CN115073479B - Extended porphyrin constructed by naphthadipyrrole with near infrared absorption property, preparation method and application thereof - Google Patents
Extended porphyrin constructed by naphthadipyrrole with near infrared absorption property, preparation method and application thereof Download PDFInfo
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 56
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 238000003786 synthesis reaction Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 230000009467 reduction Effects 0.000 claims description 11
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- -1 lithium aluminum hydride Chemical compound 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 3
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims description 3
- 229940117360 ethyl pyruvate Drugs 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012493 hydrazine sulfate Substances 0.000 claims description 3
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 3
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 3
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000000911 decarboxylating effect Effects 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 7
- 230000003595 spectral effect Effects 0.000 abstract description 6
- 238000002428 photodynamic therapy Methods 0.000 abstract description 5
- 238000003384 imaging method Methods 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 239000003504 photosensitizing agent Substances 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007626 photothermal therapy Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention discloses carbon hetero-extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property, a preparation method and application thereof. According to the invention, the naphthodipyrrole and benzene ring are introduced on the basis of the framework of the hexaporphyrin structure, so that a novel rigid carbon hetero-extended porphyrin is obtained, and spectral measurement shows rare near infrared absorption characteristics compared with similar extended porphyrins reported in literature, and the spectral property change of different redox forms is found. Because the carbon hetero-extended porphyrin has stronger absorption in biomedical application windows (793 nm,1052-1063 nm), the carbon hetero-extended porphyrin has the potential of being developed into near infrared absorption materials, photoacoustic imaging and photodynamic therapy photosensitizers.
Description
Technical Field
The invention relates to the field of near infrared absorption materials, in particular to synthesis and application of carbon hetero-extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property.
Background
Carbon hetero-extended porphyrin, namely porphyrin analogues formed by increasing the number of pyrrole units or changing the connection mode of the pyrrole units on the basis of porphyrin structure and introducing aromatic hydrocarbon or non-aromatic ring units such as benzene rings, thiophene, furan, naphthalene rings and the like. Compared with porphyrin, the carbon hetero-extended porphyrin has unique topological structure and physical and chemical properties, and is used in Huckel-The method has great advantages and potential application prospect in the aspects of aromatic conversion, chiral optics, conformational switch, stable organic free radical and the like.
In recent years, numerous chemists have focused on the construction of structurally rigid, conformationally stable carbon heteroexpanded porphyrin macrocycles. Among them, extended porphyrins containing a naphthacenedipyrrole unit are attracting attention due to their structural rigidity, and the large pi-conjugated path and unique conformational structure give them rare near infrared absorption properties to their spectra, with the potential to develop into near infrared absorption materials, photoacoustic imaging, and photodynamic therapy photosensitizers. Therefore, how to synthesize the extended porphyrin containing the naphthacenedipyrrole unit becomes a technical problem to be solved urgently, and application of the extended porphyrin containing the naphthacenedipyrrole unit is limited.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property, a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following inventive concept:
The synthesis method of the carbon hetero-extended porphyrin comprises the following synthesis route steps:
The present invention is not limited to the above synthesis conditions. Based on the framework of hexaporphyrin structure, naphthadipyrrole and benzene ring are introduced to obtain a novel rigid carbon hetero-extended porphyrin, and spectral measurement shows that compared with similar extended porphyrin reported in literature, the novel rigid carbon hetero-extended porphyrin shows rare near infrared absorption characteristics, and the spectral property change of different redox forms of the novel rigid carbon hetero-extended porphyrin is found. Because the carbon hetero-extended porphyrin provided by the invention has stronger absorption in biomedical application windows (793 nm,1052-1063 nm), the carbon hetero-extended porphyrin has the potential of being developed into near infrared absorption materials, photoacoustic imaging and photodynamic therapy photosensitizers.
According to the inventive concept, the invention adopts the following technical scheme:
an extended porphyrin constructed by naphthadipyrrole with near infrared absorption property has the following structural formula:
Wherein R 1 is at least one of hydrogen, alkyl, alkoxy, halogen substituent;
r 2 is at least one of hydrogen, alkyl, alkoxy, aryl-substituted alkyl, aryl or heteroaryl, alkylcarbonyl, alkoxycarbonyl-substituted alkyl.
Preferably, the extended porphyrin constructed by the naphthacenedipyrrole with near infrared absorption property is represented by the following structural formula of extended porphyrin I:
The invention relates to a preparation method of extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property, which comprises the following steps:
(1) In a reaction medium, 2, 3-dihydroxynaphthalene, hydrazine sulfate and hydrazine hydrate undergo nucleophilic substitution reaction to obtain an intermediate I-2, wherein the structural formula of the intermediate I-2 is as follows:
(2) The intermediate I-4 is obtained by dehydration condensation reaction of the intermediate I-2 and I-3, namely ethyl pyruvate, and has the structural formula:
(3) And (3) carrying out closed-loop reaction on the intermediate I-4 under an acidic condition by adopting an acid catalyst to obtain an intermediate I-5, wherein the structural formula of the intermediate I-5 is as follows:
(4) Adding alkali into ethylene glycol solvent, and decarboxylating intermediate I-5 in a mixed solution of ethylene glycol solvent and alkali at high temperature to obtain a reaction precursor I-6, wherein the structural formula is as follows:
(5) The paraphthaloyl chloride and 1,3, 5-trimethylbenzene undergo a Friedel-crafts reaction to produce an intermediate I-7, which has the structural formula:
(6) The intermediate I-7 is reduced by lithium aluminum hydride to a reaction precursor I-8, and the structural formula is as follows:
(7) The intermediate I-6 and I-8 are subjected to acid catalytic condensation, oxidative dehydrogenation and hydrogen iodide reduction in sequence by adopting an oxidant to obtain extended porphyrin I, and the structure is as follows:
preferably, in the synthesis of I-2, the reaction medium is any one or a mixture of more than one of normal hexane, petroleum ether, methylene dichloride, diethyl ether, toluene, ethyl acetate, dioxane, tetrahydrofuran, chloroform, methanol, ethanol, glycol and water.
Preferably, in the synthesis of I-5, the acid catalyst is any one or a mixture of trifluoroacetic acid, boron trifluoride diethyl ether, hydrochloric acid, sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid; and (3) adopting an acid catalyst to make the intermediate I-4 undergo the process of closed-loop reaction under the acidic condition for no more than 72h.
Preferably, in the synthesis of I-6, the alkali is any one or a mixture of sodium hydroxide, potassium carbonate, sodium carbonate, anhydrous sodium acetate, triethylamine and sodium acetate.
Preferably, when the intermediate I-6 and I-8 are subjected to acid catalytic condensation, oxidative dehydrogenation and hydrogen iodide reduction in sequence to obtain the extended porphyrin I, the oxidant is any one or more of air, manganese dioxide, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and tetrachlorobenzoquinone.
Preferably, the reaction temperature of the process is 0 to 200 ℃.
Preferably, in the synthesis of I-6 and I-8, methylene dichloride is used as a solvent, under the protection of nitrogen, boron trifluoride diethyl etherate is used for catalyzing and reacting overnight, after cyclization, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is used for oxidation in air, and finally triethylamine is used for neutralizing acid.
The invention relates to an application of extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property in preparing near infrared absorption materials.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. the carbon hetero-extended porphyrin structure synthesized by the invention has excellent stability and excellent stability in air;
2. the method for synthesizing the extended porphyrin has low cost, mild reaction and easy control;
3. By analyzing the ultraviolet spectrum data, the invention can show that the macrocycle has high molar extinction coefficient epsilon, such as epsilon=21500M -1cm-1 at the absorption wavelength of 1052 nm;
4. The synthesized extended porphyrin has stronger absorption in the near infrared region (793 nm,1052-1063 nm), and can be applied to the fields of near infrared absorption materials, photodynamic therapy, photothermal therapy and the like.
Drawings
FIG. 1 is a MALDI-TOF-MS data graph of compound I according to a preferred embodiment of the present invention.
FIG. 2 is an ultraviolet absorption spectrum (298 k) of the compound I according to the preferred embodiment of the present invention.
FIG. 3 is a graph (298 k) comparing the spectra of the mixture before reduction with the I spectra of the different HI.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum and proton hydrogen assignment graph (238 k) of compound I according to a preferred embodiment of the present invention.
Detailed Description
In order to better understand the technical scheme of the invention, the following detailed description is made by using specific examples of part of macrocyclic extended porphyrins.
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
In this embodiment, an extended porphyrin constructed with a naphthacenedipyrrole having near infrared absorption properties is the following structural formula of extended porphyrin i:
The synthetic route is as follows:
the preparation method of extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property comprises the following steps:
(1) Synthesis of intermediate I-2:
When the intermediate I-2 is synthesized, 2, 3-dihydroxynaphthalene I-1 (37.50 mmol), hydrazine hydrate (123.60 mmol), hydrazine sulfate (15.38 mmol) and 2mL ethanol are sequentially added into a 100mL reaction bottle according to the reactant ratio; heating to 100 ℃ for reflux reaction for 4 hours; stopping the reaction, and cooling to room temperature; pouring the reaction solution into a mixed solution of dichloromethane and methanol (CH 2Cl2/CH3 OH, V/V,40mL/10 mL), and carrying out vacuum filtration to obtain a crude product; washing the crude product with a mixed solution of dichloromethane and methanol, and separating the crude product by silica gel column chromatography to obtain a earthy yellow solid powder, namely an intermediate I-2, wherein the structural formula is as follows: The yield was 50%. The characterization results are as follows:
1H NMR(400MHz,DMSO-d6)δ7.62–7.42(m,2H),7.50(dt,J＝6.8,3.4Hz,2H),7.14(s,2H),7.09(dt,J＝6.1,3.4Hz,2H),6.33(s,2H),4.13(s,4H).
(2) Synthesis of intermediate I-4:
in the process of synthesizing the intermediate I-4, ethyl pyruvate, I-3 (4.6 mg,40 mmol), 2, 3-naphthalene dihydrazide I-2 (3.0 g,16.0 mmol) and 50mL of ethanol are sequentially added into a 100mL reaction bottle according to the proportion of reactants; the reaction was carried out at room temperature overnight, the reaction mixture was clarified, the reaction was monitored by TLC plate, the reaction was completed, and the reaction was stopped; the solvent is removed from the mixed solution under reduced pressure, and the crude product is separated by silica gel column chromatography to obtain pale yellow solid, namely intermediate I-4, which has the following structural formula: the yield was 56%. The characterization results are as follows:
1H NMR(400MHz,Chloroform-d)δ9.18(s,2H),7.69(dd,J＝6.2,3.3Hz,2H),7.66(s,3H),7.31(dq,J＝6.5,3.3Hz,2H),4.35(q,J＝7.1Hz,5H),2.22(s,6H),1.38(t,J＝7.1Hz,6H).
(3) Synthesis of intermediate I-5:
when the intermediate I-5 is synthesized, the intermediate I-4 (3.55 mmol), the paratoluenesulfonic acid hydrate (35.53 mmol) and 150mL of ethanol are sequentially added into a 100mL reaction bottle according to the ratio of reactants; heating reflux reaction for 72h, monitoring reaction by TLC plate, stopping reaction, and cooling to room temperature; the solvent is removed from the mixed solution under reduced pressure, and the crude product is separated by silica gel column chromatography to obtain green light solid powder, namely an intermediate I-5, the structural formula of which is as follows: The yield was 84%. The characterization results are as follows:
1H NMR(400MHz,DMSO-d6)δ11.88(d,J＝2.4Hz,1H),8.33(dd,J＝6.0,3.2Hz,1H),7.47(dd,J＝6.0,3.2Hz,1H),4.40(q,J＝7.0Hz,2H),1.39(t,J＝7.1Hz,4H).
(4) Synthesis of intermediate I-6:
When the intermediate I-6 is synthesized, the intermediate I-5 (2.85 mmol), potassium hydroxide (28.5 mmol) and 30mL of ethylene glycol are sequentially added into a 100mL reaction bottle under the protection of nitrogen according to the ratio of reactants; heating to 180 ℃ to reflux and react for 2 hours, monitoring the reaction by a TLC plate, stopping the reaction, and cooling to room temperature; pouring the reaction solution into 50mL of distilled water, and carrying out vacuum filtration to obtain a crude product; separating the crude product by silica gel column chromatography to obtain light blue solid, namely an intermediate I-6, which has the following structural formula: the yield was 75%. The characterization results are as follows:
1H NMR(400MHz,DMSO-d6)δ11.07(s,1H),8.17(dt,J＝6.4,3.3Hz,1H),7.35(dd,J＝6.2,3.3Hz,1H),7.24(d,J＝3.1Hz,1H),7.02(d,J＝3.0Hz,1H).
(5) Synthesis of intermediate I-7: ,
Terephthaloyl chloride (0.1 mol) 2-7 and anhydrous aluminum chloride (0.2 mol) were dissolved in a strictly dried small beaker with dichloroethane (80 mL) and stirred to obtain a uniform suspension; slowly adding the suspension into a 250mL round bottom flask containing 1,3, 5-trimethylbenzene (80 mL) 2-8, and continuously stirring; after refluxing the reaction mixture at 90 ℃ for 48 hours, it was quenched with 200mL of saturated brine and extracted with dichloromethane (4 x 100 mL); the organic extract was dried over anhydrous magnesium sulfate, filtered and dried to give pale yellow crystals, and intermediate I-7, which had the following structural formula: the yield was 56%.
(6) Synthesis of intermediate I-8: ,
Diketone compound 2-9 (0.4 mol) was dissolved in tetrahydrofuran (200 mL) under nitrogen in a 500mL round bottom flask; then, solid lithium aluminum hydride (2.2 equvi) was added to the flask a small number of times; reflux the reaction system at 80 ℃ for 24-48 hours; after the reaction is completed, slowly cooling to room temperature, adding purified water (10 mL) into the reaction system for a plurality of times, and then adding NaOH aqueous solution (2M, 5 mL) to quench the reaction; the reaction mixture was filtered and the solvent evaporated off with a rotary evaporator and finally purified by column chromatography and recrystallisation as a white pure solid I-8 of the formula: the yield was 88%. The characterization results are as follows:
1H NMR(400MHz,DMSO-d6)δ7.07(d,J＝3.1Hz,4H),6.76(s,4H),6.08(d,J＝4.1Hz,2H),5.64(d,J＝4.2Hz,2H),2.19(d,J＝2.1Hz,6H),2.14(s,12H).
(7) Synthesis of macrocyclic extended porphyrins i:
when the synthesis of the macrocyclic extended porphyrin I is carried out, naphtho-dipyrrole I-6 (1.0 mmol) and 1, 4-diaryl dibenzyl alcohol I-8 (1.0 mmol) are added into a 1000mL round bottom flask with a three-way caliber according to the proportion of reactants, and the mixture is replaced by nitrogen for a plurality of times. The redistilled CH 2Cl2 (600 mL) was introduced into the flask with a long needle under negative pressure and nitrogen sparged for 10 minutes to ensure no air remained in the flask. The mixture was stirred at room temperature for half an hour until all of the two precursor compounds dissolved, BF 3·OEt2 (64 μl,1.0 mmol) was slowly added dropwise with a microinjector, and the reaction mixture was stirred overnight protected from light. Then, 2, 3-dichloro-5, 6-dicyanobenzoquinone (DDQ) (1.5 mmol) was added as an oxidizing agent, and the reaction system was exposed to air and stirred for another 1 hour. Finally, adding a proper amount of triethylamine dropwise to the reaction system to neutralize excessive acid, continuously stirring for 10 minutes, and quenching the reaction. The crude product is firstly separated by neutral alumina, and is further purified by silica gel column chromatography to obtain a bright purple solution, at the moment, excessive HI is added for reduction, and a rotary evaporator is used for removing the solvent to obtain purer solid. Finally, recrystallizing with methanol to separate out solid with metallic luster, carrying out suction filtration and drying to obtain a clean target compound I, wherein the structural formula is as follows: The overall yield was 1.4%. The characterization results are as follows:
1H NMR(400MHz,Chloroform-d)δ10.60(s,0H),10.54–10.47(m,4H),9.61(d,J＝9.1Hz,4H),9.37(q,J＝4.1Hz,4H),8.09(d,J＝5.8Hz,4H),7.77(s,4H),7.38(s,4H),3.01(t,J＝4.4Hz,12H),2.81(d,J＝3.2Hz,13H),1.23(d,J＝3.2Hz,12H),-2.85(s,4H),-4.38(s,4H).
Experimental test analysis:
FIG. 1 is a MALDI-TOF-MS data diagram of Compound I of this example. From fig. 1, it can be seen that the mass spectrum data is consistent with the theoretical value, and the structural correctness is primarily demonstrated. FIG. 2 is a graph (298 k) showing the ultraviolet absorption spectrum of Compound I of this example. As can be seen from FIG. 2, the compound I has strong absorption signals in the Soret band 561nm and near infrared 793nm and 1063 nm. FIG. 3 is a graph (298 k) comparing the spectra of the mixture before reduction with the I spectra of the different HI. From FIG. 3, it is clear that the absorption signal of the compound I after reduction has a significant red shift. FIG. 4 shows the nuclear magnetic resonance spectrum and proton hydrogen assignment (238 k) of the compound I of this example. From FIG. 4, it can be seen that hydrogen protons in the aromatic region can be attributed one by one, and that the compound I has a remarkable aromatic character from the characteristic of chemical shift of hydrogen protons in the spectrum.
Before the reduction with hydrogen iodide, a mixture of the di-protonated product and the free-radical product is actually formed, which can be reduced in unison to the compound I under HI reduction, and the absorption of I is slightly redshifted from 1052nm to 1063nm, indicating an increase in conjugation, as can also be seen from the UV-visible spectrum.
The synthesis and application of the carbon hetero-extended porphyrin constructed by the naphthacenedipyrrole with near infrared absorption property are provided in the embodiment. According to the invention, the naphthodipyrrole and benzene ring are introduced on the basis of the framework of the hexaporphyrin structure, so that a novel rigid carbon hetero-extended porphyrin is obtained, and spectral measurement shows rare near infrared absorption characteristics compared with similar extended porphyrins reported in literature, and the spectral property change of different redox forms is found. Because the carbon hetero-extended porphyrin has stronger absorption in biomedical application windows (793 nm,1052-1063 nm), the carbon hetero-extended porphyrin has the potential of being developed into near infrared absorption materials, photoacoustic imaging and photodynamic therapy photosensitizers.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.
Claims (8)
1. An extended porphyrin constructed by naphthadipyrrole with near infrared absorption property is characterized by having the following structural formula:
2. A method for preparing extended porphyrin constructed from naphthacenedipyrrole having near infrared absorption properties according to claim 1, comprising the steps of:
(1) In a reaction medium, 2, 3-dihydroxynaphthalene, hydrazine sulfate and hydrazine hydrate undergo nucleophilic substitution reaction to obtain an intermediate I-2, wherein the structural formula of the intermediate I-2 is as follows:
(2) The intermediate I-4 is obtained by dehydration condensation reaction of the intermediate I-2 and I-3, namely ethyl pyruvate, and has the structural formula:
(3) And (3) carrying out closed-loop reaction on the intermediate I-4 under an acidic condition by adopting an acid catalyst to obtain an intermediate I-5, wherein the structural formula of the intermediate I-5 is as follows:
(4) Adding alkali into ethylene glycol solvent, and decarboxylating intermediate I-5 in a mixed solution of ethylene glycol solvent and alkali at high temperature to obtain a reaction precursor I-6, wherein the structural formula is as follows:
(5) The paraphthaloyl chloride and 1,3, 5-trimethylbenzene undergo a Friedel-crafts reaction to produce an intermediate I-7, which has the structural formula:
(6) The intermediate I-7 is reduced by lithium aluminum hydride to a reaction precursor I-8, and the structural formula is as follows:
(7) The intermediate I-6 and I-8 are subjected to acid catalytic condensation, oxidative dehydrogenation and hydrogen iodide reduction in sequence by adopting an oxidant to obtain extended porphyrin I, and the structure is as follows:
3. The method for preparing extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property according to claim 2, wherein the method comprises the following steps: in the synthesis of I-2, the reaction medium is any one or a mixture of more of normal hexane, petroleum ether, methylene dichloride, diethyl ether, toluene, ethyl acetate, dioxane, tetrahydrofuran, chloroform, methanol, ethanol, glycol and water.
4. The method for preparing extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property according to claim 2, wherein the method comprises the following steps: in the synthesis of I-5, the acid catalyst is any one or a mixture of more of trifluoroacetic acid, boron trifluoride diethyl ether, hydrochloric acid, sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid; and (3) adopting an acid catalyst to make the intermediate I-4 undergo the process of closed-loop reaction under the acidic condition for no more than 72h.
5. The method for preparing extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property according to claim 2, wherein the method comprises the following steps: in the synthesis of I-6, the alkali is any one or a mixture of sodium hydroxide, potassium carbonate, sodium carbonate, anhydrous sodium acetate, triethylamine and sodium acetate.
6. The method for preparing extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property according to claim 2, wherein the method comprises the following steps: when the intermediate I-6 and I-8 are subjected to acid catalytic condensation, oxidative dehydrogenation and hydrogen iodide reduction in sequence to obtain the extended porphyrin I, the oxidant is any one or a mixture of more than one of air, manganese dioxide, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone and tetrachlorobenzoquinone.
7. The method for preparing extended porphyrin constructed by naphthacenedipyrrole with near infrared absorption property according to claim 2, wherein the method comprises the following steps: when the intermediate I-6 and I-8 are subjected to acid catalytic condensation, oxidative dehydrogenation and hydrogen iodide reduction in sequence to prepare the extended porphyrin I, methylene dichloride is used as a solvent, under the protection of nitrogen, boron trifluoride diethyl ether acid is used for catalytic reaction overnight, after cyclization, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone is used for oxidation in the air, and finally triethylamine is used for neutralizing acid.
8. Use of an extended porphyrin built with a naphthacenedipyrrole having near infrared absorption properties according to claim 1 for the preparation of near infrared absorbing materials.
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