ 4: the SiW/ ZrO of different zirconium white charge capacity
2/ MCM-41 catalyst applications is in the preparation of p-methoxy-acetophenone
Respectively with 0.7g, 1.05g, 1.4g and 1.75gZr (NO
3)
4After 5H2O is dissolved in the 30mL deionized water fully; Pour into respectively in the 250mL three-necked flask, add MCM-41 type mesopore molecular sieve carrier 2g more respectively, flask is placed 60 ℃ of oil baths; Constantly stir simultaneously until distilled-to-dryness; Be placed on 110 ℃ baking oven inner drying 24h then, 350 ℃ of following roasting 4h in retort furnace obtain the ZrO that charge capacity (in carrier MCM-41 quality) is followed successively by 10wt%, 15wt%, 20wt% and 25wt% at last
2/ MCM-41 mesoporous molecular sieve catalyst, the quality of each catalyzer of gained was after roasting was accomplished: the quality of 10wt% ZrO2/MCM-41 is about 2.2g, 15wt% ZrO
2The quality of/MCM-41 is about 2.3g, 20wt%ZrO
2The quality of/MCM-41 is about 2.4g, 25wt% ZrO
2The quality of/MCM-41 is 2.5g; Wait until subsequent use.
Take by weighing 0.88g, 0.92g, 0.96g and 1.0g silicotungstic acid more respectively and be dissolved in fully in the 30mL deionized water (or methyl alcohol, ethanol), pour into respectively in the 250mL three-necked flask, add the ZrO of the different zirconium white charge capacity of method for preparing more respectively
2/ MCM-41 places 60 ℃ of oil baths with flask, stirs until distilled-to-dryness simultaneously constantly, is placed on 110 ℃ baking oven inner drying 24h then, 200 ℃ of following roasting 4h in retort furnace at last, and obtaining charge capacity respectively is 40wt%SiW/10wt%ZrO
2/ MCM-41,40wt%SiW/15wt%ZrO
2/ MCM-41,40wt%SiW/20wt%ZrO
2/ MCM-41,40wt%SiW/25 wt%ZrO
2/ MCM-41 loaded catalyst.
(have reflux condensation mode, CaCl at 4 50mL three-necked flask round bottoms
2Drying tube, N
2Feed mouth, thief hole) in, add methyl-phenoxide 10.8g (100mmol), diacetyl oxide 1.02g (10mmol), dodecyl (chromatography of gases analysis internal standard substance) 0.1g (0.6mmol), feed N before the reaction
2Removing steam and the foreign gas in the reaction system, after the question response liquid temp reaches 110 ℃ of temperature of reaction, add the 40wt%SiW/10wt%ZrO of above-mentioned preparation respectively
2/ MCM-41,40wt%SiW/15wt%ZrO
2/ MCM-41,40wt%SiW/20 wt%ZrO
2/ MCM-41,40wt%SiW/25wt%ZrO
2/ MCM-41 loaded catalyst 0.1g; With flask isothermal reaction in 110 ℃ of oil bath pans, constantly stir simultaneously then, behind the reaction 4h; Finish reaction; Filter to isolate catalyzer, filtrating is with the gas chromatographic analysis wherein content of methyl-phenoxide, diacetyl oxide, p-methoxy-acetophenone and the selectivity of diacetyl oxide, and the result sees table 1; 250 ~ 260 ℃ cut is collected in reaction solution rectifying, promptly gets the product p-methoxy-acetophenone.Product carries out qualitative analysis through GC-MS (CP-3800/Saturn2000 gas/matter combined instrument, kapillary look post: CP-SIL8,30m*0.25mm*0.25 μ m), confirms as p-methoxy-acetophenone.
Comparative Examples 1: the SiW/MCM-41 catalyst applications is in the preparation of p-methoxy-acetophenone
Other operational conditions are with embodiment 1, and different is that the activity of such catalysts composition only is silicotungstic acid.Prepare charge capacity by embodiment 1 said method and be used to prepare p-methoxy-acetophenone for the 40wt%SiW/MCM-41 loaded catalyst.The result sees table 1.
The SiW/ ZrO of table 1 embodiment 1 ~ 4 different zirconium white charge capacity
2The result of the catalyzer of/MCM-41 and Comparative Examples 1 preparation P-MOAP
Transformation efficiency described in the present embodiment is according to the amount of substance of the diacetyl oxide of participating in reaction and recently measuring of the amount of substance that reacts the diacetyl oxide that drops into before the beginning; The selectivity of described p-methoxy-acetophenone is confirmed according to amount shared ratio in all product amounts of reacting the p-methoxy-acetophenone that generates, down together.
Embodiment 5 ~ 7: the SiW/ ZrO of different steeping fluid preparations
2/ MCM-41 catalyst applications is in the preparation of p-methoxy-acetophenone
Other operational conditions are selected 40wt%SiW/20wt%ZrO for use with embodiment 1
2/ MCM-41 is a catalyzer, and that different is preparation SiW/ ZrO
2During/MCM-41, adopt different steeping fluids during the load silicotungstic acid.The result sees table 2.
Table 2 embodiment 5 ~ 7 different steeping fluids prepare SiW/ ZrO
2The result of the Preparation of Catalyst P-MOAP of/MCM-41
Embodiment 8 ~ 12: Different Silicon wolframic acid charge capacity is (with 20%ZrO
2/ MCM-41 quality meter) SiW/ ZrO
2/ MCM-41 catalyst applications is in the preparation of p-methoxy-acetophenone
Other operational conditions are with embodiment 1, and different is that the silicotungstic acid charge capacity is (with 20%ZrO
2/ MCM-41 quality meter) difference.Prepare the SiW/ZrO that charge capacity is followed successively by 10wt%, 20wt%, 40wt%, 60wt% and 100wt% by method described in the embodiment 1
2/ MCM-41 type mesoporous molecular sieve catalyst is used for catalysis methyl-phenoxide and diacetyl oxide and prepares p-methoxy-acetophenone.The result sees table 3.
Table 3 embodiment 8 ~ 12 Different Silicon wolframic acid charge capacity SiW/ ZrO
2The result of the Preparation of Catalyst P-MOAP of/MCM-41
Embodiment 13 ~ 15: the catalyst applications of different activation temperatures is in the preparation of p-methoxy-acetophenone
Select 40wt%SiW/20wt%ZrO for use
2/ MCM-41 is a catalyzer.Other operations are with embodiment 1, and different is the activation temperature before catalyzer uses.The result sees table 4.
The result of the Preparation of Catalyst P-MOAP of table 4 embodiment 13 ~ 15 different activation temperatures
Embodiment 16 ~ 19: the different catalyst consumption is applied to the preparation of p-methoxy-acetophenone
Select 40wt%SiW/20wt%ZrO for use
2/ MCM-41 is a catalyzer.The above-mentioned catalyzer that add different amounts respectively are used to prepare p-methoxy-acetophenone, make that the ratio of amount and the amount of catalyzer of diacetyl oxide is 1:0.05 ~ 0.4.Other operational conditions are with embodiment 1.The result sees table 5.
Table 5 embodiment 16 ~ 19 different catalysts consumptions prepare the result of P-MOAP
Embodiment 20 ~ 23: different methyl-phenoxides and diacetyl oxide feed ratio are to the influence of preparation p-MOAP
Select 40wt%SiW/20wt%ZrO for use
2/ MCM-41 is a catalyzer, and other are operated with embodiment 1, and different is to adopt the different methyl-phenoxides and the feed ratio of diacetyl oxide, keeps diacetyl oxide 1.02g (10 mmol) constant, changes the amount of methyl-phenoxide in proportion.The result sees table 6.
Table 6 embodiment 20 ~ 23 different methyl-phenoxides and diacetyl oxide feed ratio prepare the result of P-MOAP
Embodiment 24 ~ 27: the differential responses time is to the influence of preparation p-methoxy-acetophenone
Select 40wt%SiW/20wt%ZrO for use
2/ MCM-41 is a catalyzer, and other are operated with embodiment 1, and different is to adopt the different reaction times.The result sees table 7.
24 ~ 27 differential responses times of table 7 embodiment prepare the result of P-MOAP
Embodiment 28 ~ 31: the differential responses temperature is to the influence of preparation p-methoxy-acetophenone
Select 40wt%SiW/20wt%ZrO for use
2/ MCM-41 is a catalyzer, and other are operated with embodiment 1, and different is to adopt different temperature of reaction.The result sees table 8.
Table 8 embodiment 28 ~ 31 differential responses temperature are to the influence of catalytic performance
Claims (10)
1. a heterogeneous catalytic reaction prepares the method for p-methoxy-acetophenone; It is characterized in that with the methyl-phenoxide being substrate; Diacetyl oxide is an acylating reagent; Under the heterogeneous catalyst effect, carry out the Friedel-Crafts acylation reaction, obtain p-methoxy-acetophenone through aftertreatment, described heterogeneous catalyst is for the MCM-41 mesopore molecular sieve SiW/ZrO that obtains of loaded zirconia and heteropolyacid successively
2/ MCM-41 catalyzer.
2. a kind of heterogeneous catalytic reaction according to claim 1 prepares the method for p-methoxy-acetophenone, it is characterized in that: under the normal pressure, be substrate with the methyl-phenoxide, diacetyl oxide is an acylating reagent, at SiW/ZrO
2Be heated to 70 ~ 130 ℃ of reaction 1 ~ 8h under the/MCM-41 catalyst action, with the reaction solution rectification process, get 250 ~ 260 ℃ cut after reaction finishes, obtain p-methoxy-acetophenone.
3. a kind of heterogeneous catalytic reaction according to claim 2 prepares the method for p-methoxy-acetophenone, and the molar ratio that it is characterized in that methyl-phenoxide and diacetyl oxide is 1 ~ 30:1.
4. a kind of heterogeneous catalytic reaction according to claim 2 prepares the method for p-methoxy-acetophenone, and the molar ratio that it is characterized in that methyl-phenoxide and diacetyl oxide is 5 ~ 20:1.
5. a kind of heterogeneous catalytic reaction according to claim 2 prepares the method for p-methoxy-acetophenone, and the temperature of reaction that it is characterized in that the Friedel-Crafts acidylate is 90 ~ 130 ℃.
6. a kind of heterogeneous catalytic reaction according to claim 2 prepares the method for p-methoxy-acetophenone, and the reaction times that it is characterized in that the Friedel-Crafts acidylate is 2 ~ 6h.
7. a kind of heterogeneous catalytic reaction according to claim 1 prepares the method for p-methoxy-acetophenone, it is characterized in that described diacetyl oxide and SiW/ZrO
2The mass ratio of/MCM-41 catalyzer is 1:0.05 ~ 0.4.
8. a kind of heterogeneous catalytic reaction according to claim 1 prepares the method for p-methoxy-acetophenone, it is characterized in that described SiW/ZrO
2/ MCM-41 catalyzer obtains through immersion process for preparing, and concrete grammar is following:
1) preparation ZrO
2/ MCM-41: zirconium nitrate is dissolved in to process mass concentration in the deionized water be 0.5 ~ 25% zirconium metal nitrate aqueous solution; MCM-41 type mesopore molecular sieve carrier impregnation is gone in this nitrate aqueous solution; The oil bath evaporating water; Successively through 110 ℃ of oven drying 24h, 350 ℃ of roasting 4h in air atmosphere are for use more again;
2) preparation SiW/ZrO
2/ MCM-41: with silicotungstic acid water-soluble or pure in, process mass concentration and be 0.1～50% the aqueous solution or alcoholic solution, the ZrO that step 1) is obtained
2/ MCM-41 immerses in this silicon tungsten acid solution or the alcoholic solution, the oil bath evaporating water, and successively through 110 ℃ of oven dryings 24 hours, 110～800 ℃ of air atmosphere roastings 2～6 hours obtain SiW/ZrO
2/ MCM-41 catalyzer, described alcohol are ethanol or methyl alcohol, and described maturing temperature is preferably 110 ~ 300 ℃.
9. a kind of heterogeneous catalytic reaction according to claim 8 prepares the method for p-methoxy-acetophenone, it is characterized in that the zirconium white charge capacity is 10 ~ 25% of a MCM-41 type mesopore molecular sieve weight in the step 1).
10. a kind of heterogeneous catalytic reaction according to claim 8 prepares the method for p-methoxy-acetophenone, it is characterized in that step 2) in the silicotungstic acid charge capacity be ZrO
210 ~ 60 % of/MCM-41 weight.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923289A (en) * | 2015-05-04 | 2015-09-23 | 北京旭阳化工技术研究院有限公司 | Preparation method of catalyst used for acylation reaction of 2-methylnaphthalene and n-butyric anhydride |
| CN105358516A (en) * | 2013-07-05 | 2016-02-24 | 帝斯曼知识产权资产管理有限公司 | Method of acylating an aromatic compound |
| CN108727172A (en) * | 2018-06-25 | 2018-11-02 | 南京师范大学 | A kind of process for catalytic synthesis of acetanisole |
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2012
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| 《高校化学工程学报》 20080430 金滨等 负载型ZrOx/MCM-41分子筛催化alpha,beta-不饱和醛的MPV还原反应的研究 第270-276页 1-10 第22卷, 第2期 * |
| BIJU M.DEVASSY ET AL.: "Effect of calcination temperature on the catalytic activity of zirconia-supported heteropoly acids", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 冯磊等: "MCM-41负载磷钨酸催化剂的制备及其对乙酰化反应的催化性能", 《石油化工》 * |
| 金滨等: "负载型ZrOx/MCM-41分子筛催化α,β-不饱和醛的MPV还原反应的研究", 《高校化学工程学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105358516A (en) * | 2013-07-05 | 2016-02-24 | 帝斯曼知识产权资产管理有限公司 | Method of acylating an aromatic compound |
| CN105358516B (en) * | 2013-07-05 | 2018-07-06 | 帝斯曼知识产权资产管理有限公司 | For being acylated the method for aromatic compounds |
| CN104923289A (en) * | 2015-05-04 | 2015-09-23 | 北京旭阳化工技术研究院有限公司 | Preparation method of catalyst used for acylation reaction of 2-methylnaphthalene and n-butyric anhydride |
| CN108727172A (en) * | 2018-06-25 | 2018-11-02 | 南京师范大学 | A kind of process for catalytic synthesis of acetanisole |
| CN108727172B (en) * | 2018-06-25 | 2021-08-31 | 南京师范大学 | Catalytic synthesis method of p-methoxyacetophenone |
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