CN111825682A - Sulfur-oxygen fluorenyl polyporphyrin and preparation method thereof - Google Patents
Sulfur-oxygen fluorenyl polyporphyrin and preparation method thereof Download PDFInfo
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- CN111825682A CN111825682A CN201910308552.1A CN201910308552A CN111825682A CN 111825682 A CN111825682 A CN 111825682A CN 201910308552 A CN201910308552 A CN 201910308552A CN 111825682 A CN111825682 A CN 111825682A
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- Prior art keywords
- reaction
- polyporphyrin
- dibenzothiophene sulfone
- thiofluorenyl
- brominated
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 47
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 claims description 31
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 30
- -1 (4-formylphenyl) dibenzothiophene Chemical compound 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000031709 bromination Effects 0.000 claims description 15
- 238000005893 bromination reaction Methods 0.000 claims description 15
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 239000011343 solid material Substances 0.000 claims description 11
- 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 10
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims 1
- 150000004032 porphyrins Chemical group 0.000 abstract description 23
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000002153 concerted effect Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
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- 238000005406 washing Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
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- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 150000002940 palladium Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000002211 ultraviolet spectrum Methods 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 229940079593 drug Drugs 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical class C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
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Classifications
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of polymer materials, and particularly relates to thiofluorenyl polyporphyrin and a preparation method thereof. The thiofluorenyl polyporphyrin provided by the invention has a porphyrin structure and thiofluorenyl groups, and can realize bifunctional concerted catalysis, so that the thiofluorenyl polyporphyrin has potential application value.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to thiofluorenyl polyporphyrin and a preparation method thereof.
Background
Porphyrins are basic skeletons formed by four pyrroles alternately connected with a methylene structure in a compound. Due to the special chemical structure and performance of porphyrin, the porphyrin has good application prospects in the aspects of catalysts, energy utilization, solar cells and the like. Porphyrin compounds mostly have unique photophysical and photochemical properties, and the large ring conjugate structure contained in porphyrin molecules determines that the porphyrin compounds have good electronic mobility and thermal stability.
The porphyrin compounds have porphyrin basic skeleton, so that the research on storage materials, electrode materials, molecular devices, catalytic materials, novel drugs, novel catalysts and the like gradually draws attention. For example, researchers insert different metals into the center of porphyrin ligand, introduce different types of substituents, and the like, to synthesize different types of metalloporphyrin complexes to simulate biological enzymes, thereby studying their catalytic action and mechanism; porphyrin drugs can selectively exist in tumor cells and reach higher concentration, but can be rapidly metabolized in normal cells; on the other hand, porphyrin-based compounds are sensitive to environmental light stimuli, so porphyrin photosensitizers with amino functional groups are often used in photodynamic therapy, which is a particularly effective treatment for cancer.
The research shows that the porphyrin compound is a branch of disciplines with great research prospects, and the research and preparation of the novel porphyrin compound have very important significance.
Disclosure of Invention
The thiofluorenyl polyporphyrin contains porphyrin structural units, has a macrocyclic conjugated structure and a microporous structure, and has potential application value.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides thiofluorenyl polyporphyrin, which has a structure shown as a formula 1:
preferably, the thiofluorenyl polyporphyrin has a network-like pore structure.
The invention provides a preparation method of thiofluorenyl polyporphyrin in the technical scheme, which comprises the following steps:
(1) brominating dibenzothiophene sulfone to obtain brominated dibenzothiophene sulfone;
(2) reacting the brominated dibenzothiophene sulfone obtained in the step (1) with 4-formylphenylboronic acid under the action of a catalyst to obtain (4-formylphenyl) dibenzothiophene sulfone;
(3) polymerizing the (4-formylphenyl) dibenzothiophene sulfone obtained in the step (2) and pyrrole to obtain the thiofluorenyl polyporphyrin.
Preferably, in the step (1), the brominating reagent for bromination includes N-bromosuccinimide, copper bromide, liquid bromine, and N-bromosuccinimide.
Preferably, the bromination temperature is room temperature, and the bromination time is 12-24 h.
Preferably, in the step (2), the catalyst comprises a palladium catalyst.
Preferably, in the step (2), the reaction temperature is 80-100 ℃ and the reaction time is 36-60 h.
Preferably, in the step (3), the reaction temperature is 120-150 ℃ and the reaction time is 20-30 h.
Preferably, in the step (1), after bromination, post-treatment is further performed on the brominated material, and the post-treatment method includes: and dissolving the solid material obtained by the reaction by utilizing hot chlorobenzene, and standing and crystallizing to obtain the brominated dibenzothiophene sulfone crystal.
Preferably, in the step (3), after the reaction, the method further comprises purifying the reacted solid material, wherein the purification mode is soxhlet extraction.
The thiofluorenyl polyporphyrin provided by the invention has a macrocyclic conjugated structure; according to the structure characterization results of the embodiment, the compound has a microporous structure, and therefore, the compound has potential application value.
Drawings
FIG. 1 is a Soxhlet extraction apparatus used in the present invention;
FIG. 2 is an infrared spectrum of DBH-CMP-1 obtained in example 1 of the present invention;
FIG. 3 is an infrared contrast spectrum of DBH-CMP-1 and aldehyde obtained in example 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern of DBH-CMP-1 obtained in example 1 of the present invention;
FIG. 5 is a solid UV spectrum of DBH-CMP-1 obtained in example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of DBH-CMP-1 obtained in example 1 of the present invention;
FIG. 7 is a thermogram of DBH-CMP-1 obtained in example 1 of the present invention.
Detailed Description
The invention provides thiofluorenyl polyporphyrin, which has a structure shown as a formula 1:
as shown in formula 1, the thiofluorenyl polyporphyrin comprises a porphyrin skeleton and thiofluorenyl, and provides a structural basis for realizing dual-functionalization concerted catalysis. In formula 1, the dotted line connecting to the benzene ring represents a repeating unit, which is a porphyrin or benzodithiophene structural unit.
In the present invention, the sulfoxafluorenylpolyporphyrin has a network pore structure, and the pores are micropores.
The invention provides a preparation method of thiofluorenyl polyporphyrin in the technical scheme, which comprises the following steps:
(1) brominating dibenzothiophene sulfone to obtain brominated dibenzothiophene sulfone;
(2) reacting the brominated dibenzothiophene sulfone obtained in the step (1) with 4-formylphenylboronic acid under the action of a catalyst to obtain (4-formylphenyl) dibenzothiophene sulfone;
(3) and (3) carrying out polymerization reaction on the (4-formylphenyl) dibenzothiophene sulfone obtained in the step (2) and pyrrole to obtain thionofluorenyl polyporphyrin.
The present invention bromizes dibenzothiophene sulfone to obtain brominated dibenzothiophene sulfone. In the present invention, the brominating agent for bromination preferably includes N-bromosuccinimide (NBS), copper bromide or liquid bromine, more preferably N-bromosuccinimide. In the present invention, the molar ratio of the brominating agent to dibenzothiophene sulfone is preferably (1.5-2.5): 1, and more preferably (1.8-2.0): 1. In the invention, the bromination preferably uses concentrated sulfuric acid as a solvent, and the mass concentration of the concentrated sulfuric acid is preferably 98%; the mass ratio of the volume of the concentrated sulfuric acid to the dibenzothiophene sulfone is preferably (30-50) mL to 1g, and more preferably (35-45) mL to 1 g.
In the present invention, the dibenzothiophene, the brominating agent and the solvent are preferably mixed in a manner that: firstly, mixing dibenzothiophene with a brominating agent, and then dropwise adding a solvent into the mixture; the dropping speed of the solvent is based on the condition that the temperature of the mixed material liquid can be controlled within the room temperature range. In the present invention, the room temperature is preferably 25 ℃. In a particular embodiment of the invention, the mixing is preferably carried out under ice-bath cooling.
In the invention, the bromination temperature is preferably room temperature, and the bromination time is preferably 12-24 h, and more preferably 14-20 h. In the present invention, the bromination is preferably carried out under stirring conditions, and the stirring is preferably magnetic stirring. The invention has no special requirement on the stirring speed, and can fully mix all the components of the reaction materials. In the present invention, the reaction that occurs during the bromination is preferably represented by formula I:
after bromination, the process of the present invention preferably mixes the brominated material with water to precipitate a solid. In the invention, the water is preferably ice deionized water, and the mixing is preferably to slowly add the brominated material into the ice deionized water, so as to avoid overhigh temperature of a mixing system. In the present invention, the mixing is preferably accomplished under agitation conditions, the speed and manner of which can be readily understood by those skilled in the art.
After solid is precipitated, the mixture is preferably subjected to solid-liquid separation, and then the obtained solid is washed and dried, wherein the solid-liquid separation mode is preferably suction filtration; the washing detergent is preferably methanol; the drying mode is preferably drying. The invention has no special requirements on the specific parameters of the solid-liquid separation, washing and drying, and can adopt a method well known by the technical personnel in the field.
After obtaining the solid material, the present invention preferably subjects the solid material to post-treatment, and the post-treatment method preferably includes: and dissolving the solid material obtained by the reaction by utilizing hot chlorobenzene, and standing and crystallizing to obtain the brominated dibenzothiophene sulfone crystal.
In the invention, the temperature of the chlorobenzene is preferably 130-140 ℃, and more preferably 132-135 ℃. The invention has no special requirement on the dosage of the chlorobenzene, and can fully dissolve solid materials. In the present invention, the dissolution is preferably performed under stirring conditions and in a reflux state. After dissolving, the invention preferably performs standing crystallization on the obtained clear solution to obtain a brominated diphenyl propylene thiophene sulfone crystal; the temperature of the standing crystallization is preferably room temperature, and the time is preferably not less than 24 hours, and more preferably 24-30 hours.
The invention can obtain the brominated diphenyl propyl thiophene sulfone crystal through post-treatment, which is a white needle crystal.
In the present invention, the yield of the bromination step is preferably 80% or more, and more preferably 84 to 85%.
After obtaining the brominated dibenzothiophene, the invention reacts the brominated dibenzothiophene sulfone with 4-formylphenylboronic acid under the action of a catalyst to obtain (4-formylphenyl) dibenzothiophene sulfone. In the present invention, the reaction of the brominated dibenzothiophene sulfone with 4-formylphenylboronic acid is preferably represented by formula II;
in the present invention, the catalyst preferably comprises a palladium catalyst. The palladium catalyst is preferably prepared by the following steps:
mixing palladium salt, triphenylphosphine and a solvent, and reacting to obtain an intermediate material;
and mixing the intermediate material with a reducing agent, and carrying out reduction reaction to obtain the palladium catalyst.
According to the invention, the palladium salt, triphenylphosphine and a solvent are preferably mixed and reacted to obtain an intermediate material. In the present invention, the palladium salt is preferably palladium chloride; the solvent is preferably dimethyl sulfoxide (DMSO); the molar ratio of the palladium chloride to the triphenylphosphine is preferably (1.8-2.5) to 1, and more preferably 2: 1; the mass ratio of the volume of the solvent to the palladium chloride is preferably (150-250) mL:1g, more preferably (180-230) mL:1g, more preferably 200mL:1 g.
In the present invention, the reaction of palladium salt and triphenylphosphine is preferably carried out under nitrogen protection; the reaction temperature is preferably 120-140 ℃, and more preferably 125-135 ℃; the reaction time is preferably 0.5-2 h, and more preferably 1-1.5 h.
After the intermediate material is obtained, the intermediate material is preferably mixed with a reducing agent, and the palladium catalyst is obtained after reduction reaction. In the present invention, the reducing agent preferably includes hydrazine hydrate; the mass ratio of the volume of the hydrazine hydrate to the palladium salt is preferably (1.5-3) mL to 1g, and more preferably (2-2.5) mL to 1 g.
After the reduction reaction, the invention preferably carries out solid-liquid separation and washing on the materials obtained after the reduction reaction in sequence; the solid-liquid separation mode is preferably suction filtration, and the washing reagent is preferably ethanol. The invention preferably obtains the palladium (0) catalyst (Pd (PPh) with better catalytic performance by the way as above3)4)。
In the invention, the molar ratio of the brominated dibenzothiophene sulfone to the 4-formylphenylboronic acid is preferably 1: 1.5-2.5, more preferably 1: 1.8-2.2, and still more preferably 1:2. In the invention, the reaction between the brominated dibenzothiophene sulfone and 4-formylphenylboronic acid preferably takes 1, 4-dioxane as a solvent, and the dosage ratio of the solvent to the brominated dibenzothiophene sulfone is preferably (150-250) mL:0.006mol, more preferably 200mL:0.006 mol; the reaction is preferably carried out under an alkaline condition, and the pH value of a reaction system is preferably 8-10, and more preferably 9; the pH value regulator preferably comprises one or more of potassium carbonate, potassium bicarbonate, sodium carbonate and sodium bicarbonate. In the present invention, the reaction is preferably carried out under nitrogen protection.
In the invention, the reaction temperature between the brominated dibenzothiophene sulfone and the 4-formylphenylboronic acid is preferably 80-100 ℃, more preferably 85-95 ℃, and further preferably 87-90 ℃; the reaction time is preferably 24-60 h, more preferably 30-55 h, and still more preferably 35-50 h.
After the reaction, the present invention preferably subjects the reacted material to a post-treatment to remove any remaining palladium salt and alkali. The post-treatment preferably comprises: and mixing the reacted materials with acid, and then sequentially carrying out solid-liquid separation, washing and drying. In the present invention, the acid preferably includes hydrochloric acid or sulfuric acid; the hydrochloric acid is preferably diluted hydrochloric acid, the volume ratio of HCl to deionized water in the diluted hydrochloric acid is preferably (12-18): 1, more preferably (14-16): 1, and still more preferably 15: 1; the method has no special requirements on the concentration and the dosage of the dilute sulfuric acid, and can remove the residual palladium salt and alkali. After mixing, the temperature of the mixed solution is preferably lowered to 20 ℃ in the present invention to perform the next solid-liquid separation operation. In the invention, the solid-liquid separation mode is preferably suction filtration; the washing is preferably water washing; the drying is preferably oven drying. In the present invention, it is preferable to remove impurities and unreacted materials from the reaction material by the above-mentioned post-treatment to obtain pure (4-formylphenyl) dibenzothiophene sulfone.
In the present invention, the yield of the (4-formylphenyl) dibenzothiophene sulfone is preferably 65% or more, and more preferably 66 to 68%.
After (4-formylphenyl) dibenzothiophene sulfone is obtained, the (4-formylphenyl) dibenzothiophene sulfone and pyrrole are reacted to obtain the thionofluorene-based polyporphyrin. In the present invention, the reaction process of the (4-formylphenyl) dibenzothiophene sulfone with pyrrole is preferably as shown in formula III:
in the present invention, the molar ratio of the (4-formylphenyl) dibenzothiophene sulfone to pyrrole is preferably 1: (2-3), more preferably 1: (2.2-2.5), and more preferably 1: 2.2. In the present invention, the pyrrole is preferably subjected to a distillation treatment to remove oxidized pyrrole which may be contained in the pyrrole, and to eliminate adverse effects of impurities on the polymerization reaction. The present invention does not require a particular mode of operation for the distillation, and may be carried out in a manner well known to those skilled in the art. In a particular embodiment of the invention, the distillation is preferably carried out at 70 ℃ under reduced pressure.
In the present invention, the reaction between the (4-formylphenyl) dibenzothiophene sulfone and pyrrole is preferably carried out under nitrogen protection, stirring conditions and light shielding conditions; the reaction preferably uses propionic acid as a solvent, and the mass ratio of the volume of the propionic acid to the (4-formylphenyl) dibenzothiophene sulfone is preferably (60-100) mL:1g, and more preferably (70-90) mL:1 g; the reaction temperature is preferably 120-150 ℃, more preferably 125-140 ℃, and further preferably 130-135 ℃; the reaction time is preferably 20 to 30 hours, more preferably 23 to 27 hours, and still more preferably 24 to 26 hours.
After the reaction, the invention preferably further comprises purifying the solid material after the reaction to remove unreacted raw materials and residual solvent molecules of pore channels, so as to obtain the thiofluorenyl polyporphyrin with the microporous structure. In the present invention, the purification is preferably performed by Soxhlet extraction. In the present invention, the soxhlet extraction preferably comprises methanol washing and tetrahydrofuran washing sequentially; the temperature during methanol cleaning is preferably 100-30 ℃, and the temperature during tetrahydrofuran cleaning is preferably 100-120 ℃; the washing time is independently based on the clear solution obtained. After cleaning, the invention preferably dries the cleaned solid material to obtain a black solid, namely the thionofluorenyl polyporphyrin.
In the present invention, the yield of the sulfoxafluorenylpolyporphyrin is preferably 60 to 80%.
The thiofluorenyl polyporphyrin prepared by the preparation method in the technical scheme of the invention has a pore structure and a porphyrin skeleton, so that the thiofluorenyl polyporphyrin is expected to be widely applied to catalytic materials, energy raw materials or medical materials.
For further illustration of the present invention, the thiofluorenyl polyporphyrin and the preparation method thereof provided by the present invention will be described in detail below with reference to the accompanying drawings and examples, which should not be construed as limiting the scope of the present invention.
In the following embodiments, the instruments and reagents required are:
FA2004A electronic balance (shanghai precision instruments ltd);
model 85-1 magnetic stirrer (Shanghai Zhicheng appliances Co., Ltd.);
an ultrasonic cleaner (Kunshan Jielimei ultrasonic instruments Co., Ltd.);
ZNHW-II type precision electronic control instrument (Linan Hualing filtration equipment Limited, temperature range 60-140 ℃);
SHB-LHA circulating water type multipurpose vacuum pump (Shanghai Zhiwei electric Co., Ltd.);
s-4800 field emission scanning electron microscope (HITACHI Hitachi, Japan);
IRAffmity-1 Fourier transform infrared spectrometer (Shimadzu corporation, Japan, range 4000--1)；
u-4100 solid UV spectrophotometer (HITACHI Hitachi, Japan, range 800--1)；
D8Advance X-ray diffractometer (Bruker, Germany, range 3-65 °);
SDTQ600 differential thermogravimetry synchronous thermal analyzer (TA of America, N)2The temperature rise rate is increased by 10 ℃/min under the atmosphere);
beakers (100mL, 250mL, 500mL, 1000 mL);
measuring cylinders (25mL, 50 mL);
single/three neck round bottom flask (50mL, 100mL, 250 mL);
pear-shaped flask (250 mL);
a reflux condenser tube; a glass rod; a medicine spoon; a thermometer (0-200 ℃); a microsyringe; an oven; a condenser tube; a disposable dropper; a hollow plug; a Buchner funnel; filtering paper; a suction flask; a Soxhlet extraction tube; filtering paper; a Buchner funnel; and (5) pumping the filter flask.
Drugs and reagents are shown in table 1:
TABLE 1 medicine and reagent table
Example 1
(1) Preparation of brominated dibenzothiophene sulfones
2.1702g (0.01mol) of dibenzothiophene sulfone and 3.6260g (0.02mol) of NBS were weighed on an electronic balance and introduced into a 250mL single-neck flask, and the flask was placed in an ice bath and kept at a low temperature (-10 to 0 ℃). Approximately 70mL of concentrated sulfuric acid (98%) was measured as a solvent for the reaction and slowly poured into the flask (keeping the temperature of the system of materials in the flask at room temperature level). The stopper of the flask was closed, the magnetic stirring was turned on, and the reaction was carried out for 24 hours.
After the reaction was completed, the reaction mixture in the flask was slowly poured into a large beaker containing ice deionized water, and the mixture was continuously stirred with a glass rod while being added, so as to ensure that the temperature was not too high. And then carrying out suction filtration, washing the solid material obtained by suction filtration with a large amount of deionized water, finally washing with methanol, and drying in an oven to obtain brownish black powder (crude brominated dibenzothiophene sulfone).
Placing the brominated dibenzothiophene sulfone crude product obtained after drying into a single-neck flask, adding chlorobenzene (approximately just submerging the product), connecting a condenser pipe device on the flask, starting condensed water, placing the device in an oil bath pot for heating (the temperature is set to be 132 ℃, and simultaneously starting magnetic stirring, slowly adding chlorobenzene into the flask again (the solution is kept slightly boiling in the process and the chlorobenzene adding speed is not too high) when the reflux of the condenser pipe occurs and the liquid in the flask slightly boils, ending the heating and stirring until the solid is just dissolved, unloading the device when the device is hot, transferring the flask to a cool place for more than 24 hours, naturally cooling and crystallizing, filtering, washing with ethanol, and drying to obtain 3.1573g of white needle-shaped crystals (brominated dibenzothiophene sulfone crystals).
The theoretical yield was calculated from the chemical equation to be 3.7376g, while the actual yield of brominated dibenzothiophene sulfone prepared was 3.1573g, 84.47%.
(2) Preparation of (4-formylphenyl) dibenzothiophene sulfone
Palladium (0) catalyst (Pd (PPh)3)4) The preparation method comprises the following steps: palladium chloride (PbCl) was added to a 50mL single-neck flask2)0.0905g (0.0005mol), 0.6711g (0.0025mol) of triphenylphosphine. Dimethyl sulfoxide (DMSO) as a solvent, approximately 20mL of DMS was added to a single-neck flaskAnd O, connecting a condenser pipe to the flask, starting condensed water, placing the device in an oil bath pot, and starting magnetic stirring. The nitrogen protection is needed in the reaction process, and the specific operation is as follows: the upper connector of the three-connector adapter is bound with a balloon, a large amount of nitrogen is injected into the balloon, the adapter is connected to a condenser pipe, the other connector is connected with a vacuum pump through a rubber pipe, the three-connector adapter is rotated to connect the vacuum pump with the device, and the whole device is vacuumized. And then the three-head adapter is rotated to enable nitrogen in the balloon to enter the device, then the three-head adapter is vacuumized, the operation is repeated for 4 times, and then the balloon and the device are communicated with the holding device in the device and are filled with nitrogen without air. Setting the heating temperature of the oil bath kettle to be 130 ℃, and timing to react for 1h after the temperature reaches the reaction temperature. After the reaction, about 2mL (about one tube is sucked by a disposable dropper) of hydrazine hydrate is added into the single-neck flask while the solution is hot, then the solution is filtered by suction, and the solution is washed by a large amount of ethanol and finally by ether. The catalyst is directly used for the next reaction without being dried.
A three-neck flask was taken, 2.2491g (0.006mol) of brominated dibenzothiophene sulfone obtained in step (1) was added thereto, and 1.8111g (0.012mol) of 4-formylphenylboronic acid, 8.0170g (0.06mol) of anhydrous potassium carbonate and about 200mL of 1, 4-dioxane were added as a solvent. Simultaneously adding the prepared palladium catalyst, building a device (the device used for preparing the catalyst), protecting with nitrogen, starting magnetic stirring, setting the reaction temperature at 85 ℃, and reacting for more than 48 hours.
The reacted materials were treated as follows: a large beaker is taken, about 300mL of deionized water is added into the beaker, about 20mL of HCl is added into the beaker, (the HCl is 15: 1), a glass rod is gently stirred uniformly, and the beaker is placed into a refrigerator for cooling. And (3) taking out the cooled hydrochloric acid solution (20 ℃), slowly pouring the reacted materials in the three-neck flask into the hydrochloric acid solution, continuously stirring by using a glass rod in the process, performing suction filtration, washing by using a large amount of deionized water, and then putting into an oven for drying to obtain 1.5896g of (4-formylphenyl) dibenzothiophene sulfone, wherein the theoretical yield is 2.3881g, and the yield is 66.5%.
(3) Preparation of thiofluorenyl polyporphyrins
Pyrrole pretreatment: and (4) correctly putting up a distillation device, connecting a vacuum pump at the outlet of the tail connecting pipe, carrying out reduced pressure distillation on the required pyrrole, setting the distillation temperature to be 70 ℃, and distilling for later use.
A three-necked flask was charged with 0.9230g (0.002mol) of the product obtained in step (2), and 307. mu.L (0.0044mol) of freshly distilled pyrrole was added. Using propionic acid as a reaction solvent, adding 80mL of propionic acid into a flask, setting up a device (the same as the device for preparing the catalyst), starting magnetic stirring under the protection of nitrogen, and setting the reaction temperature at 130 ℃. And (4) avoiding light in the reaction process, and reacting for 24 hours after the temperature reaches 130 ℃.
And after the reaction is finished, carrying out suction filtration, washing with a large amount of ethanol, and drying to obtain a crude product porphyrin.
Performing Soxhlet extraction: a single-neck flask was taken and fitted with a Soxhlet extractor (as shown in FIG. 1). The crude porphyrin product was packed in rectangular shapes in filter paper and sealed without leakage, and a small amount of crude porphyrin product was added to each filter paper. The coated product was placed in a soxhlet extractor and solvent was introduced into the soxhlet extractor just before the product. Then a condenser pipe is put on, condensed water is started, and the whole device is placed in an oil bath pot for heating. In the experiment, methanol is used as a solvent for washing, the reaction temperature is set to be 120 ℃, and the liquid in the reflux Soxhlet extractor is heated until the liquid is transparent and clear. The solution was then replaced with tetrahydrofuran and the washing was continued, setting the reaction temperature to 117 ℃ and continuing the heating reflux until the liquid in the Soxhlet extractor became transparent again. After the reaction, the reaction solution was dried to obtain a black solid, i.e., 0.664 g of thiofluorenyl polyporphyrin, and the theoretical yield was (2.076) g, and the yield was 32.0%.
Examples 2 to 3
Porphyrins were prepared according to the procedure of example 1, except for the differences in reaction temperatures, as specified in Table 2.
TABLE 2 examples 1-3 preparation Process parameters
In table 2, the material ratio in step (1) refers to the mass ratio of dibenzothiophene sulfone to the brominating agent, the material ratio in step (2) refers to the mass ratio of brominated dibenzothiophene sulfone to 4-formylphenylboronic acid, and the material ratio in step (3) refers to the mass-to-volume ratio of (4-formylphenyl) dibenzothiophene sulfone to pyrrole.
Product structure and performance characterization
The structures of the final products obtained in examples 1-3 were characterized by infrared, ultraviolet, X-ray, scanning electron microscope and thermogravimetric methods, and the results are shown in fig. 2-7.
Infrared spectroscopy is the analysis and identification of molecules of a substance using infrared spectroscopy. The infrared absorption spectrum is a molecular vibration spectrum, and relates to detection of energy level transition caused by vibration of chemical bonds between atoms in a molecule, so that the infrared absorption spectrum can be used for detecting a specific group in a compound. FIG. 2 is an infrared spectrum of thiofluorenyl polyporphyrin (DBH-CMP-1) obtained in example 1, wherein the respective peak positions are shown in the following figure: the wavelength of the N-H telescopic vibration region is 3750-3000cm-1Here, at 3407.810cm-1Has a vibration absorption peak; the telescopic vibration region of the benzene ring framework has the wavelength of 1620 and 1450cm-1At 1610cm in the figure-1And 1456cm-1A vibration absorption peak appears in the vicinity thereof.
In addition, we compared the infrared spectrum of thionofluorene-based polyporphyrin with that of aldehyde ((4-formylphenyl) dibenzothiophenesulfone), and the results are shown in FIG. 3. From fig. 3 it can be analyzed that: the aldehyde group stretching vibration area in the aromatic aldehyde is 1715-1690cm-1And the peak marked in the figure is 1694.699cm-1Is the characteristic peak of the characteristic aldehyde group. The reaction principle for preparing porphyrin is that aldehyde group and pyrrole ring react to eliminate aldehyde group, and the vibration absorption peak of aldehyde group in the spectrum is obviously shortened and can be ignored basically, so that the chemical reaction is complete, and compared with the infrared spectrum of monomer aldehyde, the characteristic peaks of the prepared polymer are greatly shortened. In summary, the monomeric aldehyde has reacted sufficiently to give the reactionThe reaction is carried out more thoroughly, and the polymer obtained by the reaction is more consistent with the expected set structure.
XRD, i.e., X-ray diffraction, is a technique for obtaining information such as the composition of a material, the structure or form of atoms or molecules in the material, and the like by subjecting the material to X-ray diffraction and analyzing the diffraction pattern thereof, and thus the crystal form can be determined. Fig. 4 is an XRD pattern of the thionofluorenyl polyporphyrin obtained in example 1, and it can be seen from the pattern that no sharp peak appears in the pattern of the substance, and the pattern shows an irregular curve as a whole, thereby judging that the thionofluorenyl polyporphyrin prepared has no crystal form, does not belong to a crystal class, and is an amorphous class.
The ultraviolet spectrum is generated by using the absorption of ultraviolet light by molecules of a substance, and the composition, content and structure of the substance can be analyzed, measured and inferred. The ultraviolet spectrum of the thiofluorenyl polyporphyrin obtained by the invention is shown in fig. 5, and the ultraviolet spectrum shows that the thiofluorenyl polyporphyrin is black powder and has strong absorption to light, so that the absorption rates A in the spectrum are all more than 1. The figure shows that porphyrin has three relatively weak absorption peaks at lambda-312.07 nm, 321.61nm and 340.54nm, belongs to the absorption of an R band of N → pi, shows the absorption of N electronic groups, and shows that the porphyrin contains functional groups such as-C-N-, -C-S-, benzene ring and the like; the peak at the wavelength of 300nm on the spectrogram is also a peak belonging to K band absorption and is a result of transition of pi electrons to pi × anti-bonding orbitals, which is simply expressed as pi → pi ×, and indicates that the thionofluorenyl polyporphyrin contains a conjugated system consisting of a plurality of double bonds, and according to the chemical formula of the thionofluorenyl polyporphyrin, a benzene ring, a carbon-nitrogen chemical bond and a carbon-sulfur chemical bond are indeed present, and a plurality of double bond conjugated structures are contained. Except that the absorption peak exists in the wavelength range of 300-400nm, no absorption peak exists in other wavelength regions, which indicates that the obtained porphyrin is relatively pure and is not doped with other impurities.
The scanning electron microscope is used for modulating and imaging by various physical signals excited when an electron beam scans the surface of a sample. FIG. 6 is a scanning electron micrograph of thiofluorenyl polyporphyrin obtained in example 1 of the present invention, and (1) in FIG. 6 is a view at a lower magnification, which shows that all particles are overlapped and aggregated together, and the whole shows a closely packed network structure. (2) And (3) is a scanned aspect map after magnification, we can see more clearly how each particle is stacked: each particle in the sample is irregularly spherical and there are many small spherical particles that are agglomerated together to form a cluster of clusters. (2) And (3) are appearance images obtained by scanning from different angles, and it can be seen that the spherical particles are layered after being agglomerated. The reason why the particles are irregular spherical is probably that a scanning electron microscope mainly uses electron beams to scan a sample, so the sample needs to conduct the electron beams, so the sample needs to have the electric conduction capability to better scan the appearance, and porphyrin as a polymer has no good electric conduction capability because the main framework consists of carbon and hydrogen elements, so the scanned appearance is not very beautiful.
The thermogravimetry refers to an analysis method for measuring the relationship between the mass of a sample to be measured and the temperature change under the condition of program control temperature, and the thermogravimetry graph of the thionofluorenyl polyporphyrin obtained in the embodiment 1 of the invention is shown in fig. 7. As can be seen from fig. 7, the stability of the thiofluorenyl polyporphyrin gradually decreased with an increase in temperature, and the rate of weight loss slightly increased with an increase in temperature. It is seen that the weight loss of the polymer is relatively fast in the initial stage (before point a), and the weight loss rate reaches about 5% when the container is heated to about 54 ℃, probably because the polymer is a porous material and can easily absorb moisture, and the container has poor sealing property after being placed for a long time, so that the container absorbs a small amount of moisture in the air, and the weight loss in the initial stage is serious. However, before the temperature reaches 480 ℃ (shown by the point M in the figure), the residual weight of the polymer can be ensured to be more than 80%, and the weight loss rate can be controlled within 20%, namely, more than 80% of the structure of the polymer can be kept intact without being damaged, and only 20% of the decomposed structure of the polymer is damaged when the temperature is less than 450 ℃. Two stages similar to steps appear in the upper graph, namely an AB stage and a CD stage respectively, the weight loss in the two stages is relatively gentle, and basically the two stages can be regarded as no weight loss, namely, in the stage of the temperature range of 54-113 ℃ and the stage of the temperature range of 200-343 ℃, the weight loss condition of the polymer is very small compared with that of other stages, and the polymer can be roughly regarded as no weight loss. Finally, when the temperature is heated to 800 ℃ (point N in the figure), the weight loss rate of the polymer is only about 35%, only about 35% of the sample undergoes decomposition weight loss, and most of the polymer structure still remains intact. Under the high-temperature condition, the sample participating in the test can keep more than 65% of the skeleton integrity without decomposition. The analysis shows that the prepared thiofluorenyl polyporphyrin has good thermal stability.
The test results of the thiofluorenyl polyporphyrins obtained in examples 2 and 3 are similar to those of example 1, which shows that both thiofluorenyl polyporphyrins with higher purity and better thermal stability are obtained.
As can be seen from the above examples, the present invention provides a compound having a target structure, which has a highly conjugated structure and excellent stability.
The target compound required by the invention is prepared by reacting aldehyde and pyrrole under the protection of nitrogen under the shading condition, and the whole method is simple and easy to control, is easy to purify and has high yield.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A thiofluorenyl polyporphyrin has a structure as shown in formula 1:
2. the sulfoxafluorenylpolyporphyrin of claim 1, wherein the sulfoxafluorenylpolyporphyrin has a network-like pore structure.
3. The method for preparing sulfoxafluorylpolyporphyrin according to claim 1 or 2, comprising the steps of:
(1) brominating dibenzothiophene sulfone to obtain brominated dibenzothiophene sulfone;
(2) reacting the brominated dibenzothiophene sulfone obtained in the step (1) with 4-formylphenylboronic acid under the action of a catalyst to obtain (4-formylphenyl) dibenzothiophene sulfone;
(3) polymerizing the (4-formylphenyl) dibenzothiophene sulfone obtained in the step (2) and pyrrole to obtain the thiofluorenyl polyporphyrin.
4. The method of claim 3, wherein in step (1), the brominating reagent for bromination includes N-bromosuccinimide, cupric bromide and liquid bromine.
5. The preparation method according to claim 3 or 4, wherein the bromination is carried out at room temperature for 12-24 hours.
6. The method of claim 3, wherein in step (2), the catalyst comprises a palladium catalyst.
7. The preparation method according to claim 3 or 6, wherein in the step (2), the reaction temperature is 80-100 ℃ and the reaction time is 36-60 h.
8. The preparation method according to claim 3, wherein in the step (3), the reaction temperature is 120-150 ℃ and the reaction time is 20-30 h.
9. The method of claim 3, wherein in step (1), after bromination, the method further comprises post-treating the brominated material, and the post-treating comprises: and dissolving the solid material obtained by the reaction by utilizing hot chlorobenzene, and standing and crystallizing to obtain the brominated dibenzothiophene sulfone crystal.
10. The method according to claim 3, wherein the step (3) further comprises purifying the reacted solid material after the reaction by Soxhlet extraction.
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Application publication date: 20201027 |
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| RJ01 | Rejection of invention patent application after publication |