CN115069250B - Catalyst for directly synthesizing alpha-methoxy phenylacetic acid by serial catalysis of styrene and methanol and preparation method thereof - Google Patents

Catalyst for directly synthesizing alpha-methoxy phenylacetic acid by serial catalysis of styrene and methanol and preparation method thereof Download PDF

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CN115069250B
CN115069250B CN202210881943.4A CN202210881943A CN115069250B CN 115069250 B CN115069250 B CN 115069250B CN 202210881943 A CN202210881943 A CN 202210881943A CN 115069250 B CN115069250 B CN 115069250B
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catalyst
styrene
methanol
alpha
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CN115069250A (en
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刘江永
卢严烨
菅盘铭
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Yangzhou University
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Yangzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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

Abstract

The invention discloses a catalyst for directly synthesizing alpha-methoxy phenylacetic acid by serial catalysis of styrene and methanol and a preparation method thereof, wherein the catalyst is prepared from copper-cobalt composite metal oxide Co 3 O 4 /CuCo 2 O 4 The composition comprises Cu and Co in a molar ratio of 1:5-1:3. By Co 3 O 4 /CuCo 2 O 4 The catalyst is prepared through serial epoxidation of styrene and ring-opening alcoholysis of epoxy phenylethane, adding styrene, methanol and oxidant and one-step process. The catalyst disclosed by the invention is simple in preparation method and low in preparation cost, the method for synthesizing the alpha-methoxy phenylacetic acid is a heterogeneous catalytic system, the reaction effect is good, the catalyst is easy to recycle, and the catalyst has a good industrial application prospect.

Description

Catalyst for directly synthesizing alpha-methoxy phenylacetic acid by serial catalysis of styrene and methanol and preparation method thereof
Technical Field
The invention relates to a copper-cobalt composite oxide catalyst for directly synthesizing alpha-methoxyphenylacetic acid by using styrene and methanol in series catalysis and a preparation method thereof, belonging to the technical field of preparation of alpha-methoxyphenylacetic acid.
Background
Alpha-methoxyphenylacetic acid is the key side chain of the antitumor drug N- [5- ((2R) -2-methoxy-2-phenylacetyl) -1,4,5, 6-tetrahydropyrrolo [3,4-C ] pyrazol-3-yl ] -4- (4-methylpiperazin-1-yl) benzamide (PHA 739358), and it is also an important raw material or intermediate for the preparation of other organic substances. In the conventional production of alpha-methoxyphenylacetic acid, the alpha-hydroxybenzoic acid and some methylation reagents are mostly adopted for etherification, and then the alpha-hydroxybenzoic acid is separated by a NaCl crystallization method, but the post-treatment process of the method is complex, takes long time and is easy to produce toxic wastes (ChemPhotoChem 5 (2021) 235; J.am.chem.Soc.,83 (1961) 2755-2759).
In the epoxidation of styrene, alpha-methoxyphenylacetic acid is obtained as a by-product in the presence of methanol. However, such processes reported to date are all homogeneous catalytic systems using expensive and complex iron (III) complexes of bis-benzimidazolyl diamide ligands ([ Fe (p-GBBA) Cl) 2 ]Cl) (J.mol. Structure, 1011 (2012) 166-171) or arene ruthenium (II) complexes containing bis (pyrazolyl) methane ligands (Inorg. Chem.,47 (2008) 11593-11603) as catalysts. In addition, the catalyst in such systems is difficult to recycle and αThe selectivity to methoxyphenylacetic acid is very low. Therefore, a simple heterogeneous catalytic system with excellent performance is sought to synthesize the alpha-methoxy phenylacetic acid, and the method has very important practical significance.
Disclosure of Invention
In order to achieve the above purpose, the invention aims to provide a copper-cobalt composite oxide catalyst which can be applied to the direct synthesis of alpha-methoxyphenylacetic acid by the serial catalysis of styrene and methanol and a preparation method thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a catalyst for directly synthesizing alpha-methoxyphenylacetic acid by serial catalysis of styrene and methanol consists of copper-cobalt composite metal oxide Co3O4/CuCo2O4, wherein the molar ratio of Cu to Co is 1:5-1:3.
The preparation method of the catalyst comprises the following steps:
dissolving copper nitrate trihydrate, cobalt nitrate hexahydrate and urea in a mixed solution of deionized water and glycerol, uniformly stirring, transferring the solution into a hydrothermal kettle, keeping the temperature at 160-200 ℃ for 10-18 hours, cooling to room temperature, filtering, washing with deionized water and ethanol, drying and calcining to obtain the Co3O4/CuCo2O4 catalyst.
Further, the molar ratio of copper nitrate trihydrate, cobalt nitrate hexahydrate and urea is 2:4:25.
Further, the drying temperature is 60-120 ℃ and the drying time is 10-18 h; the calcination temperature is 400-600 ℃, and the calcination time is 1-4 h.
The catalyst is applied to catalyzing styrene and methanol to synthesize alpha-methoxy phenylacetic acid, and is characterized in that Co3O4/CuCo2O4 is used as a catalyst, styrene epoxidation and ring-opening alcoholysis reaction of styrene oxide are connected in series, and styrene, methanol and an oxidant are added to directly prepare the product alpha-methoxy phenylacetic acid by a one-step method.
Further, the catalyst is used in an amount of 3.2 to 9.6wt.% of styrene.
Further, the reaction temperature of the one-step method is 70-90 ℃.
Further, the oxidant is tert-butyl hydroperoxide.
Further, the molar ratio of the styrene to the oxidant is 1:2-1:4.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the copper-cobalt composite metal catalyst is simple and has low preparation cost.
(2) The method for synthesizing the alpha-methoxy phenylacetic acid is a heterogeneous catalytic system, effectively connects the epoxidation of styrene and the ring-opening alcoholysis reaction of the epoxy phenylethane in series, has high styrene conversion rate, good selectivity of the alpha-methoxy phenylacetic acid, mild reaction system conditions, easy operation, and good industrial application prospect, and can recycle the catalyst.
Drawings
FIG. 1 is Co prepared in example 1 3 O 4 /CuCo 2 O 4 XRD pattern of the catalyst.
FIG. 2 is Co prepared in example 1 3 O 4 /CuCo 2 O 4 SEM image of the catalyst.
FIG. 3 is Co prepared in example 1 3 O 4 /CuCo 2 O 4 TEM image of catalyst.
FIG. 4 is Co prepared in example 1 3 O 4 /CuCo 2 O 4 HRTEM images of catalyst.
Example 1
Weigh 2mmol Cu (NO) 3 ) 2 ·3H 2 O、4mmol Co(NO 3 ) 2 ·6H 2 Dissolving O and 1.5g urea in a mixed solution of 40mL deionized water and 2mL glycerol, stirring uniformly, transferring the solution into a hydrothermal kettle, keeping the temperature at 180 ℃ for 12 hours, cooling to room temperature, filtering, washing with deionized water and ethanol, drying a filter cake at 80 ℃ for 12 hours, and roasting at 500 ℃ for 2 hours to obtain Co 3 O 4 /CuCo 2 O 4 A catalyst.
The prepared catalyst is used for the reaction of directly synthesizing alpha-methoxy phenylacetic acid by serial catalysis of styrene and methanolIs a kind of medium. 0.1g of Co 3 O 4 /CuCo 2 O 4 The catalyst was added to 0.015mol of styrene, 0.045mol of t-butyl hydroperoxide and 16mL of methanol, and reacted at 80℃under normal pressure for 7 hours, and the obtained product was analyzed by gas chromatography, as a result, it was found that the conversion of styrene reached 94.8% and the selectivity of alpha-methoxyphenylacetic acid reached 62.5%. In addition, the cycle test performance shows that the catalytic activity and the selectivity of the alpha-methoxyphenylacetic acid are not obviously reduced after five times of continuous use of the prepared catalyst.
FIG. 1 contains Co prepared in example 1 3 O 4 /CuCo 2 O 4 XRD pattern of the catalyst;
FIG. 2 is Co prepared in example 1 3 O 4 /CuCo 2 O 4 SEM image of the catalyst;
FIG. 3 is Co prepared in example 1 3 O 4 /CuCo 2 O 4 TEM image of catalyst;
FIG. 4 is Co prepared in example 1 3 O 4 /CuCo 2 O 4 HRTEM images of catalyst.
Comparative example 1
The same as in example 1, except that no catalyst was added. The catalytic performance test was carried out in the same manner as in example 1, and the result after 7 hours of reaction showed that: the styrene conversion was 4.4% and the selectivity to alpha-methoxyphenylacetic acid was 11.0%.
Example 2
Example 1 was repeated, except that 0.05g of Co was added 3 O 4 /CuCo 2 O 4 The catalyst is put into a reaction kettle. Under the same other reaction conditions, the conversion of styrene was 70.0% and the selectivity of α -methoxyphenylacetic acid was 56.0%.
Example 3
Example 1 was repeated, except that 0.15g of Co was added 3 O 4 /CuCo 2 O 4 The catalyst is put into a reaction kettle. Under the same other reaction conditions, the conversion of styrene was 95.0% and the selectivity of α -methoxyphenylacetic acid was 53.4%.
Example 4
Example 1 was repeated, except that the catalytic reaction temperature was 70 ℃. Under the same reaction conditions, the conversion of styrene was 81.0% and the selectivity of α -methoxyphenylacetic acid was 62.0%.
Example 5
Example 1 was repeated, except that the catalytic reaction temperature was 90 ℃. Under the same other reaction conditions, the conversion of styrene was 99.5% and the selectivity of α -methoxyphenylacetic acid was 49.4%.
Example 6
Example 1 was repeated, except that the molar ratio of styrene to t-butyl hydroperoxide was 1:2. Under the same reaction conditions, the conversion of styrene was 71.5% and the selectivity of α -methoxyphenylacetic acid was 41.5%.
Example 7
Example 1 was repeated, except that the molar ratio of styrene to t-butyl hydroperoxide was 1:4. Under the same other reaction conditions, the conversion of styrene was 95.4% and the selectivity of α -methoxyphenylacetic acid was 56.9%.
Example 8
Example 1 was repeated with the difference that the catalytic reaction time was 5h. Under otherwise identical reaction conditions, the conversion of styrene was 78.0% and the selectivity of α -methoxyphenylacetic acid was 58.0%.
Example 9
Example 1 was repeated with the difference that the catalytic reaction time was 6h. Under the same other reaction conditions, the conversion of styrene was 89.2%, and the selectivity of α -methoxyphenylacetic acid was 58.2%.
Example 10
Example 1 was repeated with the difference that the catalytic reaction time was 8h. Under the same other reaction conditions, the conversion of styrene was 97.2%, and the selectivity of α -methoxyphenylacetic acid was 60.3%.
From the above experimental results, the following conclusions can be drawn: (1) When the catalyst amount was increased from 0.05g to 0.15g, the styrene conversion was significantly increased because the active sites of the reaction were increased as the catalyst amount increased. Although the conversion rate was improved, the selectivity of α -methoxyphenylacetic acid was lowered because more benzaldehyde was formed as a byproduct. The selectivity of alpha-methoxyphenylacetic acid is highest when the catalyst amount is 0.1g, and from a comprehensive point of view, 0.1g of the catalyst should be selected. (2) The conversion of styrene increases with increasing reaction temperature, while the selectivity for alpha-methoxyphenylacetic acid decreases with increasing reaction temperature. The high temperature is beneficial to the improvement of the reactivity, but side reactions exist, such as styrene can generate benzaldehyde more easily under the environment of higher temperature, and Cheng Huanyang phenylethane is not generated easily so as to react with methanol again. The reaction temperature of 80℃is a preferred reaction parameter in view of catalytic activity and selectivity. (3) The conversion of styrene increases significantly as the ratio of styrene to TBHP increases from 1:2 to 1:3. However, this does not represent the higher the amount of oxidant used, since there is only a slight increase in conversion when the styrene to TBHP ratio is increased to 1:4. Moreover, too much amount of the oxidizing agent affects the selectivity of α -methoxyphenylacetic acid, because as the amount of the oxidizing agent becomes larger, the concentration of the oxidizing agent becomes larger, resulting in a stronger oxidizing ability such that c=c of the styrene side chain is liable to be broken, and a large amount of by-products are generated. Therefore, the ratio of styrene to TBHP is 1:3, which is the most suitable condition. (4) In the early stage of the reaction, the conversion rate of the styrene is rapidly increased along with the increase of the reaction time, and the conversion rate of the styrene is slowly increased after 7 hours until the conversion rate reaches almost 100% at 9 hours. The selectivity of alpha-methoxyphenylacetic acid also increased gradually over time but decreased slightly after 7 hours because alpha-methoxyphenylacetic acid reacted with methanol to form some ester by-products. In the sum, the yield of the obtained alpha-methoxyphenylacetic acid was highest during the reaction for 7 hours.
It will be readily appreciated by those skilled in the art that the foregoing description of the embodiments has been provided for the purpose of illustration only and not for the purpose of limiting the invention, and that any such extensions, modifications, alternatives, improvements etc. that fall within the spirit and principles of the invention shall fall within the scope of the present invention.

Claims (7)

1. A catalyst for directly synthesizing alpha-methoxyphenylacetic acid by serial catalysis of styrene and methanol is characterized by comprising a copper-cobalt composite metal oxide Co 3 O 4 /CuCo 2 O 4 The composition comprises the following components, wherein the molar ratio of Cu to Co is 1:5-1:3;
the preparation method of the catalyst comprises the following steps:
dissolving copper nitrate trihydrate, cobalt nitrate hexahydrate and urea in a mixed solution of deionized water and glycerol, uniformly stirring, transferring the solution into a hydrothermal kettle, keeping the temperature at 160-200 ℃ for 10-18 hours, cooling to room temperature, filtering, washing with deionized water and ethanol, drying and calcining to obtain Co 3 O 4 /CuCo 2 O 4 A catalyst;
wherein the molar ratio of the copper nitrate trihydrate, the cobalt nitrate hexahydrate and the urea is 2:4:25.
2. The catalyst for directly synthesizing alpha-methoxyphenylacetic acid by serial catalysis of styrene and methanol as set forth in claim 1, wherein the drying temperature is 60-120 ℃ and the drying time is 10-18 h; the calcination temperature is 400-600 ℃, and the calcination time is 1-4 hours.
3. The use of the catalyst according to claim 1 for catalyzing the synthesis of alpha-methoxyphenylacetic acid from styrene and methanol, wherein Co 3 O 4 /CuCo 2 O 4 The catalyst is prepared through serial epoxidation of styrene and ring-opening alcoholysis of epoxy phenylethane, adding styrene, methanol and oxidant and one-step process.
4. The use according to claim 3, wherein the catalyst is used in an amount of 3.2 to 9.6 wt% of styrene.
5. The use according to claim 3, wherein the one-step process has a reaction temperature of 70-90 ℃ and a reaction time of 5-8 h.
6. Use according to claim 3, wherein the oxidizing agent is t-butyl hydroperoxide.
7. The use according to claim 3, wherein the molar ratio of styrene to oxidant is 1:2 to 1:4.
CN202210881943.4A 2022-07-26 2022-07-26 Catalyst for directly synthesizing alpha-methoxy phenylacetic acid by serial catalysis of styrene and methanol and preparation method thereof Active CN115069250B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387908A (en) * 2021-05-31 2021-09-14 扬州大学 Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113387908A (en) * 2021-05-31 2021-09-14 扬州大学 Application of magnesium cobaltate catalyst in selective oxidation reaction of styrene

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