CN116510784A - Metal carbonyl-based polymetallic complex catalyst and preparation method and application thereof - Google Patents

Metal carbonyl-based polymetallic complex catalyst and preparation method and application thereof Download PDF

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CN116510784A
CN116510784A CN202310503162.6A CN202310503162A CN116510784A CN 116510784 A CN116510784 A CN 116510784A CN 202310503162 A CN202310503162 A CN 202310503162A CN 116510784 A CN116510784 A CN 116510784A
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porphyrin
product
stirring
catalyst
drying
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黄家辉
任周
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
    • 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
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a metal carbonyl-based polymetallic complex catalyst and a preparation method and application thereof, and belongs to the technical field of epoxy compound carbonylation reaction; the change of the relative position between porphyrin monomer molecules connected by flexible chains forms a flexible and variable intramolecular pi-pi stacking structure, accelerates the carbonylation step rate, improves the carbonylation selectivity and the catalyst stability, has high activity, selectivity and stability in the process of catalyzing the conversion of epoxide into beta-lactone, and lays a foundation for industrial application of epoxide carbonylation reaction.

Description

Metal carbonyl-based polymetallic complex catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of epoxy compound carbonylation reaction, and in particular relates to a metal carbonyl-based polymetallic porphyrin-based [ Lewis acid ]] x+ [Co(CO) 4 ] z y- Preparation of catalyst and its preparation in ring-expanding carbonylationThe application of the beta-lactone is provided.
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, BF is used 3 ·Et 2 O、B(C 6 F 5 ) 3 And SnCl 4 In order to catalyze the carbonylation reaction of propylene oxide, the catalyst has poor capability of activating epoxy compounds by Lewis acid serving as a cocatalyst, so that the carbonylation activity is low. 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, lewis acid is metal-centered, porphyrin (porphyrine=TPP) derivative, salen (salen) derivative, phthalocyanine derivative as ligand, forms mononuclear metal complex with metal through N, O atom, the metal complex is near-plane structure, and leadsThe intermolecular pi-pi stacking effect is relatively rigid, and the activity and selectivity of carbonylation are reduced to a certain extent. The carbonylation reactions reported to date all require high pressure, homogeneous [ (salph) Al (THF) as a small combination of coatings 2 ][Co(CO) 4 ]The yield of the catalyst for catalyzing the carbonylation of propylene oxide is 93%, so that development of a novel polynuclear coordinated metal complex is urgently needed, the activity and selectivity of the carbonylation catalyst are further improved, and the pressure of the carbonylation reaction is reduced.
[Lewis acid] + [Co(CO) 4 ] - The reaction mechanism of the catalyst for catalyzing the carbonylation of epoxide is as follows: (1) [ Lewis acid ]] + Activating the epoxide; (2) [ Co (CO) 4 ] - Attack activated epoxide to form ring-opened intermediates; (3) CO intercalates CO-alkyl bonds to form CO-acyl bonds; (4) ring closure to release the catalyst to form beta-lactone.
Thus, the development of [ Lewis acid ] with novel ligand-type metal complexes] 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
Aiming at the technical problems in the background art, the invention aims to provide a metallocarbonyl-based polymetallic porphyrin-based [ Lewis acid ]] x+ [Co(CO) 4 ] z y- The catalyst is composed of a polymetallic complex formed by porphyrin polymer ligand (Lewis acid) and metal and a metal carbonyl compound, porphyrin monomers are connected through a bridging group containing ester groups, anhydride bonds, ether bonds and acyloxy groups to form the porphyrin polymer ligand, the carbonyl compound is cobalt carbonyl anions, the density of high-concentration delocalized pi electrons is formed among bridged porphyrin monomers in the catalyst, pi-pi stacking effect is improved, high-concentration Lewis acid cations and active species can be locally enriched, and the oxygen coordination of the Lewis acid cations and the epoxide activates carbon-oxygen bonds and the activityThe species is taken as a counter ion, nucleophilic attack on a carbon-oxygen bond enables epoxide ring opening, and the active species with high local concentration improves the activity of epoxide carbonylation; in the polymetallic complex with flexible chains connected, the relative position among porphyrin monomers is changed to form a flexible and variable intramolecular pi-pi stacking structure, so that coordination bonds formed by oxygen of the Lewis acid and epoxide are easy to break to form an initial catalyst active center, the ring-closing rate of beta-lactone in the carbonylation step is accelerated, and the selectivity of carbonylation and the stability of the catalyst are improved. In a tank reactor, a metallocarbonyl-based poly-porphyrin-based [ Lewis acid ]] x+ [M(CO) w ] z y- The catalyst catalyzes epoxide to be converted into beta-lactone, has high activity, selectivity and stability, and lays a foundation for industrial application of epoxide carbonylation reaction.
The technical scheme of the invention is as follows:
metal carbonyl-based polymetallic porphyrin-based [ Lewis acid ]] x+ [M(CO) w ] z y- The catalyst consists of a polymetallic complex formed by porphyrin polymer ligand and metal and a metal carbonyl compound, wherein the porphyrin polymer ligand is formed by connecting porphyrin monomers through bridging groups containing ester groups, anhydride bonds, ether bonds and acyloxy groups, and the coordination metal M of the porphyrin polymer ligand 1 One or more than two of Ti, ga, zn, cr, fe, al, rh, pd, mn, ni, cu, mg, and the metal carbonyl compound is [ M (CO) w ] z y- 。
Based on the above technical solution, preferably, the catalyst structure is as follows:
based on the technical proposal, preference is given toThe coordination metal M 1 Preferably Al and Cr; r in the porphyrin monomer molecule 1 is-H, -CH 3 、-OCH 3 、-Cl、-Br、-NO 2 One or more than two of R 1 preferably-H or-Cl, R 2 is-H, -CH 3 、-Cl、-NO 2 One or more than two of R 2 preferably-H or-Cl, X is one of-F, -Cl and-Br; n is an integer of 0 to 12.
Based on the technical scheme, preferably, the [ M ] 1 2 -dimer] x+ [M(CO) w ] z y- Wherein x is 2 or 4, [ M ] 1 3 -trimer] x+ [M(CO) w ] z y- Wherein x is 3 or 6, [ M ] 1 4 -tetramer] x+ [M(CO) w ] z y- Wherein x is 4 or 8, representing the cationic charge on the lewis acid; w is an integer of 2-10 and represents the number of metal carbonyl anions; [ M ] 1 2 -dimer] x+ [M(CO) w ] z y- Wherein z is 1,2 or 4, [ M ] 1 3 -trimer] x+ [M(CO) w ] z y- Wherein z is 2, 4 or 6, [ M ] 1 4 -tetramer] x+ [M(CO) w ] z y- Wherein z is 4 or 8, and represents the number of metal carbonyl anions; [ M ] 1 2 -dimer] x+ [M(CO) w ] z y- Wherein y is 2 or 4, [ M ] 1 3 -trimer] x+ [M(CO) w ] z y- Wherein y is 3 or 6, [ M ] 1 4 -tetramer] x+ [M(CO) w ] z y- Wherein y is 4 or 8, and represents the charge number of the metal carbonyl anion.
Based on the above technical scheme, preferably, the metal carbonyl compound is formed by Cr (CO) 6 、Co 2 (CO) 8 、Mn 2 (CO) 10 、Ni(CO) 4 、Co 4 (CO) 12 、Fe 3 (CO) 12 One or more of them are reacted with strong alkali.
Based on the technical prescriptionPreferably, the metal carbonyl is [ Co (CO) 4 ] - 。
In another aspect, the present invention provides a method for preparing the catalyst, which mainly comprises the following steps:
(1) The porphyrin polymer ligand is synthesized chemically, and the structure of the porphyrin polymer ligand is shown as follows:
(2) Dissolving porphyrin polymer ligand in organic solvent, slowly dripping Et in ice bath under inert gas atmosphere 2 AlCl or Et 2 Stirring AlH organic solution for 1-10h, removing solvent in the reaction solution, purifying the obtained solid product by a silica gel column, using chloroform-ethanol (5:1-500:1) or dichloromethane-ethanol (5:1-500:1) mixed solution as eluent to obtain purified solid, and drying in vacuum to obtain an aluminum porphyrin polymer complex;
alternatively, the multimeric porphyrin ligand is dissolved in an organic solvent, heated to boiling, and an excess of CrCl is added 2 Or CrCl 3 Reacting for 1-12 h, cooling to room temperature, transferring to ice water, filtering the mixed solution, washing with ice water, and vacuum drying to obtain the chromium porphyrin polymer complex;
(3) Co is taken 2 (CO) 8 Dissolving in organic solvent, adding strong base under inert atmosphere, stirring at room temperature for 2-12 h, filtering, washing and vacuum drying the product to obtain [ Co (CO) 4 ] - ；
(4) Dissolving the aluminum porphyrin polymer complex or the chromium porphyrin polymer complex obtained in the step (2) in an organic solvent, and adding the [ Co (CO) obtained in the step (3) under an inert atmosphere 4 ]Stirring for 2-12 h at 50-30 ℃, filtering, washing and drying to obtain the catalyst.
Based on the above technical scheme, preferably, the preparation method of the porphyrin dimer 1 comprises the following steps:
(a) Dissolving benzaldehyde and p-hydroxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing at 120-160 ℃, dripping newly distilled pyrrole, heating and refluxing for 10-100 min, stopping heating, decompressing and distilling to obtain 1/5-1/2 of the original volume of the organic acid, adding ethanol, stirring overnight at room temperature, filtering and washing with ethanol, drying, purifying a solid product by a neutral alumina column, collecting a third-band product as eluent, and vacuum drying at 40-100 ℃ for 2-8H to obtain 5- (p-hydroxyphenyl) -10,15, 20-triphenylporphyrin (H) 2 MHTPP)；
(b) Adding H to a round bottom flask containing a desiccant 2 And (3) slowly dropwise adding the fumaroyl chloride into the round-bottomed flask by MHTPP and chloroform, stirring for 12-72 h at normal temperature, concentrating the crude product, purifying by a silica gel column, collecting the first-band product, and drying in vacuum at 40-100 ℃ for 2-8 h to obtain the final product.
Based on the above technical solution, preferably, the molar ratio of benzaldehyde to p-hydroxybenzaldehyde=6 to 1; the organic acid is one of formic acid, acetic acid or propionic acid; the drying agent is one of anhydrous sodium sulfate, anhydrous calcium chloride and calcium hydride.
Based on the above technical scheme, preferably, the preparation method of porphyrin dimer 2 comprises the following steps:
(a) Dissolving benzaldehyde and p-carboxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing, dripping newly distilled pyrrole, heating and refluxing for 10-100 min, after stopping heating, decompressing and distilling to obtain 1/5-1/2 of the original volume of the organic acid, adding a mixture of methanol and water, stirring overnight at room temperature, filtering and washing with the mixture of methanol and water, purifying the solid product by a silica gel column, collecting the second-band product, and vacuum drying at 50-150 ℃ for 2-8H to obtain 5- (p-carboxyphenyl) -10,15, 20-triphenylporphyrin (H) 2 CTPP)；
(b) Will H 2 Placing CTPP into a round bottom flask, adding anhydrous dichloromethane or chloroform, stirring under ice salt bath for 10-60 min, adding dicyclohexylcarbodiimide catalyst, stirringStopping stirring for 12-48 h, purifying the concentrated crude product by a silica gel chromatographic column, using dichloromethane as eluent, collecting a first band product, and drying to obtain the final product.
Based on the above technical solution, preferably, the molar ratio of benzaldehyde to p-carboxybenzaldehyde=6 to 1; the organic acid is one of formic acid, acetic acid or propionic acid.
Based on the above technical scheme, preferably, the preparation method of porphyrin dimer 3 comprises the following steps:
h prepared by the method 2 Dissolving MHTPP in N, -N-Dimethylformamide (DMF), adding sodium metal into the solution, stirring to be green, standing, adding 1, 4-p-diiodobenzene, stirring and refluxing for 20-120 min, stirring and cooling to room temperature, extracting a reaction system with dichloromethane and distilled water, performing reduced pressure distillation to obtain a crude product, purifying the crude product by a silica gel chromatographic column, collecting a target product of a second band by using chloroform as an eluent, and drying to obtain the target product.
Based on the above technical scheme, preferably, the preparation method of the porphyrin dimer 4 is as follows:
h synthesized by the method 2 Dissolving MHTPP and NaOH in DMF, heating and refluxing, adding 1, 4-dihalogen-2, 5-dinitrobenzene, adding a plurality of drops of sulfuric acid, refluxing for 1-10h, cooling, mixing the reaction liquid with chloroform, extracting with water, removing chloroform, passing the crude product through a chromatographic column filled with silica gel, using one of n-hexane-dichloromethane, cyclohexane-dichloromethane and n-hexane-chloroform mixed liquid as eluent, collecting, concentrating and drying to obtain the product.
Based on the above technical scheme, preferably, the preparation method of the porphyrin dimer 5 comprises the following steps:
h synthesized by the method 2 Adding MHTPP into a bottle, adding dichloromethane or chloroform for dissolution under inert atmosphere, adding anhydrous aluminum chloride or triethylamine as a catalyst, gradually dripping succinyl chloride into an ice-water bath, stirring for reaction for 2-10 h, concentrating, passing the crude product through a silica gel chromatographic column, taking chloroform as eluent, collecting the product of the first zone, and drying to obtain the product.
Based on the above technical scheme, preferably, the preparation method of the porphyrin trimer 1 is as follows:
(a) Dissolving benzaldehyde and p-carboxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing, dropwise adding freshly distilled pyrrole, heating and refluxing for 10-100 min, after stopping heating, distilling the original volume of 1/5-1/2 of the organic acid under reduced pressure, adding a mixture of methanol and water, stirring overnight at room temperature, filtering and washing the solid product with a mixed solution of methanol and water, purifying the solid product by a silica gel column, collecting a third-band product, and drying the third-band product in vacuum at 50-150 ℃ for 2-8 h to obtain 5,15- (dicarboxyphenyl) -10, 20-diphenylporphyrin;
(b) Adding 5,15- (dicarboxyphenyl) -10, 20-diphenyl porphyrin into a round bottom flask, adding anhydrous dichloromethane or chloroform, stirring for 10-60 min in an ice salt bath, adding dicyclohexylcarbodiimide catalyst, stirring for 12-48 h, stopping, purifying the concentrated crude product by a silica gel chromatographic column, using dichloromethane as eluent, collecting a second product, and drying to obtain the product.
Based on the above technical scheme, preferably, the preparation method of the porphyrin trimer 2 is as follows:
(a) Dissolving benzaldehyde and p-hydroxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing at 120-160 ℃, dropwise adding newly distilled pyrrole, heating and refluxing for 10-100 min, after stopping heating, distilling out 1/5-1/2 of the original volume of the organic acid under reduced pressure, adding ethanol, stirring overnight at room temperature, filtering and washing with ethanol, drying, purifying a solid product by a neutral alumina column, collecting chloroform as eluent, collecting a second-band product, and vacuum-drying at 40-100 ℃ for 2-8 h to obtain 5,15- (di-p-hydroxyphenyl) -10, 20-diphenylporphyrin;
(b) Adding 5,15- (di-p-hydroxyphenyl) -10, 20-diphenyl porphyrin into a round bottom flask, adding metallic sodium into the solution, stirring to be green, standing, adding 1, 4-p-diiodobenzene, stirring and refluxing for 20-120 min, stirring and cooling to room temperature, extracting a reaction system with dichloromethane and distilled water, distilling under reduced pressure to obtain a crude product, purifying the crude product by a silica gel chromatographic column, collecting chloroform as an eluent, collecting a target product of a third band, and drying to obtain the target product.
Based on the above technical scheme, preferably, the preparation method of the porphyrin tetramer 1 is as follows:
putting the prepared 5- (p-carboxyphenyl) -10,15, 20-triphenylporphyrin and 5,15- (dicarboxyphenyl) -10, 20-diphenylporphyrin into a round-bottom flask according to the mol ratio of 1:1, adding anhydrous dichloromethane or chloroform, stirring for 10-60 min under an ice salt bath, adding dicyclohexylcarbodiimide catalyst, stirring for 12-48 h, stopping, purifying the concentrated crude product by a silica gel chromatographic column, using dichloromethane as eluent, collecting a fourth product, and drying to obtain the product.
Based on the above technical solution, preferably, the molar ratio of benzaldehyde to p-hydroxybenzaldehyde=6 to 1; the organic acid is one of formic acid, acetic acid or propionic acid; the drying agent is one of anhydrous sodium sulfate, anhydrous calcium chloride and calcium hydride;
the molar ratio of the benzaldehyde to the p-carboxybenzaldehyde is=6-1; the organic acid is one of formic acid, acetic acid or propionic acid.
Based on the above technical scheme, preferably, the organic solvent used for preparing the aluminum porphyrin polymer complex in the step (2) is one of chloroform, dichloromethane, methanol, ethanol, diethyl ether and tetrahydrofuran, and preferably the solvent is chloroform.
Based on the above technical scheme, preferably, co (CO) is prepared in the step (3) 4 ]The organic solvent used is one or both of tetrahydrofuran or tetrahydropyran, preferably tetrahydrofuran; the strong alkali is one of sodium hydroxide and potassium hydroxide.
Based on the above technical scheme, preferably, the organic solvent used in the step (4) 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 invention also provides application of the catalyst in catalyzing epoxide ring-expanding carbonylation to prepare beta-lactone.
Based on the technical scheme, the carbonylation process adopts a reactorIs a kettle reactor, wherein the substrates selected for carbonylation are Ethylene Oxide (EO) and Propylene Oxide (PO) and 1, 2-Butylene Oxide (BO), and the molar ratio of the substrate to the catalyst n EO /n Co ＝100～5000、n PO /n Co ＝100～5000、n BO /n Co =100 to 5000, preferably the ratio n EO /n Co ＝200～2000、n PO /n Co ＝200～2000、n BO /n Co =200 to 2000; the pressure of carbonylation is 1-7.0 MPa; the reaction temperature is 40-70 ℃; the reaction time is 1-12 h; the reaction solvent is one of ethylene glycol dimethyl ether and tetrahydrofuran.
The beneficial effects of the invention are as follows:
1. the homogeneous phase metal carbonyl group poly metal porphyrin group [ Lewis acid ]] x+ [M(CO) w ] z y- In the catalyst, in the polymetallic complex in the Lewis acid, a strong pi-pi stacking effect in molecules is formed among porphyrin molecular monomers, high-concentration metal cations and active species can be locally enriched, the carbonylation activity is improved, and the bridge connection among porphyrin molecules is flexible connection, so that pi-pi stacking in porphyrin molecules in the polymetallic is flexible and changeable, coordination bonds formed by oxygen in the Lewis acid and epoxide are easy to break, an initial catalyst active center is formed, the ring-closing rate of beta-lactone in the carbonylation speed-determining step is accelerated, and the carbonylation selectivity and the catalyst stability are improved.
2. Bimetallic [ Lewis acid ] coordinated with the existing homogeneous central mononuclear] + [Co(CO) z ] - Compared with the carbonylation technology of the catalyst, the Lewis acid provided by the invention has the advantages that a plurality of porphyrin complexes with central coordination are connected through flexible chains, and a plurality of metal interactions and local enrichment of active species in the ligands greatly improve the activity, selectivity and stability of carbonylation, reduce the pressure of the carbonylation reaction and save the cost for industrial application of the carbonylation.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings to which the embodiments relate will be briefly described.
FIG. 1 shows the activity of the catalysts of example 5 and comparative example 6 for catalyzing PO carbonylation reactions for various cycles
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
6.4mL (0.06 mol) of benzaldehyde, 2.44g (0.02 mol) of p-hydroxybenzaldehyde are dissolved in 200mL of propionic acid and are condensed and refluxed in an oil bath at 140 ℃, 5.6mL (0.08 mL) of pyrrole is added dropwise, the mixture is heated and refluxed for 30min, after stopping heating, about 60mL of propionic acid is distilled off under reduced pressure, 150mL of ethanol is added, stirring is carried out at room temperature overnight, the mixture is filtered, washed and dried with ethanol, and the mixture is passed through a column with neutral alumina, CHCl 3 Collecting the third band of product hydroxyporphyrin as eluent, and then changing into V (CHCl) 3 ) Leaching the mixed solution of V (ethanol) =10:1, and vacuum drying the obtained product in a water bath at 70 ℃ for 4 hours to obtain the 5- (p-hydroxyphenyl) -10,15, 20-triphenylporphyrin (H) 2 MHTPP)。
Into a round bottom flask containing a calcium chloride desiccant was added 0.4g of H 2 MHTPP and 60mL of chloroform, 10uL of fumaroyl chloride is slowly added dropwise into a round bottom flask, stirring is carried out for 48 hours at normal temperature, the crude product is concentrated, the crude product is purified by a silica gel column, the first band product is collected, and water bath at 70 ℃ is dried in vacuum for 4 hours, so that 0.27g of porphyrin dimer 1 is obtained.
0.5g of porphyrin dimer 1 was dissolved in chloroform, 0.5mL of diethyl aluminum chloride (2M n-hexane solution) was slowly added dropwise under nitrogen atmosphere in an ice bath, stirred for 5 hours, the solvent was evaporated and dried to obtain a solid product, the crude solid product was purified by passing through a silica gel column, and a mixture of ethanol and methylene chloride or a mixture of ethanol and chloroform was used as a eluting agent to obtain a purified solid, and after vacuum drying, 0.4g of aluminum porphyrin dimer 1 complex was obtained.
0.5g of porphyrin dimer 1 is weighed and dissolved in 50mL of DMF, 0.2g of chromium chloride is added at 170 ℃ to react for 2 hours, the reaction solution is cooled to room temperature and then transferred into ice water, the mixed solution is filtered and washed by the ice water, and 0.45g of chromium porphyrin dimer 1 complex is obtained after vacuum drying at 120 ℃.
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).
0.0496g of the aluminum porphyrin dimer 1 complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl aluminum porphyrin dimer 1 complex catalyst.
0.0513g of the chromium porphyrin dimer 1 complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin dimer 1 complex catalyst. The technical route of the cobalt carbonyl metalloporphyrin dimer 1 catalyst in this example is shown below.
Example 2
Dissolving 2.7g of p-carboxybenzaldehyde and 5.5mL of benzaldehyde in 200mL of propionic acid, heating and refluxing, dropwise adding 5mL of freshly distilled pyrrole, reacting for 1H, distilling off part of propionic acid under reduced pressure, cooling, adding 100mL of a mixed solution of methanol and water, stirring at room temperature overnight, filtering under reduced pressure, washing with the mixed solution of methanol and water until the solid is purple, purifying the crude product by a silica gel column, collecting the second product, and vacuum drying at 70 ℃ for 4H to obtain 5- (p-carboxyphenyl) -10,15, 20-triphenylporphyrin (H) 2 CTPP)。
0.4g of H is weighed 2 CTPP is put into an original bottom flask, 200mL of anhydrous dichloromethane is added, and after stirring for 20min under an ice salt bath, 10 is added0mg of dicyclohexylcarbodiimide catalyst, stirring for 12 hours, stopping, purifying the concentrated crude product by a silica gel chromatographic column, collecting a first band product by using methylene dichloride as an eluent, and drying to obtain 0.1g of porphyrin dimer 2.
0.5g of porphyrin dimer 2 is weighed and dissolved in 50mL of DMF, 0.18g of chromium chloride is added at 170 ℃ to react for 2 hours, the reaction solution is cooled to room temperature and then transferred into ice water, the mixed solution is filtered and washed by the ice water, and 0.48g of chromium porphyrin dimer 2 complex is obtained after vacuum drying at 120 ℃.
KCo(CO) 4 The synthesis method of (2) is the same as that of example 1.
0.0508g of chromium porphyrin dimer 2 complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin dimer 2 complex catalyst. The technical route of the cobalt carbonyl metalloporphyrin dimer 2 catalyst in this example is shown below.
Example 3
0.25g of H prepared above was weighed out 2 Dissolving MHTPP in 100mL of DMF, adding metallic sodium into the solution, stirring to be green, standing, adding 0.0795g of 1, 4-p-diiodobenzene, stirring and refluxing for 45min, stopping refluxing, stirring and cooling to room temperature, extracting the reaction system with dichloromethane and distilled water, performing reduced pressure distillation to obtain a crude product, purifying the crude product by a silica gel chromatographic column, taking chloroform as an eluent, collecting a target product of a second band, and drying to obtain 0.14g of porphyrin dimer 3.
0.5g of porphyrin dimer 3 is weighed and dissolved in 50mL of DMF, 0.25g of chromium chloride is added at 170 ℃ to react for 2 hours, the reaction solution is cooled to room temperature and then transferred into ice water, the mixed solution is filtered and washed by the ice water, and 0.49g of chromium porphyrin dimer 3 complex is obtained after vacuum drying at 120 ℃.
KCo(CO) 4 The synthesis method of (2) is the same as that of example 1.
0.0515g of the chromium porphyrin dimer 3 complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin dimer 3 complex catalyst. The technical route of the cobalt carbonyl metalloporphyrin dimer 3 catalyst in this example is shown below.
Example 4
Weighing 0.4g of H synthesized by the above 2 And (3) dissolving MHTPP and 0.15g of NaOH in DMF, heating and refluxing, adding 1, 4-dichloro-2, 5-dinitrobenzene into 0.1 when the solvent turns green, adding 2-3 drops of sulfuric acid, refluxing for 6 hours, mixing the reaction liquid with chloroform after cooling, extracting with water, removing chloroform, passing the crude product through a chromatographic column filled with silica gel, and collecting, concentrating and drying cyclohexane-dichloromethane as eluent to obtain 0.35g of porphyrin dimer 4.
0.5g of porphyrin dimer 4 was weighed and dissolved in 50mL of DMF at 170 ℃, 0.21g of chromium chloride was added for reaction for 2 hours, the reaction solution was cooled to room temperature and transferred to ice water, the mixed solution was filtered and washed with ice water, and after vacuum drying at 120 ℃, 0.48g of chromium porphyrin dimer 4 was obtained.
KCo(CO) 4 The synthesis method of (2) is the same as that of example 1.
0.0588g of the chromium porphyrin dimer 4 complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin dimer 4 complex catalyst. The technical route of cobalt carbonyl metalloporphyrin dimer 4 catalyst in this example is shown below.
Example 5
Weighing 0.4g of H prepared above 2 MHTPP is added into a three-mouth bottle, 0.02g of triethylamine is added under inert atmosphere as a catalyst, 20mL of dichloromethane is added for dissolution, 50uL of succinyl chloride is slowly added dropwise under ice water bath, and stirring reaction is carried out for 2h. Concentrating the reaction solution, passing the crude product through a silica gel chromatographic column, eluting with chloroform, collecting the first band product, and drying to obtain porphyrin dimer 5.
0.5g of porphyrin dimer 5 is weighed and dissolved in 50mL of DMF at 170 ℃, 0.19g of chromium chloride is added for reaction for 2 hours, the reaction solution is cooled to room temperature and then transferred into ice water, the mixed solution is filtered and washed by the ice water, and after vacuum drying at 120 ℃, 0.51g of chromium porphyrin dimer 5 is obtained.
KCo(CO) 4 The synthesis method of (2) is the same as that of example 1.
0.0546g of the chromium porphyrin dimer 5 complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin dimer 5 complex catalyst. The technical route of the cobalt carbonyl metalloporphyrin dimer 5 catalyst in this example is shown below.
Example 6
Dissolving 2.7g of p-carboxybenzaldehyde and 2.5g of benzaldehyde in 200mL of propionic acid, heating and refluxing, dropwise adding 5mL of freshly distilled pyrrole, reacting for 1h, distilling off part of propionic acid under reduced pressure, cooling, adding 100mL of a mixed solution of methanol and water, stirring at room temperature overnight, carrying out vacuum filtration under reduced pressure, washing with the mixed solution of methanol and water, purifying the crude product by a silica gel column, collecting the product of a third band, and carrying out vacuum drying at 100 ℃ for 4h to obtain 5,15- (dicarboxyphenyl) -10, 20-diphenylporphyrin.
2.0g of 5- (p-carboxyphenyl) -10,15, 20-triphenylporphyrin and 1.068g of 5,15- (dicarboxyphenyl) -10, 20-diphenylporphyrin are weighed into a round-bottom flask, anhydrous methylene dichloride is added, after stirring for 30min under ice salt bath, 300mg of dicyclohexylcarbodiimide catalyst is added, stirring is stopped after 24h, the concentrated crude product is purified by a silica gel chromatographic column, methylene dichloride is used as eluent, a second band product is collected, and the porphyrin trimer 1 is obtained after drying.
0.0516g of the chromium porphyrin trimer 1 complex was weighed out and dissolved in 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 The mixture is reacted overnight at 0 ℃, filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin trimer 1 complex catalyst. The technical route for the cobalt carbonyl metalloporphyrin trimer 1 catalyst in this example is shown below.
Example 7
2.1mL (0.02 mol) of benzaldehyde, 2.44g (0.02 mol) of p-hydroxybenzaldehyde are dissolved in 200mL of propionic acid and are condensed and refluxed in an oil bath at 140 ℃, 5.6mL (0.08 mL) of pyrrole is added dropwise, the mixture is heated and refluxed for 30min, after stopping heating, about 60mL of propionic acid is distilled off under reduced pressure, 150mL of ethanol is added, stirring is carried out at room temperature overnight, the mixture is filtered, washed and dried with ethanol, and the mixture is passed through a column with neutral alumina, CHCl 3 And collecting a second band of products as eluent, and vacuum drying the second band of products in a water bath at 70 ℃ for 4 hours to obtain the 5,15- (dihydroxyphenyl) -10, 20-diphenylporphyrin.
Weighing 0.5g of H prepared above 2 Dissolving MHTPP and 0.55g of 5,15- (dihydroxyphenyl) -10, 20-diphenyl porphyrin in 100mL of DMF, adding metallic sodium into the solution, stirring to be green, standing, adding 0.2385g of 1, 4-p-diiodobenzene, stirring and refluxing for 45min, stopping refluxing, stirring and cooling to room temperature, extracting a reaction system by using dichloromethane and distilled water, decompressing and distilling to obtain a crude product, purifying the crude product by a silica gel chromatographic column, taking chloroform as an eluent, collecting a target product of a second band, and drying to obtain 0.15g of porphyrin trimer 2.
0.5g of porphyrin trimer 2 is weighed and dissolved in 50mL of DMF, 0.3g of chromium chloride is added at 170 ℃ to react for 2 hours, the reaction solution is cooled to room temperature and then transferred into ice water, the mixed solution is filtered and washed by the ice water, and 0.51g of chromium porphyrin trimer 2 complex is obtained after vacuum drying at 120 ℃.
KCo(CO) 4 The synthesis method of (2) is the same as that of example 1.
0.0505g of chromium porphyrin trimer 2 complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin dimer 3 complex catalyst. The technical route for the cobalt carbonyl metalloporphyrin trimer 2 catalyst in this example is shown below.
Example 8
2.0g of 5- (p-carboxyphenyl) -10,15, 20-triphenylporphyrin and 2.136g of 5,15- (dicarboxyphenyl) -10, 20-diphenylporphyrin are weighed into a round-bottom flask, anhydrous methylene dichloride is added, stirring is carried out for 30min under ice salt bath, 400mg of dicyclohexylcarbodiimide catalyst is added, stirring is stopped after 24h, the concentrated crude product is purified by a silica gel chromatographic column, methylene dichloride is used as eluent, and a fourth band product is collected and dried, thus obtaining porphyrin tetramer 1.
0.0500g of the chromium porphyrin tetramer 1 complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl chromium porphyrin tetramer 1 complex catalyst. The technical route of the cobalt carbonyl metalloporphyrin tetramer 1 catalyst in this example is shown below.
Comparative example 1
In J.org.chem.2001,66,5424, a catalyst [ Ph 3 P＝] 2 NCo(CO) 4 /BF 3 ·H 2 O uses ethylene glycol dimethyl ether as solvent, the ratio of substrate and catalyst n (sub.)/n #Cat=50, catalyzing propylene oxide carbonylation reaction for 24h at 80 ℃ reaction temperature at CO reaction pressure of 6.2 MPa.
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 ]-catalytic propylene oxide carbonylation reaction for 1h at a reaction temperature of 22 ℃ under CO reaction pressure of 0.1MPa with ethylene glycol dimethyl ether (DME) as solvent, ratio of substrate to catalyst 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 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.
0.0500g of tetraphenylporphyrin chromium complex was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 The solid is reacted overnight at 0 ℃, and the cobalt carbonyl tetraphenylporphyrin chromium complex catalyst is obtained after filtering, washing and drying. The technical route of the cobalt carbonyl tetraphenyl porphyrin chromium complex catalyst in this example is shown below.
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Comparative example 7
1.0g of organic matter 1 is weighed and placed in a round-bottom flask, 0.8g of 4-chloro- (1-heptyl) - (1, 7-diphenyl) phosphine chloride is added under inert atmosphere, ultra-dry THF is added for stirring and dissolution, a small amount of Na is added for stirring and reaction for 4 hours in an ice-water bath, the reaction liquid is filtered and washed by the THF, a crude product is obtained after vacuum drying, the crude product is subjected to a silica gel column, dichloromethane is used as eluent, a second band of product is collected, and the target product 1 is obtained after drying.
0.0504g of the target product 1 catalyst was weighed into 10mL of ultra-dry tetrahydrofuran, and 0.0015g of KCo (CO) was added under an inert atmosphere 4 Is reacted overnight at 0 ℃, and is filtered, washed and dried by THF to obtain the cobalt carbonyl double chromium 1 complex catalyst. The technical route of the cobalt carbonyl double chromium complex catalyst in this example is shown below.
Application example: use of the catalysts prepared in comparative examples 6-7 and examples 1-8 in a reaction for preparing beta-lactone starting from ethylene oxide, propylene oxide and 1, 2-butylene oxide.
Kettle type reaction conditions: weighing a certain mass of cobalt carbonyl metalloporphyrin polymer or cobalt carbonyl tetraphenyl porphyrin chromium complex catalyst or cobalt carbonyl double chromium catalyst, adding into a 50mL reaction kettle, adding 10mL of ultra-dry THF, adding 1.56g of ethylene oxide, 2.06g of propylene oxide or 2.56g of cobalt carbonyl double chromium catalyst1, 2-epoxybutane, wherein n EO /n Co ＝500、n PO /n Co ＝500、n BO /n Co =500, the kettles in examples 1-8 were filled with CO at 3.0MPa and reacted at 60 ℃ for 3h; the kettles in comparative examples 6 and 7 were charged with CO at 3.0 MPa.
Reaction conditions for catalyst recycle in example 5 and comparative example 6: in a glove box, vacuumizing and separating the catalyst and the product after catalyzing the carbonylation of propylene oxide at 40-60 ℃, adding the separated catalyst into a reaction kettle, adding a certain amount of propylene oxide, filling CO at 3.0MPa into the kettle, reacting for 3 hours at 60 ℃, and testing the cycle stability of the carbonylation of the catalyst under the same cycle conditions.
The liquid phase product was analyzed off-line, with a DB-1701 capillary chromatographic column, and the FID detector analyzed for epoxide and beta-lactone content.
The beta-lactone yields, selectivities and TOF results of carbonylation during the preparation of beta-lactone according to the above procedure are shown in table 1.
TABLE 1 homogeneous [ Lewis acid ]] x+ [Co(CO) z ] y- Catalyst catalyzed epoxide carbonylation reaction results
Note that: [ a ]]n EO /n Co ；[b]n PO /n Co ；[c]n BO /n Co
The results show that: as is evident from the comparison of the results of examples 1-8 and comparative examples 1-7, the catalyst of the present invention, which consists of metalloporphyrin multimer and cobalt carbonyl anion, is significantly superior to other catalysts in both activity and selectivity for catalyzing the carbonylation of ethylene oxide and propylene oxide. The metalloporphyrin polymer complex with a special structure in the catalyst forms flexible pi-pi stacking effect, so that the epoxide carbonylation under low pressure has higher activity and selectivity, and the industrial application of the cobalt carbonyl metal polyporphyrin-based catalyst is further promoted.
The invention has been described in detail above but is not limited to the specific embodiments described herein. Other modifications and variations can be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. Metal carbonyl-based polymetallic porphyrin-based [ Lewis acid ]] x+ [M(CO) w ] z y- The catalyst is characterized by comprising a polymetallic complex formed by porphyrin polymer ligand and metal and a metal carbonyl compound, wherein the porphyrin polymer ligand is formed by connecting porphyrin monomers through bridging groups containing ester groups, anhydride bonds, ether bonds and acyloxy groups, and the coordination metal M of the porphyrin polymer ligand 1 One or two or more of Ti, ga, zn, cr, fe, al, rh, pd, mn, ni, cu, mg, and the metal carbonyl compound is [ M (CO) w ] z y- 。
2. The catalyst of claim 1, wherein the catalyst structure is as follows:
3. the catalyst of claim 2 wherein said coordinating metal M 1 Al and Cr; r in the porphyrin monomer molecule 1 is-H, -CH 3 、-OCH 3 、-Cl、-Br、-NO 2 One or both ofAbove, n is an integer of 0-12;
the [ M ] 1 2 -dimer] x+ [M(CO) w ] z y- Wherein x is 2 or 4, [ M ] 1 3 -trimer] x+ [M(CO) w ] z y- Wherein x is 3 or 6, [ M ] 1 4 -tetramer] x+ [M(CO) w ] z y- Wherein x is 4 or 8; w is an integer of 2 to 10; [ M ] 1 2 -dimer] x+ [M(CO) w ] z y- Wherein z is 1,2 or 4, [ M ] 1 3 -trimer] x+ [M(CO) w ] z y- Wherein z is 2, 4 or 6, [ M ] 1 4 -tetramer] x+ [M(CO) w ] z y- Wherein z is 4 or 8; [ M ] 1 2 -dimer] x+ [M(CO) w ] z y- Wherein y is 2 or 4, [ M ] 1 3 -trimer] x+ [M(CO) w ] z y- Wherein y is 3 or 6, [ M ] 1 4 -tetramer] x+ [M(CO) w ] z y- Where y is 4 or 8.
4. The catalyst of claim 2, wherein the metal carbonyl is preferably [ Co (CO) ] 4 ] - 。
5. The method for preparing a catalyst according to any one of claims 1 to 4, comprising the steps of:
(1) The porphyrin polymer ligand is synthesized chemically, and the structure of the porphyrin polymer ligand is shown as follows:
(2) Dissolving porphyrin polymer ligand in organic solvent, slowly dripping Et in ice bath under inert gas atmosphere 2 AlCl or Et 2 Stirring AlH organic solution for 1-10h, removing solvent in the reaction solution, purifying the obtained solid product by a silica gel column to obtain purified solid, and vacuum drying to obtain an aluminum porphyrin polymer complex;
alternatively, the multimeric porphyrin ligand is dissolved in an organic solvent, heated to boiling, and an excess of CrCl is added 2 Or CrCl 3 Reacting for 1-12 h, cooling to room temperature, transferring to ice water, filtering the mixed solution, washing with ice water, and vacuum drying to obtain the chromium porphyrin polymer complex;
(3) Co is taken 2 (CO) 8 Dissolving in organic solvent, adding strong base under inert atmosphere, stirring at room temperature for 2-12 h, filtering, washing and vacuum drying the product to obtain [ Co (CO) 4 ] - ；
(4) Dissolving the aluminum porphyrin polymer complex or the chromium porphyrin polymer complex obtained in the step (2) in an organic solvent, and adding the [ Co (CO) obtained in the step (3) under an inert atmosphere 4 ] - Stirring for 2-12 h at-50-30 ℃, filtering, washing and drying to obtain the catalyst.
6. The method of claim 5, wherein the method of preparing porphyrin dimer 1 comprises the steps of:
(a) Dissolving benzaldehyde and p-hydroxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing at 120-160 ℃, dripping newly distilled pyrrole, heating and refluxing for 10-100 min, stopping heating, decompressing and distilling to obtain 1/5-1/2 of the original volume of the organic acid, adding ethanol, stirring overnight at room temperature, filtering and washing with ethanol, drying, purifying a solid product by a neutral alumina column, collecting a third-band product by using trichloromethane as eluent, and vacuum drying for 2-8 h at 40-100 ℃ to obtain the 5- (p-hydroxy)Phenyl) -10,15, 20-triphenylporphyrin (H) 2 MHTPP)；
(b) Adding H to a round bottom flask containing a desiccant 2 Slowly dripping fumaryl chloride into the MHTPP and chloroform, stirring for 12-72 h at normal temperature, concentrating the crude product, purifying by a silica gel column, collecting the first product, and vacuum drying at 40-100 ℃ for 2-8 h to obtain the final product;
the preparation method of porphyrin dimer 2 comprises the following steps:
(a) Dissolving benzaldehyde and p-carboxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing, dripping newly distilled pyrrole, heating and refluxing for 10-100 min, after stopping heating, decompressing and distilling to obtain 1/5-1/2 of the original volume of the organic acid, adding a mixture of methanol and water, stirring overnight at room temperature, filtering and washing with the mixture of methanol and water, purifying the solid product by a silica gel column, collecting the second-band product, and vacuum drying at 50-150 ℃ for 2-8H to obtain 5- (p-carboxyphenyl) -10,15, 20-triphenylporphyrin (H) 2 CTPP)；
(b) Will H 2 Placing CTPP into a round bottom flask, adding anhydrous dichloromethane or chloroform, stirring for 10-60 min under ice salt bath, adding dicyclohexylcarbodiimide catalyst, stirring for 12-48 h, stopping, purifying the concentrated crude product with silica gel chromatographic column, eluting with dichloromethane, collecting the first band product, and drying;
the preparation method of porphyrin dimer 3 comprises the following steps:
h prepared by the method 2 Dissolving MHTPP in N, -N-Dimethylformamide (DMF), adding sodium metal into the solution, stirring to be green, standing, adding 1, 4-p-diiodobenzene, stirring and refluxing for 20-120 min, stirring and cooling to room temperature, extracting a reaction system with dichloromethane and distilled water, performing reduced pressure distillation to obtain a crude product, purifying the crude product by a silica gel chromatographic column, collecting a target product of a second zone by using chloroform as an eluent, and drying to obtain the target product;
the preparation method of porphyrin dimer 4 is as follows:
h synthesized by the method 2 Dissolving MHTPP and NaOH in DMF, heating and refluxing, adding 1, 4-dihalogen-2, 5-dinitrobenzene, simultaneously adding a plurality of drops of sulfuric acid, refluxingReacting for 1-10h, cooling, mixing the reaction solution with chloroform, extracting with water, removing chloroform, passing the crude product through a chromatographic column filled with silica gel, using one of n-hexane-dichloromethane, cyclohexane-dichloromethane and n-hexane-chloroform mixed solution as eluent, collecting, concentrating and drying to obtain the product;
the preparation method of porphyrin dimer 5 comprises the following steps:
h synthesized by the method 2 Adding MHTPP into a bottle, adding dichloromethane or chloroform under inert atmosphere for dissolution, adding anhydrous aluminum chloride or triethylamine as a catalyst, gradually dripping succinyl chloride into an ice-water bath, stirring for reaction for 2-10 h, concentrating, passing the crude product through a silica gel chromatographic column, using chloroform as eluent, collecting the first-band product, and drying to obtain the product;
the preparation method of the porphyrin trimer 1 comprises the following steps:
(a) Dissolving benzaldehyde and p-carboxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing at 120-160 ℃, dropwise adding newly-steamed pyrrole, heating and refluxing for 10-100 min, stopping heating, distilling under reduced pressure to obtain 1/5-1/2 of the original volume of the organic acid, adding a mixture of methanol and water, stirring overnight at room temperature, filtering, washing with a mixed solution of methanol and water, purifying a solid product by a silica gel column, collecting a product of a third band, and drying in vacuum at 50-150 ℃ for 2-8 h to obtain 5,15- (dicarboxyphenyl) -10, 20-diphenylporphyrin;
(b) Adding 5,15- (dicarboxyphenyl) -10, 20-diphenyl porphyrin into a round bottom flask, adding anhydrous dichloromethane or chloroform, stirring for 10-60 min in an ice salt bath, adding dicyclohexylcarbodiimide catalyst, stirring for 12-48 h, stopping, purifying the concentrated crude product by a silica gel chromatographic column, using dichloromethane as eluent, collecting a second product, and drying to obtain the product;
the preparation method of the porphyrin trimer 2 comprises the following steps:
(a) Dissolving benzaldehyde and p-hydroxybenzaldehyde in organic acid according to a certain molar ratio, condensing and refluxing at 120-160 ℃, dropwise adding newly distilled pyrrole, heating and refluxing for 10-100 min, after stopping heating, distilling out 1/5-1/2 of the original volume of the organic acid under reduced pressure, adding ethanol, stirring overnight at room temperature, filtering and washing with ethanol, drying, purifying a solid product by a neutral alumina column, collecting chloroform as eluent, collecting a second-band product, and vacuum-drying at 40-100 ℃ for 2-8 h to obtain 5,15- (di-p-hydroxyphenyl) -10, 20-diphenylporphyrin;
(b) Adding 5,15- (di-p-hydroxyphenyl) -10, 20-diphenyl porphyrin into a round bottom flask, adding metallic sodium into the solution, stirring to be green, standing, adding 1, 4-p-diiodobenzene, stirring and refluxing for 20-120 min, stirring and cooling to room temperature, extracting a reaction system with dichloromethane and distilled water, distilling under reduced pressure to obtain a crude product, purifying the crude product by a silica gel chromatographic column, using chloroform as an eluent, collecting a target product of a third zone, and drying to obtain the target product;
the preparation method of the porphyrin tetramer 1 comprises the following steps:
putting the prepared 5- (p-carboxyphenyl) -10,15, 20-triphenylporphyrin and 5,15- (dicarboxyphenyl) -10, 20-diphenylporphyrin into a round-bottom flask according to the mol ratio of 1:1, adding anhydrous dichloromethane or chloroform, stirring for 10-60 min under an ice salt bath, adding dicyclohexylcarbodiimide catalyst, stirring for 12-48 h, stopping, purifying the concentrated crude product by a silica gel chromatographic column, using dichloromethane as eluent, collecting a fourth product, and drying to obtain the product.
7. The method according to claim 6, wherein the molar ratio of benzaldehyde to p-hydroxybenzaldehyde is=6 to 1; the molar ratio of the benzaldehyde to the p-carboxybenzaldehyde is=6-1; the organic acid is one of formic acid, acetic acid or propionic acid; the drying agent is one of anhydrous sodium sulfate, anhydrous calcium chloride and calcium hydride.
8. The method according to claim 5, wherein the organic solvent used for preparing the aluminum porphyrin polymer complex in the step (2) is one of chloroform, methylene chloride, methanol, ethanol, diethyl ether and tetrahydrofuran;
preparation of [ Co (CO) in step (3) 4 ] - The organic solvent is tetrahydrofuran or tetrahydropyranOne or both of (a) and (b); the strong alkali is one of sodium hydroxide and potassium hydroxide;
the organic solvent used in the step (4) is one or more of ethylene glycol dimethyl ether (DME), tetrahydrofuran (THF), tetrahydropyran, 2-methyltetrahydrofuran, 1, 4-dioxane, toluene, 1, 2-difluorobenzene and diethyl ether.
9. Use of the catalyst of any one of claims 1-4 for catalyzing the ring-expanding carbonylation of epoxides to produce beta-lactones.
10. The process according to claim 9, wherein the substrates selected for the carbonylation are Ethylene Oxide (EO) and Propylene Oxide (PO) and 1, 2-Butylene Oxide (BO), the molar ratio n of substrate to catalyst EO /n Co ＝100～5000、n PO /n Co ＝100～5000、n BO /n Co =100 to 5000; the pressure of carbonylation is 1-7.0 MPa; the reaction temperature is 40-70 ℃; the reaction time is 1-12 h; the reaction solvent is one of ethylene glycol dimethyl ether and tetrahydrofuran.
CN202310503162.6A 2023-05-06 2023-05-06 Metal carbonyl-based polymetallic complex catalyst and preparation method and application thereof Pending CN116510784A (en)

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