CN110143878A - A kind of preparation method of methyl p-methoxy cinnamate - Google Patents
A kind of preparation method of methyl p-methoxy cinnamate Download PDFInfo
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a kind of preparation methods of methyl p-methoxy cinnamate.Methyl acetate, methanol, sodium methoxide and cyclic ether are added in condensation reaction kettle, reacted under reflux temperature；Then P-methoxybenzal-dehyde is added, while reaction solution being circulated through to the reaction bed of loading catalyst, the reaction was continued for reflux heat preservation after P-methoxybenzal-dehyde feeds, and the water for reacting generation is separated off.The water generated by the addition and removal of methanol and cyclic ether, catalyst usage amount can be down to very low level, by the way that reaction solution is circulated through the reaction bed equipped with metal oxide catalyst, it converts methyl p-methoxy cinnamate in time by the 3- methoxyl group -3- p-methoxyphenyl methyl propionate generated in reaction process, improve the purity and yield of product, it is not necessarily to acid-base neutralization process simultaneously, extra waste water and other solid wastes are not generated, compared with traditional handicraft, with equal or higher conversion ratio and selectivity, lower production cost, more environmentally-friendly.
Description
Technical field
The invention belongs to chemical fields, are related to the preparation method of p-methoxycinnamic acid ester, and in particular to methoxyl group meat
The preparation method of acid methylester.
Background technique
The advanced ester of p-methoxycinnamic acid ester, especially p-methoxycinnamic acid is excellent ultraviolet absorbing agent, can be used
Make chemical sun.Methyl p-methoxy cinnamate is the raw material for synthesizing the advanced ester of p-methoxycinnamic acid, in pharmaceutical field
There is important application.
Currently, it is that raw material passes through that the preparation method of the p-methoxycinnamic acid ester of industrial mainstream, which is P-methoxybenzal-dehyde,
The preparation of Claisen-Schmidt reaction route:
P-methoxybenzal-dehyde, methyl acetate use the highly basic such as sodium methoxide to urge as catalyst in conventional hydrocarbon solvent
Change reaction, the mixture that 2~6h is obtained is reacted at 40~65 DEG C, obtains corresponding product after post-treated.
Chinese patent CN105503596 discloses a kind of preparation method of sun-screening agent Octyl methoxycinnamate, should
Method uses Claisen-Schmidt route, and P-methoxybenzal-dehyde, Methyl Acetates, alcohol sodium solution, isooctanol are mixed and stirred
It mixes uniformly, is reacted 3~8 hours at 55~75 DEG C.Then pH=12~14 are adjusted with non-oxidizing acid, depressurize and it is warming up to 70~
When 110 DEG C of reactions 2~8, low boiling point solvent is recycled, then with acid elution reaction solution to neutrality, is obtained pair by desolventizing, rectifying
The different monooctyl ester of methoxy cinnamic acid and recycle isooctanol.Patent report total recovery has reached more satisfactory water 87~90%
It is flat, but the molar ratio of catalyst sodium methoxide and Octyl methoxycinnamate is (1~1.2): 1, catalyst amount is big, catalysis
Agent is at high cost, needs to use a large amount of sour neutralization systems alkalinity after simultaneous reactions, can generate a large amount of waste water and increase environmental protection costs, should
The concrete content of 3- alkoxy -3- p-methoxyphenyl propionic ester is not mentioned in patent.
United States Patent (USP) US5527947 discloses a kind of improved method for preparing cinnamate compound, this method comprises:
(a) C1-C4 alkyloxybenzaldehydes and acetic acid C1-C4 Arrcostab are dissolved in conventional hydrocarbon solvent；(b) in temperate condition and alkali
Make to be formed by solution reaction in the presence of metal overbase；(c) it is acidified resulting mixture；(d) the esterification acetic acid, and from
The acetic acid of esterification is stripped in mixture；(e) make remaining C1-C4 alkane in the presence of the strong polybasic acids or bases metal salt suspension
Oxygroup cinnamic acid C1-C4 Arrcostab and C1-C4 alkoxy cinnamic acid are reacted with C5-C14 alkanol；(f) recovery product.Patent report
Road total recovery 83~87%, the patent greatly reduce waste liquid yield, but catalyst sodium methoxide by cleverly solvent circulation
Molar ratio with Octyl methoxycinnamate is 1.06:1, however it remains catalyst amount is big, and catalyst is at high cost to ask
Topic, while the concrete content of 3- alkoxy -3- p-methoxyphenyl propionic ester is not mentioned in the patent yet.
Japan Patent JPS617236A, which is described, uses metal alkoxide as alkali, passes through the contracting between benzaldehyde and acetic acid esters
Close the method that reaction prepares cinnamate.But due to there is 4.7~12.5% 3- methoxyl group -3- phenylpropionic acid ester by-product raw
At so this method needs purification step, such as distills in order to isolate cinnamate from reaction mixture.Therefore, the party
There are some problems, such as lower yield, difficult by-product purification and processing for method.
Japan Patent JP3786528B2 discloses a kind of method for preparing cinnamate comprising makes benzene in the presence of a base
Formaldehyde and methyl acetate are condensed.Then after being added without additional solvent or additional solvent is added, reaction mixing is handled with liquid acid
Object contains in reaction solution before handling to convert corresponding cinnamate for the 3- alkoxy -3- phenylpropionic acid ester in mixture
There is the 3- alkoxy -3- phenylpropionic acid ester of 7~16% molar ratios.Patent report total recovery 82~97.5%, but catalyst gold
Belong to 1~2 equivalent of the preferred benzaldehyde of alkoxide dosage, catalyst amount is big, and catalyst is at high cost, needs to use after simultaneous reactions
A large amount of acid neutralization system alkalinity can generate a large amount of waste water and increase environmentally friendly cost.
Deutsche Bundespatent EP0165521 discloses any Subs-tituted cinnamates and any substituted beta-alkoxy-β-phenylpropionic acid
The preparation method of ester, catalyst charge and benzaldehyde molar ratio 1.1:1, dosage is big, and catalyst is at high cost, while and in acid
Alkali neutralization process can generate a large amount of waste water, increase environmentally friendly cost, in order to prepare any substituted beta-alkoxy-β-phenylpropionic acid ester
It needs to be added alkali metal hydroxide at any Subs-tituted cinnamates to handle reaction solution.
German patent DE 3028417 discloses the preparation process of p-methoxycinnamic acid ester, catalyst charge with to first
Oxygroup benzaldehyde molar ratio 0.67:1, although catalyst charge decreases compared with other patent disclosure values, additional amount
It is still bigger than normal, high expensive, while a large amount of waste water can be generated in N-process, increase environmentally friendly cost.
In order to improve the yield and purity of methyl p-methoxy cinnamate, the method that patent JP617236 is used is by 3- first
The separation of oxygroup -3- p-methoxyphenyl methyl propionate, this method can reduce reaction yield, and the method that patent JP283462 is used is
Reaction solution containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate after reaction is handled with liquid acid, by 3- methoxyl group -3-
P-methoxyphenyl methyl propionate is converted into methyl p-methoxy cinnamate, and although this method improves reaction yield, but be related to
Multiple acid-base neutralization process, brine waste amount increase, and the method that patent EP0165521 is used is to contain 3- methoxy after reacting
The reaction solution of base -3- p-methoxyphenyl methyl propionate is handled with alkaline hydrated oxide, by 3- methoxyl group -3- p-methoxyphenyl
Methyl propionate is converted into methyl p-methoxy cinnamate, has same problem with patent JP283462.
In view of the deficiency of the route, the technique for developing a kind of low catalyst cost and safety and environmental protection is very important.It should
Technique should have the conversion ratio equal or higher with above-mentioned technique and selectivity, lower production cost, more environmentally-friendly, to overcome
The technological deficiency of above-mentioned technique.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of methyl p-methoxy cinnamate, compared with traditional handicraft,
This method has equal or higher conversion ratio and selectivity, lower production cost, more environmentally-friendly.
In order to reach the goals above, technical scheme is as follows:
A method of methyl p-methoxy cinnamate being prepared, described method includes following steps:
A) methyl acetate, methanol, sodium methoxide and cyclic ether are added in condensation reaction kettle, stirred under reflux temperature heat preservation
0.2~1h；
B) P-methoxybenzal-dehyde is added into condensation reaction kettle, while reaction solution being circulated through and has loaded catalyst
Reaction bed, reflux heat preservation the reaction was continued 0.5~5h after P-methoxybenzal-dehyde feeds, the water generated in reaction process pass through
Rectifying column, condensing heat exchanger and inorganic infiltration evaporation film device are separated off.
Reaction route of the present invention is shown below:
It is of the invention prepare methyl p-methoxy cinnamate during, water can be generated, sodium methoxide contacts easily raw with water
At methanol and sodium hydroxide, therefore following reaction is inevitable:
CH3ONa+H2O→CH3OH+NaOH
In order to reach purpose of the present invention, inventor dexterously joined a certain amount of methanol, to guarantee to react
The additive amount of journey sodium methoxide is in very low level, therefore following reaction is vital to the present invention:
CH3OH+NaOH→CH3ONa+H2O
The addition of methanol causes the main reaction rate of P-methoxybenzal-dehyde and methyl acetate to be substantially reduced, selectivity of product
Decline, this is that inventor did not expected.It is explored by many experiments, inventor in the system it is surprisingly found that be added
The problem of reaction rate reduces caused by appropriate specific cyclic ether can solve because of methanol addition.
Water and/or methanol that P-methoxybenzal-dehyde and methyl acetate reaction generate and the water energy that sodium hydroxide reaction generates
Enough timely and effectively remove also is necessary the present invention.
It is of the invention prepare methyl p-methoxy cinnamate during, can also generate by-product 3- methoxyl group -3- to first
Phenyl methyl propionate:
In order to not increase quantity of three wastes while obtaining methyl p-methoxy cinnamate with high-purity in high yield, the present invention is adopted
Method is to allow reaction solution to circulate through the reaction bed equipped with special metal oxide catalyst during reacting and carrying out, will
3- methoxyl group -3- p-methoxyphenyl the methyl propionate generated in reaction process is converted into methyl p-methoxy cinnamate in time.
The additional amount of conventional processing routes catalyst sodium alkoxide is very big, the molar ratio of sodium alkoxide and substrate P-methoxybenzal-dehyde
Generally higher than 1:1, wherein the sodium alkoxide of the overwhelming majority can not have catalytic action with the water reaction generated is reacted, while for height
Yield and high-purity obtain p-methoxycinnamic acid ester, need to mix reaction using liquid acid and/or alkaline hydrated oxide
Object is handled, this all can cause waste liquid amount huge.
The method of the present invention can dexterously solve the problems, such as that sodium alkoxide reacts with water and leads to failure, and then greatly reduce catalysis
Agent usage amount, reduces catalyst cost, which can also mix reaction without using liquid acid and/or alkaline hydrated oxide
High yield high-purity obtains methyl p-methoxy cinnamate product in the case that object is handled, and greatly reduces three-protection design
Cost.
The method of the present invention passes through the addition of methanol and specific cyclic ether, and removes reaction life in time during the reaction
At water, and then reduce catalyst sodium methoxide usage amount, urged by circulating through reaction solution equipped with special metal oxide
The reaction bed of agent converts the 3- methoxyl group -3- p-methoxyphenyl methyl propionate generated in reaction process in time to first
Oxygroup methyl cinnamate improves the purity and yield of product methyl p-methoxy cinnamate, while the present invention is not necessarily to acid-base neutralization
Catalyst usage amount can be greatly reduced by this route in process, be not necessarily to additional acid-base neutralization, do not generate extra waste water and other
Solid waste, and then production cost is saved, to reach purpose of the present invention.
The molar ratio of methyl acetate and P-methoxybenzal-dehyde is 1.1~10:1, preferably 2~8:1 in the step a).
The molar ratio of methanol and P-methoxybenzal-dehyde is 2~100:1, preferably 5~15:1 in the step a).
Cyclic ether is preferably dioxanes, trioxane, 1,3- dioxanes, 1,3- dioxolane in the step a), more preferably
1,3- dioxolane.
The molar ratio of cyclic ether and methanol is 0.2~1:1, preferably 0.4~0.6:1 in the step a).
In the step a) molar ratio of sodium methoxide and P-methoxybenzal-dehyde be 0.05~0.5:1, preferably 0.15~
0.3:1。
The feed time of P-methoxybenzal-dehyde is 0.5~2h, preferably 1~1.5h in the step b).
Preferably, the charge temperature of P-methoxybenzal-dehyde and the holding temperature after charging are reflux in step b)
Temperature.
Preferably, the reflux soaking time in the step b) after P-methoxybenzal-dehyde charging is preferably 1~3h.
The temperature and pressure of reaction bed is preferably consistent with condensation reaction kettle temperature and pressure in the step b).
The admission space of reaction bed catalyst is preferably 1/ that condensation reaction kettle material total volume is added in the step b)
10~1/3, more preferable 1/6~1/4.
The circular flow of reaction solution described in the step b) is preferably able to guarantee reaction solution to be recycled one in every 5~10 minutes
It is secondary.
The composition of the catalyst loaded in reaction bed in the step b) is as follows: being calculated with the gross mass of each substance, γ-oxygen
Change aluminium 53.1~81.6%, calcium oxide 3.2~6.4%, magnesia 3~6.5%, cerium oxide 0.5~2.2%, manganese oxide 50~
500ppm preferably 105~315ppm, 30~400ppm of rheium oxide, preferably 50~215ppm, Aluminum sol 10.2~32.3%.
Preferably, the mass ratio of the manganese oxide in the step b) in reaction bed in the catalyst of filling and rheium oxide is
0.3~10, preferably 0.5~6.
A method of preparing catalyst in step b) of the present invention, comprising the following steps:
1) gama-alumina and polyethylene glycol are uniformly mixed；Then calcium oxide, magnesia, cerium oxide, oxidation are added thereto
Manganese and rheium oxide are uniformly mixed；
2) it obtains that Aluminum sol is added in mixture to step 1), forms, dry, roasting obtains catalyst.
In the preparation method of catalyst of the present invention, the dosage of each substance is as follows: with the total weight of each substance,
Gama-alumina 50~80%, polyethylene glycol 2~7%, calcium oxide 3~6%, magnesia 3~6%, cerium oxide 0.5
~2%, 50~500ppm of manganese oxide preferably 100~300ppm, 30~400ppm of rheium oxide, preferably 50~200ppm, Aluminum sol
(in terms of the solid masses in Aluminum sol) 10~30%.
Preferably, in the preparation method of the catalyst, the mass ratio of manganese oxide and rheium oxide is 0.3~10, preferably 0.5
~6.
A certain proportion of manganese oxide and rheium oxide are added, concerted catalysis effect can be played with the main active component in catalyst
It answers, significantly improves catalyst to the activity of 3- methoxyl group in removing 3- methoxyl group -3- p-methoxyphenyl methyl propionate.
The effect of polyethylene glycol in the step 1) is pore-creating, and number-average molecular weight preferably 1000~6000 can also make
It is substituted with other organic pore-forming agents.
The effect of Aluminum sol of the present invention is binder, and solid content is 20~25wt%, other bondings also can be used
Agent substitution.
The molding mode of catalyst can be spin or extrusion, preferably extrusion in the step 2).
Drying temperature in the step 2) is 95~110 DEG C, preferably 98~102 DEG C, drying time 12~24 hours, excellent
It selects 15 hours.
The temperature of roasting in the step 2) is 450~650 DEG C, and calcining time is 10~15 hours, preferably 580~
It is roasted 10~12 hours at 620 DEG C.
The present invention can carry out under pressurization, normal pressure or reduced pressure, preferably carry out under nitrogen atmosphere.
Detailed description of the invention
Fig. 1 is the flow diagram of a specific embodiment of the method for the present invention.
Wherein, 1: P-methoxybenzal-dehyde；2: condensation reaction kettle；3: rectifying column；4: condensing heat exchanger；5: inorganic infiltration vapour
Change film device；6: water；7: reflux pump；8: circulating pump；9: reaction bed；10: discharging.
Specific embodiment
Further description is done to the present invention below by following embodiment, but the present invention is not limited to this.
The quantitative analysis of each organic matter involved in the present invention is carried out in Agilent 7890B type gas-chromatography, gas
Phase chromatographic conditions are as follows:
Chromatographic column: Agilent HP-5 capillary chromatographic column (specification is 30m × 0.32mm × 0.25 μm)
Injector temperature: 280 DEG C
Split ratio: 30: 1
Column flow: 1.5ml/min
Column temperature: 100 DEG C of 0.5min
15 DEG C/min is increased to 260 DEG C, keeps 8min
Detector temperature: 280 DEG C, hydrogen flowing quantity: 35ml/min
Air mass flow: 350ml/min
The present invention is further illustrated below by specific embodiment.
Catalyst preparation:
Embodiment 1:
Xiang Erzhe after 529.7 grams of gama-alumina powder are uniformly mixed with 70 grams of polyethylene glycol (molecular weight 1000) powder
30 grams of lime powders, 60 grams of magnesium oxide powders, 10 grams of cerium oxide, 100 milligrams of manganese oxide, 200 millis are sequentially added in mixture
Gram rheium oxide powder is stirring evenly and then adding into the solution containing 300 grams of Aluminum sols, and extrusion technique carries out shaping of catalyst, at 100 DEG C
It is 15 hours dry, it is roasted 10 hours at 600 DEG C, obtains catalyst 1.
Embodiment 2:
Xiang Erzhe after 769.6 grams of gama-alumina powder are uniformly mixed with 35 grams of polyethylene glycol (molecular weight 3000) powder
60 grams of lime powders, 30 grams of magnesium oxide powders, 5 grams of cerium oxide, 300 milligrams of manganese oxide, 100 milligrams are sequentially added in mixture
Rheium oxide powder is stirring evenly and then adding into the solution containing 100 grams of Aluminum sols, and extrusion technique carries out shaping of catalyst, dry at 100 DEG C
It dry 15 hours, is roasted 10 hours at 600 DEG C, obtains catalyst 2.
Embodiment 3:
It is mixed to the two after 500 grams of gama-alumina powder are uniformly mixed with 60 grams of polyethylene glycol (molecular weight 4000) powder
It closes in object and sequentially adds 60 grams of lime powders, 60 grams of magnesium oxide powders, 20 grams of cerium oxide, 200 milligrams of manganese oxide, 150 milligrams
Rheium oxide powder is stirring evenly and then adding into the solution containing 300 grams of Aluminum sols, and extrusion technique carries out shaping of catalyst, dry at 100 DEG C
It dry 15 hours, is roasted 10 hours at 600 DEG C, obtains catalyst 3.
Embodiment 4:
Xiang Erzhe after 799.65 grams of gama-alumina powder are uniformly mixed with 20 grams of polyethylene glycol (molecular weight 6000) powder
40 grams of lime powders, 30 grams of magnesium oxide powders, 10 grams of cerium oxide, 300 milligrams of manganese oxide, 50 milligrams are sequentially added in mixture
Rheium oxide powder is stirring evenly and then adding into the solution containing 100 grams of Aluminum sols, and extrusion technique carries out shaping of catalyst, dry at 100 DEG C
It dry 15 hours, is roasted 10 hours at 600 DEG C, obtains catalyst 4.
Catalyst composition is shown in Table 1.
1 catalyst 1-4 of table composition
Comparative example 1:
Other than not adding manganese oxide powder, remaining condition and embodiment 1 are consistent, obtain comparative catalyst 1.
Comparative example 2:
Other than not adding rheium oxide powder, remaining condition and embodiment 1 are consistent, obtain comparative catalyst 2.
Comparative example 3:
Other than not adding manganese oxide and rheium oxide powder, remaining condition and embodiment 1 are consistent, obtain comparative catalyst 3.
Comparative catalyst's composition is shown in Table 2.
2 comparative catalyst 1-3 of table composition
Methyl p-methoxy cinnamate preparation:
Embodiment 5:
296 grams of methyl acetates, 80 grams of methanol, 8.1 grams of sodium methoxide solids and 92.5 grams of 1,3- are added into condensation reaction kettle
Dioxolane 68 grams of P-methoxybenzal-dehyde is added by pipeline, together after stirred under reflux temperature keeps the temperature 0.2h into reaction kettle
Reaction solution is circulated through the reaction bed equipped with 90.8 milliliters of catalyst 1 by Shi Qidong circulating pump, and 6.54 kgs/hr of internal circulating load,
Feed duration 1h, continues reflux heat preservation 1h after charging, the water generated in reaction process by rectifying column, condensing heat exchanger and
Inorganic infiltration evaporation film device separation is removed in time, and cooling separation product, obtains 86.4 grams to methoxycinnamate after reaction
Sour methyl esters (yield 90wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.78wt%.
Embodiment 6:
222 grams of methyl acetates, 240 grams of methanol, 4.05 grams of sodium methoxide solids and 333 grams of 1,3- are added into condensation reaction kettle
Dioxolane 68 grams of P-methoxybenzal-dehyde is added by pipeline, together after stirred under reflux temperature keeps the temperature 0.5h into reaction kettle
Reaction solution is circulated through the reaction bed equipped with 173.4 milliliters of catalyst 2 by Shi Qidong circulating pump, and 7.43 kgs/hr of internal circulating load,
Feed duration 1.2h, continues reflux heat preservation 1.5h after charging, and the water generated in reaction process passes through rectifying column, condensing heat-exchange
Device and the separation of inorganic infiltration evaporation film device are removed in time, and cooling separation product, obtains 90.3 grams to methoxyl group after reaction
Methyl cinnamate (yield 94.1wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity
99.75wt%.
Embodiment 7:
222 grams of methyl acetates, 160 grams of methanol, 5.4 grams of sodium methoxide solids and 148 grams of 1,3- are added into condensation reaction kettle
Dioxolane 68 grams of P-methoxybenzal-dehyde is added by pipeline, together after stirred under reflux temperature keeps the temperature 0.2h into reaction kettle
Reaction solution is circulated through the reaction bed equipped with 150.9 milliliters of catalyst 3 by Shi Qidong circulating pump, and 3.62 kgs/hr of internal circulating load,
Feed duration 1.5h, continues reflux heat preservation 1h after charging, and the water generated in reaction process passes through rectifying column, condensing heat exchanger
And inorganic infiltration evaporation film device separation is removed in time, cooling separation product, obtains 89.3 grams to methoxyl group meat after reaction
Acid methylester (yield 93wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.68wt%.
Embodiment 8:
185 grams of methyl acetates, 128 grams of methanol, 8.1 grams of sodium methoxide solids and 176 gram of two evil are added into condensation reaction kettle
Alkane is added 68 grams of P-methoxybenzal-dehyde into reaction kettle by pipeline, started simultaneously after stirred under reflux temperature keeps the temperature 0.6h
Reaction solution is circulated through the reaction bed equipped with 113 milliliters of catalyst 4 by circulating pump, and 6.78 kgs/hr of internal circulating load, feed duration
1h, continues reflux heat preservation 2h after charging, the water generated in reaction process passes through rectifying column, condensing heat exchanger and inorganic infiltration
Vaporization film device separation is removed in time, after reaction cooling separation product, obtains 85.4 grams of methyl p-methoxy cinnamates (
Rate 89wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.80wt%.
Embodiment 9:
148 grams of methyl acetates, 192 grams of methanol, 8.1 grams of sodium methoxide solids and 216 gram of three evil are added into condensation reaction kettle
Alkane after stirred under reflux temperature keeps the temperature 1h, 68 grams of P-methoxybenzal-dehyde is added by pipeline, while starting is followed into reaction kettle
Reaction solution is circulated through the reaction bed equipped with 158 milliliters of catalyst 1 by ring pump, and 5.42 kgs/hr of internal circulating load, feed duration
1.5h, continues reflux heat preservation 1h after charging, the water generated in reaction process passes through rectifying column, condensing heat exchanger and inorganic infiltration
The separation of vaporization film device is removed in time thoroughly, and cooling separation product, obtains 86.4 grams of methyl p-methoxy cinnamates after reaction
(yield 90wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.76wt%.
Embodiment 10:
222 grams of methyl acetates, 240 grams of methanol, 6.75 grams of sodium methoxide solids and 396 grams of 1,3- are added into condensation reaction kettle
Dioxanes 68 grams of P-methoxybenzal-dehyde is added by pipeline, simultaneously after stirred under reflux temperature keeps the temperature 0.8h into reaction kettle
Start circulating pump and reaction solution is circulated through into the reaction bed equipped with 155.5 milliliters of catalyst 2,5.6 kgs/hr of internal circulating load, adds
Expect duration 1.3h, continue reflux heat preservation 3h after charging, the water generated in reaction process by rectifying column, condensing heat exchanger and
Inorganic infiltration evaporation film device separation is removed in time, and cooling separation product, obtains 83.5 grams to methoxycinnamate after reaction
Sour methyl esters (yield 87wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.73wt%.
Embodiment 11:
74 grams of methyl acetates, 80 grams of methanol, 8.1 grams of sodium methoxide solids and 92.5 grams of 1,3- bis- are added into condensation reaction kettle
Oxygen five rings is added 68 grams of P-methoxybenzal-dehyde into reaction kettle by pipeline, opened simultaneously after stirred under reflux temperature keeps the temperature 1h
Reaction solution is circulated through the reaction bed equipped with 64.5 milliliters of catalyst 3 by dynamic circulating pump, 3.87 kgs/hr of internal circulating load, is fed
Duration 1.5h, continues reflux heat preservation 2h after charging, the water generated in reaction process passes through rectifying column, condensing heat exchanger and nothing
The separation of machine infiltration evaporation film device, is removed in time, and cooling separation product, obtains 81.6 grams of p-methoxycinnamic acids after reaction
Methyl esters (yield 85wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.79wt%.
Embodiment 12:
111 grams of methyl acetates, 160 grams of methanol, 4.05 grams of sodium methoxide solids and 185 grams of 1,3- are added into condensation reaction kettle
Dioxolane 68 grams of P-methoxybenzal-dehyde is added by pipeline, together after stirred under reflux temperature keeps the temperature 0.5h into reaction kettle
Reaction solution is circulated through the reaction bed equipped with 132 milliliters of catalyst 4 by Shi Qidong circulating pump, 4.53 kgs/hr of internal circulating load, is added
Expect duration 1.2h, continue reflux heat preservation 3h after charging, the water generated in reaction process by rectifying column, condensing heat exchanger and
Inorganic infiltration evaporation film device separation, is removed in time, and cooling separation product, obtains 84.5 grams to methoxycinnamate after reaction
Sour methyl esters (yield 88wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.85wt%.
Comparative example 4:
Other than being added without methanol, remaining condition and embodiment 5 are consistent, obtain 28.8 grams of methyl p-methoxy cinnamates
(yield 30wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.73wt%.
Comparative example 5:
Other than being added without cyclic ether, remaining condition and embodiment 5 are consistent, obtain 62.4 grams of methyl p-methoxy cinnamates
(yield 65wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity 99.76wt%.
Comparative example 6:
Other than the water not generated to reaction removes, remaining condition and embodiment 5 are consistent, obtain 19.2 grams to methoxy
Base methyl cinnamate (yield 20wt% is not detected containing 3- methoxyl group -3- p-methoxyphenyl methyl propionate), purity
99.78wt%.
Comparative example 7:
It is outer in addition to handling without using reaction bed reaction solution, remaining condition and embodiment 5 unanimously, obtain 69.2 grams it is right
P-Methoxymethylcinnamate (yield 72.1wt%), purity 99.73wt% obtain 3- methoxyl group -3- p-methoxyphenyl propionic acid
17.5 grams of methyl esters.
Comparative example 8:
Other than catalyst 1 is replaced with comparative catalyst 1, remaining condition and embodiment 5 are consistent, obtain 78.7 grams to first
Oxygroup methyl cinnamate (yield 82wt%), purity 99.75wt% obtain 3- methoxyl group -3- p-methoxyphenyl methyl propionate
10 grams.
Comparative example 9:
Other than catalyst 1 is replaced with comparative catalyst 2, remaining condition and embodiment 5 are consistent, obtain 76.8 grams to first
Oxygroup methyl cinnamate (yield 80wt%), purity 99.73wt% obtain 3- methoxyl group -3- p-methoxyphenyl methyl propionate
11 grams.
Comparative example 10:
Other than catalyst 1 is replaced with comparative catalyst 3, remaining condition and embodiment 5 are consistent, obtain 73 grams to methoxy
Base methyl cinnamate (yield 76wt%), purity 99.77wt% obtain 3- methoxyl group -3- p-methoxyphenyl methyl propionate
13.5 grams.
Comparative example 11:
In addition to 1,3- dioxolane to be replaced with to the tetrahydrofuran (90 grams) of equimolar ratio outside, remaining condition and embodiment 5
Unanimously, obtaining 67.2 grams of methyl p-methoxy cinnamates, (yield 70wt% is not detected containing 3- methoxyl group -3- to methoxybenzene
Base methyl propionate), purity 99.78wt%.
Finally it should be noted that above embodiments are only described to the preferred embodiment of the present invention, rather than it is right
The limitation of the scope of the present invention, although the invention is described in detail with reference to the preferred embodiments, the ordinary skill of this field
The all variations and modifications that personnel should be appreciated that modification or equivalent replacement of the technical solution of the present invention are made and make, should all
It falls within the scope of protection determined by the claims of the present invention.
Claims (10)
1. a kind of preparation method of methyl p-methoxy cinnamate, includes the following steps:
A) methyl acetate, methanol, sodium methoxide and cyclic ether are added in condensation reaction kettle, stirred under reflux temperature heat preservation 0.2
~1h；
B) P-methoxybenzal-dehyde is added into condensation reaction kettle, while reaction solution being circulated through to the reaction for having loaded catalyst
Bed, reflux heat preservation the reaction was continued 0.5~5h after P-methoxybenzal-dehyde feeds, the water generated in reaction process pass through rectifying
Tower, condensing heat exchanger and inorganic infiltration evaporation film device are separated off.
2. the method according to claim 1, wherein methyl acetate and P-methoxybenzal-dehyde in the step a)
Molar ratio be 1.1~10:1, preferably 2~8:1.
3. method according to claim 1 or 2, which is characterized in that methanol and P-methoxybenzal-dehyde in the step a)
Molar ratio be 2~100:1, preferably 5~15:1.
4. method according to claim 1 to 3, which is characterized in that cyclic ether is selected from dioxanes, three evils in the step a)
Alkane, 1,3- dioxanes and 1, one of 3- dioxolane or a variety of, preferably 1,3- dioxolane.
5. method described in -4 according to claim 1, which is characterized in that the molar ratio of cyclic ether and methanol is in the step a)
0.2~1:1, preferably 0.4~0.6:1.
6. method according to any one of claims 1-5, which is characterized in that reaction bed catalyst in the step b)
Admission space is preferably 1/10~1/3, more preferable 1/6~1/4 that condensation reaction kettle material total volume is added.
7. method according to claim 1 to 6, which is characterized in that reaction solution described in the step b) follows
Circulation be preferably able to guarantee every 5~10 minutes by reaction solution circulation primary.
8. method according to any one of claims 1-7, which is characterized in that loaded in reaction bed in the step b)
The composition of catalyst is as follows: with the total weight of each substance, gama-alumina 53.1~81.6%, calcium oxide 3.2~6.4%, oxygen
Change magnesium 3~6.5%, cerium oxide 0.5~2.2%, 50~500ppm of manganese oxide preferably 105~315ppm, rheium oxide 30~
400ppm, preferably 50~215ppm, Aluminum sol 10.2~32.3%.
9. according to the method described in claim 8, it is characterized in that, the mass ratio of the manganese oxide and rheium oxide be 0.3~10,
It is preferred that 0.5~6.
10. method according to claim 8 or claim 9, which is characterized in that the preparation method of catalyst in the step b), packet
Include following steps:
1) gama-alumina and polyethylene glycol are uniformly mixed；Then thereto be added calcium oxide, magnesia, cerium oxide, manganese oxide and
Rheium oxide is uniformly mixed；
2) it obtains that Aluminum sol is added in mixture to step 1), forms, dry, roasting obtains catalyst.
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| CN115466179A (en) * | 2021-06-11 | 2022-12-13 | 大加香料技术(天津)有限公司 | Preparation method of isooctyl p-methoxycinnamate |
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Cited By (2)
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| CN115466179A (en) * | 2021-06-11 | 2022-12-13 | 大加香料技术(天津)有限公司 | Preparation method of isooctyl p-methoxycinnamate |
| CN115466179B (en) * | 2021-06-11 | 2024-02-02 | 大加香料技术(天津)有限公司 | Preparation method of isooctyl p-methoxycinnamate |
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