CN113546683B - Application of covalent organic framework material based on porphyrin in photocatalytic oxidation cyclization reaction - Google Patents
Application of covalent organic framework material based on porphyrin in photocatalytic oxidation cyclization reaction Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 40
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 20
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 238000007363 ring formation reaction Methods 0.000 title claims abstract description 13
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical class CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000001678 irradiating effect Effects 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- KOJMPSBVVZYIJD-UHFFFAOYSA-N 2-methyl-3a,4,5,5a-tetrahydropyrrolo[3,4-c]quinoline-1,3-dione Chemical class CN(C(C1C2=C3C=CC=CC3NC1)=O)C2=O KOJMPSBVVZYIJD-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 230000002194 synthesizing effect Effects 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- ALXPZLQBSUZCHN-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-dicarbaldehyde Chemical compound C1=CC(C=O)(C=O)CC=C1C1=CC=CC=C1 ALXPZLQBSUZCHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- UVAJHKGWZQPAEZ-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.NC2=CC=CC=C2 Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.NC2=CC=CC=C2 UVAJHKGWZQPAEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- KJJYDECLTBAKCK-UHFFFAOYSA-N 1-(3-bromophenyl)pyrrole-2,5-dione Chemical compound BrC1=CC=CC(N2C(C=CC2=O)=O)=C1 KJJYDECLTBAKCK-UHFFFAOYSA-N 0.000 claims description 2
- FECSFBYOMHWJQG-UHFFFAOYSA-N 1-(4-bromophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Br)=CC=C1N1C(=O)C=CC1=O FECSFBYOMHWJQG-UHFFFAOYSA-N 0.000 claims description 2
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 claims description 2
- SBKKXWSZVVDOLR-UHFFFAOYSA-N 1-(4-fluorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(F)=CC=C1N1C(=O)C=CC1=O SBKKXWSZVVDOLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000009849 vacuum degassing Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000007243 oxidative cyclization reaction Methods 0.000 abstract description 8
- 238000007036 catalytic synthesis reaction Methods 0.000 abstract description 2
- 125000000147 tetrahydroquinolinyl group Chemical class N1(CCCC2=CC=CC=C12)* 0.000 abstract description 2
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 abstract 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 17
- 238000006053 organic reaction Methods 0.000 description 14
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 13
- -1 tetrahydroquinoline compound Chemical class 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
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- 238000002474 experimental method Methods 0.000 description 6
- 230000033116 oxidation-reduction process Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 150000003530 tetrahydroquinolines Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- LBUJPTNKIBCYBY-UHFFFAOYSA-N tetrahydroquinoline Natural products C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- ICLZNGAELWYHKL-CAPFRKAQSA-N (E)-3-[5-[5-[4-(N-phenylanilino)phenyl]thiophen-2-yl]thiophen-2-yl]prop-2-enoic acid Chemical compound OC(=O)\C=C\c1ccc(s1)-c1ccc(s1)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 ICLZNGAELWYHKL-CAPFRKAQSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003288 anthiarrhythmic effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
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- REPFNYFEIOZRLM-UHFFFAOYSA-N chembl376444 Chemical compound C1=CC(N)=CC=C1C(C1=CC=C(N1)C(C=1C=CC(N)=CC=1)=C1C=CC(=N1)C(C=1C=CC(N)=CC=1)=C1C=CC(N1)=C1C=2C=CC(N)=CC=2)=C2N=C1C=C2 REPFNYFEIOZRLM-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
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- 238000006352 cycloaddition reaction Methods 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000000324 neuroprotective effect Effects 0.000 description 1
- HDVPIMZXLWNIIP-UHFFFAOYSA-N nickel 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Ni].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 HDVPIMZXLWNIIP-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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Abstract
The invention relates to the technical field of catalytic synthesis, in particular to application of a covalent organic framework material based on porphyrin in photocatalytic oxidation cyclization reaction, wherein the structure of the covalent organic framework material based on porphyrin is shown as a formula I:
N-methyltetrahydro-1H-pyrrolo [3,4-c]The synthesis method of the-quinoline-1, 3 (2H) -dione derivative comprises the following steps: adding the N, N-dimethylaniline derivative and the maleimide derivative into an organic solvent to obtain a solution A; adding a material of the formula I into the solution A to obtain a solution B; and irradiating the solution B with visible light to obtain the product. According to the invention, a metal-free covalent organic framework based on a porphyrin structure is used as a photosensitizer, oxygen is used as an oxidant, and an oxidative cyclization reaction of N, N-dimethylaniline derivatives and maleimide derivatives is realized under visible light irradiation, so that tetrahydroquinoline compounds are efficiently constructed; the method has the advantages of green and mild conditions, repeated utilization of the photosensitizer, improved utilization rate of the photosensitizer, reduced cost and contribution to industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of catalytic synthesis, in particular to application of a covalent organic framework material based on porphyrin in photocatalytic oxidation cyclization reaction.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Tetrahydroquinolines are important building blocks found in many natural products and synthetic drugs, with a wide range of biological activities such as antibacterial, neuroprotective, antiarrhythmic, etc. Due to the importance of its structureThe synthesis of tetrahydroquinolines has been the focus of study by chemists. N-methyltetrahydro-1H-pyrrolo [3,4-c]-quinoline-1, 3 (2H) -dione, as an important intermediate in pharmaceutical synthesis, is widely used in the synthesis of many organic drugs and organic molecules. Among them, the oxidative cyclization reaction between N, N-dimethylaniline and maleimide is one of the effective methods for constructing a tetrahydroquinoline skeleton. In 2011, the Miura group utilized CuCl 2 /O 2 The catalytic combination of the catalyst realizes the oxidative cyclization reaction between N, N-dimethylaniline and maleimide, and the tetrahydroquinoline compound is successfully constructed. Subsequent studies have found that the oxidative cyclization reaction between N, N-dimethylaniline and maleimide can be similarly achieved by using tert-butyl hydroperoxide (TBHP) as an oxidizing agent and copper (II) or tetrabutylammonium iodide (TBAI) as a catalyst, thereby constructing tetrahydroquinoline compounds with high efficiency.
Compared with the traditional organic reaction, the visible light catalytic organic reaction is paid attention to because of a series of advantages of low cost, high efficiency, green environmental protection and the like, and in 2012, the Bian group utilizes Ru (bpy) 3 Cl 2 As a photosensitizer, the oxidation cyclization reaction of N, N-dimethylaniline and maleimide is realized under the irradiation of visible light, and the tetrahydroquinoline compound is successfully constructed. In 2016, bissenber group utilized [ Cu (dap) 2 ] + As a photosensitizer, trifluoroacetic acid is used to promote oxidative quenching of the photosensitizer, and oxidative cyclization of N, N-dimethylaniline and maleimide is achieved. In 2018, wu group utilized Ru (bpy) 3 Cl 2 Co (dmgH) as photosensitizer 2 The pyCl is used as a catalyst to realize cyclization reaction of N, N-dimethylaniline and maleimide, protons and electrons removed by a substrate in situ react with the maleimide in a transfer hydrogenation reaction, and the construction of the tetrahydroquinoline compound is realized under the condition of redox neutrality. In 2019, de Sarkar group constructed tetrahydroquinoline compounds under visible light catalysis using tetraphenylporphyrin nickel NiTPP as a photosensitizer.
Most photosensitizers applied to the photocatalytic organic reaction at the present stage are known in the prior art as metal organic compounds with complex structures and organic small molecules with difficult synthesis; the photocatalysis organic reaction is carried out, and meanwhile, the reaction rate of the photocatalysis organic reaction is high, so that more byproducts are generated in the reaction, and the photosensitizer cannot be recycled; most of the metals used in the metal organic compound used as the photosensitizer are noble metals, which greatly increases the cost of the reaction.
Therefore, how to design and synthesize a material to replace metal organic small molecules for photocatalytic reaction and recycle to achieve the purpose of green chemistry is a key for further development of the photocatalytic field.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide an application of a covalent organic framework material based on porphyrin in photocatalytic oxidation cyclization reaction, wherein the covalent organic framework material based on porphyrin has no noble metal carried thereon, but has oxidation-reduction potential reaching 0.95eV, so that the application range of the covalent organic framework material as a photocatalyst in photocatalytic organic reaction is greatly improved, and the covalent organic framework material based on porphyrin structure is used as a novel photocatalyst in catalytic oxidation cycloaddition reaction to synthesize N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivatives, and can be repeatedly used for many times without reducing activity, so that the covalent organic framework material can successfully replace metal organic micromolecules as photosensitizers in the reaction, and the catalytic yield is up to 70%.
In order to achieve the above object, the technical scheme of the present invention is as follows:
in a first aspect of the invention, there is provided the use of a porphyrin-based covalent organic framework material having the structure of formula i:
in a second aspect of the present invention, there is provided a method of synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative, the method comprising the steps of:
1) Adding the N, N-dimethylaniline derivative and the maleimide derivative into an organic solvent to obtain a solution A;
2) Adding a metal-free covalent organic framework material based on a porphyrin structure into the solution A as a photocatalyst to obtain a solution B;
3) The solution B was irradiated with visible light to give N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivatives.
In a third aspect of the present invention, there is provided a method of preparing the porphyrin-based covalent organic framework material comprising the steps of:
adding o-dichlorobenzene and n-butanol into 5,10,15, 20-tetra (4-aminobenzene) porphyrin and 4, 4-biphenyl dicarboxaldehyde, vacuum degassing and heating for reaction to obtain a covalent organic framework material H based on porphyrin 2 p-Bph-COF。
The specific embodiment of the invention has the following beneficial effects:
porphyrin-based covalent organic framework material H in embodiments of the present invention 2 Although the p-Bph-COF is not loaded with noble metal, the oxidation-reduction potential of the p-Bph-COF reaches 0.95eV, so that the application range of the p-Bph-COF serving as a photocatalyst in photocatalytic organic reactions is greatly improved, and most photocatalytic organic reactions can be catalyzed by the oxidation-reduction potential of the p-Bph-COF;
in the prior art, in the work of taking porphyrin small molecules as photocatalysts for catalyzing oxidation cyclization reaction, most of porphyrin small molecules and derivatives thereof are carried with noble metals to raise the oxidation reduction potential of the small molecules so as to meet the requirement of photocatalysis because the oxidation reduction potential of the porphyrin small molecules is insufficient to meet the requirement of catalyzing the reaction, but the cost of the reaction is greatly increased, and the covalent organic framework material H based on porphyrin in the embodiment of the invention 2 The p-Bph-COF can solve the problem of using noble metal and can be recycled, so that the cost of the reaction is greatly reduced;
in the embodiment of the invention, the covalent organic framework material based on porphyrin structure is used as a novel photocatalyst for catalyzing oxidative cyclization reaction, and is firstly applied to the oxidative cyclization reaction to prepare and synthesize N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione, and has high universality and repeatability, and belongs to heterogeneous catalysis which can be repeatedly utilized without reducing activity; the metal organic micromolecules are successfully replaced to be used as a photocatalyst for reaction, and the catalytic yield can reach 70%;
according to the invention, a metal-free covalent organic framework based on a porphyrin structure is used as a photosensitizer, oxygen is used as an oxidant, and the oxidation cyclization reaction of the N, N-dimethylaniline derivative and the maleimide derivative is realized under visible light irradiation, so that the tetrahydroquinoline compound is efficiently constructed. The method has the advantages of green and mild conditions, repeated utilization of the photosensitizer, improved utilization rate of the photosensitizer, reduced cost and contribution to industrial popularization and application.
In the embodiment of the invention, the LED blue light is used as a visible light source, the reaction condition is green and mild, and the operation is simple.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a PXRD pattern of the H2p-Bph-COF photocatalyst prepared in example 1;
FIG. 2 is an ultraviolet-visible absorption spectrum, an energy gap conversion chart, and a cyclic voltammogram of the H2p-Bph-COF photocatalyst prepared in example 1; wherein, fig. 2a is an ultraviolet visible absorption spectrum, the small graph in fig. 2a is an energy gap conversion graph, and fig. 2b is a cyclic voltammogram;
FIG. 3 is an SEM image of H2p-Bph-COF prepared in example 1;
FIG. 4 is a thermogravimetric curve of H2p-Bph-COF prepared in example 1;
FIG. 5 is a graph showing the adsorption of nitrogen by H2p-Bph-COF prepared in example 1;
FIG. 6 is a pore size distribution curve of H2p-Bph-COF prepared in example 1;
FIG. 7 is a leaching experiment of the H2p-Bph-COF catalytic reaction prepared in example 1;
FIG. 8 is a three-fold repeat experiment of the H2p-Bph-COF catalytic reaction prepared in example 1;
FIG. 9 is a test of hydrogen peroxide generation; FIG. 9a is a sodium iodide solution which turns yellow after oxidation; fig. 9b is a solution of unoxidized sodium iodide.
FIG. 10 is a PXRD diagram of H2p-Bph-COF before and after a cycling experiment;
FIG. 11 is a hydrogen spectrum of the product N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione;
FIG. 12 is a carbon spectrum of the product N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
Compared with the traditional organic reaction, the visible light catalytic organic reaction provides a green and mild way for the construction of tetrahydroquinoline compounds due to a series of advantages of low cost, high efficiency, green environmental protection and the like. In the prior art, most of photocatalysts used in the visible light catalytic oxidation cyclization reaction are small molecular compounds such as metal complexes, organic dyes and the like, and when the photocatalytic organic reaction is carried out, more byproducts can be generated due to the fact that the reaction rate of the photocatalysis is high, and the photocatalysts cannot be recycled; most of the metals used in addition to the metal organic compound as a photocatalyst are noble metals, which greatly increases the cost of the reaction. At present, no report of visible light catalysis of the reaction by using a metal-free covalent organic framework material based on a porphyrin structure as a photocatalyst exists.
In view of this, in one embodiment of the present invention, there is provided the use of a porphyrin-based covalent organic framework material having the structure of formula i:
porphyrin as a common photocatalyst is applied to the synthesis of a covalent organic framework, so that the problem that the photocatalyst cannot be recovered for secondary use after the photocatalytic reaction is performed can be well solved; additionally by covalent organic framework material H based on porphyrin 2 Characterization of p-Bph-COF photochemistry and electrochemical properties found that the material, although not carrying noble metals, has also reached a redox potential of 0.95eV which has been able to catalyze most photocatalytic organic reactions, which greatly improves H 2 The p-Bph-COF is applied to the application range of photocatalytic organic reaction as a photocatalyst.
In one embodiment of the present invention, there is provided a method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative, comprising the steps of:
1) Adding the N, N-dimethylaniline derivative and the maleimide derivative into an organic solvent to obtain a solution A;
2) Adding a metal-free covalent organic framework material based on a porphyrin structure into the solution A as a photocatalyst to obtain a solution B;
3) The solution B was irradiated with visible light to give N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivatives.
The technical problem to be solved by the embodiment of the invention is to efficiently construct the N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative by using a metal-free covalent organic framework material based on a porphyrin structure as a photocatalyst and catalyzing the oxidative cyclization reaction of N, N-dimethylaniline and maleimide by visible light. The method uses covalent organic framework material based on porphyrin structure as photocatalyst, does not need to load any metal, and can realize multiple cycle use of photocatalyst without reducing activity, and the whole reaction condition is green, mild and efficient.
In one or more embodiments, the N, N-dimethylaniline derivatives have the following structural formula:
wherein R is selected from: F. cl, br, OMe or Me.
In one or more embodiments, the maleimide derivative is selected from one or more of the following: n- (4-fluorophenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-bromophenyl) maleimide, N- (4-methoxy) maleimide, N- (3-bromophenyl) maleimide.
In one or more embodiments, in step 1), the organic solvent is selected from one or more of the following: chloroform, acetone, tetrahydrofuran, 1, 4-dioxane, toluene and ethanol;
preferably, the organic solvent is selected from chloroform, acetone or toluene, more preferably chloroform; the organic solvent selected in the embodiment has a certain influence on the catalytic effect, and when chloroform, acetone or toluene is used as the solvent, the catalytic yield of the reaction in the system is higher, which can be comparable with that of porphyrin small molecules loaded with noble metals.
In one or more embodiments, in step 1), the concentration of the maleimide derivative in solution a is from 0.033mol/L to the saturation concentration;
in one or more embodiments, in step 2), the photosensitizer concentration is from 0.00004 to 0.00006mol/L; further preferably 0.00005mol/L; the photosensitizer has the best catalytic effect as a catalyst under the concentration, and the highest catalytic yield;
in one or more embodiments, step 3) is performed in an oxygen atmosphere;
in one or more embodiments, the light source used for the visible light irradiation in step 3) is LED blue light;
in one or more embodiments, the time for which the solution B is irradiated with visible light in step 3) is 8 to 18 hours, preferably 14 hours, at which reaction time the catalytic yield of the reaction is high.
In one embodiment of the present invention, a method for preparing the porphyrin-based covalent organic framework material is provided, comprising the following steps:
in one or more embodiments, the precipitate is collected by filtration after the heating reaction is complete, washed and dried in vacuo; preferably, anhydrous THF and acetone are used for the washing; the vacuum drying is carried out at 110 to 130℃and preferably 120 ℃.
The invention is further illustrated and described below in connection with specific examples.
Example 1
Synthesis of porphyrin-based covalent organic framework Material H 2 p-Bph-COF：
Metal-free 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin (H) 2 TAPP) (32.38 mg,0.05 mmol) and o-dichlorobenzene/n-butanol (3/1, by volume; 1 mL) was degassed by three free pump-thaw cycles of 4, 4-biphenyldicarboxaldehyde (21.02 mg,0.10 mmol) in a glass tube (10 mL); the tube was sealed and heated at 120 ℃ for 3 days. The precipitate was collected by filtration, washed with anhydrous THF and acetone, and dried under vacuum overnight at 120 ℃.
From FIG. 1, it can be seen that H 2 The p-Bph-COF has good crystallinity, H 2 The strong diffraction peaks at 3.3℃and 7.5℃of the PXRD pattern of p-Bph-COF correspond to the (1, 0) and (0, 1, 0) crystal planes, respectively.
Fig. 2a shows that the absorption of the material is very broad, and the Eg = +1.75eV of the material is obtained according to the energy gap conversion formula, and the cyclic voltammetry test of the material in fig. 2-b gives a redox potential of about 0.95eV, which can already catalyze most photocatalytic organic reactions.
As can be observed by Scanning Electron Microscopy (SEM), H 2 The p-Bph-COF has regular surface morphology and uniform particle size, and the morphology can be maintained substantially after the reaction (fig. 3) with good stability to support multiple sets of cycling experiments. Thermogravimetric analysis (TGA) showed H when the temperature was raised to 300 °c 2 The p-Bph-COF still showed no significant weight loss and good thermal stability (fig. 4).
As can be seen from FIGS. 5 and 6, the adsorption-desorption test using nitrogen demonstrated that the material had an adsorption capacity of 253.2cm at 77K 3 g -1 And the pore size is mainly distributed at 2.3nm.
Example 2
H 2 Synthesis of N-methyltetrahydro-1H-pyrrolo [3,4-c ] by catalytic oxidation cyclization of p-Bph-COF]-quinoline-1, 3 (2H) -dione:
n, N-dimethylaniline (0.20 mmol, 2.0 eq), maleimide (0.10 mmol, 1.0 eq), H2p-Bph-COF (8 mg, 5 mol%) were placed in a pre-dried standard glass reaction tube, chloroform was added as solvent, irradiated with blue LED under oxygen atmosphere for 14H, and the catalyst was collected by centrifugation. The organic layer was separated and the solvent removed in vacuo and purified by column chromatography on silica gel (ethyl acetate/petroleum ether=1/3, v/v) to give the product N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione. The yield of the obtained product was 70%. Nuclear magnetic hydrogen spectrum, carbon spectrum and mass spectrum identify the product as N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione.
The hydrogen spectrum and the carbon spectrum of the product N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione are shown in FIG. 11 and FIG. 12 respectively.
The catalytic yield of the reaction of the example reaches 70%, which is comparable to that of porphyrin small molecule with noble metal carried.
To illustrate H 2 Heterogeneous catalytic properties of p-Bph-COF, leaching experiments were performed. After the reaction was carried out for 5 hours, the photocatalyst was filtered out from the reaction solution, and the reaction was continued by placing the filtrate under the same conditions for 6 hours without any further increase in yield, which proved that the reaction process was indeed heterogeneous catalysis, as shown in fig. 7. Thus further study H 2 The recycling of p-Bph-COF is used to investigate whether the material can achieve the same catalytic efficiency in the case of multiple cycling experiments, and to collect the catalyst H after each catalysis by centrifugation 2 p-Bph-COF, washed with chloroform, dried at 80 ℃ and used for the next catalytic reaction under the same conditions. As heterogeneous catalyst, the material can be repeated at least three more times and the yield can be maintained at 70%, as shown in fig. 8. Then, the mechanism of the reaction is checked, and the sodium iodide solution is used for verification because superoxide anions are generated and hydrogen peroxide is generated in the reaction process, as shown in fig. 9. In addition, the comparison of the PXRD diffraction patterns before and after the reaction shows that the photocatalyst still maintains good crystallinity before and after the reaction, as shown in FIG. 10.
Example 3
The difference is that the solvent used is acetone as in example 2.
Example 4
The difference is that tetrahydrofuran is used as the solvent in example 2.
Example 5
The difference is that the solvent used is 1, 4-dioxane as in example 2.
Example 6
The difference is that toluene is the solvent of choice as in example 2.
Example 7
The difference is that the solvent used is ethanol as in example 2.
Example 8
The difference as in example 2 is that the photosensitizer H2p-Bph-COF is added in an amount of 3mg.
Example 9
The difference as in example 2 is that the amount of photosensitizer H2p-Bph-COF added is 5mg.
Example 10
The difference as in example 2 is that the photosensitizer H2p-Bph-COF is added in an amount of 10mg.
Example 11
The difference is that the reaction time is 3h as in example 2.
Example 12
The difference is that the reaction time is 6h as in example 2.
Example 13
The difference is that the reaction time is 8h as in example 2.
Example 14
The difference was that the reaction time was 10h as in example 2.
Example 15
The difference is that the reaction time is 12h as in example 2.
Example 16
The difference was that the reaction time was 16h as in example 2.
Example 17
The difference is that the reaction time is 18h as in example 2.
Example 18
The difference from example 2 is that the feed ratio of dimethylaniline to maleimide is 1:1.
example 19
The difference from example 2 is that the feed ratio of dimethylaniline to maleimide is 3:1.
example 20
The same as in example 2, except that the feeding ratio of dimethylaniline to maleimide was 1:2.
example 21
The difference is that the volume of chloroform as the organic solvent added was 1mL as in example 2.
Example 22
The difference is that the volume of chloroform as the organic solvent added was 2mL as in example 2.
Example 23
The difference is that the volume of chloroform as the organic solvent added was 4mL as in example 2.
Example 24
The difference is that the volume of chloroform as the organic solvent added was 5mL as in example 2.
TABLE 1 product yields (%)
As can be seen from the above embodiments, H 2 Synthesis of N-methyltetrahydro-1H-pyrrolo [3,4-c ] by catalytic oxidation cyclization of p-Bph-COF]The reaction conditions of quinoline-1, 3 (2H) -dione, different solvents and different reaction times and different photocatalytic amounts all have an influence on the yield of the product; when chloroform, acetone or toluene is adopted as the solvent, the reaction catalysis yield in the system is higher, and particularly when chloroform is adopted as the solvent, the reaction catalysis yield in the system can reach 70 percent, which is comparable to the catalysis yield of porphyrin small molecules loaded with noble metals, and the oxidation-reduction potential of covalent organic framework materials based on porphyrin structures is proved to be improved to a certain extent relative to porphyrin catalysts under the small molecules.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. The application of a porphyrin-based covalent organic framework material in synthesizing N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivatives in photocatalytic oxidation cyclization reaction is characterized in that the structure of the porphyrin-based covalent organic framework material is shown as a formula I:
the N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivatives are N, N-dimethylaniline derivatives and maleimide derivatives, and are prepared by using a covalent organic framework based on porphyrin as a photosensitizer, oxygen as an oxidant and irradiation of visible light.
2. The use of claim 1, wherein the porphyrin-based covalent organic framework material is prepared by the following method:
adding o-dichlorobenzene and n-butanol into 5,10,15, 20-tetra (4-aminobenzene) porphyrin and 4, 4-biphenyl dicarboxaldehyde, vacuum degassing and heating for reaction to obtain a covalent organic framework material H based on porphyrin 2 p-Bph-COF。
3. The use according to claim 2, wherein the volume ratio of o-dichlorobenzene to n-butanol is 2-4:1;
alternatively, the relative molar content of 4, 4-biphenyldicarboxaldehyde to 5,10,15, 20-tetrakis (4-aminobenzene) porphyrin is 2:1, a step of;
or the temperature of the heating reaction is 110-130 ℃;
or filtering and collecting precipitate after the heating reaction is finished, washing and vacuum drying; vacuum drying is carried out at 110-130 ℃.
4. The use according to claim 3, wherein the volume ratio of o-dichlorobenzene to n-butanol is 3:1.
5. the use according to claim 3, wherein the temperature of the heating reaction is 120 ℃.
6. The use according to claim 3, wherein the washing uses anhydrous THF and acetone.
7. Use according to claim 3, wherein the vacuum drying is carried out at 120 ℃.
8. A method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative, comprising the steps of:
1) Adding the N, N-dimethylaniline derivative and the maleimide derivative into an organic solvent to obtain a solution A;
2) Adding the porphyrin-based covalent organic framework material of claim 1 as a photosensitizer into solution a to obtain solution B;
3) The solution B was irradiated with visible light to give N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivatives.
9. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 8, wherein the N, N-dimethylaniline derivative has the following structural formula:
wherein R is selected from: F. cl, br, OMe or Me.
10. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 8, wherein the maleimide derivative is selected from one or more of the following: n- (4-fluorophenyl) maleimide, N- (4-chlorophenyl) maleimide, N- (4-bromophenyl) maleimide, N- (3-bromophenyl) maleimide.
11. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 8, wherein in step 1), the organic solvent is selected from one or more of the following: chloroform, acetone, tetrahydrofuran, 1, 4-dioxane, toluene and ethanol.
12. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 11, wherein the organic solvent is selected from the group consisting of chloroform, acetone, and toluene.
13. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 12, wherein the organic solvent is chloroform.
14. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 8, wherein in step 1), the concentration of the maleimide derivative in the solution A is from 0.033mol/L to a saturated concentration.
15. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 8, wherein the concentration of the photosensitizer is 0.00004-0.00006 mol/L.
16. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 15, wherein the photosensitizer concentration is 0.00005mol/L.
17. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 8, wherein step 3) is performed in an oxygen atmosphere;
or, the light source used for the irradiation of the visible light in the step 3) is LED blue light;
or, the time for irradiating the solution B with visible light in the step 3) is 8-18 h.
18. The method for synthesizing an N-methyltetrahydro-1H-pyrrolo [3,4-c ] -quinoline-1, 3 (2H) -dione derivative according to claim 17, wherein the time for irradiating the solution B with visible light is 14H.
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