CN112898544A - Difunctional conjugated microporous polymer containing pyrimidine ring and cyano and preparation method thereof - Google Patents
Difunctional conjugated microporous polymer containing pyrimidine ring and cyano and preparation method thereof Download PDFInfo
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 58
- 125000000714 pyrimidinyl group Chemical group 0.000 title claims abstract description 15
- 125000004093 cyano group Chemical group *C#N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- TXLYDSYKOVELCW-UHFFFAOYSA-N 4-[2,6-bis(4-formylphenyl)pyrimidin-4-yl]benzaldehyde Chemical compound C(=O)C1=CC=C(C=C1)C1=NC(=CC(=N1)C1=CC=C(C=C1)C=O)C1=CC=C(C=C1)C=O TXLYDSYKOVELCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- FUQCKESKNZBNOG-UHFFFAOYSA-N 2-[4-(cyanomethyl)phenyl]acetonitrile Chemical compound N#CCC1=CC=C(CC#N)C=C1 FUQCKESKNZBNOG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 17
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 150000007514 bases Chemical class 0.000 claims description 11
- DPVIABCMTHHTGB-UHFFFAOYSA-N 2,4,6-trichloropyrimidine Chemical compound ClC1=CC(Cl)=NC(Cl)=N1 DPVIABCMTHHTGB-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 9
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 8
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003230 pyrimidines Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000013315 hypercross-linked polymer Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KDEDDZHPJJHRBR-UHFFFAOYSA-N 1-(2-hydroxyethoxymethyl)-5-methyl-6-thiophen-2-ylpyrimidine-2,4-dione Chemical compound OCCOCN1C(=O)NC(=O)C(C)=C1C=1SC=CC1 KDEDDZHPJJHRBR-UHFFFAOYSA-N 0.000 description 1
- HDMHBHNRWDNNCD-UHFFFAOYSA-N 1-[(2-hydroxyethoxy)methyl]-6-(phenylsulfanyl)thymine Chemical class OCCOCN1C(=O)NC(=O)C(C)=C1SC1=CC=CC=C1 HDMHBHNRWDNNCD-UHFFFAOYSA-N 0.000 description 1
- JUYLMPWKVWDXBE-UHFFFAOYSA-N 4-pyrimidin-2-ylbenzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=NC=CC=N1 JUYLMPWKVWDXBE-UHFFFAOYSA-N 0.000 description 1
- 208000030507 AIDS Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000725303 Human immunodeficiency virus Species 0.000 description 1
- 208000005016 Intestinal Neoplasms Diseases 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
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- 239000002274 desiccant Substances 0.000 description 1
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- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 229960002949 fluorouracil Drugs 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 206010017758 gastric cancer Diseases 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 201000002313 intestinal cancer Diseases 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/143—Side-chains containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
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Abstract
The invention relates to the technical field of conjugated microporous polymers, and provides a bifunctional conjugated microporous polymer containing a pyrimidine ring and a cyano group and a preparation method thereof. The conjugated microporous polymer provided by the invention is obtained by polymerizing 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile, has a pyrimidine ring and a cyano group, and is a novel bifunctional conjugated microporous polymer. The conjugated microporous polymer provided by the invention is a crystal material with a fibrous structure, has certain ultraviolet absorption capacity, and has wide application prospects in the fields of gas adsorption, photocatalysis and the like. The preparation method provided by the invention has simple steps and is easy to operate.
Description
Technical Field
The invention relates to the technical field of conjugated microporous polymers, in particular to a difunctional conjugated microporous polymer containing a pyrimidine ring and a cyano group and a preparation method thereof.
Background
The pyrimidine compounds are hexatomic heterocyclic compounds containing two nitrogen atoms in a molecular structure, have the effects of resisting fungi and regulating plant growth due to the particularity of the pyrimidine ring structure, and can be used for preparing pesticides, herbicides, bactericides and the like. When the complex forms a metal ion complex, the activity, the effective period and the half-life period of the original drug can be prolonged, and the toxicity to mammals can be reduced. In addition to the above applications, the pyrimidine compounds have wide applications in medical medicine, especially in anticancer and anti-AIDS aspects, for example, 5-fluorouracil is a metabolism-resistant and anti-tumor drug widely used in clinical medicine, and has good clinical effects on treating various cancers such as intestinal cancer and gastric cancer, and monomers or derivatives thereof have anti-tumor effects. The 1- [ (2-hydroxyethoxy) methyl ] -6- (thiophenyl) thymine (HEPT) compounds have stronger HIV virus inhibition effect and lower toxic and side effect, and the compounds have wide drug resistance effect. Therefore, the development prospect of the pyrimidine compounds is very wide.
Organic porous polymers (POPs) are a novel polymer material with high specific surface area and adjustable pore structure. Compared with metal organic framework materials and inorganic porous materials, POPs have the characteristics of designability of molecules, adjustable pore structure and function and the like. The materials based on POPs are classified into 4 types, namely covalent organic framework polymers (COFs), hypercrosslinked polymers (HCPs), self-polymerized microporous Polymers (PIMs) and Conjugated Microporous Polymers (CMPs).
In recent years, CMPs have received attention from a wide range of researchers as emerging organic porous materials. The material is characterized in that the material has diversity of pi-conjugated structures of construction units. Building units include phenyl, arene, heterocyclic aromatic and macrocyclic rings, and since there are fewer restrictions on the size, geometry and functional groups of the building units, the porosity of CMPs can be systematically adjusted as needed, optimizing their structure.
Based on the diversity of construction units and reaction types, CMPs materials provide a valuable platform for the development of novel organic porous materials. The CMPs material has the characteristics, so that the CMPs material has wide application in the fields of gas adsorption, heterogeneous catalysis, electrochemistry, photocatalysis, luminescent devices, chemical sensors and the like.
Although the CMPs materials have been greatly developed in various fields in recent years, and the CMPs materials for different applications are widely researched and prepared, the variety of the CMPs materials is still few, and the development of novel conjugated microporous polymers is a research hotspot in the field, and no research report is found in the field about bifunctional conjugated microporous polymers containing both pyrimidine rings and cyano groups.
Disclosure of Invention
In view of the above, the present invention provides a bifunctional conjugated microporous polymer containing a pyrimidine ring and a cyano group, and a preparation method thereof. The conjugated microporous polymer provided by the invention has a pyrimidine ring and a cyano group, and is a novel conjugated microporous polymer.
In order to achieve the above object, the present invention provides the following technical solutions:
a bifunctional conjugated microporous polymer containing a pyrimidine ring and a cyano group is obtained by polymerizing 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile, and has a structure shown in a formula I:
the invention provides a preparation method of the bifunctional conjugated microporous polymer, which comprises the following steps:
under the action of a first alkaline compound, 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzene diacetonitrile are subjected to polymerization reaction to obtain the bifunctional conjugated microporous polymer with the structure shown in the formula I.
Preferably, the preparation method of the 2,4, 6-tri (4-formylphenyl) pyrimidine comprises the following steps: under the action of a second basic compound and a palladium catalyst, carrying out Suzuki coupling reaction on 2,4, 6-trichloropyrimidine and 4-formylphenylboronic acid to obtain 2,4, 6-tri (4-formylphenyl) pyrimidine.
Preferably, the first basic compound and the second basic compound independently comprise one or more of potassium carbonate, cesium carbonate and triethylamine.
Preferably, the palladium catalyst is tetrakis (triphenylphosphine) palladium; the solvent for the Suzuki coupling reaction comprises one or more of toluene, dioxane, mesitylene, methanol, ethanol, tert-butyl alcohol and water.
Preferably, the molar ratio of the 2,4, 6-trichloropyrimidine to the 4-formylphenylboronic acid is (1-3) to (8-12).
Preferably, the Suzuki coupling reaction is carried out under a reflux condition, and the reaction time is 70-75 h.
Preferably, the solvent for polymerization reaction comprises one or more of 1, 4-dioxane, toluene and trimethylbenzene.
Preferably, in the step (2), the molar ratio of the 2,4, 6-tri (4-formylphenyl) pyrimidine to the 1, 4-benzenediacetonitrile is (0.8-1.2) to (1.2-1.8).
Preferably, the temperature of the polymerization reaction is 110-130 ℃, and the time is 70-75 h.
The invention provides a difunctional conjugated microporous polymer containing a pyrimidine ring and a cyano group, which is obtained by polymerizing 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile and has a structure shown in a formula I. The conjugated microporous polymer provided by the invention has a pyrimidine ring and a cyano group, and is a novel bifunctional conjugated microporous polymer. The conjugated microporous polymer provided by the invention is a crystal material with a fibrous structure, has certain ultraviolet absorption capacity, and has wide application prospects in the fields of gas adsorption, photocatalysis and the like.
The invention provides a preparation method of the bifunctional conjugated microporous polymer. The preparation method provided by the invention has simple steps and is easy to operate.
Drawings
FIG. 1 is a chart of the infrared spectrum of 2,4, 6-tris (4-formylphenyl) pyrimidine obtained in example 1;
FIG. 2 is a nuclear magnetic spectrum of 2,4, 6-tris (4-formylphenyl) pyrimidine obtained in example 1;
FIG. 3 is a comparison of the IR spectra of ZLD-CMP, 2,4, 6-tris (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile obtained in example 1;
FIG. 4 is a graph comparing the UV absorption of ZLD-CMP, 2,4, 6-tris (4-formylphenyl) pyrimidine, and 1, 4-benzenediacetonitrile in example 1;
FIG. 5 is the XRD diffraction pattern of ZLD-CMP in example 1;
FIG. 6 is a scanning electron micrograph of ZLD-CMP in example 1 at different magnifications.
Detailed Description
The invention provides a difunctional conjugated microporous polymer containing a pyrimidine ring and a cyano group, which is obtained by polymerizing 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile and has a structure shown in a formula I:
in formula I:
the three-terminal-linked group of (A) is
The two terminal-attached group of (A) is
The invention also provides a preparation method of the bifunctional conjugated microporous polymer, which comprises the following steps:
and (2) carrying out polymerization reaction on the 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile under the action of a first alkaline compound to obtain the bifunctional conjugated microporous polymer with the structure shown in the formula I.
In the present invention, the preparation method of the 2,4, 6-tris (4-formylphenyl) pyrimidine comprises the following steps: under the action of a second basic compound and a palladium catalyst, carrying out Suzuki coupling reaction on 2,4, 6-trichloropyrimidine and 4-formylphenylboronic acid to obtain 2,4, 6-tri (4-formylphenyl) pyrimidine. In the invention, the second basic compound preferably comprises one or more of potassium carbonate, cesium carbonate and triethylamine, more preferably a mixture of potassium carbonate and cesium carbonate, and the molar ratio of potassium carbonate to cesium carbonate in the mixture is preferably 1: 1; the palladium catalyst is preferably tetrakis (triphenylphosphine) palladium; the solvent for Suzuki coupling reaction preferably comprises one or more of toluene, dioxane, mesitylene, methanol, ethanol, tert-butyl alcohol and water, more preferably a mixed solvent of toluene, ethanol and water, wherein the volume ratio of toluene, ethanol and water in the mixed solvent is preferably 5:1:1, and the ethanol is preferably absolute ethanol.
In the invention, the molar ratio of the 2,4, 6-trichloropyrimidine to the 4-formylphenylboronic acid is preferably (1-3): 8-12), more preferably (1.5-2.5): 9-11), further preferably 2:9, and the molar ratio of the 2,4, 6-trichloropyrimidine to the second basic compound is preferably 1: 6; the molar ratio of the 2,4, 6-trichloropyrimidine to the palladium catalyst is preferably 2: 0.3; the invention has no special requirements on the dosage of the solvent, and can ensure that the reaction is carried out smoothly.
In the invention, the Suzuki coupling reaction is preferably carried out under a reflux condition, and the reaction time is preferably 70-75 h, more preferably 72 h; the Suzuki coupling reaction is preferably carried out under magnetic stirring.
In the embodiment of the present invention, it is preferable that 2,4, 6-trichloropyrimidine, 4-formylphenylboronic acid, the second basic mixture, the palladium catalyst and the solvent are mixed, a stirring magnet is added to the mixture, nitrogen gas is bubbled through the mixture for 5min to remove oxygen in the system, and then the mixture is heated to the reflux temperature under magnetic stirring to carry out the reaction.
After the Suzuki coupling reaction is completed, the obtained product liquid is preferably subjected to post-treatment to obtain the 2,4, 6-tri (4-formylphenyl) pyrimidine. In the present invention, the post-treatment preferably comprises the steps of: cooling the obtained product liquid to room temperature, extracting with water and dichloromethane, and sequentially drying and filtering the obtained organic phase to obtain filtrate; and (3) removing the solvent from the filtrate by rotary evaporation, washing and recrystallizing the obtained residue in sequence, and drying the obtained recrystallized product to obtain the 2,4, 6-tri (4-formylphenyl) pyrimidine. In the present invention, the drying agent for drying the organic phase is preferably anhydrous magnesium sulfate; washing the residue with a detergent, preferably absolute ethyl alcohol, preferably by ultrasonic washing; the solvent for recrystallization is preferably acetone; the drying temperature for drying the recrystallized product is preferably 45 ℃ and the drying time is preferably 12 hours.
In a specific embodiment of the present invention, the reaction formula of the Suzuki coupling reaction is shown as formula a:
after the 2,4, 6-tri (4-formylphenyl) pyrimidine is obtained, the invention carries out polymerization reaction on the 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile under the action of a first alkaline compound to obtain the bifunctional conjugated microporous polymer with the structure shown in the formula I. In the present invention, the first basic compound preferably includes one or more of potassium carbonate, cesium carbonate and triethylamine, more preferably cesium carbonate; the solvent for polymerization preferably comprises one or more of 1, 4-dioxane, toluene and trimethylbenzene, and more preferably 1, 4-dioxane.
In the invention, the molar ratio of the 2,4, 6-tri (4-formylphenyl) pyrimidine to the 1, 4-benzenediacetonitrile is preferably (0.8-1.2): (1.2-1.8), more preferably (0.9-1.1): 1.3-1.6), and further preferably 1: 1.5; the molar ratio of the 2,4, 6-tri (4-formylphenyl) pyrimidine to the first alkaline compound is preferably 8-9: 1; the invention has no special requirements on the dosage of the solvent, and can ensure that the reaction is carried out smoothly.
In the invention, the temperature of the polymerization reaction is preferably 110-130 ℃, more preferably 120 ℃, and the time of the polymerization reaction is preferably 70-75 h, more preferably 72 h; the polymerization reaction is preferably carried out under vacuum-tight conditions.
In the embodiment of the present invention, it is preferable that 2,4, 6-tris (4-formylphenyl) pyrimidine, 1, 4-benzenediacetonitrile, a first basic compound and a solvent are mixed, the mixture is sonicated and subjected to nitrogen deaeration, then sealed under vacuum, and then heated to the polymerization reaction temperature to perform the reaction. In the present invention, the time of the ultrasonic treatment is preferably 2min, and the time of the nitrogen deaeration is preferably 5 min.
In the present invention, the reaction formula of the polymerization reaction is shown as formula b:
after the polymerization reaction is finished, the invention preferably carries out post-treatment on the obtained product feed liquid to obtain the bifunctional conjugated microporous polymer with the structure shown in the formula I. In the present invention, the post-treatment preferably comprises the steps of: and cooling the obtained product liquid to room temperature, carrying out centrifugal treatment to obtain a precipitate, washing the precipitate, and drying to obtain the conjugated microporous polymer with the structure shown in the formula I. In the present invention, the washing is preferably repeated with water and THF, and the drying is preferably carried out at 120 ℃ for 10 hours.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
2,4, 6-trichloropyrimidine (0.3750g, 2mmol), 4-formylphenylboronic acid (1.4020g, 9mmol), potassium carbonate (0.7501g, 6mmol), cesium carbonate (1.9504g, 6mmol), tetrakis (triphenylphosphine) palladium (3.5008g, 0.3mmol) were accurately weighed using an electronic balance, and then toluene (25mL), anhydrous ethanol (5mL) and distilled water (5mL) were sequentially added thereto as a reaction solvent. After the magnet was placed, nitrogen was bubbled through the mixture for 5min, and then the mixture was refluxed at 100 ℃ and stirred to react for 72 h. And (3) finishing the reaction, cooling to room temperature, extracting the mixture after the reaction with distilled water (100mL) and dichloromethane (100mL), separating to obtain an upper organic phase liquid, adding anhydrous magnesium sulfate for drying, filtering to obtain a solvent, carrying out rotary evaporation on the solvent, adding anhydrous ethanol for ultrasonic oscillation washing, then recrystallizing with acetone, keeping the temperature in an oven at 45 ℃, standing and drying for 12 hours, and finally obtaining an off-white solid, namely the 2,4, 6-tris (4-formylphenyl) pyrimidine, wherein the yield is 0.3735g, and the yield is 47.8%.
In a reaction kettle2,4, 6-tris (4-formylphenyl) pyrimidine (25.18mg, 0.064mmol), 1, 4-benzenediacetonitrile (14.99mg, 0.096mmol), 1, 4-dioxane (2mL) and cesium carbonate (124mg, 0.575mmol) were added. The mixture was sonicated for 2min, then bubbled with nitrogen for 5min, sealed under vacuum, and the reaction heated at 120 ℃ for 72 h. After the reaction kettle is cooled to room temperature, the precipitate is centrifugally taken out and is treated by H2And washing O and THF for several times, and drying in vacuum at 120 ℃ for 10h to obtain yellow powder, namely the bifunctional conjugated microporous polymer with the structure shown in the formula I, which is recorded as ZLD-CMP, and the yield is about 82%.
Structural characterization:
FIG. 1 is an infrared spectrum of 2,4, 6-tris (4-formylphenyl) pyrimidine obtained in this example; in FIG. 1, the wavelength is 1697.3cm-1The peak is a stretching vibration peak (1710-1695 cm) of C ═ O bond in aldehyde group-1). The wavelength is 1566.1cm-1The peak is the stretching vibration peak of C ═ N bond in pyrimidine (1580-1520 cm)-1). The wavelength is 1207.4cm-1The peak at (A) is the bending vibration peak of the C-C bond in the benzene ring skeleton (1000--1In between). Wavelength of 779.2cm-1The peak at (B) is the out-of-plane bending vibration peak (1000--1In between).
FIG. 2 is a nuclear magnetic spectrum of 2,4, 6-tris (4-formylphenyl) pyrimidine obtained in this example. In FIG. 2, δ (ppm)10.17(s,3H) is the peak of H in aldehyde group at 1; delta (ppm)8.15-8.05(s,6H) is the peak of H in the benzene ring at 2; delta (ppm)8.52-8.45(s,6H) is the peak of H in the 3 benzene ring; delta (ppm)8.20(s,1H) is the peak for H in the pyrimidine ring at 4; the remaining peaks: delta (ppm)7.26 is CDCl3Peak of medium H; delta (ppm)1.56 is H2Peak of H in O. The results in FIGS. 1-2 show that the off-white solid obtained in the present invention is indeed 2,4, 6-tris (4-formylphenyl) pyrimidine.
FIG. 3 is a comparison of IR spectra for ZLD-CMP, 2,4, 6-tris (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile. As can be seen from the analysis in FIG. 3, the wavelength of the infrared spectrum of 1, 4-benzenediacetonitrile is 2248.9cm-1The peak of (A) is a characteristic absorption peak of a C ≡ N bond in a cyano group (2260-2210 cm)-1In between), and this characteristic peak is not observed in ZLD-CMP, which is caused byThe degree of conjugation of the polymer is enhanced, resulting in a red shift of the characteristic absorption peak of the C ≡ N bond to a wavelength of 2362.8cm-1The position of (a). In contrast, when the infrared spectra of 2,4, 6-tris (4-formylphenyl) pyrimidine and ZLD-CMP were compared, it was found that the original spectrum was 1697.3cm-1The stretching vibration peak of C ═ O bond in the aldehyde group of (a) disappeared, since the aldehyde group on 2,4, 6-tris (4-formylphenyl) pyrimidine was substituted with other groups, and it could be confirmed that ZLD-CMP compound indeed had the structure shown in formula I.
FIG. 4 is a graph comparing the UV absorption of ZLD-CMP, 2,4, 6-tris (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile. As can be seen from the analysis in FIG. 4, 2,4, 6-tris (4-formylphenyl) pyrimidine shows the strongest absorption peak at a wavelength of 337.5 nm. 1, 4-Benzenediacetonitrile showed the strongest absorption peak at a wavelength of 342.5 nm. The ZLD-CMP has the strongest absorption peak at the wavelength of 347.5nm-464.5nm and has certain ultraviolet light and visible light absorption capacity. This is because the degree of conjugation of the system increases after the reaction of 2,4, 6-tris (4-formylphenyl) pyrimidine with 1, 4-benzenediacetonitrile, so that the absorption band shifts in the long-wavelength direction.
FIG. 5 is an XRD diffraction pattern of ZLD-CMP. According to the analysis of FIG. 5, there are several peaks in the ZLD-CMP, which indicates that ZLD-CMP belongs to the class of crystalline materials.
FIG. 6 is a scanning electron micrograph of ZLD-CMP at different magnifications, with the left side at 2 micron and the right side at 5 micron. As can be seen from FIG. 6, ZLD-CMP is a fibrous structure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A bifunctional conjugated microporous polymer containing a pyrimidine ring and a cyano group, which is obtained by polymerizing 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzenediacetonitrile, and has a structure shown in a formula I:
2. the method for preparing the bifunctional conjugated microporous polymer according to claim 1, comprising the steps of:
under the action of a first alkaline compound, 2,4, 6-tri (4-formylphenyl) pyrimidine and 1, 4-benzene diacetonitrile are subjected to polymerization reaction to obtain the bifunctional conjugated microporous polymer with the structure shown in the formula I.
3. The method of claim 2, wherein the 2,4, 6-tris (4-formylphenyl) pyrimidine is prepared by a method comprising the steps of: under the action of a second basic compound and a palladium catalyst, carrying out Suzuki coupling reaction on 2,4, 6-trichloropyrimidine and 4-formylphenylboronic acid to obtain 2,4, 6-tri (4-formylphenyl) pyrimidine.
4. The method according to claim 3, wherein the first basic compound and the second basic compound independently comprise one or more of potassium carbonate, cesium carbonate and triethylamine.
5. The production method according to claim 3, wherein the palladium catalyst is tetrakis (triphenylphosphine) palladium; the solvent for the Suzuki coupling reaction comprises one or more of toluene, dioxane, mesitylene, methanol, ethanol, tert-butyl alcohol and water.
6. The method according to claim 3, wherein the molar ratio of the 2,4, 6-trichloropyrimidine to the 4-formylphenylboronic acid is (1-3) to (8-12).
7. The preparation method according to any one of claims 3 to 6, wherein the Suzuki coupling reaction is carried out under reflux conditions for 70 to 75 hours.
8. The method according to claim 2, wherein the solvent for polymerization comprises one or more of 1, 4-dioxane, toluene, and trimethylbenzene.
9. The method according to claim 2 or 8, wherein the molar ratio of 2,4, 6-tris (4-formylphenyl) pyrimidine to 1, 4-benzenediacetonitrile in the step (2) is (0.8 to 1.2): (1.2 to 1.8).
10. The method according to claim 2, wherein the polymerization reaction is carried out at a temperature of 110 to 130 ℃ for 70 to 75 hours.
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| CN108754662A (en) * | 2018-05-16 | 2018-11-06 | 福州大学 | The preparation method of covalent class triazine structure light emitting organic semi polymer nanofiber and its Photocatalyzed Hydrogen Production application |
| CN111848891A (en) * | 2020-08-12 | 2020-10-30 | 台州学院 | Covalent organic polymer based on 2,4, 6-tri (4-formylphenyl) pyrimidine and preparation method thereof |
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| CN108754662A (en) * | 2018-05-16 | 2018-11-06 | 福州大学 | The preparation method of covalent class triazine structure light emitting organic semi polymer nanofiber and its Photocatalyzed Hydrogen Production application |
| CN111848891A (en) * | 2020-08-12 | 2020-10-30 | 台州学院 | Covalent organic polymer based on 2,4, 6-tri (4-formylphenyl) pyrimidine and preparation method thereof |
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| WO2023065714A1 (en) * | 2021-10-20 | 2023-04-27 | 浙江时间新材料有限公司 | Pyrimidine- and cyano group-based bifunctional conjugated microporous polymer, and preparation method therefor and application thereof |
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