CN116023243B - Preparation method of avobenzone - Google Patents

Preparation method of avobenzone Download PDF

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Publication number
CN116023243B
CN116023243B CN202310029642.3A CN202310029642A CN116023243B CN 116023243 B CN116023243 B CN 116023243B CN 202310029642 A CN202310029642 A CN 202310029642A CN 116023243 B CN116023243 B CN 116023243B
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tert
catalyst
avobenzone
reaction
butyl benzoate
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CN116023243A (en
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徐文立
刘建军
曾诚
陈春宏
刘豪
高胜明
汪敦佳
殷国栋
卢忠勇
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Huangshihan Micro Technology Co ltd
HUBEI MEIKAI CHEMICAL CO Ltd
Huanggang Meifeng Chemical Technology Co ltd
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Huangshihan Micro Technology Co ltd
HUBEI MEIKAI CHEMICAL CO Ltd
Huanggang Meifeng Chemical Technology Co ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The application discloses a preparation method of avobenzone, which comprises the following steps: mixing p-tert-butyl benzoate with a catalyst to obtain a mixed material; adding p-methoxy acetophenone into a reaction vessel, stirring and heating; dropwise adding the mixture into the reaction container under the protection of inert gas or in a vacuum state, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a reaction material; and (3) treating the reaction material to obtain an avobenzone product. The application can prepare the avobenzone product under the condition of no solvent or less solvent, the preparation method is safe, the solvent loss is small, the generated waste liquid is less, the raw material cost and the waste liquid treatment cost are reduced, and the prepared avobenzone product has high purity and yield and low impurity content.

Description

Preparation method of avobenzone
Technical Field
The application relates to the field of sunscreens, in particular to a preparation method of avobenzone.
Background
In order to protect the human body from excessive ultraviolet radiation, ultraviolet absorbers having a safe and efficient absorption of ultraviolet radiation are widely used in cosmetics, hair care products, textile treatments and detergents.
Avobenzone (CAS number 70356-09-1) is Sup>A UV-A type ultraviolet absorber, has better absorption in the UVA band range, and is widely applied to sun-screening products.
At present, the mainstream avobenzone preparation method generally takes p-tert-butyl benzoate and p-methoxyacetophenone as raw materials, and adopts an alkaline catalyst to prepare the avobenzone product through Claisen condensation in a nonpolar solvent such as toluene or xylene. However, the nonpolar solvents such as toluene or xylene are inflammable and explosive dangerous materials, the polarity is small, static enrichment is easy to generate, a large safety risk exists in the production process, the solvent loss is large, a large amount of waste liquid can be generated, the cost is increased, and meanwhile, the solvent can remain in the product, and the product quality is reduced.
Disclosure of Invention
In view of the above, the application provides a preparation method of avobenzone, which can prepare high-purity avobenzone.
The technical scheme of the application is realized as follows:
in a first aspect, the present application provides a method for preparing avobenzone, comprising the steps of:
mixing p-tert-butyl benzoate with a catalyst to obtain a mixed material;
adding p-methoxy acetophenone into a reaction vessel, stirring and heating;
dropwise adding the mixture into the reaction container under the protection of inert gas or in a vacuum state, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a reaction material;
and (3) treating the reaction material to obtain an avobenzone product.
Alternatively, in some embodiments of the present application, in the step of mixing p-tert-butyl benzoate with a catalyst to obtain a mixed material, the catalyst is a solid catalyst or an alcohol solution of the catalyst, and the catalyst is at least one selected from sodium alkoxide and potassium alkoxide.
Alternatively, in some embodiments of the application, the solid catalyst has a particle size of 5 to 500um, preferably 150 to 300um.
Alternatively, in some embodiments of the present application, the solvent of the alcoholic solution of the catalyst is selected from at least one of methanol, ethanol, propanol and butanol, and the concentration of the catalyst in the alcoholic solution of the catalyst is 10% to 40%.
Alternatively, in some embodiments of the present application, the p-tert-butyl benzoate is selected from at least one of methyl p-tert-butylbenzoate, ethyl p-tert-butylbenzoate, propyl p-tert-butylbenzoate, and butyl p-tert-butylbenzoate.
Alternatively, in some embodiments of the application, the molar ratio of the catalyst to the p-methoxyacetophenone is (0.8-2.0): 1, wherein the molar ratio of the p-tert-butyl benzoate to the p-methoxyacetophenone is (2.0-20.0): 1.
Optionally, in some embodiments of the application, before or after adding the p-methoxyacetophenone to the reaction vessel, further comprising:
adding p-tert-butyl benzoate to the reaction vessel;
Wherein the molar ratio of the p-tert-butyl benzoate added into the reaction vessel to the p-tert-butyl benzoate in the mixture is 1 (0.5-6).
Alternatively, in some embodiments of the present application, the step of adding p-methoxyacetophenone to the reaction vessel and stirring to raise the temperature is performed at a temperature of 60 to 90 ℃.
Optionally, in some embodiments of the present application, the mixture is added dropwise into the reaction container under the protection of the inert gas or in a vacuum state, and a heat preservation reaction is performed after the addition is completed, so as to obtain a reaction material, wherein the inert gas is nitrogen, and the vacuum degree in the vacuum state is between-0.070 Mpa and-0.099 Mpa.
Alternatively, in some embodiments of the present application, the dropping time is 30 to 300min, the reaction temperature at the time of dropping is 60 to 90 ℃, the incubation time is 30 to 300min, and the incubation temperature is 60 to 90 ℃.
According to the technical scheme provided by the application, the mixture of the p-tert-butyl benzoate and the catalyst is dropwise added into the p-methoxyacetophenone, and the avobenzone product is prepared under the condition of no solvent or less solvent, so that the preparation method has the advantages of avoiding the use of non-polar solvents such as toluene or xylene, along with small safety risk, small solvent loss and less generated waste liquid, reducing the raw material cost and waste liquid treatment cost, reducing the solvent residue in the product and improving the product quality; in addition, the p-tert-butyl benzoate is mixed with the catalyst, so that the self-condensation reaction of the p-methoxy acetophenone under the action of the catalyst can be avoided, and the impurity content of the product is further reduced; the mixture of the p-tert-butyl benzoate and the catalyst is dropwise added into the p-methoxyacetophenone, so that the reaction rate can be improved, the contact time of the catalyst and the p-methoxyacetophenone can be reduced, and the product purity and yield can be improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a process for preparing avobenzone in accordance with a first embodiment of the present application;
FIG. 2 is a schematic flow chart of a process for preparing avobenzone in accordance with a second embodiment of the present application;
Fig. 3 is a schematic flow chart of a method for preparing avobenzone according to a third embodiment of the present application.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application based on the embodiments of the present application. Furthermore, it should be understood that the detailed description is presented herein for purposes of illustration and description only, and is not intended to limit the application. In the present application, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the term "including" means "including but not limited to". Various embodiments of the application may exist in a range of forms; it should be understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the application; it is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2,3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present application, "and/or" describing the association relationship of the association object means that there may be three relationships, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
The application provides a preparation method of avobenzone, referring to fig. 1, the preparation method of avobenzone comprises the following steps:
step S10, mixing p-tert-butyl benzoate with a catalyst to obtain a mixed material;
Step S20, adding the p-methoxy acetophenone into a reaction container, stirring and heating;
step S30, dropwise adding the mixture into the reaction container under the protection of inert gas or in a vacuum state, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a reaction material;
and step S40, treating the reaction materials to obtain an avobenzone product.
The inventor researches a preparation method of avobenzone, and discovers that: in the preparation process of avobenzone, p-tert-butyl benzoate, p-methoxyacetophenone and an alkaline catalyst are used as raw materials, and the avobenzone product is prepared in a nonpolar solvent such as toluene or xylene. The nonpolar solvents such as toluene or xylene are inflammable and explosive dangerous materials, the polarity is small, static enrichment is easy to generate, a large safety risk exists in the production process, the nonpolar solvents such as toluene or xylene are difficult to recycle, the solvent loss is large, a large amount of waste liquid can be generated, the cost is increased, meanwhile, the solvents can remain in the product, and the product quality is reduced. In view of the above, the application adds the mixture of the p-tert-butyl benzoate and the catalyst into the p-methoxy acetophenone, and prepares the avobenzone product under the condition of no solvent or less solvent, thereby avoiding the use of non-polar solvents such as toluene or xylene, and the preparation method has the advantages of low safety risk, small solvent loss and less waste liquid, reduces the cost of raw materials and waste liquid treatment, reduces the residual of the solvent in the product, and improves the quality of the product; in addition, the p-tert-butyl benzoate is mixed with the catalyst, so that the self-condensation reaction of the p-methoxy acetophenone under the action of the catalyst can be avoided, and the impurity content of the product is further reduced; the mixture of the p-tert-butyl benzoate and the catalyst is dropwise added into the p-methoxyacetophenone, so that the reaction rate can be improved, the contact time of the catalyst and the p-methoxyacetophenone can be reduced, and the product purity and yield can be improved.
In step S10, p-tert-butyl benzoate is mixed with a catalyst, instead of p-methoxyacetophenone, in consideration of the fact that p-methoxyacetophenone itself undergoes a condensation reaction under the action of the catalyst after being mixed with the catalyst, impurities are generated. Therefore, the p-tert-butyl benzoate is mixed with the catalyst, so that compared with the mixing of the p-methoxyacetophenone with the catalyst, the condensation reaction of the p-methoxyacetophenone can be avoided, the purity and the yield of the avobenzone product are improved, and the impurity content of the avobenzone product is reduced.
In step S10, as a preferred embodiment, the p-tert-butyl benzoate and the catalyst may be mixed under the protection of an inert gas, and then the mixed solution of the p-tert-butyl benzoate and the catalyst may be stirred at room temperature to uniformly mix the p-tert-butyl benzoate and the catalyst, thereby obtaining a mixed material. Wherein the inert gas may be at least one of nitrogen and argon, preferably nitrogen.
In some embodiments, in step S10, the catalyst is a basic catalyst, the basic catalyst is an alkali metal alkoxide, the alkali metal alkoxide is selected from at least one of potassium alkoxide and sodium alkoxide, the potassium alkoxide includes at least one of potassium methoxide, potassium ethoxide, and potassium isopropoxide, and the sodium alkoxide includes at least one of sodium methoxide, sodium ethoxide, and sodium isopropoxide.
In some embodiments, in step S10, the catalyst is a solid catalyst or an alcoholic solution of a catalyst selected from at least one of sodium alkoxide and potassium alkoxide.
As a preferred embodiment, in step S10, the catalyst is a solid catalyst, for example, the catalyst is sodium methoxide solid powder, potassium ethoxide solid powder, mixed solid powder of sodium methoxide and potassium ethoxide, or the like. The particle diameter of the solid catalyst is 5 to 500um, and as an example, the particle diameter of the solid catalyst may be 5 to 150um, 150 to 300um, 300 to 400um, 400 to 500um, etc., preferably 150 to 300um. The smaller the particle diameter of the solid catalyst is, the larger the surface area of the solid catalyst is, and the particle diameter of the solid catalyst is controlled within the range, so that the purity and the yield of avobenzone products are improved.
In some embodiments, when the catalyst is an alcoholic solution of the catalyst, the solvent of the alcoholic solution of the catalyst is selected from at least one of methanol, ethanol, propanol, and butanol, e.g., the catalyst is a methanolic solution of sodium methoxide, ethanolic solution of potassium ethoxide, and the like. The concentration of the catalyst in the alcohol solution of the catalyst is 10% -40%, and as an example, the concentration of the catalyst in the alcohol solution of the catalyst can be 10%, 20%, 30%, 40%, etc., and the concentration of the catalyst in the alcohol solution of the catalyst is controlled within the range, which is helpful for improving the purity and yield of avobenzone product.
It should be noted that when using an alcohol solution of the catalyst, a larger evaporation amount of equipment is required to ensure that alcohol produced by the reaction and alcohol carried in by the solvent are evaporated together, otherwise if the alcohol solvent cannot be evaporated in time, the alcohol solvent may be reversibly reacted to form byproducts to affect the product quality and yield.
In some embodiments, the p-tert-butyl benzoate is selected from at least one of methyl p-tert-butylbenzoate, ethyl p-tert-butylbenzoate, propyl p-tert-butylbenzoate, and butyl p-tert-butylbenzoate, preferably methyl p-tert-butylbenzoate.
In some embodiments, the molar ratio of catalyst to p-methoxyacetophenone is (0.8-2.0): 1, as an example, the molar ratio of catalyst to p-methoxyacetophenone may be 0.8: 1. 1: 1. 1.2: 1. 1.5: 1. 1.8: 1. 2.0:1, etc. The molar ratio of the catalyst to the p-methoxyacetophenone is too low, namely the catalyst amount is too small, the reaction of the p-tert-butyl benzoate and the p-methoxyacetophenone is incomplete, and the purity and the yield of the avobenzone product are low; the molar ratio of the catalyst to the p-methoxyacetophenone is too high, namely the amount of the catalyst is too large, so that the p-methoxyacetophenone can generate condensation reaction, the purity and the yield of the avobenzone product are reduced, and the impurity content of the avobenzone product is increased. Therefore, the molar ratio of the catalyst to the p-methoxyacetophenone is controlled within the range, which is helpful for improving the purity and yield of the avobenzone product and reducing the impurity content of the avobenzone product.
In some embodiments, the molar ratio of p-tert-butyl benzoate to p-methoxyacetophenone is (2.0-20.0): 1, i.e. the molar ratio of p-tert-butyl benzoate to p-methoxyacetophenone may be 2.0, as an example: 1. 5.0: 1. 8.0: 1. 10.0: 1. 12.0: 1. 16.0: 1. 18.0: 1. 20.0:1, etc. The molar ratio of the p-tert-butyl benzoate to the p-methoxyacetophenone is too low, namely the amount of the p-tert-butyl benzoate is too small, and the reaction is easy to cure; the molar ratio of p-tert-butyl benzoate to p-methoxyacetophenone is too large, namely the amount of p-tert-butyl benzoate is too large, the purity and yield of avobenzone product are not changed any more, and the cost of raw materials is increased. Therefore, the control of the molar ratio of the p-tert-butyl benzoate to the p-methoxyacetophenone is in the range, and the purity and the yield of the avobenzone product can be improved on the premise of controlling the cost of raw materials.
In step S20, the temperature of stirring and heating is 60-90 ℃, for example, the temperature of stirring and heating can be 60 ℃, 70 ℃, 80 ℃, 90 ℃ and the like, and then the mixed material is added dropwise after the temperature is raised, so that the activity of the raw material is improved, the reaction speed is improved, the purity and yield of the avobenzone product are improved, and the impurity content of the avobenzone product is reduced.
In some embodiments, the reaction vessel after stirring and heating may be pure p-methoxyacetophenone liquid, or a mixed solution of p-methoxyacetophenone and p-tert-butyl benzoate. Referring to fig. 2, when a mixed solution of p-methoxyacetophenone and p-tert-butyl benzoate is stirred in the reaction vessel after heating, the step S20 before or after adding p-methoxyacetophenone to the reaction vessel may include the following steps:
Step S11, adding p-tert-butyl benzoate into the reaction vessel; wherein the molar ratio of the p-tert-butyl benzoate added to the reaction vessel to the p-tert-butyl benzoate in the mixture is 1: (0.5-6).
In some embodiments, the p-tert-butyl benzoate may be added to the reaction vessel before or after the addition of the p-methoxyacetophenone to the reaction vessel, and then the mixed solution of p-methoxyacetophenone and p-tert-butyl benzoate may be stirred to raise the temperature.
In some embodiments, in step S11, the molar ratio of the p-tert-butyl benzoate added to the reaction vessel to the p-tert-butyl benzoate in the mixture is 1 (0.5-6), and as an example, the molar ratio of the p-tert-butyl benzoate added to the reaction vessel to the p-tert-butyl benzoate in the mixture may be 1:0.5, 1: 1. 1: 2. 1: 3. 1: 4. 1: 5. 1:6, etc.
In some embodiments, considering that too much para-tertiary butyl benzoate contributes little to the purity and yield of the avobenzone product, but rather increases the raw material cost, the ratio of the total molar amount of para-tertiary butyl benzoate added to the reaction vessel to the molar amount of para-tertiary butyl benzoate in the mixture to the molar amount of para-methoxyacetophenone can be controlled to be (2.0-20.0): 1. if the p-tert-butyl benzoate added into the reaction vessel is Amol, the p-tert-butyl benzoate in the mixture is Bmol, and the p-methoxyacetophenone is Cmol, (a+b): c= (2.0 to 20.0): 1.
In the step S30, the mixture is dripped into a reaction container, namely, the mixture of the p-tert-butyl benzoate and the catalyst is dripped into the p-methoxyacetophenone, on one hand, the initial reaction concentration is higher, the reaction speed is higher, and the reaction yield can be improved; on the other hand, the reaction speed is faster, so that the contact time of the catalyst and the p-methoxyacetophenone can be reduced, the generation of impurities by the condensation reaction of the p-methoxyacetophenone caused by the contact of the catalyst and the p-methoxyacetophenone is reduced, the purity of the avobenzone product is improved, and the impurity content of the avobenzone product is reduced.
In step S30, the inert gas is at least one of nitrogen and argon, preferably nitrogen; the degree of vacuum in the vacuum state is-0.070 Mpa to-0.099 Mpa, and as an example, the degree of vacuum may be-0.070 Mpa, -0.075Mpa, -0.080Mpa, -0.085Mpa, -0.090Mpa, -0.095Mpa, -0.099Mpa, or the like. The vacuum degree is controlled within the range, which is helpful for improving the purity and yield of avobenzone product and reducing the impurity content of avobenzone product.
In step S30, the dripping time is 30-300 min, and as an example, the dripping time may be 30min, 60min, 90min, 120min, 150min, 180min, 210min, 240min, 270min, 300min, etc.; the reaction temperature at the time of the dropwise addition is 60 to 90℃and, as an example, the reaction temperature at the time of the dropwise addition may be 60℃70℃80℃90℃or the like. The dropping time and the dropping temperature are controlled within the range, so that the p-tert-butyl benzoate and the p-methoxyacetophenone are fully contacted and reacted, the purity and the yield of the avobenzone product are improved, and the impurity content of the avobenzone product is reduced.
In step S30, the time of the incubation reaction is 30-300 min, and as an example, the time of the incubation reaction may be 30min, 60min, 90min, 120min, 150min, 180min, 210min, 240min, 270min, 300min, etc.; the temperature of the incubation reaction is 60 to 90 ℃, and as an example, the temperature of the incubation reaction may be 60 ℃,70 ℃, 80 ℃, 90 ℃, or the like. The heat preservation reaction ensures that the p-tert-butyl benzoate and the p-methoxy acetophenone react completely, and reduces the impurity content of the avobenzone product.
The avobenzone product in step S40 is a purified avobenzone product obtained by treating the reaction material, and the treatment mode of the reaction material includes, but is not limited to, a mode of combining distillation and crystallization, a distillation mode, and the like. For example, when the reaction mass is treated by a combination of distillation and crystallization, the solvent in the reaction mass is removed by distillation under reduced pressure, and then an alcohol crystallization solvent is added to the solvent-removed reaction mass to obtain an avobenzone purified product; when the reaction materials are treated in a distillation manner, the solvent, the raw materials and the impurities can be separated by sequentially carrying out multistage distillation on the reaction materials, so that the avobenzone purified product can be obtained. Referring to fig. 3, when the reaction material is treated by a combination of distillation and crystallization, step S40 may be implemented as follows:
s41, regulating the pH of the reaction material to 3-6, standing for layering, and separating an organic layer;
step S42, performing reduced pressure distillation on the organic layer to obtain a crude avobenzone product;
And step S43, crystallizing, filtering and drying the crude avobenzone product to obtain the avobenzone product.
In some embodiments, in step S41, the pH of the reaction mass is adjusted by a mixed solution of an acid and water, the acid being at least one of acetic acid and hydrochloric acid, the mixed solution of an acid and water removing unreacted basic catalyst and other water-soluble impurities from the reaction mass. The water layer and the organic layer can be separated by standing and layering, and the organic layer can be separated by removing the water layer.
Since the p-tert-butyl benzoate is excessive relative to the p-methoxyacetophenone, the organic layer separated includes unreacted p-tert-butyl benzoate, and the excessive p-tert-butyl benzoate in the organic layer can be recovered through step S42.
In some embodiments, in step S43, the crude avobenzone product is crystallized by a crystallization solvent, where the crystallization solvent is an alcohol solvent, such as methanol, ethanol, etc., and the crystallization solvent can effectively remove impurities in the final product during crystallization, thereby improving the purity of the avobenzone product.
In some embodiments, in step S43, the drying temperature is 30 to 70 ℃, and as an example, the drying temperature may be 30 ℃, 40 ℃,50 ℃, 60 ℃, 70 ℃, or the like.
The technical scheme and effect of the present application will be described in detail by the following specific examples and comparative examples, which are only some examples of the present application, and are not intended to limit the present application in any way.
Example 1
Under the protection of nitrogen, 28.0mol of p-tert-butyl benzoate and 8.0mol of solid sodium methoxide are put into a dry and clean batching kettle, and the particle size of the solid sodium methoxide is 150-300 um, and the mixture is obtained by stirring and mixing uniformly at room temperature.
Adding 7.0mol of liquid p-methoxyacetophenone into a dry and clean condensation reaction kettle, stirring and heating to 70 ℃, opening a vacuum valve to control the vacuum degree in the condensation reaction kettle to be-0.095 Mpa, opening a dripping valve to drip the mixed material, wherein the dripping time is 60min, and the reaction temperature during dripping is 70 ℃.
After the dripping is finished, the reaction is continued under the vacuum state with the vacuum degree of-0.095 Mpa at the temperature of 75 ℃ for 150min to obtain the reaction material.
Transferring the reaction material into 200L of acid aqueous solution containing 8.5mol of acetic acid for hydrolysis reaction, standing for layering after the hydrolysis reaction is completed, and separating out an organic layer; the organic layer is distilled under reduced pressure to recover excessive p-tert-butyl benzoate; crystallizing the residual distillation residue with 5kg of methanol, filtering and drying to obtain avobenzone product.
Example 2
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
the solid sodium methoxide was 14mol.
Example 3
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The methyl p-tert-butylbenzoate was 14mol.
Example 4
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
the methyl p-tert-butylbenzoate was 70mol.
Example 5
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The particle size of the solid sodium methoxide is 5-150 um.
Example 6
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
the particle size of the solid sodium methoxide is 300-500 um.
Example 7
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
After liquid p-methoxyacetophenone is put into a dry and clean condensation reaction kettle, stirring and heating to 60 ℃.
Example 8
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
After liquid p-methoxyacetophenone is put into a dry and clean condensation reaction kettle, stirring and heating to 90 ℃.
Example 9
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
the dripping time is 30min.
Example 10
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The dripping time is 200min.
Example 11
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The dropping time is 300min.
Example 12
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
vacuum degree is-0.07 Mpa.
Example 13
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The vacuum degree is-0.099 Mpa.
Example 14
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The incubation temperature was 60 ℃.
Example 15
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The incubation temperature was 90 ℃.
Example 16
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The incubation time was 30min.
Example 17
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
The incubation time was 300min.
Example 18
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
18.0mol of p-tert-butyl benzoate is put into a dry and clean batching kettle, 10.0mol of p-tert-butyl benzoate is put into a dry and clean condensation reaction kettle, and 7.0mol of liquid p-methoxyacetophenone is put into the condensation reaction kettle.
Example 19
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
14.0mol of p-tert-butyl benzoate is put into a dry and clean batching kettle, 14.0mol of p-tert-butyl benzoate is put into a dry and clean condensation reaction kettle, and 7.0mol of liquid p-methoxyacetophenone is put into the condensation reaction kettle.
Example 20
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
9.5mol of p-tert-butyl benzoate is put into a dry and clean batching kettle, 18.5mol of p-tert-butyl benzoate is put into a dry and clean condensation reaction kettle, and 7.0mol of liquid p-methoxyacetophenone is put into the condensation reaction kettle.
Example 21
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
21.0mol of p-tert-butyl benzoate is put into a dry and clean batching kettle, 7.0mol of p-tert-butyl benzoate is put into a dry and clean condensation reaction kettle, and 7.0mol of liquid p-methoxyacetophenone is put into the condensation reaction kettle.
Example 22
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
24mol of p-tert-butyl benzoate is put into a dry and clean batching kettle, 4mol of p-tert-butyl benzoate is put into a dry and clean condensation reaction kettle, and 7.0mol of liquid p-methoxyacetophenone is put into the condensation reaction kettle.
Example 23
This embodiment is substantially the same as embodiment 1, except that in this embodiment:
the catalyst is methanol solution of sodium methoxide, and the concentration of sodium methoxide in the catalyst is 30%.
Comparative example 1
This comparative example is substantially the same as example 1 except that in this comparative example:
The solid sodium methoxide was 3.5mol.
Comparative example 2
This comparative example is substantially the same as example 1 except that in this comparative example:
the solid sodium methoxide was 17.5mol.
Comparative example 3
This comparative example is substantially the same as example 1 except that in this comparative example:
the p-tert-butyl benzoate was 7.0mol.
Comparative example 4
This comparative example is substantially the same as example 1 except that in this comparative example:
the p-tert-butyl benzoate was 84.0mol.
Comparative example 5
This comparative example is substantially the same as example 1 except that in this comparative example:
the particle size of the solid sodium methoxide is 550-700 um.
Comparative example 6
This comparative example is substantially the same as example 1 except that in this comparative example:
The dropping time is 20min, and the reaction temperature is 100 ℃ during dropping.
Comparative example 7
This comparative example is substantially the same as example 1 except that in this comparative example:
The vacuum degree is 0.05Mpa.
Comparative example 8
This comparative example is substantially the same as example 1 except that in this comparative example:
When p-tert-butyl benzoate and solid sodium methoxide are added into a dry and clean batching kettle, 5L of dimethylbenzene is also added; when liquid p-methoxyacetophenone was charged into the dry and clean condensation reactor, 5L of xylene was also charged.
Comparative example 9
This comparative example is substantially the same as example 1 except that in this comparative example:
Liquid p-methoxyacetophenone was added dropwise to the mixture.
The yields of the above examples and comparative examples, as well as the purity and impurity content of the avobenzone produced, were examined and the results are reported in Table I.
List one
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From Table one can see:
The yield of the preparation method of each example is above 90.3%, the purity of the prepared avobenzone is above 98.8%, the purity of the avobenzone is higher than that of comparative example 8, and meanwhile, the impurity content of each example is less than 0.09%, and the purity of each example is lower than that of comparative example 8. Furthermore, it was examined that the xylene residue of comparative example 8 was 920ppm, that is, avobenzone having high yield, high purity, low impurity content and low residue could be produced by the method of the present application.
Further, comparative examples 1 to 2 and comparative examples 1 to 2, it can be seen that the purity or yield of each example is higher than that of the comparative example, illustrating the control of the molar ratio of catalyst to p-methoxyacetophenone (0.8 to 2.0): 1, which is helpful to improve the purity or yield of avobenzone product.
Comparative examples 1, 3-4 and comparative examples 3 to 4, it can be seen that the molar ratio of p-tert-butyl benzoate to p-methoxyacetophenone of comparative example 3 is 1:1, namely, the dosage of the p-tertiary butyl benzoate is too small, the reaction can be solidified and can not be completed; the molar ratio of p-tert-butyl benzoate to p-methoxyacetophenone of comparative example 4 was 12:1, i.e. the purity and yield of avobenzone product are no longer changed when the amount of p-tert-butyl benzoate is too large.
Comparative examples 1, 5-6 and comparative example 5, the purity and yield of comparative example 5 were lower than those of each example, and it was found that controlling the particle size of the solid catalyst to 5 to 500um helps to improve the purity and yield of avobenzone product.
Comparative examples 1, 7 to 11 and comparative example 6, the purity of comparative example 6 was lower than that of each example, the yield of comparative example 6 was lower than that of each example, and the impurity content of comparative example 6 was higher than that of each example, indicating that the dropping time was controlled to be 30 to 300 minutes, the reaction temperature at the time of dropping was 60 to 90 ℃, which was helpful for improving the purity and yield of avobenzone product and reducing the impurity content of avobenzone product.
Comparative examples 1, 12 to 13 and comparative example 7, the purity of comparative example 7 was lower than that of each example, the yield of comparative example 7 was lower than that of each example, and the impurity content of comparative example 7 was higher than that of each example, indicating that controlling the vacuum degree between-0.070 Mpa and-0.099 Mpa helps to improve the purity and yield of avobenzone product and reduce the impurity content of avobenzone product.
Comparing example 1, example 18 to example 22, it can be seen that the purity and yield of avobenzone product prepared by mixing all of the p-tert-butyl benzoate with the catalyst, and mixing a part of the p-tert-butyl benzoate with the catalyst, and another part of the p-tert-butyl benzoate with the p-methoxyacetophenone are both good, the impurity content is lower, and the effect of both is equivalent.
In addition, as can be seen from comparative examples 1 and 9, the dropwise addition of the mixed solution of p-tert-butyl benzoate and the catalyst to p-methoxyacetophenone contributes to the improvement of purity and yield of avobenzone product and the reduction of impurity content of avobenzone product, relative to the dropwise addition of p-methoxyacetophenone to the mixed solution of p-tert-butyl benzoate and the catalyst.
Comparing example 1 with example 23, it can be seen that the use of a solid catalyst helps to increase the purity and yield of avobenzone product relative to the use of an alcoholic solution of the catalyst.
The above describes in detail the preparation method of avobenzone provided by the embodiment of the present application, and specific examples are applied herein to illustrate the principle and embodiments of the present application, and the above description of the examples is only for helping to understand the method and core idea of the present application; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in light of the ideas of the present application, the present description should not be construed as limiting the present application.

Claims (9)

1. The preparation method of avobenzone is characterized by comprising the following steps of:
mixing p-tert-butyl benzoate with a catalyst to obtain a mixed material;
adding p-methoxy acetophenone into a reaction vessel, stirring and heating;
dropwise adding the mixture into the reaction container under the protection of inert gas or in a vacuum state, and carrying out heat preservation reaction after the dropwise adding is finished to obtain a reaction material;
treating the reaction material to obtain an avobenzone product;
In the step of mixing p-tert-butyl benzoate with a catalyst to obtain a mixed material, the catalyst is a solid catalyst or an alcohol solution of the catalyst, and the catalyst is at least one of sodium alkoxide and potassium alkoxide;
The molar ratio of the catalyst to the p-methoxyacetophenone is (0.8-2.0): 1, wherein the molar ratio of the p-tert-butyl benzoate to the p-methoxyacetophenone is (2.0-20.0): 1.
2. The method according to claim 1, wherein the solid catalyst has a particle size of 5 to 500 μm.
3. The method according to claim 2, wherein the particle size of the solid catalyst is 150 to 300 μm.
4. The method according to claim 1, wherein the solvent of the alcoholic solution of the catalyst is at least one selected from the group consisting of methanol, ethanol, propanol and butanol, and the concentration of the catalyst in the alcoholic solution of the catalyst is 10% to 40%.
5. The method according to claim 1, wherein the p-tert-butyl benzoate is at least one selected from the group consisting of methyl p-tert-butylbenzoate, ethyl p-tert-butylbenzoate, propyl p-tert-butylbenzoate and butyl p-tert-butylbenzoate.
6. The process according to any one of claims 1 to 5, wherein the process further comprises, before or after adding p-methoxyacetophenone to the reaction vessel:
adding p-tert-butyl benzoate to the reaction vessel;
Wherein the molar ratio of the p-tert-butyl benzoate added into the reaction vessel to the p-tert-butyl benzoate in the mixture is 1 (0.5-6).
7. The method according to claim 1, wherein in the step of adding p-methoxyacetophenone to the reaction vessel and stirring and heating, the temperature of stirring and heating is 60-90 ℃.
8. The method according to claim 1, wherein the inert gas is nitrogen and the vacuum degree is-0.070 Mpa to-0.099 Mpa.
9. The preparation method according to claim 1, wherein the dropwise addition time is 30 to 300min, the reaction temperature at the dropwise addition time is 60 to 90 ℃, the incubation time is 30 to 300min, and the incubation temperature is 60 to 90 ℃.
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