CN103724361B - Containing ester bond symmetrical molecule pincers Series of Porphyrins and preparation method thereof - Google Patents
Containing ester bond symmetrical molecule pincers Series of Porphyrins and preparation method thereof Download PDFInfo
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- porphyrin
- chloroform
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 100
- 210000000080 chela (arthropods) Anatomy 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 88
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 54
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 46
- -1 porphyrin compound Chemical class 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003480 eluent Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000010898 silica gel chromatography Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000741 silica gel Substances 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 16
- 229960001866 silicon dioxide Drugs 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- NUSORQHHEXCNQC-UHFFFAOYSA-N [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Cu].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NUSORQHHEXCNQC-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 12
- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- WNGGWVAYNUANOX-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(O)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical compound [N]1C2=CC=C1C=C(N1)C=C(O)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 WNGGWVAYNUANOX-UHFFFAOYSA-N 0.000 claims description 8
- RNGSTWPRDROEIW-UHFFFAOYSA-N [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RNGSTWPRDROEIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 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 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 19
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 10
- 201000005202 lung cancer Diseases 0.000 description 10
- 208000020816 lung neoplasm Diseases 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GWEDZEGGJIRIKE-UHFFFAOYSA-N N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(O)=C2C1=CC=CC=C1 Chemical compound N1C2=CC([N]3)=CC=C3C=C(N3)C=CC3=CC([N]3)=CC=C3C=C1C(O)=C2C1=CC=CC=C1 GWEDZEGGJIRIKE-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007849 functional defect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- QUKUNZDPKPLYGS-UHFFFAOYSA-N propanoic acid;1h-pyrrole Chemical compound CCC(O)=O.C=1C=CNC=1 QUKUNZDPKPLYGS-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000000439 tumor marker Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
Abstract
The invention provides containing ester bond symmetrical molecule pincers Series of Porphyrins and preparation method thereof, its structural formula is as follows:
this series compound molecular formula is for being followed successively by C
96h
62n
8o
4, C
96h
58n
8o
4zn
2, C
96h
58n
8o
4cl
2mn
2, C
96h
58n
8o
4cu
2, C
96h
58n
8o
4ni
2, C
96h
58n
8o
4co
2.In the present invention, free alkali porphyrin P is obtained after carboxyl phenyl-10,15,20-Triphenylporphyrin and a part Resorcinol generation condensation reaction by bimolecular 5-; Synthesis free alkali porphyrin P again with MnCl
24H
2o, ZnCl
2, CuCl
2, NiCl
26H
2o, CoCl
26H
2o is obtained by reacting corresponding metal porphyrins.Synthesized serial porphyrin is all the Molecular Tweezers compounds with particular cavity size; Detection aldoketones can be developed as further, amine, the sensitive material of arene.
Description
Technical field
The present invention relates to a kind of novel porphyrin compound and derivative thereof, especially for Series of Porphyrins containing ester bond symmetrical molecule pincers detecting propyl benzene and preparation method thereof.
Background technology
Porphyrin compound has good light, heat and chemical stability, has very strong characteristic electron absorption spectrum in visible region.In recent years, utilize electronic structure and the photoelectric properties of Porphyrin and its Complexes uniqueness, design and synthesis photoelectric functional material and device have become research field very active in the world.Molecular Tweezers porphyrin refers to the macromole that porphyrin monomer is connected by covalent linkage, is divided into two large types by the constitutional features of linker: one is flexible open to the outside world type porphyrin, and it is that the meso-phenyl of two porphyrin rings is with the flexible singly-bound connection of covalency; Two is biporphins of rigidity " face-to-face " type, and it is the biporphin connected by the carbon on the group as conjugated system or the porphines core by two porphyrin monomers such as ethynyl, phenyl ring, vinyl and the direct key of carbon.Porphyrin Molecule pincers can be used as the reactive center that light catches antenna, mimic photosynthesis effect, the model compound of energy and transfer transport.Porphyrin polymer is optical, electrical in the modern times, demonstrate tempting prospect in the high-tech area of magnetic material.Porphyrin Molecule pincers compound is in molecular recognition, and catalysis, also there is good application prospect in the fields such as degraded trade effluent.
Such as, Porphyrin Molecule pincers compound detects tumour by photodynamic therapy, and their Performance Ratio porphyrin monomeric compounds are in these areas superior.But, at present can be few for medical Porphyrin Molecule pincers classes of compounds, detection perform is incomplete, therefore, design and synthesize novel structure and the Molecular Tweezers porphyrin compound with good function is that one of ordinary skill in the art have problem to be solved, there is great economic benefit and social benefit.
Summary of the invention
Few for prior art Porphyrin Molecule pincers classes of compounds, the deficiency of functional defect, the object of this invention is to provide a kind of novel Molecular Tweezers porphyrin compound containing ester bond symmetry, and the Molecular Tweezers series metal porphyrin compound containing ester bond symmetry, the sensitive material becoming breath detection of lung cancer patient for exploitation provides reliable selection, to meet the needs of medical detection.
The present invention also provides the preparation method of the described Molecular Tweezers Series of Porphyrins containing ester bond symmetry.
To achieve these goals, the present invention adopts following technical scheme: a kind of containing ester bond symmetrical molecule pincers porphyrin compound, it is characterized in that, its structural formula is:
Wherein, M is 2H, and compound molecule formula is C
96h
62n
8o
4, be called for short free alkali porphyrin P.
The present invention also provides a kind of containing ester bond symmetrical molecule pincers series metal porphyrin compound, and its structural formula is:
Wherein, M is Zn, MnCl, Cu, Ni or Co; Be referred to as series metal porphyrin;
M is Zn, and compound molecule formula is C
96h
58n
8o
4zn
2;
M is MnCl, and compound molecule formula is C
96h
58n
8o
4cl
2mn
2;
M is Cu, and compound molecule formula is C
96h
58n
8o
4cu
2;
M is Ni, and compound molecule formula is C
96h
58n
8o
4ni
2;
M is Co, and compound molecule formula is C
96h
58n
8o
4co
2.
The present invention also provides the described preparation method containing ester bond symmetrical molecule pincers porphyrin compound, comprises the steps:
1) synthesize monohydroxy porphyrin: in 250ml three-necked flask, add 2.6 ~ 3g p-Hydroxybenzaldehyde successively, 5.5 ~ 6ml phenyl aldehyde and 200 ~ 250ml propionic acid, stir, ebuillition of heated; Then, drip 30 ~ 40ml propionic acid solution that 5 ~ 5.5ml newly steams pyrroles, continue stirring and refluxing 1 ~ 1.5 hour;
Thereafter, in the reaction solution of cool to room temperature, add 1 ~ 1.5 liter of redistilled water, regulate pH=8-9 with saturated sodium bicarbonate solution, staticly settle, suction filtration, obtain violet solid, vacuum-drying; Post crossed by recycle silicon glue, and chloroform makees eluent, collects the second colour band, obtains monohydroxy porphyrin;
2) free alkali porphyrin P is synthesized: get 50 ~ 80mlDMF(N, dinethylformamide), add 2 ~ 2.5gCaH
2, stirring and refluxing 24 ~ 36 hours, it is for subsequent use that decompression steams solvent; Then, in three-necked flask, add 6.4 ~ 6.6mg terephthalic acid successively under ice bath, 30 ~ 40mgEDCHCl, 50 ~ 55mgDMAP, the DMF(N of 20 ~ 30ml drying, dinethylformamide), fully react 30 ~ 45 minutes under nitrogen protection after mixing; Add the monohydroxy porphyrin that 50 ~ 60mg step 1) obtains, lucifuge reaction 24 ~ 36h under room temperature;
After photoresponse to be avoided terminates, distilled water is added and saturated aqueous common salt washs in reaction system, first use distilled water wash three times, in reaction system, add 30 ~ 40ml distilled water at every turn, the water washing of 30 ~ 40ml saturated common salt is added once again in reaction system, after abundant washing, use anhydrous MgSO
4dry organic layer; Then, be spin-dried for solvent, fill post with silica gel, the mixed solvent re-using (V:V)=3:2 chloroform and sherwood oil does elutriant, collects the second band purple product, obtains free alkali porphyrin P, productive rate 50%.
Further, the present invention also provides a kind of preparation method containing ester bond symmetrical molecule pincers series metal porphyrin compound, comprises the steps:
Take 100 ~ 120mg free alkali porphyrin P in three-necked flask, add 30 ~ 40mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, add the DMF solution that 20ml contains 200 ~ 400mg metal-salt, heating reflux reaction 1 ~ 3h under nitrogen protection, back flow reaction temperature 120 ~ 140 DEG C;
150ml redistilled water is added, with 50ml chloroform extraction 3 times after cooling; Rotate solvent evaporated;
Thick product is added on silicagel column, first washes away unreacted free alkali porphyrin P with chloroform, then uses the chloroform of volume ratio (V:V)=10:1 and alcohol mixed solvent to make eluent, and the second band is target product metal porphyrins.
Described metal-salt is ZnCl
2, CuCl
2, NiCl
2, CoCl
2or MnCl
2.
Further, the invention still further relates to containing ester bond symmetrical molecule pincers porphyrin compound for detecting the application of propyl benzene.And containing ester bond symmetrical molecule pincers series metal porphyrin compound for detecting the application of propyl benzene.
Compared to existing technology, the present invention has following beneficial effect:
1, Molecular Tweezers metal porphyrins of the present invention obtains by after bimolecular 5-p-hydroxybenzene-10,15,20-Triphenylporphyrin and the condensation of a part terephthalic acid; Connected by bridge crosslinking structure between two molecules, synthesized serial porphyrin is all the Molecular Tweezers compounds with particular cavity size; Its ester bond functional group is in cavity structure microenvironment, intermolecular hydrogen bonding can be passed through, the multi-acting forces such as Van der Waals force and detected object effect, two porphyrin rings are by pi-pi accumulation effect, the reactive forces such as coordinate bond and detected object effect, ester bond functional group and Liang Ge porphyrin ring chromophore synergy, can realize the special of detected object and Sensitive Detection.
2, Molecular Tweezers metal porphyrins dimer free alkali porphyrin of the present invention and series metal porphyrin, because the electron-withdrawing power of different metal atom is different, and on the impact difference that porphyrin ring conjugated structure brings after coordination, after finally showing as different metal porphyrin and free alkali porphyrin and propyl benzene molecularity, different responses is formed in visible region, 6 kinds of porphyrins are configured to cross response sensor array, the detection to propyl benzene gas can be realized.Particularly as the sensitive material of lung cancer patient breath mark hexanal, and then provide reliable selection for developing the sensitive material becoming breath detection of lung cancer patient.Detection aldoketones can be developed as further, amine, the sensitive material of arene.
3, adopt the method for dimer synthon free alkali porphyrin of the present invention and series metal porphyrin compound, preparation process is simple, and productive rate is respectively up to more than 75% and 90%, greatly reduces synthesis difficulty, significantly improves reaction income.
4, in the preparation process of mono carboxylic porphyrin, adopt volume ratio be the mixing solutions of the pyrrole propanoic acid of the distillation of 1:1 as reaction soln, the impurity in product can be reduced, improve speed of reaction.
Accompanying drawing explanation
Fig. 1 is the structure iron of Molecular Tweezers free alkali porphyrin and metalloporphyrin.
Fig. 2 is the ultraviolet-visible spectrogram of Molecular Tweezers free alkali porphyrin in chloroform.
Fig. 3 is the infrared spectrogram of Molecular Tweezers free alkali porphyrin.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of Molecular Tweezers free alkali porphyrin.
Fig. 5 is the poor spectrogram that porphyrin array detects propyl benzene gas.
Embodiment
Below in conjunction with specific embodiment, the present invention is contained to Molecular Tweezers porphyrin compound and the preparation method of ester bond symmetry, and be described in further detail for the application detecting propyl benzene.
One, a kind of Molecular Tweezers porphyrin compound containing ester bond symmetry.
The structural formula of described porphyrin compound is as shown in Figure 1:
The described Molecular Tweezers porphyrin compound containing anhydride bond symmetry, when M is 2H, molecular formula is C
96h
62n
8o
4, be called for short free alkali porphyrin P.
The described Molecular Tweezers series metal porphyrin compound containing anhydride bond symmetry: M is Zn, MnCl, Cu, Ni or Co.
When M is Zn, molecular formula is C
96h
58n
8o
4zn
2;
When M is MnCl, molecular formula is C
96h
58n
8o
4cl
2mn
2;
When M is Cu, molecular formula is C
96h
58n
8o
4cu
2;
When M gets Ni, molecular formula is C
96h
58n
8o
4ni
2;
When M is Co, molecular formula is C
96h
58n
8o
4co
2.
Two, preparation method.
DMF in the present invention refers to DMF, and EDCHCl refers to 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride, and DMAP refers to (DMAP).
1, a kind of synthetic method of the Molecular Tweezers porphyrin compound (i.e. free alkali porphyrin P) containing ester bond symmetry:
1) synthesis of monohydroxy phenyl porphyrin: add 2.6g p-Hydroxybenzaldehyde successively in 250ml three-necked flask, 5.5ml phenyl aldehyde and 200ml propionic acid, stir, ebuillition of heated; Then, drip the 30ml propionic acid solution that 5ml newly steams pyrroles, continue stirring and refluxing 1h;
Thereafter, in the reaction solution of cool to room temperature, add 1L redistilled water, regulate pH=8-9 with saturated sodium bicarbonate solution, staticly settle, suction filtration, obtain violet solid, vacuum-drying; Cross post with 100-200 order silica gel again, chloroform makees eluent, collects the second band, obtains monohydroxy porphyrin.
2) synthesis of free alkali porphyrin P: get 50mlDMF(N, dinethylformamide), add 2gCaH
2, stirring and refluxing 24 hours, decompression steams solvent and is dry chloroform, with to be used; Then, in three-necked flask, add 6.4mg terephthalic acid successively under ice bath, the DMF(N of 30mgEDCHCl, 50mgDMAP, 20ml drying, dinethylformamide), fully react 30 minutes under nitrogen protection after mixing; Add the monohydroxy porphyrin that 50mg step 1) obtains, lucifuge reaction 24h under room temperature.
After photoresponse to be avoided terminates, in reaction system, add distilled water and saturated aqueous common salt washs, first use distilled water wash three times, in reaction system, add 30ml distilled water at every turn, in reaction system, add the water washing of 30ml saturated common salt once again, fully after washing, use anhydrous MgSO
4dry organic layer; Then, be spin-dried for solvent, with 100-200 order silica gel dress post, the mixed solvent re-using (V:V)=3:2 chloroform and sherwood oil does elutriant, collects the second band purple product, obtains free alkali porphyrin P, productive rate 50%.
The synthetic method of the Molecular Tweezers series metal porphyrin compound 2, containing ester bond symmetry:
2.2.1 the synthetic method of zinc protoporphyrin ZnP:
Take 100mg free alkali porphyrin P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds the DMF solution that 20ml contains 200mgZnCl2, heating reflux reaction 1h under nitrogen protection, back flow reaction temperature 140 DEG C.150ml redistilled water is added, with 50ml chloroform extraction 3 times after cooling.Rotate solvent evaporated, obtain the thick product of zinc protoporphyrin ZnP; Thick for zinc protoporphyrin ZnP product is carried out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P with chloroform, then use eluent, the second band is target product zinc protoporphyrin ZnP; Vacuum-drying, obtains violet solid, productive rate 90%.
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol.
2.2.2 copper porphyrin CuP synthetic method:
Take 100mg free alkali porphyrin P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 260mgCuCl
2dMF solution, heating reflux reaction 1h under nitrogen protection, back flow reaction temperature 140 DEG C, adds 150ml redistilled water after cooling, with 50ml chloroform extraction 3 times.Rotate solvent evaporated, obtain the thick product of copper porphyrin CuP, thick for copper porphyrin CuP product is carried out silica gel column chromatography separation, first wash away unreacted free alkali porphyrin P with chloroform, then use eluent, the second band is target product copper porphyrin CuP; Vacuum-drying, obtains brick-red solid, productive rate 90%.
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol.
2.2.3 nickel-porphyrin NiP synthetic method
Take 100mg free alkali porphyrin P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 360mgNiCl26H
2the DMF solution of O, heating reflux reaction 2h under nitrogen protection, back flow reaction temperature 140 DEG C.150 milliliters of redistilled waters are added, with 50 milliliters of chloroform extractions 3 times after cooling.Rotate solvent evaporated, obtain the thick product of nickel-porphyrin NiP, nickel-porphyrin NiP is carried out silica gel column chromatography separation, first wash away unreacted free alkali porphyrin P with chloroform, then use eluent, the second band is target product copper porphyrin CuP; Vacuum-drying, obtains burgundy solid, productive rate 90%.
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol.
2.2.4 Cob altporphyrin CoP synthetic method
Take 100mg free alkali porphyrin P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 360mgCoCl26H
2the DMF solution of O, heating reflux reaction 2h under nitrogen protection, back flow reaction temperature 140 DEG C.Add 150ml redistilled water after cooling, with 50ml chloroform extraction 3 times, rotate solvent evaporated, obtain the thick product of Cob altporphyrin CoP; Thick for Cob altporphyrin CoP product is carried out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P with chloroform, then use eluent, the second band is target product copper porphyrin CuP; Vacuum-drying, obtains brick-red solid, productive rate 90%.
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol.
2.2.5 manganoporphyrin MnClP synthetic method
Take 100mg free alkali porphyrin P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 300mgMnCl
24H
2the DMF solution of O, heating reflux reaction 3h, back flow reaction temperature 140 DEG C.150ml redistilled water is added, with 50ml chloroform extraction 3 times after cooling.Rotate solvent evaporated, obtain the thick product of manganoporphyrin MnClP.Thick for manganoporphyrin MnClP product is carried out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P with chloroform, then use eluent, the second band is target product copper porphyrin CuP; Vacuum-drying, obtains green solid, productive rate 90%.
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol.
Three, structural characterization:
Use proton nmr spectra, uv-vis spectra, infrared spectra and ultimate analysis to the novel Molecular Tweezers porphyrin compound containing anhydride bond symmetry of the present invention, and the structure of the Molecular Tweezers series metal porphyrin compound containing anhydride bond symmetry characterizes, and proves to have synthesized target compound.
1, uv-vis spectra: be concentration be 1 × 10 with ultraviolet spectrophotometer test
-6the uv-vis spectra of the free alkali porphyrin of mol/L, as shown in Figure 2, by seeing in figure at 419nm, free alkali porphyrin occurs that strong Soret is with, there are four typical Q bands at 516nm, 552nm, 590nm, 645nm in test result.There is strong Soret band in zinc protoporphyrin, occurs that Q is with at 548nm at 420nm place.
Table 1 is the ultraviolet spectrum data of porphyrin compound, and strong Soret band appears in free alkali porphyrin at 419nm place as can be seen from the table, occurs four typical Q bands at 516nm, 552nm, 590nm, 645nm.There is strong Soret band in zinc protoporphyrin, occurs that Q is with at 548nm at 420nm place.There is strong Soret band at 416nm in copper porphyrin, occurs that Q is with at 540nm place.There is strong Soret band at 416nm in nickel-porphyrin, occurs that Q is with at 524nm place.There is strong Soret band at 478nm in manganoporphyrin, occurs that Q is with at 585nm and 620nm place.There is strong Soret band at 432nm in Cob altporphyrin, occurs that Q is with at 550nm place.
The ultraviolet spectrum data of table 1 porphyrin compound
| Compound | Solvant | Soret bands | Q bands |
| P | CH 2Cl 2 | 419 | 516，552，590，645 |
| ZnP | CH 2Cl 2 | 420 | 548 |
| CuP | CH 2Cl 2 | 416 | 540 |
| NiP | CH 2Cl 2 | 416 | 524 |
| CoP | CH 2Cl 2 | 432 | 550 |
| MnClP | CH 2Cl 2 | 478 | 585，620 |
2, infrared spectrogram: test free alkali porphyrin and metal porphyrins with infrared spectrometer, is illustrated in figure 3 the infrared spectrogram of free alkali porphyrin, and as can be seen from Figure, free alkali porphyrin is at 3317cm
-1and 966cm
-1there is the flexible and flexural vibration characteristic frequency of pyrroles N-H key in pyrrole ring in place, at 2919cm
-1and 2850cm
-1the vibration peak occurred is attributed to CH
2c-H vibrational frequency, 1745cm
-1for carbonyl vibration peak in ester group.
If table 2 is the ir data of metalloporphyrin, after can finding out and form metalloporphyrin in table, 3317cm
-1place's absorption peak disappears and 966cm
-1the absorption peak red shift at place is to 997-1011cm
-1near, show to define M-P key, after reason is atom N on porphyrin ring and metal-complexing, cause large ring vibration to strengthen, absorption peak shifts to high frequency region.After forming metalloporphyrin, the charateristic avsorption band of ester bond is compared with free alkali porphyrin and be there is no considerable change, shows that the impact that metal ion causes this key is limited.
The ir data of table 2 metalloporphyrin
| Assignment | Intensity | ZnP | CuP | NiP | CoP | MnClP |
| V C-H | s | 2923 | 2923 | 2923 | 2925 | 2923 |
| V C-H | s | 2852 | 2852 | 2852 | 2853 | 2852 |
| V C=O | s | 1738 | 1741 | 1739 | 1739 | 1740 |
| V C=C | m | 1597 | 1599 | 1599 | 1601 | 1600 |
| V C=N | m | 1486 | 1494 | 1494 | 1494 | 1490 |
| V C-H(pyrrole) | m | 1199 | 1198 | 1198 | 1200 | 1201 |
| V C-C-N(pyrrole) | m | 1072 | 1075 | 1075 | 1074 | 1066 |
| V C-H(pyrrole) | m | 997 | 1003 | 1008 | 1009 | 1011 |
| V C-H(pyrrole) | m | 796 | 799 | 797 | 797 | 803 |
3, proton nmr spectra
1hNMR as shown in Figure 4, is the proton nmr spectra of free alkali porphyrin
1hNMR, wherein reagent is CDCl
3, δ :-2.76 (s, 4H, NH) as can be seen from Figure, 7.71-7.72 (m, 4H, ArH), 7.77 – 7.80 (m, 18H, ArH), 8.22-8.25 (m, 12H, ArH), 8.32 – 8.34 (d, 4H, ArH), (8.62 s, 4H, ArH), (8.86-8.94 m, 16H, py-CH).
4, ultimate analysis, respectively ultimate analysis test is carried out to free alkali porphyrin and metalloporphyrin, test result is as shown in table 3, as can be seen from table, relative error between the theoretical content of each element and test content is less than 5%, its in allowed limits, the content of each element meets the content of each element in target product.
The results of elemental analyses of table 3 porphyrin compound
Comprehensive above structural characterization digital proof has synthesized target product.
Four, qualitative detection is carried out to propyl benzene.
By simultaneous test, show that novel cpd of the present invention and lung cancer marker propyl benzene have response, qualitative detection can be carried out to hexanal:
1, the structure of sensor array:
Sensor array adopts hydrophobic polyvinylidene fluoride film as base material, can effectively prevent atmospheric moisture pair array from detecting the impact caused.Adopt the manual point sample of kapillary by concentration be the solution point of the Novel series compound of the present invention of 1 × 10-6mol/L on base material, then the array chip made sealing is stored in nitrogen dark surrounds, keeps its reactive behavior.
2, distribution and detection:
Air distributing device adopts existing producer gas generator (volume 10L), wears air interchanger, heating unit and circulation device.
Ventilation: open valve, do carrier gas with nitrogen, by the gas displacement in producer gas generator, to make for nitrogen is filled in whole producer, then valve-off;
Heating: with liquid-transfering gun accurate measuring 10 μ L liquid propyl benzene, proceed to rapidly on the heating piece in producer gas generator, control Heating temperature (< decomposition temperature) and time (<30s), close heating chamber;
Circulation: ON cycle pump (power 10L/min) 20min, makes gas fully mix, closes recycle pump;
By air distributing device give vent to anger and inlet mouth dock with detection system respectively, the recycle pump (power 5L/min) of open detection device, make detection system stable;
Detect: open porphyrin sensing detection device, acquisition time be 0,1,2,3,4, the RGB information of porphyrin array reflection spectrum under 5min;
Finally, analyze in the RGB information of the reflection spectrum of the six kinds of porphyrin compounds gathered input computer software, this software is the sensing detection software (technician grasping basic programmed method all can complete and write) of the porphyrin array write based on medium filtering and thresholding dividing method.
Analytical results as being followed successively by free alkali porphyrin (green) in Fig. 5, Fig. 5 from left to right, zinc protoporphyrin (apricot), manganoporphyrin (orange), copper porphyrin (sap green), nickel-porphyrin (yellow-green colour), Cob altporphyrin (dark yellow).As can be seen from the figure, produce the response of degree varies after different metalloporphyrins and propyl benzene effect, these six kinds of porphyrins can form a cross response array, realize the detection to propyl benzene gas.
Five, embody rule.
Molecular Tweezers porphyrin compound containing ester bond symmetry of the present invention, and the Molecular Tweezers series metal porphyrin compound containing ester bond symmetry is used for the sensitive material as lung cancer patient breath mark propyl benzene, detects having a extensive future of propyl benzene.Because the electron-withdrawing power of different metal atom is different, and on the impact difference that porphyrin ring conjugated structure brings after coordination, after finally showing as different metal porphyrin and free alkali porphyrin and propyl benzene molecularity, different responses is formed in visible region, 6 kinds of porphyrins are configured to cross response sensor array, the detection to propyl benzene gas can be realized.Particularly as the sensitive material of lung cancer patient breath mark propyl benzene, and then provide reliable selection for developing the sensitive material becoming breath detection of lung cancer patient.Detection aldoketones can be developed as further, amine, the sensitive material of arene.
The present invention is used for the novel cpd of detection of lung cancer breath propyl benzene, the method of the 3rd part is adopted whether to detect in patient exhalation air containing propyl benzene, when detecting in patient exhalation air containing propyl benzene, then represent that this patient probably suffers from lung cancer, if do not detect propyl benzene, think that this patient does not suffer from lung cancer.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (6)
1. the preparation method containing ester bond symmetrical molecule pincers porphyrin compound, is characterized in that, comprise the steps:
1) synthesize monohydroxy porphyrin: in 250ml three-necked flask, add 2.6 ~ 3g p-Hydroxybenzaldehyde successively, 5.5 ~ 6ml phenyl aldehyde and 200 ~ 250ml propionic acid, stir, ebuillition of heated; Then, drip 30 ~ 40ml propionic acid solution that 5 ~ 5.5ml newly steams pyrroles, continue stirring and refluxing 1 ~ 1.5 hour;
Thereafter, in the reaction solution of cool to room temperature, add 1 ~ 1.5 liter of redistilled water, regulate pH=8-9 with saturated sodium bicarbonate solution, staticly settle, suction filtration, obtain violet solid, vacuum-drying; Post crossed by recycle silicon glue, and chloroform makees eluent, collects the second band product, obtains monohydroxy porphyrin;
2) free alkali porphyrin P is synthesized: get 50 ~ 80mlDMF, add 2 ~ 2.5gCaH
2, stirring and refluxing 24 ~ 36 hours, it is for subsequent use that decompression steams solvent; Then, in three-necked flask, add 6.4 ~ 6.6mg terephthalic acid successively under ice bath, 30 ~ 40mgEDCHCl, 50 ~ 55mgDMAP, the DMF of 20 ~ 30ml drying, fully react 30 ~ 45 minutes under nitrogen protection after mixing; Add 50 ~ 60mg step 1) the monohydroxy porphyrin that obtains, lucifuge reaction 24 ~ 36h under room temperature;
After photoresponse to be avoided terminates, distilled water is added and saturated aqueous common salt washs in reaction system, first use distilled water wash three times, in reaction system, add 30 ~ 40ml distilled water at every turn, the water washing of 30 ~ 40ml saturated common salt is added once again in reaction system, after abundant washing, use anhydrous MgSO
4dry organic layer; Then, be spin-dried for solvent, obtain the thick product of free alkali porphyrin P; The thick product of free alkali porphyrin P is carried out silica gel column chromatography separation, then uses elution, collect the second band purple product, obtain free alkali porphyrin P, namely described containing ester bond symmetrical molecule pincers porphyrin compound; Its structural formula is:
Wherein, M is 2H, and compound molecule formula is C
96h
62n
8o
4.
2. the preparation method as claimed in claim 1 containing ester bond symmetrical molecule pincers porphyrin compound, it is characterized in that, described preparation method's step 2) silica gel column chromatography be separated adsorption column adopt 100 ~ 200 object silica gel, eluent adopt volume ratio be the chloroform of 10 ~ 13:1 and the mixing solutions of ethanol.
3. the preparation method containing ester bond symmetrical molecule pincers series metal porphyrin compound, is characterized in that, comprise the steps:
Take 100 ~ 120mg free alkali porphyrin according to claim 1 P in three-necked flask, add 30 ~ 40mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, add the DMF solution that 20ml contains 200 ~ 400mg metal-salt, heating reflux reaction 1 ~ 3h under nitrogen protection, back flow reaction temperature 120 ~ 140 DEG C; Described metal-salt is ZnCl
2, CuCl
2, NiCl
2, CoCl
2or MnCl
2;
150ml redistilled water is added, with 50ml chloroform extraction 3 times after cooling; Rotate solvent evaporated;
Thick product is added on silicagel column, first washes away unreacted free alkali porphyrin P according to claim 1 with chloroform, then uses the chloroform of volume ratio (V:V)=10:1 and alcohol mixed solvent to make eluent, and the second band is target product metal porphyrins; Its structural formula is:
Wherein, M is Zn, MnCl, Cu, Ni or Co; Be referred to as series metal porphyrin;
M is Zn, and compound molecule formula is C
96h
58n
8o
4zn
2;
M is MnCl, and compound molecule formula is C
96h
58n
8o
4cl
2mn
2;
M is Cu, and compound molecule formula is C
96h
58n
8o
4cu
2;
M is Ni, and compound molecule formula is C
96h
58n
8o
4ni
2;
M is Co, and compound molecule formula is C
96h
58n
8o
4co
2.
4. the preparation method as claimed in claim 3 containing ester bond symmetrical molecule pincers series metal porphyrin compound, is characterized in that, comprise zinc protoporphyrin ZnP, copper porphyrin CuP, nickel-porphyrin NiP, Cob altporphyrin CoP and manganoporphyrin MnClP:
1) synthetic method of zinc protoporphyrin ZnP:
Take 100mg free alkali porphyrin according to claim 1 P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 200mgZnCl
2dMF solution, heating reflux reaction 1h under nitrogen protection, back flow reaction temperature 140 DEG C; 150ml redistilled water is added, with 50ml chloroform extraction 3 times after cooling; Rotate solvent evaporated; Obtain the thick product of zinc protoporphyrin ZnP; Thick for zinc protoporphyrin ZnP product is carried out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P according to claim 1 with chloroform, then use eluent, the second band is target product zinc protoporphyrin ZnP; The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol;
2) copper porphyrin CuP synthetic method:
Take 100mg free alkali porphyrin according to claim 1 P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 260mgCuCl
2dMF solution, heating reflux reaction 1h under nitrogen protection, back flow reaction temperature 140 DEG C; 150ml redistilled water is added, with 50ml chloroform extraction 3 times after cooling; Rotate solvent evaporated, obtain the thick product of copper porphyrin CuP; Thick for copper porphyrin CuP product is carried out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P according to claim 1 with chloroform, then use eluent, the second band is target product copper porphyrin CuPCuP;
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol;
3) nickel-porphyrin NiP synthetic method:
Take 100mg free alkali porphyrin according to claim 1 P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 360mgNiCl
26H
2the DMF solution of O, heating reflux reaction 2h under nitrogen protection, back flow reaction temperature 140 DEG C; Add 150ml redistilled water after cooling, with 50ml chloroform extraction 3 times, rotate solvent evaporated; Thick product carries out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P according to claim 1 with chloroform, then uses eluent, and the second band is target product nickel-porphyrin NiP;
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol;
4) Cob altporphyrin CoP synthetic method:
Take 100mg free alkali porphyrin according to claim 1 P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 360mgCoCl
26H
2the DMF solution of O, heating reflux reaction 2h under nitrogen protection, back flow reaction temperature 140 DEG C; Add 150ml redistilled water after cooling, with 50ml chloroform extraction 3 times, rotate solvent evaporated; Thick product carries out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P according to claim 1 with chloroform, then uses eluent, and the second band is target product Cob altporphyrin CoP;
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol;
5) manganoporphyrin MnClP synthetic method:
Take 100mg free alkali porphyrin according to claim 1 P in three-necked flask, add 30mlDMF, stirring and dissolving, logical nitrogen eliminates the oxygen in reaction system, adds 20ml and contains 300mgMnCl
24H
2the DMF solution of O, heating reflux reaction 3h under nitrogen protection, back flow reaction temperature 140 DEG C; 150ml redistilled water is added, with 50ml chloroform extraction 3 times after cooling; Rotate solvent evaporated and obtain the thick product of manganoporphyrin MnClP; Thick for manganoporphyrin MnClP product is carried out silica gel column chromatography separation, first washes away unreacted free alkali porphyrin P according to claim 1 with chloroform, then use eluent, the second band is target product manganoporphyrin MnClP;
The adsorption column that described silica gel column chromatography is separated adopts 100 ~ 200 object silica gel, and eluent adopts volume ratio to be the chloroform of 10:1 and the mixing solutions of ethanol.
5. preparing the application in propyl benzene test material containing ester bond symmetrical molecule pincers porphyrin compound as claimed in claim 1.
6. preparing the application in propyl benzene test material containing ester bond symmetrical molecule pincers series metal porphyrin compound as claimed in claim 3.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2159227A1 (en) * | 2008-08-26 | 2010-03-03 | Ricoh Company, Ltd. | Two-photon absorption material and application thereof |
| CN102863450A (en) * | 2012-10-15 | 2013-01-09 | 重庆大学 | Novel compound for detecting hexanal exhaled by lung cancer patient |
Family Cites Families (1)
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2159227A1 (en) * | 2008-08-26 | 2010-03-03 | Ricoh Company, Ltd. | Two-photon absorption material and application thereof |
| CN102863450A (en) * | 2012-10-15 | 2013-01-09 | 重庆大学 | Novel compound for detecting hexanal exhaled by lung cancer patient |
Non-Patent Citations (4)
| Title |
|---|
| 卟啉传感的肺病早期诊断技术研究;侯长军,等;《中国仪器仪表学会医疗仪器分会第四次全国会员***暨2009年学术年会论文集》;20090408;第183-185页 * |
| 卟啉和金属卟啉二聚物的合成;黄荣彬，等;《厦门大学学报自然科学版》;19870531;第26卷(第3期);第336-340页，全文，尤其实验部分 * |
| 卟啉和金属卟啉二聚物的合成;黄荣彬，等;《厦门大学学报自然科学版》;19870531;第26卷(第3期);第336-340页，全文，尤其是实验部分 * |
| 基于卟啉化学传感器的肺癌呼出气体检测***;罗小刚;《仪器仪表学报》;20100831;第31卷(第8期);第216-222页 * |
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