CN116731024A - Preparation method and application of copper porphyrin metal organic cage with photocatalytic oxidation primary amine coupling performance - Google Patents

Preparation method and application of copper porphyrin metal organic cage with photocatalytic oxidation primary amine coupling performance Download PDF

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CN116731024A
CN116731024A CN202310544775.4A CN202310544775A CN116731024A CN 116731024 A CN116731024 A CN 116731024A CN 202310544775 A CN202310544775 A CN 202310544775A CN 116731024 A CN116731024 A CN 116731024A
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tapp
solid
reaction
pdca
primary amine
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段春迎
何旭旭
景旭
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc

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Abstract

The invention discloses a preparation method and application of a copper porphyrin metal organic cage with a photocatalytic oxidation primary amine coupling performance. The invention uses copper porphyrin derivative as organic ligand Cu-TAPP, which has good light absorption performance and oxygen activating capacity, and uses the copper porphyrin derivative as photosensitive ligand through being combined with Zn 2+ The metal organic cage photocatalyst is synthesized by coordination self-assembly. The organic ligand Cu-TAPP and the auxiliary ligand PDCA are connected through metallic zinc, so that a cage-shaped structure with a large cavity is effectively constructed. Its wide open window and large cavity facilitate the substrateThe molecule enters, the conjugation system with large porphyrin provides an advantageous binding site for the aromatic molecule, the cage structure and the substrate molecule are combined to shorten the distance between the two, the transfer rate of electrons is accelerated, and primary amine substrates are effectively oxidized into corresponding imine products. The reaction system has good reactivity to various primary amine substrates, and provides a new method for the photo-catalytic oxidative coupling of primary amine.

Description

Preparation method and application of copper porphyrin metal organic cage with photocatalytic oxidation primary amine coupling performance
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to a preparation method and application of a copper porphyrin metal organic cage with a photocatalytic oxidation primary amine coupling performance.
Background
Imine is an organic compound having a carbon-nitrogen double bond, and has been widely used in the medical and biological fields because of its high reactivity and excellent antibacterial effect (Marques C S, burke a j. Chemcatchem,2011,3 (4): 635-645). The traditional synthesis method of the imine is formed by dehydration of primary amine and aldehyde by taking Lewis acid as a catalyst, but the method has the problems of long reaction time, high reaction temperature and the like. Another current method for synthesizing imine is to take green and easily available oxygen as oxidant and obtain the imine through coupling of photo-catalytic oxidation primary amine. However, this approach is also somewhat challenging, and most organic compounds first lack efficient light absorption and therefore are less photocatalytic. In addition, while many noble metal complexes have good photocatalytic properties, the high cost limits their large-scale application. Therefore, the search for a photocatalyst which is cheap and easy to obtain, simple and environment-friendly is the main direction of research.
Photocatalysis converts light energy into chemical energy, providing a green sustainable method for the synthesis of valuable organic chemicals. Porphyrin molecules have a highly conjugated 18 pi-electron aromatic system (Poulos t.chem.rev., 2014,114 (7): 3919-3962.) and can bind to aromatic molecules through weak interactions, and their electronic properties can be controlled by metal ions bound to the core structure, so that porphyrin molecules have a wide visible light absorption capacity. At the same time, porphyrins can activate oxygen to reactive oxygen species (Chen Y Z, wang Z U, W H, et al j.am.chem.soc.,2017,139 (5): 2035-2044), which facilitates the progress of the oxidation reaction. However, porphyrin molecules tend to aggregate easily, resulting in reduced photocatalytic efficiency, and thus a more elaborate structure is required to solve these problems.
The metal organic cage is a special supermolecular material, which takes an organic ligand as a framework, takes metal cations as nodes, and forms a definite cavity structure through self-assembly of the subassemblies. The built metal organic cage has obvious light absorption capacity through introducing photosensitive organic ligand, the stereo conjugated structure solves the problem of easy aggregation of material, and the unique synthetic hosts have clear cavities to provide various weak interactions to identify and encapsulate organic substrate, stabilize intermediate and regulate reaction kinetics, and the near-distance ultrafast photoinduced electron transfer between the host and the guest inside the cavity can speed up the reaction.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method and application of a copper porphyrin metal organic cage with photocatalytic oxidation primary amine coupling performance. The copper porphyrin metal organic cage prepared by the method disclosed by the invention has weak interaction with substrate molecules in the cavity, so that the distance between the copper porphyrin metal organic cage and the substrate molecules is shortened, and the electron transfer rate is accelerated. Meanwhile, after the cage-shaped compound is constructed, the catalyst has good solubility and a wider light absorption range, is favorable for reaction, is convenient to prepare, and has a green reaction process by taking oxygen as oxidant light as energy.
The invention uses copper porphyrin derivative as organic ligand Cu-TAPP, which has good light absorption performance and oxygen activating capacity, and uses the copper porphyrin derivative as photosensitive ligand through being combined with Zn 2+ The metal organic cage photocatalyst is synthesized by coordination self-assembly. The organic ligand Cu-TAPP and the auxiliary ligand PDCA are connected through metallic zinc, so that a cage-shaped structure with a large cavity is effectively constructed. The wide open window and the large cavity are favorable for entering substrate molecules, the large conjugated system of porphyrin provides favorable binding sites for aromatic molecules, the cage structure and the substrate molecules are combined to shorten the distance between the two, the transfer rate of electrons is accelerated, and primary amine substrates are effectively oxidized into corresponding imine products. The reaction system has good reactivity to various primary amine substrates, and provides a new method for the photo-catalytic oxidative coupling of primary amine.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a process for preparing copper-porphyrin metal-organic cage with photo-catalytic oxidation primary amine coupling performance includes such steps as preparing copper-5, 10,15, 20-tetra (4-amino group)Phenyl) porphyrin Cu-TAPP is used as an organic ligand, 2-pyridine formaldehyde PDCA is used as an auxiliary ligand, and Zn in metal zinc salt 2+ As a node, a metal organic cage Zn-Cu-TAPP-PDCA is formed by a solvothermal method, and the synthetic route is as follows:
Zn 2+ +Cu-TAPP+PDCA→Zn-Cu-TAPP-PDCA；
the metal zinc salt is one or more than two of bis [ bis (trifluoromethylsulfonyl) imide ] zinc, zinc trifluoromethane sulfonate and zinc perchlorate hexahydrate;
the organic ligand Cu-TAPP has the following (A) molecular structural formula:
the auxiliary ligand PDCA has the following (B) molecular structural formula:
the preparation method of the Zn-Cu-TAPP-PDCA comprises the following steps:
step 1: p-nitrobenzaldehyde and acetic anhydride were mixed at 1:1.6 to 1:1.8 in propionic acid at 130-140 deg.c for 1-2 hr, and then slowly dropping pyrrole to make the molar ratio of p-nitrobenzaldehyde to pyrrole 1:0.95 to 1:1.05, continuing to react for 1-2 h after the dripping is finished, and cooling to room temperature after the reaction is finished; filtering the reaction solution, washing the reaction solution with methanol to remove impurities on the surface, and drying the solid in vacuum for 12-16 h; dissolving the dried solid in pyridine and heating and refluxing for 3-5 h; after the reaction is finished, the solution is placed in a refrigerator to be cooled for 3 to 5 hours, then filtered, and then washed by methanol and acetone in sequence until the soluble impurities are completely washed, so as to obtain a deep purple solid A;
step 2: adding concentrated hydrochloric acid into the solid A obtained in the step 1 to ensure that the concentration of the solid A in the concentrated hydrochloric acid is 16.67-20 g/L; then adding tin dichloride dihydrate, and reacting for 8-10 hours at 80-85 ℃, wherein the solid A and the tin dichloride dihydrateThe molar ratio of (2) is 1:14 to 1:16; after the reaction was completed, it was cooled to room temperature, and then NH was added to an ice-water bath 3 ·H 2 O adjusts the pH of the reaction solution to be neutral; then filtering, washing for a plurality of times by using deionized water to obtain green solid, placing the green solid in a vacuum drying oven for drying for 12-16 hours, washing by using acetone until the color of the filtrate is lighter, and spin-drying the filtrate to obtain a bright purple solid B;
step 3: mixing the solid B obtained in the step 2 with copper acetate monohydrate according to the weight ratio of 1: 3-1: 5 in a volume ratio of 1: (0.8-1.2): (2.5-3.5) in DMF, methanol and chloroform at 75-80 ℃ for 20-28 h; after the reaction is finished, removing chloroform and methanol by rotary evaporation, adding deionized water into the residual solution, stirring for 20-40 min, filtering, washing with deionized water, and vacuum drying for 5-7 h to obtain a blue-violet solid, namely the organic ligand Cu-TAPP;
step 4: mixing the organic ligand Cu-TAPP obtained in the step 3, the metal zinc salt and the auxiliary ligand PDCA according to the proportion of 1: (1.2-1.4): (3.6-4.5) to dry acetonitrile; the reaction liquid is vacuumized, introduced with nitrogen for 2 to 4 times and reacts for 42 to 54 hours at the temperature of 75 to 80 ℃; and after the reaction is finished, diethyl ether is diffused into the reaction solution to obtain a brown-purple solid, namely a target compound Zn-Cu-TAPP-PDCA.
The copper porphyrin metal organic cage prepared by the method is applied to a photo-catalytic oxidation primary amine coupling reaction.
The beneficial effects of the invention are as follows: the copper porphyrin metal organic cage Zn-Cu-TAPP-PDCA prepared by the method can be coupled into corresponding imine products by photo-catalytic oxidation primary amine under the irradiation of an LED light source. Zn-Cu-TAPP-PDCA can include substrate molecules to shorten the distance between the two molecules, so that the electron transfer rate is accelerated, and meanwhile, the wide light absorption capacity of copper porphyrin can effectively absorb light to transfer O through electrons 2 Activation to O 2 ·- The method realizes the coupling of the photocatalytic oxidation primary amine to generate imine, and has high conversion rate and good substrate applicability.
Drawings
FIG. 1 is a schematic diagram of the structure of the target compound Zn-Cu-TAPP-PDCA of example 1.
FIG. 2 is a mass spectrum of the target compound Zn-Cu-TAPP-PDCA of example 1.
FIG. 3 is an ultraviolet-visible spectrum absorption diagram of the objective compound Zn-Cu-TAPP-PDCA of example 4.
FIG. 4 is a cyclic voltammogram of the target compound Zn-Cu-TAPP-PDCA of example 5.
Detailed Description
The invention is further described below with reference to examples and figures.
EXAMPLE 1 preparation of Zn-Cu-TAPP-PDCA
Step 1: 21.9g of p-nitrobenzaldehyde and 21.79mL of acetic anhydride are dissolved in 500mL of propionic acid, the mixture is reacted for 1h at 130 ℃, then 9.54mL of pyrrole is slowly added dropwise, the reaction is continued for 1h after the dropwise addition is finished, and the mixture is cooled to room temperature after the reaction is finished. The reaction solution was then filtered and washed with methanol to remove surface impurities, and the solid was dried in vacuo for 12h. The dried solid was dissolved in 200mL of pyridine and heated to reflux for 3h. After the reaction was completed, the solution was cooled in a refrigerator for 3 hours. Filtering, washing with methanol and acetone in turn until the soluble impurities are completely washed, and obtaining the dark purple solid 5,10,15, 20-tetra (4-nitrophenyl) porphyrin.
Step 2: the dark purple solid obtained in step 1, 4g, was weighed, followed by the addition of 200mL of concentrated hydrochloric acid and 15.79g of tin dichloride dihydrate, and reacted at 80℃for 8 hours. After the reaction was completed, it was cooled to room temperature, and then NH was added to an ice-water bath 3 ·H 2 O adjusts the pH to neutral. Filtering, washing with deionized water for multiple times to obtain green solid, and drying the solid in a vacuum drying oven for 12h. The solid was washed with acetone until the filtrate was lighter in color and the filtrate was spin-dried to give a bright purple solid of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
Step 3: the bright purple solid 5,10,15, 20-tetra (4-aminophenyl) porphyrin (200 mg, 0.294 mmol) obtained in step 2, copper acetate monohydrate (176.1 mg, 0.882 mmol) was weighed, followed by the sequential addition of 20mL DMF, 16mL methanol and 50mL chloroform and reaction at 75℃for 20h. And after the reaction is finished, removing chloroform and methanol by rotary evaporation, adding deionized water into the residual solution, stirring for 20min, filtering, washing with the deionized water, and drying for 5h to obtain a bluish violet solid, namely the organic ligand Cu-TAPP.
Step 4: the organic ligand Cu-TAPP (73 mg, 0.1 mmol) from step 3, bis [ bis (trifluoromethylsulfonyl) imide ] zinc (75.1 mg, 0.12 mmol) and the ancillary ligand PDCA (34. Mu.L, 0.36 mmol) were taken up in 30mL dry acetonitrile. The reaction solution was subjected to vacuum pumping and nitrogen introduction for 3 times, and reacted at 75℃for 42 hours. After the reaction, 300mL of diethyl ether is diffused into the reaction solution to obtain a brown-purple solid, namely a target compound Zn-Cu-TAPP-PDCA. The structure diagram is shown in fig. 1, and the mass spectrum is shown in fig. 2.
EXAMPLE 2 preparation of Zn-Cu-TAPP-PDCA
Step 1: 21.9g of p-nitrobenzaldehyde and 23.15mL of acetic anhydride are dissolved in 550mL of propionic acid, the mixture is reacted for 1.5h at 135 ℃, then 10.0mL of pyrrole is slowly added dropwise, the reaction is continued for 1.5h after the dropwise addition is finished, and the mixture is cooled to room temperature after the reaction is finished. The reaction solution was then filtered and washed with methanol to remove surface impurities, and the solid was dried in vacuo for 14h. The dried solid was dissolved in 220mL pyridine and heated to reflux for 4h. After the reaction was completed, the solution was cooled in a refrigerator for 4 hours. Filtering, washing with methanol and acetone in turn until the soluble impurities are completely washed, and obtaining the dark purple solid 5,10,15, 20-tetra (4-nitrophenyl) porphyrin.
Step 2: the dark purple solid obtained in step 1, 4g, was weighed, followed by addition of 240mL of concentrated hydrochloric acid and 16.92g of tin dichloride dihydrate, and reacted at 82℃for 9h. After the reaction was completed, it was cooled to room temperature, and then NH was added to an ice-water bath 3 ·H 2 O adjusts the pH to neutral. Filtering, washing with deionized water for multiple times to obtain green solid, and drying the solid in a vacuum drying oven for 14h. The solid was washed with acetone until the filtrate was lighter in color and the filtrate was spin-dried to give a bright purple solid of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
Step 3: the bright purple solid obtained in step 2, 5,10,15, 20-tetra (4-aminophenyl) porphyrin (200 mg, 0.294 mmol), copper acetate monohydrate (234.78 mg, 1.176 mmol) were weighed, followed by the addition of 20mL DMF, 20mL methanol and 60mL chloroform in this order and reacted at 78℃for 24h. And after the reaction is finished, removing chloroform and methanol by rotary evaporation, adding deionized water into the residual solution, stirring for 30min, filtering, washing with the deionized water, and drying for 6h to obtain a bluish violet solid, namely the organic ligand Cu-TAPP.
Step 4: the organic ligand Cu-TAPP from step 3 (73 mg, 0.1 mmol), zinc triflate (47.26 mg, 0.13 mmol) and the ancillary ligand PDCA (38. Mu.L, 0.4 mmol) were taken up in 35mL dry acetonitrile. The reaction solution was subjected to vacuum pumping and nitrogen introduction for 3 times, and reacted at 78℃for 48 hours. After the reaction, 350mL of diethyl ether is diffused into the reaction solution to obtain a brown-purple solid, namely a target compound Zn-Cu-TAPP-PDCA.
EXAMPLE 3 preparation of Zn-Cu-TAPP-PDCA
Step 1: 21.9g of p-nitrobenzaldehyde and 24.5mL of acetic anhydride are dissolved in 600mL of propionic acid, the mixture is reacted for 2 hours at 140 ℃, then 10.54mL of pyrrole is slowly added dropwise, the reaction is continued for 2 hours after the dropwise addition is finished, and the mixture is cooled to room temperature after the reaction is finished. The reaction solution was then filtered and washed with methanol to remove surface impurities, and the solid was dried in vacuo for 16h. The dried solid was dissolved in 240mL of pyridine and heated to reflux for 5h. After the reaction was completed, the solution was cooled in a refrigerator for 5 hours. Filtering, washing with methanol and acetone in turn until the soluble impurities are completely washed, and obtaining the dark purple solid 5,10,15, 20-tetra (4-nitrophenyl) porphyrin.
Step 2: the dark purple solid from step 1, 4g, was weighed, followed by 280mL of concentrated hydrochloric acid and 18.05g of tin dichloride dihydrate, and reacted at 85℃for 10 hours. After the reaction was completed, it was cooled to room temperature, and then NH was added to an ice-water bath 3 ·H 2 O adjusts the pH to neutral. Filtering, washing with deionized water for multiple times to obtain green solid, and drying the solid in a vacuum drying oven for 16h. The solid was washed with acetone until the filtrate was lighter in color and the filtrate was spin-dried to give a bright purple solid of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
Step 3: the bright purple solid obtained in step 2, 5,10,15, 20-tetra (4-aminophenyl) porphyrin (200 mg, 0.294 mmol), copper acetate monohydrate (293.49 mg, 1.47 mmol) were weighed, followed by the sequential addition of 20mL DMF, 24mL methanol and 70mL chloroform, and reacted at 80℃for 28h. And after the reaction is finished, removing chloroform and methanol by rotary evaporation, adding deionized water into the residual solution, stirring for 40min, filtering, washing with the deionized water, and drying for 7h to obtain a bluish violet solid, namely the organic ligand Cu-TAPP.
Step 4: the organic ligand Cu-TAPP (73 mg, 0.1 mmol) obtained in step 3, zinc perchlorate hexahydrate (52.13 mg, 0.14 mmol) and the ancillary ligand PDCA (42.8. Mu.L, 0.45 mmol) were weighed into 40mL of dry acetonitrile. The reaction solution was subjected to vacuum pumping and nitrogen introduction for 3 times, and reacted at 80℃for 54 hours. After the reaction, 400mL of diethyl ether is diffused into the reaction solution to obtain a brown-purple solid, namely a target compound Zn-Cu-TAPP-PDCA.
Example 4 UV-visible absorption Spectrometry test
2.3mg of Zn-Cu-TAPP-PDCA was dissolved in 2mL of acetonitrile to prepare a solution having a concentration of 1X 10 -4 The solution of M was subjected to uv-vis absorption spectroscopy. First, 2mL acetonitrile was added to each of the quartz test cell and the reference cell to scan the baseline to remove the effect of the background of the solution, followed by pipetting 10. Mu.L of 1X 10 -4 Adding the Zn-Cu-TAPP-PDCA solution of M into a test tank, and stirring for 1min to ensure that the solution is uniformly mixed. The ultraviolet-visible absorption spectrum of Zn-Cu-TAPP-PDCA is shown in figure 3, and the strong light absorption capacity and wide light absorption band of Zn-Cu-TAPP-PDCA provide favorable conditions for photocatalytic oxidation of primary amine due to Soret and Q band absorption of porphyrin characteristics and strong light absorption band at 405nm and multiple visible light absorption bands in the range of 500-700 nm.
Example 5 electrochemical Performance test
3.45mg of Zn-Cu-TAPP-PDCA was dissolved in 3mL of acetonitrile to prepare 1X 10 -4 M, then 116.4mg of tetrabutylammonium hexafluorophosphate was added as a supporting electrolyte, and the solution was purged with nitrogen for 10 minutes to exclude the influence of oxygen reduction peaks, and cyclic voltammetry was performed using a three-electrode system. The glassy carbon electrode is used as a working electrode, the platinum wire is used as a counter electrode, and the Ag/AgCl electrode is used as a reference electrode. The test was performed at room temperature and the cyclic voltammetry test spectrum of Zn-Cu-TAPP-PDCA is shown in FIG. 4. The electrochemical test result shows that the Cu-Cage has multiple groups of reduction peaks at-1.1V, -1.37V and-1.89V. Reduction potential of Cu-Cage relative to O 2 /O 2 ·- More negative (-0.56V) indicating that Cu-Cage has the ability to drive O 2 Conversion to O 2 ·- 。
EXAMPLE 6 photocatalytic Oxidation of benzylamine coupling applications
Zn-Cu-TAPP-PDCA (2.3 mg, 2X 10) -4 mmol, 1 mol%) benzylamine (2.2. Mu.L, 2X 10) -2 mmol) was dissolved in 2mL acetonitrile and added to a photoreaction quartz tube, a rubber stopper was plugged onto the quartz tube and oxygen was introduced for 10 minutes to maintain an oxygen atmosphere in the tube, after sealing, the reaction was carried out at room temperature under irradiation of 395nm LED blue light for 6 hours, after the reaction was completed, the conversion of benzylamine was calculated by nuclear magnetism, the yield was 98%, and a high conversion rate indicated that Zn-Cu-TAPP-PDCA could efficiently oxidize benzylamine to the corresponding imine product.
EXAMPLE 7 use of photocatalytic Oxidation of benzylamine derivatives in coupling reactions
P-chlorobenzylamine (2X 10) was weighed out separately -2 mmol), p-methoxybenzylamine (2X 10) -2 mmol) and p-bromobenzylamine (2X 10) -2 mmol) was added to different quartz tubes, followed by addition of Zn-Cu-TAPP-PDCA (2.3 mg, 2X 10) -4 mmol, 1 mol%) and 2mL acetonitrile, the quartz tube is plugged with a rubber plug and oxygen is introduced for 10 minutes to keep an oxygen atmosphere in the tube, after sealing, the reaction is carried out for 6 hours at room temperature under irradiation of 395nm LED blue light, and after the reaction is finished, the conversion of different primary amine substrates by nuclear magnetism is calculated, and the yields are 95%, 93% and 84% respectively. This result shows that the synthesized Zn-Cu-TAPP-PDCA has higher conversion rate for different primary amines and good substrate applicability.

Claims (3)

1. A preparation method of a copper porphyrin metal organic cage with photocatalytic oxidation primary amine coupling performance is characterized in that copper-5, 10,15, 20-tetra (4-aminophenyl) porphyrin Cu-TAPP is used as an organic ligand, 2-pyridylaldehyde PDCA is used as an auxiliary ligand, and Zn in a metal zinc salt is used as Zn 2+ As a node, a metal organic cage Zn-Cu-TAPP-PDCA is formed by a solvothermal method, and the synthetic route is as follows:
Zn 2+ +Cu-TAPP+PDCA→Zn-Cu-TAPP-PDCA；
the metal zinc salt is one or more than two of bis [ bis (trifluoromethylsulfonyl) imide ] zinc, zinc trifluoromethane sulfonate and zinc perchlorate hexahydrate;
the organic ligand Cu-TAPP has the following (A) molecular structural formula:
the auxiliary ligand PDCA has the following (B) molecular structural formula:
2. the method for preparing the copper porphyrin metal organic cage with the photocatalytic oxidation primary amine coupling performance according to claim 1, which is characterized by comprising the following specific steps:
step 1: p-nitrobenzaldehyde and acetic anhydride were mixed at 1:1.6 to 1:1.8 in propionic acid at 130-140 deg.c for 1-2 hr, and then slowly dropping pyrrole to make the molar ratio of p-nitrobenzaldehyde to pyrrole 1:0.95 to 1:1.05, continuing to react for 1-2 h after the dripping is finished, and cooling to room temperature after the reaction is finished; filtering the reaction solution, washing the reaction solution with methanol to remove impurities on the surface, and drying the solid in vacuum for 12-16 h; dissolving the dried solid in pyridine and heating and refluxing for 3-5 h; after the reaction is finished, the solution is placed in a refrigerator to be cooled for 3 to 5 hours, then filtered, and then washed by methanol and acetone in sequence until the soluble impurities are completely washed, so as to obtain a deep purple solid A;
step 2: adding concentrated hydrochloric acid into the solid A obtained in the step 1 to ensure that the concentration of the solid A in the concentrated hydrochloric acid is 16.67-20 g/L; then adding tin dichloride dihydrate, and reacting for 8-10 hours at the temperature of 80-85 ℃, wherein the mole ratio of the solid A to the tin dichloride dihydrate is 1:14 to 1:16; after the reaction was completed, it was cooled to room temperature, and then NH was added to an ice-water bath 3 ·H 2 O adjusts the pH of the reaction solution to be neutral; then filtering, washing for a plurality of times by using deionized water to obtain green solid, placing the green solid in a vacuum drying oven for drying for 12-16 hours, washing by using acetone until the color of the filtrate is lighter, and spin-drying the filtrate to obtain a bright purple solid B;
step 3: mixing the solid B obtained in the step 2 with copper acetate monohydrate according to the weight ratio of 1: 3-1: 5 in a volume ratio of 1: (0.8-1.2): (2.5-3.5) in DMF, methanol and chloroform at 75-80 ℃ for 20-28 h; after the reaction is finished, removing chloroform and methanol by rotary evaporation, adding deionized water into the residual solution, stirring for 20-40 min, filtering, washing with deionized water, and vacuum drying for 5-7 h to obtain a blue-violet solid, namely the organic ligand Cu-TAPP;
step 4: mixing the organic ligand Cu-TAPP obtained in the step 3, the metal zinc salt and the auxiliary ligand PDCA according to the proportion of 1: (1.2-1.4): (3.6-4.5) to dry acetonitrile; the reaction liquid is vacuumized, introduced with nitrogen for 2 to 4 times and reacts for 42 to 54 hours at the temperature of 75 to 80 ℃; and after the reaction is finished, diethyl ether is diffused into the reaction solution to obtain a brown-purple solid, namely a target compound Zn-Cu-TAPP-PDCA.
3. The application of the copper porphyrin metal organic cage with the photocatalytic oxidation primary amine coupling performance prepared by adopting the preparation method of claim 1 or 2 in the photocatalytic oxidation primary amine coupling reaction.
CN202310544775.4A 2023-05-15 2023-05-15 Preparation method and application of copper porphyrin metal organic cage with photocatalytic oxidation primary amine coupling performance Pending CN116731024A (en)

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