CN116041284A - Application of metal nitrogen turnover porphyrin-cobalt carbonyl multifunctional catalyst in preparation of beta-lactone by catalyzing epoxide - Google Patents

Application of metal nitrogen turnover porphyrin-cobalt carbonyl multifunctional catalyst in preparation of beta-lactone by catalyzing epoxide Download PDF

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CN116041284A
CN116041284A CN202211600026.0A CN202211600026A CN116041284A CN 116041284 A CN116041284 A CN 116041284A CN 202211600026 A CN202211600026 A CN 202211600026A CN 116041284 A CN116041284 A CN 116041284A
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porphyrin
nitrogen
metal
pyrrole
reversed
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CN116041284B (en
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黄家辉
任周
陈小艳
徐铮
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/31—Aluminium
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium

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Abstract

The invention discloses an application of a metal nitrogen turnover porphyrin-cobalt carbonyl multifunctional catalyst in preparing beta-lactone by catalyzing epoxide, belonging to the technical field of beta-lactone preparation. The catalyst disclosed by the invention consists of Lewis acid metal nitrogen eversion porphyrin and cobalt carbonyl, wherein the metal nitrogen eversion porphyrin is a special metal complex formed by the nitrogen eversion porphyrin and metal and is internally and externally fully coordinated, and a bimetallic site in the metal nitrogen eversion porphyrin is used for synergistically activating the ring opening process of the epoxide, so that the activation rate of the epoxide is improved; when the inner core of the nitrogen-turned porphyrin ligand is coordinated with the metal in the center, the metal cations in high valence state can be stabilized by adopting all deprotonation forms, so that the release of Lewis acid cations in the step of carbonylation reaction is accelerated, the beta-lactone is closed, and the selectivity of the beta-lactone is improved. The catalyst of the invention catalyzes epoxide to be converted into beta-lactone, has high activity and selectivity, and lays a foundation for industrial application of epoxide carbonylation reaction.

Description

Application of metal nitrogen turnover porphyrin-cobalt carbonyl multifunctional catalyst in preparation of beta-lactone by catalyzing epoxide
Technical Field
The invention belongs toThe technical field of beta-lactone preparation, in particular to a homogeneous phase metal nitrogen flip porphyrin-cobalt carbonyl [ Lewis acid ]] x+ [Co(CO) z ] y- The application of the multifunctional catalyst in catalyzing epoxide ring-expanding carbonylation to prepare beta-lactone.
Background
Beta-lactone is an important intermediate in chemical industry, and is an important monomer for synthesizing chemical products such as succinic anhydride, succinic acid, beta-hydroxy acid, acrylic acid, poly-beta-hydroxy fatty acid ester (PHA for short) and the like. PHA has wide application in the fields of degradable materials, food packaging, biomedicine, industrial fermentation and the like due to excellent biodegradability, environmental compatibility, biocompatibility and optical performance. Beta-lactones themselves can also be used in the medical industry as special disinfectants, and therefore, there is an increasing industrial demand for beta-lactones, but the synthesis of beta-lactones is somewhat challenging, limiting its industrial application.
The main synthetic route to beta-lactones is the carbonylation of epoxy compounds. The Alper problem group uses a single metal (Ph 3 P＝) 2 NCo(CO) 4 As main catalyst, with different Lewis acids BF 3 ·Et 2 O、B(C 6 F 5 ) 3 And SnCl 4 In order to catalyze the propylene oxide carbonylation reaction by the cocatalyst, the yield of the beta-butyrolactone is improved from 0% to 77% by adding the cocatalyst, and the catalyst has the problems of poor capability of activating epoxy compounds by Lewis acid and low carbonylation activity. Rieger group found Co 2 (CO) 8 /AlR 3 (r=me, et, bu) catalyzed carbonylation of propylene oxide at 95 ℃ for 2 hours under 6.0MPa CO with 100% PO conversion and 92% β -butyrolactone selectivity, using a simple lewis acid AlR 3 The activity of the catalyst is improved to a certain extent, but the acidity of the Lewis acid is strong, the rate of ring closure of carbonylation reaction into ester is influenced, the selectivity of beta-butyrolactone is low, and the catalyst is only limited to catalyzing carbonylation of propylene oxide and has no universality to other epoxy compounds. Classical homogeneous bimetallic [ Lewis acid ] developed by Coates topic group] + [Co(CO) 4 ] - The catalyst takes metal as a center, porphyrin (porphyrine=tpp) derivative, salen (salen) derivative and phthalocyanine derivative as ligands to form a metal complex, and the special Lewis acid cation and cobalt carbonyl anion in the catalyst improve the activity and selectivity of carbonylation, but the catalyst can enable epoxy compounds to carry out double carbonylation reaction to generate anhydride, and reduce the selectivity of beta-lactone.
[Lewis acid] + [Co(CO) 4 ] - The reaction mechanism of the catalyst for catalyzing the carbonylation of epoxide is as follows: (1) [ Lewis acid ]] + Activating an epoxy compound; (2) [ Co (CO) 4 ] - Attack the activated epoxide to form a ring-opened intermediate; (3) CO intercalates CO-alkyl bonds to form CO-acyl bonds; (4) ring closure to release the catalyst to form beta-lactone.
Currently reported [ Lewis acid ]] + [Co(CO) 4 ] - The process of catalyzing the epoxide carbonylation reaction remains to be investigated in three ways: (1) The Lewis acid reported at present is mainly coordinated with central metal through N, O ligand to form a central coordinated mononuclear metal complex, and other coordination forms and polynuclear metal coordinated complexes are still to be explored; (2) The activity and selectivity of the catalysts reported so far remain to be further improved; (3) Most of the catalysts reported so far require the catalysis of epoxide carbonylation reactions at high pressure.
Thus, a metal complex [ Lewis acid ] having a novel coordination form was developed] x+ [Co(CO) z ] y- The catalyst has high activity and selectivity when catalyzing the carbonylation of epoxide in a kettle reactor under mild conditions, and can further promote the application of homogeneous catalyst in industry.
Disclosure of Invention
The technical problems described in the background art are solved. The invention aims to provide a [ Lewis acid ]] x+ [Co(CO) z ] y- The catalyst is applied to the preparation of beta-lactone by catalyzing epoxide ring-expanding carbonylation. The catalyst of the invention is formed by turning porphyrin and metal nitrogen by Lewis acidThe multifunctional catalyst consists of cobalt carbonyl as the anion and metal nitrogen turning porphyrin as the metal complex with special structure and with complete internal and external coordination formed by nitrogen turning porphyrin ligand, cr and Al. The Lewis acid has a coordination structure of a stable inner core and a flexible outer bimetallic site, and the bimetallic site in the structure cooperates with the ring opening process of the activated epoxide, so that the activation rate of the epoxide is improved; when the inner core of the nitrogen-turned porphyrin ligand is coordinated with the metal in the center, the metal cations in high valence state (J.Am.chem.Soc.2002, 124, 5622) can be stabilized by adopting all deprotonation forms, so that the release of Lewis acid cations in the step of carbonylation reaction is accelerated, beta-lactone ring closure is realized, the selectivity of beta-lactone is improved, and in a kettle reactor, the metal nitrogen-turned porphyrin-cobalt carbonyl catalyst can catalyze epoxide to beta-lactone with high activity and high selectivity, thereby laying a foundation for industrial application of epoxide carbonylation reaction.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a [ Lewis acid ]] x+ [Co(CO) z ] y- The application of the multifunctional catalyst in preparing beta-lactone by catalyzing epoxide is shown in a formula (I) or a formula (II),
Figure BDA0003997081220000031
the catalyst consists of Lewis acid metal nitrogen eversion porphyrin and cobalt carbonyl, wherein the metal nitrogen eversion porphyrin is an internal and external full-coordination metal complex formed by nitrogen eversion porphyrin ligand or pyrrole-substituted nitrogen eversion porphyrin ligand and metal, and is a metal M coordinated with the inner core and the outer periphery of the ligand 1 One or more than two of Ga, zn, cr, fe, al, rh, mn, ni, cu; cobalt carbonyl is [ Co (CO) z ] y- 。
Based on the technical scheme, preferably, the metal M 1 Al and Cr are preferred.
Based on the technical scheme, the nitrogen-reversed porphyrin ligand and the nitrogen-reversed porphyrin ligand are preferableR in pyrrole substituted nitrogen-flipped porphyrin ligand is H, CH 3 、OCH 3 One or more of F, cl is preferably H or Cl.
Based on the above technical scheme, preferably, x is an integer from 1 to 3, representing the cationic charge on the lewis acid; z is 3 or 4 and represents the number of carbonyl groups in the cobalt carbonyl anion; y is an integer of 1-3, and represents the number of cobalt carbonyl anions.
Based on the technical scheme, the [ Co (CO) z ] y- Preferably [ Co (CO) 4 ] - 。
Based on the technical scheme, preferably, the preparation method of the metal nitrogen-everted porphyrin-cobalt carbonyl or metal pyrrole-substituted nitrogen-everted porphyrin-cobalt carbonyl catalyst mainly comprises the following steps of:
combining an aluminum-coordinated nitrogen-reversed porphyrin complex or an aluminum-coordinated pyrrole-substituted nitrogen-reversed porphyrin complex with [ Co (CO) ] 4 ] - Dissolving in solvent, stirring at-50-30 deg.c for 2-12 hr, filtering, washing and vacuum drying to obtain the said product;
or chromium-coordinated nitrogen-reversed porphyrin complex or chromium-coordinated pyrrole-substituted nitrogen-reversed porphyrin complex [ Co (CO) ] 4 ] - Dissolving in solvent, stirring at-50-30 deg.c for 2-12 hr, filtering, washing and vacuum drying.
Based on the above technical scheme, preferably, the solvent is one or more than two of ethylene glycol dimethyl ether (DME), tetrahydrofuran (THF), tetrahydropyran, 2-methyltetrahydrofuran, 1, 4-dioxane, toluene, 1, 2-difluorobenzene and diethyl ether, and preferably the solvent is tetrahydrofuran; the drying temperature is 25-120 ℃.
Based on the above technical scheme, preferably, the preparation method of the metal coordinated nitrogen-reversed porphyrin complex and pyrrole substituted nitrogen-reversed porphyrin complex mainly comprises the following steps:
dissolving nitrogen-reversed porphyrin ligand or pyrrole-substituted nitrogen-reversed porphyrin ligand into solvent, adding Et under inert atmosphere 2 AlCl，Et 2 The molar ratio of AlCl to nitrogen-reversed porphyrin ligand or pyrrole-substituted nitrogen-reversed porphyrin ligand is 3-6, and the room temperature condition isStirring and reacting for 2-10 h, vacuum drying the reaction liquid, purifying the solid product by a silica gel column, and vacuum drying at 40-120 ℃ for 2-8 h to obtain the solid product;
alternatively, the nitrogen-reversed porphyrin ligand or pyrrole-substituted nitrogen-reversed porphyrin ligand is dissolved in a solvent, and CrCl is added 3 ，CrCl 3 The molar ratio of the raw materials to the nitrogen-turned porphyrin-based ligand or pyrrole-substituted nitrogen-turned porphyrin-based ligand is 4-8, stirring and reacting for 2-10 hours at 70-200 ℃, vacuum drying the reaction liquid, filtering the crude product by a sand core funnel, washing 1-10 times by methylene dichloride, and vacuum drying for 2-8 hours at 40-120 ℃ to obtain the product.
Based on the above technical scheme, preferably, the solvent used for preparing the aluminum coordinated nitrogen-reversed porphyrin complex and the aluminum coordinated pyrrole-substituted nitrogen-reversed porphyrin complex is one of chloroform, dichloromethane, methanol, ethanol, diethyl ether and tetrahydrofuran, and the preferred solvent is dichloromethane; the solvent used for preparing the chromium coordinated nitrogen-reversed porphyrin complex and the chromium coordinated pyrrole-substituted nitrogen-reversed porphyrin complex is one or two of N, N-dimethylformamide or azomethyl pyrrolidone, and the solvent is preferably N, N-dimethylformamide.
Based on the above technical scheme, preferably, the preparation method of the nitrogen-everting porphyrin ligand mainly comprises the following steps:
dissolving the newly steamed pyrrole and benzaldehyde or p-chlorobenzaldehyde in a solvent, adding methanesulfonic acid, stirring the mixed solution for 0.1-5 h under the condition of room temperature, adding chloranil as an oxidant, continuously stirring for 1-10 min, adding triethylamine, continuously stirring for 1-30 min, collecting a yellow-green color ribbon after a chromatographic column is filled with the reaction mixed solution, carrying out spin drying, further purifying, passing through the chromatographic column, collecting a yellow-green component after a mixed system of one or two of n-hexane/dichloromethane, n-hexane/chloroform and petroleum ether/ethyl acetate is used as an eluent, and carrying out spin drying to obtain the nitrogen-reversed porphyrin ligand.
Based on the technical scheme, preferably, the solvent is one or two of chloroform, dichloromethane, diethyl ether and tetrahydrofuran, and is preferably dichloromethane; the alumina packed in the column includes acidic alumina, neutral alumina and basic alumina, preferably neutral alumina.
Based on the above technical scheme, preferably, the preparation method of the pyrrole substituted nitrogen turnover porphyrin ligand mainly comprises the following steps:
adding the prepared nitrogen-turned porphyrin ligand into a three-mouth bottle, adding excessive freshly steamed pyrrole, adding N, N-dimethylformamide as a solvent, and adding BF 3 ·OEt 2 And (3) taking the mixture as a catalyst, refluxing and stirring for 1-5 h, spin-drying the reaction mixture, filling the reaction mixture into a chromatographic column with aluminum peroxide, taking dichloromethane or chloroform as an eluent, collecting a product, and spin-drying to obtain the pyrrole-substituted nitrogen turnover porphyrin ligand.
Based on the technical scheme, preferably, the molar ratio of the pyrrole to the nitrogen flip porphyrin ligand is 2-6, and the alumina filled in the chromatographic column comprises acidic alumina, neutral alumina and basic alumina, preferably neutral alumina.
Based on the above technical scheme, preferably, the [ Co (CO) 4 ] - The preparation method of the (C) mainly comprises the following steps:
co is to be 2 (CO) 8 Dissolving in solvent, adding strong alkali, stirring at room temperature for 2-12 hr, filtering, washing with solvent for several times, and vacuum drying at room temperature to obtain [ Co (CO) 4 ] - 。
Based on the above technical scheme, preferably, the solvent is one or two of tetrahydrofuran or tetrahydropyran, preferably the solvent is tetrahydrofuran; the strong alkali is one of sodium hydroxide and potassium hydroxide.
Based on the above technical scheme, preferably, the main reactor for preparing beta-lactone by catalyzing epoxide is a kettle reactor, wherein epoxide is Ethylene Oxide (EO) or Propylene Oxide (PO), and the molar ratio of epoxide to catalyst is 100-5000, preferably 200-2000; the pressure of CO is 1-7.0 MPa; the reaction temperature is 40-70 ℃; the reaction time is 1-12 h; the reaction solvent is ethylene glycol dimethyl ether or tetrahydrofuran.
The beneficial effects of the invention are as follows:
1. the book is provided withThe application of metal nitrogen flip porphyrin-cobalt carbonyl [ Lewis acid ]] x+ [Co(CO) z ] y- The multifunctional catalyst has special Lewis acid structure with inner core and outer bimetal sites coordinated, and the synergistic effect of the inner and outer bimetal sites can raise the activation rate of epoxy compound and further raise the activity of the catalyst. When the nitrogen-upturned porphyrin ligand substituted by the pyrrole nitrogen-upturned porphyrin ligand in the Lewis acid is coordinated with the central metal, the structure adopts a completely deprotonated form, can stabilize metal cations in a high valence state, accelerates the release of Lewis acid cations in the carbonylation reaction, leads the beta-lactone to be closed, and improves the selectivity of the beta-lactone.
2. With the existing homogeneous phase [ Lewis acid ]] + [Co(CO) z ] - Compared with the kettle type carbonylation technology of the catalyst, the Lewis acid of the invention has nitrogen-turned porphyrin or pyrrole-substituted nitrogen-turned porphyrin as a ligand, and the inner core and the periphery of the ligand are coordinated with metal to form a special structure coordinated with double metal sites, thereby improving the activity and the selectivity of carbonylation, reducing the pressure of carbonylation reaction and saving the cost for industrial application of carbonylation.
Detailed Description
The following detailed description of the invention is provided in connection with examples, but the implementation of the invention is not limited thereto, and it is obvious that the examples described below are only some examples of the invention, and that it is within the scope of protection of the invention to those skilled in the art to obtain other similar examples without inventive faculty.
Example 1
Benzaldehyde (0.530 g,5 mmol) and freshly distilled pyrrole (0.3355 g,5 mmol) are added into a three-necked flask, 300mL of dichloromethane is added for dissolution, methanesulfonic acid (0.6027 g,3.55 mmol) is added under Ar atmosphere, after stirring for 30min at room temperature under dark condition, tetrachlorobenzoquinone (0.1082 g,4.4 mmol) is added, stirring for 1min again, triethylamine (2 mL) is added, reaction is carried out for 10min under dark condition, the reaction mixture is passed through a chromatographic column filled with neutral alumina, yellow green color tape is collected, dried by spin, further purification is carried out, the neutral alumina is passed through the column, and the mixture of n-hexane/dichloromethane=1:1 is taken as eluent, yellow green components are collected, and 0.3028g of nitrogen-reversed porphyrin ligand is obtained by spin drying.
To a three-necked flask, nitrogen-reversed porphyrin ligand (0.0800 g,0.128 mmol) was added, 40mL of methylene chloride was slowly added dropwise with 0.32mL of diethyl aluminum chloride (2M in n-hexane) under nitrogen atmosphere in an ice bath, and the mixture was stirred for 3 hours, and the reaction mixture was dried in vacuo, and the solid product was purified by silica gel column and dried in vacuo at 60℃for 4 hours to give 0.0739g of metal aluminum nitrogen-reversed porphyrin complex.
Weighing 0.6000g of Co 2 (CO) 8 Is dissolved in 30mL of ultra-dry tetrahydrofuran or tetrahydropyran, 0.8000g of KOH is added under inert atmosphere, the mixture is stirred for 8 hours at room temperature, and the product is filtered, washed and dried under vacuum to obtain 0.4500g of KCo (CO) 4 Is a solid of (a).
0.1000g of the metal aluminum nitrogen eversion porphyrin complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0546g of KCo (CO) was added under an inert atmosphere 4 And (3) reacting the solid overnight at 0 ℃, filtering, washing and drying to obtain the cobalt carbonyl metal aluminum nitrogen eversion porphyrin complex catalyst.
In a glove box, weighing 0.0547g of metal aluminum nitrogen flip porphyrin-cobalt carbonyl catalyst, adding the catalyst into a 25mL reaction kettle, adding 10mL of ultra-dry tetrahydrofuran, adding 3.2g of propylene oxide or 2.43g of ethylene oxide, sealing the reaction kettle, filling 3.0MPa of CO into the reaction kettle, and reacting for 3 hours at 60 ℃, wherein the reaction is a kettle-type reaction system-1.
Example 2
The preparation method of the nitrogen-reversed porphyrin ligand is the same as that described above;
into a three-necked flask were added nitrogen-reversed porphyrin ligand (0.1000 g,0.16 mmol) and freshly distilled pyrrole (0.5360 g,0.8 mmol), dissolved in 50mL of N, N-dimethylformamide, and BF was added 3 ·OEt 2 (0.02 mmol) and refluxing for 2h, spin-drying the reaction mixture, passing through a neutral alumina filled chromatographic column, collecting the product by using dichloromethane or chloroform as an eluent, and spin-drying to obtain 0.0664g pyrrole-substituted nitrogen-reversed porphyrin ligand.
Pyrrole-substituted nitrogen-everting porphyrin (0.0800 g,0.1176 mmol) was added into a three-necked flask, 40mL of methylene chloride was added, 0.3mL of diethyl aluminum chloride (2M n-hexane solution) was slowly added dropwise under nitrogen atmosphere in an ice bath, the mixture was stirred for 3 hours, the reaction solution was dried in vacuo, the solid product was purified by silica gel column and dried in vacuo at 60℃for 4 hours to obtain 0.0734g of metal aluminum pyrrole-substituted nitrogen-everting porphyrin complex.
KCo(CO) 4 The preparation method is the same as the above.
0.1000g of metalloaluminopyrrole substituted nitrogen flip porphyrin complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0556g of KCo (CO) was added under an inert atmosphere 4 The solid is reacted overnight at 0 ℃, and the metal aluminum pyrrole substituted nitrogen turnover porphyrin-cobalt carbonyl catalyst is obtained after filtering, washing and drying.
In a glove box, 0.0581g of metal aluminum pyrrole substituted nitrogen turnover porphyrin-cobalt carbonyl catalyst is weighed and added into a 25mL reaction kettle, 10mL of ultra-dry tetrahydrofuran is added, 3.2g of propylene oxide or 2.43g of ethylene oxide is added, after the reaction kettle is sealed, CO of 3.0MPa is filled into the reaction kettle, and the reaction is carried out for 3 hours at 60 ℃, thus obtaining a kettle type reaction system-2.
Example 3
The preparation method of the nitrogen-reversed porphyrin ligand is the same as that described above;
a three-necked flask was charged with a nitrogen-reversed porphyrin ligand (0.0800 g,0.1176 mmol), 50mL of N, N-dimethylformamide was added for dissolution, chromium chloride (0.0723 g,0.588 mmol) was added, the reaction mixture was refluxed for 2 hours, the obtained crude solid product was purified by a silica gel column, and a mixed solution of ethanol and methylene chloride was used as a eluting agent to obtain a purified solid, and after vacuum drying, 0.0859g of a metal chromium nitrogen-reversed porphyrin complex was obtained.
KCo(CO) 4 The preparation method is the same as the above.
0.1000g of the metal chromium nitrogen eversion porphyrin complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0489g of KCo (CO) was added under an inert atmosphere 4 And (3) reacting the solid overnight at 0 ℃, filtering, washing and drying to obtain the metal chromium nitrogen upturned porphyrin-cobalt carbonyl catalyst.
In a glove box, weighing 0.0577g of metal chromium nitrogen flip porphyrin-cobalt carbonyl catalyst, adding the catalyst into a 25mL reaction kettle, adding 10mL of ultra-dry tetrahydrofuran, adding 3.2g of propylene oxide or 2.43g of ethylene oxide, sealing the reaction kettle, filling 3.0MPa of CO into the reaction kettle, and reacting at 60 ℃ for 3 hours, wherein the reaction is a kettle-type reaction system-3.
Example 4
The preparation method of the pyrrole substituted nitrogen turnover porphyrin ligand is the same as the above;
pyrrole substituted nitrogen turnover porphyrin ligand (0.0800 g,0.1176 mmol) is added into a three-port bottle, 50mL of N, N-dimethylformamide is added for dissolution, chromium chloride (0.0723 g,0.588 mmol) is added, reflux is carried out for 2h, the obtained crude solid product is purified through a silica gel column after the reaction liquid is dried in vacuum, a mixed solution of ethanol and dichloromethane is used as a eluting agent, purified solid is obtained, and 0.0866g of metal chromium pyrrole substituted nitrogen turnover porphyrin complex is obtained after the vacuum drying.
KCo(CO) 4 The preparation method is the same as the above.
0.1000g of the metal chromium pyrrole substituted nitrogen turnover porphyrin complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0359g of KCo (CO) was added under an inert atmosphere 4 And (3) reacting the solid overnight at 0 ℃, filtering, washing and drying to obtain the metal chromium pyrrole substituted nitrogen turnover porphyrin-cobalt carbonyl catalyst.
In a glove box, 0.0597g of metal chromium pyrrole substituted nitrogen flip porphyrin-cobalt carbonyl catalyst is weighed and added into a 25mL reaction kettle, 10mL of ultra-dry tetrahydrofuran is added, 3.2g of propylene oxide or 2.43g of ethylene oxide is added, after the reaction kettle is sealed, CO of 3.0MPa is filled into the reaction kettle, and the reaction is carried out for 3 hours at 60 ℃, thus obtaining a kettle type reaction system-4.
Example 5
To a three-necked flask were added p-chlorobenzaldehyde (0.7000 g,5 mmol) and freshly distilled pyrrole (0.3355 g,5 mmol), dissolved in 300mL of dichloromethane, and under Ar atmosphere, methanesulfonic acid (0.6027 g,3.55 mmol) was added, after stirring for 30min at room temperature in the absence of light, tetrachlorobenzoquinone (0.1082 g,4.4 mmol) was added, stirring for 1min again, triethylamine (2 mL) was added, reaction was carried out for 10min in the absence of light, the reaction mixture was passed through a neutral alumina-filled chromatographic column, the yellow-green color tape was collected, dried by spin, further purification was carried out, the neutral alumina was passed through the column, and the mixture of n-hexane/dichloromethane=1:1 was used as eluent, the yellow-green component was collected, and dried by spin to obtain 0.3334g of chloro-substituted nitrogen-reversed porphyrin ligand.
To a three-necked flask was added chlorine-substituted nitrogen-reversed porphyrin (0.108 g,0.128 mmol), 40mL of methylene chloride was added, and 0.32mL of diethylaluminum chloride (2M in n-hexane) was slowly added dropwise under nitrogen atmosphere in an ice bath, and stirred for 3 hours, the reaction solution was dried in vacuo, and the solid product was purified by silica gel column, dried in vacuo at 60℃for 4 hours to give 0.0739g of metal aluminum chlorine-substituted nitrogen-reversed porphyrin complex.
KCo(CO) 4 The preparation method is the same as the above.
0.1000g of metal aluminum chloride substituted nitrogen turnover porphyrin complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0546g of KCo (CO) was added under an inert atmosphere 4 And (3) reacting the solid overnight at 0 ℃, filtering, washing and drying to obtain the metal aluminum chloride substituted nitrogen-reversed porphyrin-cobalt carbonyl catalyst.
In a glove box, 0.0600g of metal aluminum chloride substituted nitrogen turnover porphyrin-cobalt carbonyl catalyst is weighed and added into a 25mL reaction kettle, 10mL of ultra-dry tetrahydrofuran is added, 3.2g of propylene oxide or 2.43g of ethylene oxide is added, after the reaction kettle is sealed, CO of 3.0MPa is filled into the reaction kettle, and the reaction is carried out for 3 hours at 60 ℃, and is a kettle type reaction system-5.
Example 6
The preparation method of the chloro-substituted nitrogen-everting porphyrin ligand is the same as that described above;
to a three-necked flask was added chlorine-substituted nitrogen-reversed porphyrin (0.1080 g,0.128 mmol), 50mL of N, N-dimethylformamide was added for dissolution, chromium chloride (0.0723 g,0.588 mmol) was added, the reaction mixture was refluxed for 2 hours, the obtained crude solid product was purified by silica gel column, and a mixed solution of ethanol and methylene chloride was used as a eluting agent to obtain a purified solid, and after vacuum drying, 0.095g of a metal chromium chlorine-substituted nitrogen-reversed porphyrin complex was obtained.
KCo(CO) 4 The preparation method is the same as the above.
0.1000g of the chromium metal chloride substituted nitrogen flip porphyrin complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0489g of KCo (CO) was added under an inert atmosphere 4 And (3) reacting the solid overnight at 0 ℃, filtering, washing and drying to obtain the metal chromium-chlorine substituted nitrogen-reversed porphyrin-cobalt carbonyl catalyst.
In a glove box, 0.0650g of metal chromium-chlorine substituted nitrogen flip porphyrin-cobalt carbonyl catalyst is weighed and added into a 25mL reaction kettle, 10mL of ultra-dry tetrahydrofuran is added, 3.2g of propylene oxide or 2.43g of ethylene oxide is added, after the reaction kettle is sealed, CO of 3.0MPa is filled into the reaction kettle, and the reaction is carried out for 3 hours at 60 ℃, thus obtaining a kettle type reaction system-6.
Comparative example 1
In J.org.chem.2001,66,5424, a catalyst [ Ph 3 P＝] 2 NCo(CO) 4 /BF 3 ·H 2 O propylene oxide carbonylation was catalyzed with ethylene glycol dimethyl ether as solvent, substrate and catalyst ratio n (sub.)/n (cat.) =50, at a CO reaction pressure of 6.2MPa, at a reaction temperature of 80 ℃ for 24h.
Comparative example 2
Co is reported in chem. Eur. J.2003,8,6 literature 2 (CO) 4 /AlMe 3 The ratio of substrate to catalyst n (sub.)/n (cat.) =1200 was catalyzed for 16h at a CO reaction pressure of 6.0MPa and a reaction temperature of 95 ℃.
Comparative example 3
In org. Lett.2006,8,3709-3712, a homogeneous [ (salph) Al (THF) is reported 2 ] + [Co(CO) 4 ] - Propylene oxide carbonylation was catalyzed for 1h at a reaction temperature of 22 ℃ under a CO reaction pressure of 0.1MPa with ethylene glycol dimethyl ether (DME) as solvent, substrate to catalyst ratio n (sub.)/n (cat.) =100.
Comparative example 4
In org. Lett.2006,8,3709-3712, a homogeneous [ Cp ] is reported 2 Ti(THF) 2 ] + [Co(CO) 4 ] - The epoxybutane carbonylation reaction was catalyzed for 1h at a reaction temperature of 22 ℃ under a CO reaction pressure of 0.69MPa, with ethylene glycol dimethyl ether (DME) as solvent, with a substrate to catalyst ratio of n (sub.)/n (cat.) =100.
Comparative example 5
In org. Lett.2006,8,3709-3712, a homogeneous [ (TPP) Cr (THF) is reported 2 ] + [Co(CO) 4 ] - Propylene oxide carbonylation was catalyzed for 1h at a reaction temperature of 22 ℃ under a CO reaction pressure of 0.1MPa with ethylene glycol dimethyl ether (DME) as solvent, substrate to catalyst ratio n (sub.)/n (cat.) =100.
Comparative example 6
Tetraphenylporphyrin (1.0000 g,1.626 mmol) was added to a three-necked flask, 40mL of methylene chloride was added thereto, 1mL of diethyl aluminum chloride (2M in n-hexane) was slowly added dropwise thereto under nitrogen atmosphere in an ice bath, and the mixture was stirred for 3 hours, the reaction solution was dried in vacuo, and the solid product was purified by a silica gel column and dried in vacuo at 60℃for 4 hours to obtain 0.8500g of tetraphenylporphyrin aluminum complex.
0.1000g of tetraphenylporphyrin aluminum complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0286g of KCo (CO) was added under an inert atmosphere 4 The solid is reacted overnight at 0 ℃, and the cobalt carbonyl tetraphenylporphyrin aluminum catalyst is obtained after filtration, washing and drying.
In a glove box, 0.0448g of cobalt carbonyl tetraphenylporphyrin aluminum catalyst is weighed and added into a 25mL reaction kettle, 10mL of ultra-dry tetrahydrofuran is added, 3.2g of propylene oxide or 2.43g of ethylene oxide is added, after the reaction kettle is sealed, 6.0MPa of CO is filled into the reaction kettle, and the reaction is carried out for 3 hours at 60 ℃.
Comparative example 7
Tetraphenylporphyrin (1.0000 g,1.626 mmol) was added into a three-necked flask, 50mL of N, N-dimethylformamide was added for dissolution, chromium chloride (0.7731 g,4.878 mmol) was added, the reaction solution was refluxed for 2 hours, the obtained crude solid product was purified by a silica gel column, a mixed solution of ethanol and methylene chloride was used as a eluting agent, and 1.2000g of tetraphenylporphyrin chromium complex was obtained after vacuum drying.
0.1000g of tetraphenylporphyrin chromium complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0175g of KCo (CO) was added under an inert atmosphere 4 The solid is reacted overnight at 0 ℃, and the cobalt carbonyl tetraphenylporphyrin chromium catalyst is obtained after filtration, washing and drying.
In a glove box, 0.0462g of cobalt carbonyl tetraphenylporphyrin chromium catalyst is weighed and added into a 25mL reaction kettle, 10mL of ultra-dry tetrahydrofuran is added, 3.2g of propylene oxide or 2.43g of ethylene oxide is added, after the reaction kettle is sealed, 6.0MPa of CO is filled into the reaction kettle, and the reaction is carried out for 3 hours at 60 ℃.
The liquid phase product was analyzed off-line, with a DB-1701 capillary chromatographic column, and the FID detector analyzed the propylene oxide and ethylene oxide and beta-lactone content.
The catalysts of examples 1-6 and comparative examples 1-7 were used to catalyze the carbonylation of propylene oxide and ethylene oxide with the conversion and selectivity of beta-lactone and TOF results shown in table 1.
TABLE 1 results of carbonylation reactions of epoxy Compounds catalyzed by the catalysts of examples 1-6 and comparative examples 1-7
Figure BDA0003997081220000151
Note that: [ a ]]n PO /n Co ；[b]n EO /n Co ；[c]n BO /n Co
From the comparison of the results, the lewis acid nitrogen turns over the bimetallic site structure coordinated by the inner core and the periphery in porphyrin to improve the carbonylation activity and the capability of improving the carbonylation activity: cr > Al, pyrrole substituted nitrogen flip porphyrin metal coordination formed Lewis acid, so that the selectivity of beta-lactone is obviously improved, and the metal complex with a new coordination form reduces the pressure of carbonylation reaction, thereby further promoting the application of the metal nitrogen flip porphyrin-cobalt carbonyl catalyst in industry.
The invention has been described in detail above but is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A [ Lewis acid ]] x+ [Co(CO) z ] y- Multifunctional catalyst for preparing epoxide by catalysisThe application of the beta-lactone is characterized in that the catalyst is shown as a formula (I) or a formula (II),
Figure FDA0003997081210000011
the catalyst consists of Lewis acid metal nitrogen eversion porphyrin and cobalt carbonyl, wherein the metal nitrogen eversion porphyrin is an internal and external full-coordination metal complex formed by nitrogen eversion porphyrin ligand or pyrrole-substituted nitrogen eversion porphyrin ligand and metal, and is a metal M coordinated with the inner core and the outer periphery of the ligand 1 One or more than two of Ga, zn, cr, fe, al, rh, mn, ni, cu; cobalt carbonyl is [ Co (CO) z ] y- 。
2. The use according to claim 1, wherein the metal M 1 Al and Cr; r in the nitrogen-reversed porphyrin ligand and pyrrole-substituted nitrogen-reversed porphyrin ligand is H, CH 3 、OCH 3 One or more of F, cl is preferably H or Cl.
3. The use according to claim 1, wherein x is an integer from 1 to 3, z is 3 or 4, and y is an integer from 1 to 3.
4. The use according to claim 2, characterized in that the preparation method of the metal nitrogen-everted porphyrin-cobalt carbonyl catalyst or the metal pyrrole-substituted nitrogen-everted porphyrin-cobalt carbonyl catalyst mainly comprises the following steps:
combining an aluminum-coordinated nitrogen-reversed porphyrin complex or an aluminum-coordinated pyrrole-substituted nitrogen-reversed porphyrin complex with [ Co (CO) ] 4 ] - Dissolving in solvent, stirring at-50-30 deg.c for 2-12 hr, filtering, washing and vacuum drying to obtain the said product;
or chromium-coordinated nitrogen-reversed porphyrin complex or chromium-coordinated pyrrole-substituted nitrogen-reversed porphyrin complex [ Co (CO) ] 4 ] - Dissolving in solvent, stirring at-50-30 deg.c for 2-12 hr, filtering, washing, vacuum drying,obtaining the product.
5. The use according to claim 4, wherein the preparation of the metal-coordinated nitrogen-reversed porphyrin complex and the metal-coordinated pyrrole-substituted nitrogen-reversed porphyrin complex essentially comprises the steps of:
dissolving nitrogen-reversed porphyrin ligand or pyrrole-substituted nitrogen-reversed porphyrin ligand into solvent, adding Et under inert atmosphere 2 AlCl，Et 2 The molar ratio of AlCl to nitrogen-turned porphyrin ligand or pyrrole-substituted nitrogen-turned porphyrin ligand is 3-6, stirring and reacting for 2-10 h at room temperature, vacuum drying the reaction liquid, purifying the solid product by a silica gel column, and vacuum drying to obtain the product;
alternatively, the nitrogen-reversed porphyrin ligand or pyrrole-substituted nitrogen-reversed porphyrin ligand is dissolved in a solvent, and CrCl is added 3 ，CrCl 3 Stirring and reacting with nitrogen-turning porphyrin ligand or pyrrole-substituted nitrogen-turning porphyrin ligand for 2-10 h at 70-200 ℃, vacuum drying the reaction solution, filtering the crude product by a sand core funnel, washing with dichloromethane for 1-10 times, and vacuum drying to obtain the product;
the solvent is one or more than two of ethylene glycol dimethyl ether (DME), tetrahydrofuran (THF), tetrahydropyran, 2-methyltetrahydrofuran, 1, 4-dioxane, toluene, 1, 2-difluorobenzene and diethyl ether, and preferably the solvent is tetrahydrofuran; the drying temperature is 25-120 ℃.
6. The use according to claim 5, wherein the preparation method of the nitrogen-everting porphyrin ligand mainly comprises the following steps:
dissolving the newly steamed pyrrole and benzaldehyde or p-chlorobenzaldehyde in a solvent, adding methanesulfonic acid, stirring for 0.1-5 h at room temperature under inert gas, adding chloranil as an oxidant, continuously stirring for 1-10 min, adding triethylamine, continuously stirring for 1-30 min, collecting a yellow green color band from a reaction mixture, spin-drying, further passing through the chromatographic column, collecting a yellow green component from a mixed system of one or two of n-hexane/dichloromethane, n-hexane/chloroform and petroleum ether/ethyl acetate, and spin-drying to obtain a nitrogen-turned porphyrin ligand;
the preparation method of the pyrrole substituted nitrogen turnover porphyrin ligand mainly comprises the following steps:
adding the prepared nitrogen-reversed porphyrin ligand into a reaction vessel, adding excessive freshly steamed pyrrole, adding N, N-dimethylformamide as a solvent, and adding BF 3 ·OEt 2 And (3) taking the mixture as a catalyst, refluxing and stirring for 1-5 h, spin-drying the reaction mixture, filling the reaction mixture into a chromatographic column with aluminum peroxide, taking dichloromethane or chloroform as an eluent, collecting a product, and spin-drying to obtain the pyrrole-substituted nitrogen turnover porphyrin ligand.
7. The use according to claim 6, wherein the molar ratio of pyrrole to nitrogen-reversed porphyrin ligand is 2-6, and the alumina packed in the column comprises acidic alumina, neutral alumina and basic alumina, preferably neutral alumina.
8. The use according to claim 1, wherein said [ Co (CO) z ] y- Is [ Co (CO) 4 ] - Said [ Co (CO) 4 ] - The preparation method of the (C) mainly comprises the following steps:
co is to be 2 (CO) 8 Dissolving in solvent, adding strong alkali, stirring at room temperature for 2-12 hr, filtering, washing with solvent for several times, and vacuum drying at room temperature to obtain [ Co (CO) 4 ] - 。
9. The use according to claim 8, wherein the solvent is one or both of tetrahydrofuran or tetrahydropyran, preferably the solvent is tetrahydrofuran; the strong alkali is one of sodium hydroxide and potassium hydroxide.
10. Use according to claim 1, characterized in that the main reactor for the catalytic epoxide preparation of β -lactone is a tank reactor, wherein the epoxide is ethylene oxide or propylene oxide, the molar ratio of epoxide to catalyst being 100-5000, preferably 200-2000; the pressure of CO is 1-7.0 MPa; the reaction temperature is 40-70 ℃; the reaction time is 1-12 h; the reaction solvent is ethylene glycol dimethyl ether or tetrahydrofuran.
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