CN110092722B - Method for catalytic synthesis of 4-acyl aralkyl phenol derivative - Google Patents
Method for catalytic synthesis of 4-acyl aralkyl phenol derivative Download PDFInfo
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- CN110092722B CN110092722B CN201910476976.9A CN201910476976A CN110092722B CN 110092722 B CN110092722 B CN 110092722B CN 201910476976 A CN201910476976 A CN 201910476976A CN 110092722 B CN110092722 B CN 110092722B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for catalytically synthesizing a 4-acyl aralkyl phenol derivative. Under the catalytic action of modified attapulgite solid acid, cumylphenol and an acylating agent are catalyzed to generate a 4-acyl aralkyl phenol derivative, the solid catalyst is attapulgite clay, natural attapulgite clay is subjected to thermalization treatment at a certain temperature, and the acidity of the attapulgite clay is regulated and controlled by Lewis acid at different temperatures to catalyze the cumylphenol and the acylating agent to generate the 4-acyl aralkyl phenol derivative. The reaction has the characteristics of mild reaction conditions, low cost of the used catalyst, environmental friendliness, simple process, easy separation of the catalyst, reusability and the like.
Description
Technical Field
The invention belongs to the field of synthesis of small molecular compounds, and relates to a method for catalytically synthesizing a 4-acyl aralkyl phenol derivative.
Background
The triphenol compounds are mainly used as raw materials of high molecular compounds such as epoxy resin, polycarbonate and the like, and can also be used as photoresist and additives of the high molecular compounds. The 4-acyl aralkyl phenol derivative is an important intermediate for synthesizing triphenol compounds.
At present, the main method for synthesizing the 4-acyl aralkyl phenol derivative serving as the triphenol compound precursor is mainly synthesis of isopropenyl acetophenone and phenols. (patent document: Japanese patent laid-open publication No. S62-084035). It is well known that raw material isopropenylacetophenone is not only active and difficult to preserve, but also high in price and low in synthesis yield. In contrast, a known synthesis method using a p-cumylphenol compound as a raw material (patent document: CN 107011124A) catalyzes a reaction between the p-cumylphenol compound and an acylating agent using aluminum trichloride as a catalyst. The catalyst is not easy to recycle, and the waste water after reaction contains a large amount of aluminum salt, which causes certain harm to the environment. Therefore, a green and efficient catalyst is required for synthesizing the 4-acyl aralkyl phenol derivative.
Disclosure of Invention
The invention aims to provide an economical and green preparation method of a 4-acyl aralkyl phenol derivative, the process is environment-friendly, the condition is mild, and the catalyst can be reused, so that the defects of serious pollution, more waste liquid, complex post-treatment and the like in the prior art are overcome.
Another object of the present invention is to provide a green and highly efficient catalyst for the catalytic synthesis of 4-acylaralkylphenol derivatives.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for catalytically synthesizing a 4-acyl aralkyl phenol derivative is characterized in that modified attapulgite solid acid is used as a catalyst, p-cumylphenol and an acylation reagent are catalyzed to generate the 4-acyl aralkyl phenol derivative, wherein the modified attapulgite solid acid catalyst is obtained by using attapulgite as a precursor, modifying the attapulgite with acid through protonic acid or Lewis acid, and roasting and activating the modified attapulgite solid acid catalyst at the temperature of 100-1000 ℃; the reaction route is as follows:
the acylating agent is selected from
Wherein X is a halogen atom. X ═ Cl, Br
When the catalyst is prepared, the Lewis acid is preferably tetrabutyl titanate, stannic chloride pentahydrate, ammonium metatungstate and tantalum pentachloride, the weight ratio of the Lewis acid to the attapulgite is preferably 1:1-20, and the roasting activation time is preferably 1-24 hours. Further preferably, the Lewis acid is tin tetrachloride pentahydrate, and the roasting activation time is 2-5 hours.
The acylating agent is preferably acetyl chloride, acetyl bromide, acetic acid or acetic anhydride. Acetyl chloride is further preferred.
The molar ratio of p-cumylphenol to the acylating agent is preferably 1:2 to 4, more preferably 1: 3.
The reaction solvent is preferably dichloromethane, chloroform, toluene and dichloroethane; dichloromethane is preferred.
The reaction temperature for catalytically synthesizing the 4-acyl aralkyl phenol derivative is preferably 0-30 ℃, and the reaction time is preferably 2-4 h.
The weight ratio of the p-cumylphenol to the modified attapulgite solid acid catalyst is preferably 1:1-2, more preferably 1:1.3-1.7, and most preferably 1: 1.5.
As a further optimization of the method of the invention, a reaction solvent and a catalyst are added into a reaction vessel, an acylating agent is dripped at room temperature, after the dripping is finished, the mixture is stirred for a plurality of minutes, p-cumylphenol is added, after the dripping is finished, the mixture is kept warm and stirred for reaction, a solid catalyst is separated and filtered, the filtrate is poured into ice water, the reaction solvent is added for extraction, layering and water washing are carried out, the solvent is evaporated in a rotary manner, a target product 4-acyl aralkyl phenol derivative is obtained, and the filtered solid catalyst can be reused after being activated.
Preferably, in the reaction, the acylating agent acetyl chloride is added at 10 ℃, after the addition, the reaction is carried out at 25 ℃ for the best time, and the best reaction time is 2.5 h.
Preferably, the catalyst is obtained by using attapulgite clay as a precursor, modifying the attapulgite clay with Lewis acid and roasting and activating the attapulgite clay at the temperature of 600 ℃ at 300-.
Preferably, the solid catalyst of the immobilized tin oxide is prepared by baking tin tetrachloride pentahydrate and attapulgite at the temperature of 500 ℃ in a muffle furnace at the weight ratio of 1:15 and the stirring temperature of 45 ℃ for 48 hours.
The invention has the following advantages:
the solid acid catalyst used in the invention has high activity, good selectivity to products, environmental protection, insolubility in water, easy separation and low cost.
2, the natural mineral attapulgite is used as a catalyst precursor, so that the catalyst is economical and easy to obtain, the added value of mineral resources can be improved, and the development and utilization of the mineral resources in China are promoted.
3 the catalyst is simple to separate and can be repeatedly used, and the catalytic efficiency is not obviously reduced.
Detailed Description
The following examples further illustrate the present invention in detail, but the contents of the present invention are not limited thereto.
Example 1
A method for preparing a catalytic 4-acyl aralkyl phenol derivative comprises the following steps:
preparing a catalyst: taking 1.5g of attapulgite clay, adding 20mL of prepared 1M sulfuric acid, stirring at room temperature for 52h, standing and aging for 12h, centrifugally separating out lower-layer precipitates, washing with water until the pH value becomes neutral, drying at 60 ℃, grinding, drying in a vacuum drying oven at 110 ℃ for 2h, slowly heating to 300 ℃ in a muffle furnace, and activating for 3h to obtain the required catalyst, namely the sulfuric acid-treated attapulgite clay catalyst.
Acylation: 30mL of methylene chloride as a solvent was placed in a 100mL round-bottom flask, and 0.32g of the above catalyst was taken out and placed in the round-bottom flask. And (2) placing a magnetic stirrer into the round-bottom flask, placing the round-bottom flask into a 10 ℃ oil bath pot, keeping the temperature and stirring, slowly dropwise adding 0.213mL of acylation reagent acetyl chloride into the round-bottom flask, slowly adding 0.2121g of weighed p-cumylphenol into the round-bottom flask after dropwise adding, heating to 25 ℃, and stirring and refluxing for 2.5 hours.
And (3) filtering: and (3) separating the solid catalyst from the reaction system liquid by decompression separation of the system.
Washing with water: the filtered liquid is poured into a pear-shaped separating funnel, and 100ml of ice water is added for shaking and washing. After standing, 30ml of dichloromethane was added for extraction. Standing for layering, and separating the lower layer solution.
And (3) rotary steaming: the lower layer solution is decompressed and evaporated to remove the solvent. Only the esterified product was obtained, and the desired 4-acylaralkylphenol was not obtained.
Examples 2 to 3
The same as in example 1 was repeated except that the protonic acid added in the preparation of the catalyst was changed. The results are shown in Table 1
TABLE 1
Examples 1-3 it can be seen that protonic acids are not suitable for use in the preparation of catalysts for catalyzing 4-acylaralkylphenol derivatives.
Example 4
A method for preparing a catalytic 4-acyl aralkyl phenol derivative comprises the following steps:
preparing a catalyst: taking 1.5g of attapulgite clay, adding 10mL of prepared 0.1g of stannic chloride pentahydrate aqueous solution, stirring for 48h at 45 ℃, standing and aging for 12h, drying for 12h in a forced air drying oven, slowly heating to 500 ℃ in a muffle furnace, and activating for 3h to obtain the required catalyst.
Acylation: 30ml of methylene chloride as a solvent was put into a 100ml round-bottom flask, and 0.32g of the above catalyst was taken out and put into the round-bottom flask. Putting a magnetic stirrer into the round-bottom flask, placing the round-bottom flask in a 10 ℃ oil bath, keeping the temperature and stirring, taking 0.213ml (3mol) of acylation reagent acetyl chloride, slowly dropwise adding the acetyl chloride into the round-bottom flask, slowly adding weighed 0.2121g of p-cumylphenol into the round-bottom flask after dropwise adding, heating to 25 ℃, and carrying out stirring reflux reaction for 2.5 hours.
And (3) filtering: and (3) separating the solid catalyst from the reaction system liquid by decompressing and separating the system.
Washing with water: pouring the filtered liquid into a pear-shaped separating funnel, adding 100ml of ice water, and washing by shaking. After standing, 30ml of dichloromethane was added for extraction. Standing for layering, and separating the lower layer solution.
And (3) rotary steaming: the solution was evaporated under reduced pressure. The expected product is obtained in 84% yield. The target product is confirmed to be 4-acyl aralkyl phenol through nuclear magnetic spectrum.
1 H NMR(400MHz,CDCl 3 )δ(ppm)1.69(s,6H,2×CH 3 ),2.28(s,3H,OCOCH 3 ),2.57(s,3H,CH 3 CO),6.99(d,J＝5.76,2H,ArH),7.20(d,J＝5.64,2H,ArH),7.32(d,J＝5.48,2H,ArH),7.87(d,J＝5.84,2H,ArH)
Catalyst reactivation: the solid obtained in the filtration step was washed clean with distilled water and activated in a muffle furnace at 500 ℃ for three hours for further use.
Examples 5 to 7
The same as in example 4 was followed except that the Lewis acid added in the catalyst preparation was changed. The results are shown in Table 2.
TABLE 2
Examples 4-7 show that the catalyst prepared by using the stannic chloride pentahydrate modified attapulgite clay is significantly superior to other Lewis acids in terms of selectivity and catalytic efficiency.
Examples 8 to 10
The same as in example 4 is followed except that the mass of the attapulgite clay in the catalyst preparation is changed and the mass ratio of the Lewis acid to the attapulgite clay is adjusted. The results are shown in Table 3:
TABLE 3
Examples 11 to 13
The same as in example 4 was repeated except that the solvent used in the acylation reaction was changed. The results are shown in Table 4:
TABLE 4
Examples 14 to 16
The same as in example 4 is followed except that the acylating agent in the acylation reaction is changed. The results are shown in Table 5:
TABLE 5
Examples 17 to 18
The same procedure as in example 4 was repeated except that the amount of acetyl chloride used in the acylation reaction was changed. The results are shown in Table 6:
TABLE 6
Examples 19 to 21
The same as in example 4 was repeated except that the reaction temperature in the acylation reaction was changed. The results are shown in Table 7:
TABLE 7
Examples 22 to 24
The reaction time in the acylation reaction was changed only, and the rest was the same as in example 4. The results are shown in Table 8:
TABLE 8
Examples 25 to 28
The recovered catalyst was used, and the rest was the same as in example 4. The results are shown in Table 9:
TABLE 9
The above examples show that the 4-acyl aralkyl phenol derivative is prepared by using attapulgite clay as a catalyst precursor and modifying the attapulgite clay with different acids to react cumylphenol with an acylating agent. Compared with the Lewis acid catalysis process, the catalysis process is green and pollution-free, and the catalyst can be repeatedly used, thereby showing good industrial application prospect.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (8)
1. A method for catalytically synthesizing a 4-acyl aralkyl phenol derivative is characterized in that modified attapulgite solid acid is used as a catalyst, p-cumylphenol and an acylation reagent are catalyzed to generate the 4-acyl aralkyl phenol derivative, wherein the modified attapulgite solid acid catalyst is obtained by using attapulgite clay as a precursor, modifying the attapulgite clay with acid by stannic chloride pentahydrate, and roasting and activating at the temperature of 300-600 ℃; the weight ratio of the tin tetrachloride pentahydrate to the attapulgite clay is 1:1-20, and the roasting activation time is 2 hours to 5 hours; the reaction route is as follows:
the acylating agent is selected from
Wherein X is Br or Cl.
2. The method for the catalytic synthesis of a 4-acylaralkylphenol derivative according to claim 1, wherein the reaction solvent for the catalytic synthesis of the 4-acylaralkylphenol derivative is selected from the group consisting of dichloromethane, chloroform, toluene and dichloroethane.
3. The method for the catalytic synthesis of a 4-acylaralkylphenol derivative according to claim 2, wherein the reaction solvent for the catalytic synthesis of the 4-acylaralkylphenol derivative is selected from dichloromethane.
4. The method for the catalytic synthesis of 4-acylaralkylphenol derivatives according to claim 1, wherein the reaction temperature is 0-30 ℃ and the reaction time is 1-6 hours.
5. The process for the catalytic synthesis of 4-acylaralkylphenol derivatives according to claim 1, characterized in that the molar ratio of p-cumylphenol to acylating agent is 1: 2-3.
6. The catalytic synthesis method of 4-acyl aralkyl phenol derivatives according to claim 1, wherein the weight ratio of the p-cumylphenol to the modified attapulgite solid acid catalyst is 1: 1-2.
7. The catalytic synthesis method of 4-acyl aralkyl phenol derivatives of claim 6, wherein the weight ratio of the p-cumylphenol to the modified attapulgite solid acid catalyst is 1: 1.5-1.7.
8. The method for catalytically synthesizing a 4-acylaralkylphenol derivative according to any one of claims 1 to 7, characterized in that a reaction solvent and a catalyst are added to a reaction vessel, an acylating agent is dropped at room temperature, the mixture is stirred for several minutes after the dropping, p-cumylphenol is added, the mixture is stirred at a constant temperature after the addition, the solid catalyst is separated and filtered, the filtrate is poured into ice water, the reaction solvent is added for extraction, the mixture is layered, washed with water, and the solvent is evaporated by rotation to obtain the target product, namely the 4-acylaralkylphenol derivative, and the filtered solid catalyst can be reused after being activated.
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| US4803268A (en) * | 1984-10-02 | 1989-02-07 | Ciba-Geigy Corporation | Process for the preparation of cyclohexanedionecarboxylic acid derivatives |
| CN101987299A (en) * | 2009-08-06 | 2011-03-23 | 中国科学院兰州化学物理研究所 | Attapulgite clay-supported heteropoly acid phase-transfer catalyst for oxidative desulfurization of fuel |
| CN104211588A (en) * | 2009-05-19 | 2014-12-17 | 本州化学工业株式会社 | 4-acylaralkylphenol derivative |
| CN105013514A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | attapulgite clay loaded Lewis acid catalyst, preparation method and applications thereof |
| CN109569579A (en) * | 2018-12-26 | 2019-04-05 | 淮南安信泰科技有限公司 | A kind of method of the immobilized tungsten oxide preparation tributyl citrate of attapulgite clay |
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| CN102806063B (en) * | 2012-09-04 | 2014-09-17 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Preparation method of attapulgite clay adsorbent for degumming and decoloration of palm oil |
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| US4803268A (en) * | 1984-10-02 | 1989-02-07 | Ciba-Geigy Corporation | Process for the preparation of cyclohexanedionecarboxylic acid derivatives |
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| CN101987299A (en) * | 2009-08-06 | 2011-03-23 | 中国科学院兰州化学物理研究所 | Attapulgite clay-supported heteropoly acid phase-transfer catalyst for oxidative desulfurization of fuel |
| CN105013514A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | attapulgite clay loaded Lewis acid catalyst, preparation method and applications thereof |
| CN109569579A (en) * | 2018-12-26 | 2019-04-05 | 淮南安信泰科技有限公司 | A kind of method of the immobilized tungsten oxide preparation tributyl citrate of attapulgite clay |
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