CN104926708A - Bisindole amide receptor, preparation method therefor and application thereof - Google Patents
Bisindole amide receptor, preparation method therefor and application thereof Download PDFInfo
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- CN104926708A CN104926708A CN201510246077.1A CN201510246077A CN104926708A CN 104926708 A CN104926708 A CN 104926708A CN 201510246077 A CN201510246077 A CN 201510246077A CN 104926708 A CN104926708 A CN 104926708A
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- acceptor
- indole
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- amides
- suction filtration
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims abstract description 61
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims abstract description 57
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims abstract description 57
- -1 indole acyl chloride Chemical class 0.000 claims abstract description 55
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000967 suction filtration Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012043 crude product Substances 0.000 claims abstract description 11
- 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 abstract description 10
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000005457 ice water Substances 0.000 claims abstract description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 150000002475 indoles Chemical class 0.000 claims description 9
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003814 drug Substances 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 4
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 239000000706 filtrate Substances 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 58
- 239000000243 solution Substances 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000872 buffer Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 150000001457 metallic cations Chemical class 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- JKMHFZQWWAIEOD-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid Chemical compound OCC[NH+]1CCN(CCS([O-])(=O)=O)CC1 JKMHFZQWWAIEOD-UHFFFAOYSA-N 0.000 description 3
- 206010027439 Metal poisoning Diseases 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 208000008127 lead poisoning Diseases 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- ZNJHFNUEQDVFCJ-UHFFFAOYSA-M sodium;2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid;hydroxide Chemical compound [OH-].[Na+].OCCN1CCN(CCS(O)(=O)=O)CC1 ZNJHFNUEQDVFCJ-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000007995 HEPES buffer Substances 0.000 description 2
- 206010033799 Paralysis Diseases 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 208000007502 anemia Diseases 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000002232 neuromuscular Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 208000011580 syndromic disease Diseases 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 208000000044 Amnesia Diseases 0.000 description 1
- 208000031091 Amnestic disease Diseases 0.000 description 1
- 206010002383 Angina Pectoris Diseases 0.000 description 1
- 206010048962 Brain oedema Diseases 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 206010019842 Hepatomegaly Diseases 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 241001662043 Icterus Species 0.000 description 1
- 206010022998 Irritability Diseases 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 208000036626 Mental retardation Diseases 0.000 description 1
- 208000009525 Myocarditis Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 208000013738 Sleep Initiation and Maintenance disease Diseases 0.000 description 1
- 208000010513 Stupor Diseases 0.000 description 1
- 102000003929 Transaminases Human genes 0.000 description 1
- 108090000340 Transaminases Proteins 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000006986 amnesia Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003705 background correction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 208000006752 brain edema Diseases 0.000 description 1
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000005189 cardiac health Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- QFSKIUZTIHBWFR-UHFFFAOYSA-N chromium;hydrate Chemical compound O.[Cr] QFSKIUZTIHBWFR-UHFFFAOYSA-N 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000000509 infertility Diseases 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 231100000535 infertility Toxicity 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 206010022437 insomnia Diseases 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical class [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- CKFMJXZQTNRXGX-UHFFFAOYSA-L iron(2+);diperchlorate Chemical compound [Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O CKFMJXZQTNRXGX-UHFFFAOYSA-L 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QFAXIZQBSCGJMA-UHFFFAOYSA-N mercury;hydrate Chemical compound O.[Hg] QFAXIZQBSCGJMA-UHFFFAOYSA-N 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 230000007472 neurodevelopment Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 210000000578 peripheral nerve Anatomy 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 208000018316 severe headache Diseases 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 230000006438 vascular health Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Health & Medical Sciences (AREA)
- Indole Compounds (AREA)
Abstract
The invention provides a bisindole amide receptor, a preparation method therefor and an application thereof. The preparation method comprises: dissolving indole into anhydrous ether to obtain a mixture I; slowly adding oxalyl chloride into the mixture I under violent stirring in ice-water bath, carrying out suction filtration on a reaction liquid after reacting for one hour, and washing precipitates obtained by suction filtration to obtain an intermediate indole acyl chloride; dissolving the intermediate indole acyl chloride into ethyl acetate to obtain a mixture II, adding hydrazine hydrate into the mixture II and then adding a phase transfer catalyst PEG-400 drop by drop, adding a NaOH solution with mass fraction of 5% after carrying out stirring reaction for 10 minutes at the room temperature, then, carrying out stirring reaction for one hour at the room temperature, carrying out suction filtration on the reaction liquid, and washing and drying precipitates subjected to the suction filtrate, thereby obtaining a bisindole amide receptor crude product.The bisindole amide receptor can be used for efficiently and quickly detecting and identifying lead ions, and plays an important role in the fields such as biology, medicine, environment and the like.
Description
Technical field
The invention belongs to technical field of environmental detection, particularly relate to a kind of two indole amides acceptor and preparation method thereof and application.
Background technology
Lead is widely distributed on the earth, rich content and one of the most serious environmental pollutant.Although lead slightly can improve the growth of hypogenetic rat to have scholar to think, its nutritional necessary needs further to study confirmation.
In fact, it is more plumbous to environment and healthy disadvantageous effect for paying close attention to.Lead ion is the harmful heavy metal cation of a class, and numerous disease is as all relevant with lead poisoning in amnesia, irritability, anaemia, Muscle paralysis and mental retardation etc.The clinical manifestation of acute lead poisoning is Metallic Flavour in Nausea and vomiting, mouth, angina abdominis, stool band blood, severe headache, extremely tired, insomnia, peripheral nerve paralysis, severe patient cerebral edema and occur faint from fear, stupor, liver enlargement, icterus index and transaminase obviously raise.The principal character of chronic lead poisoning is neuromuscular syndromes (neuromuscular syndrome), and can cause anaemia, injury of the kidney, masculinity and femininity infertility, fetation is abnormal, and neurodevelopment is abnormal.Plumbous have adverse influence to heart and vascular health, and as caused, myocarditis, ecg scanning are abnormal, heart rate is abnormal, hypertension, vascular deterioration etc.
Therefore, efficiently, fast detection and Identification lead ion play an important role in fields such as biological, medicine and environment, design and synthesis have highly selective and highly sensitive lead ion identification receptor in the urgent need to.
Summary of the invention
The object of the present invention is to provide a kind of two indole amides acceptor.
Another object of the present invention is the preparation method providing above-mentioned pair of indole amides acceptor.
Another object of the present invention is to provide the application of above-mentioned pair of indole amides acceptor in its lead ion identification.
The present invention is achieved in that a kind of two indole amides acceptor, and described acceptor has the chemical structure that is shown below:
Invention further provides the preparation method of above-mentioned pair of indole amides acceptor, comprise the following steps:
(1) indoles is dissolved in anhydrous diethyl ether, in ice-water bath, under violent stirring, slowly adds oxalyl chloride, react after 1 hour, by reaction solution suction filtration, by the throw out washing after suction filtration, obtain intermediate indole acyl chlorides; Wherein, the molecular volume of described indoles, ether and oxalyl chloride is than being 1mol:(20 ~ 40) mL:(1 ~ 2) mol;
(2) by described intermediate indole acid chloride dissolves in ethyl acetate, add hydrazine hydrate, dropwise add phase-transfer catalyst PEG-400 again, after stirred at ambient temperature reacts 10 minutes, add the NaOH solution of mass concentration 5% again, stirred at ambient temperature reacts 1 hour, by reaction solution suction filtration, by the throw out washing after suction filtration, drying, obtain two indole amides acceptor crude product; Wherein, the molecular volume of described intermediate indole acyl chlorides, ethyl acetate, hydrazine hydrate, PEG-400 and NaOH solution is than being 1mol:(15 ~ 30) mL:(0.5 ~ 1) mol:(0.3 ~ 0.8) mL:(8 ~ 15) mL.
Preferably, in step (1), described washing is for wash three times with 5mL anhydrous diethyl ether.
Preferably, in step (1), the molecular volume of described indoles, ether and oxalyl chloride is than being 1mol:30mL:1mol.
Preferably, in step (2), described washing is that inorganic salt are removed in the throw out 15mL washing after suction filtration, then washs three times by 5mL ethyl acetate.
Preferably, in step (2), the molecular volume of described intermediate indole acyl chlorides, ethyl acetate, hydrazine hydrate, PEG-400 and NaOH solution is than being 1mol:20mL:0.5mol:0.3mL:10mL.
Preferably, in step (2), by dimethyl formamide DMF and H
2after O successively adds and carries out recrystallization in described pair of indole amides acceptor crude product, obtain two indole amides acceptor; Wherein, described DMF, H
2the Molar of O, two indole amides acceptor crude product is than being 5ml:0.5ml:1mol.
Invention further provides the above-mentioned pair of application of indole amides acceptor in lead ion identification.
The present invention overcomes the deficiencies in the prior art, a kind of two indole amides acceptor and preparation method thereof and application are provided, by indoles is dissolved in anhydrous diethyl ether, slowly oxalyl chloride is added under violent stirring in ice-water bath, react after 1 hour, by reaction solution suction filtration, by the throw out washing after suction filtration, obtain intermediate indole acyl chlorides, by intermediate indole acid chloride dissolves in ethyl acetate, add hydrazine hydrate, dropwise add phase-transfer catalyst PEG-400 again, after stirred at ambient temperature reacts 10 minutes, add the NaOH solution of mass concentration 5% again, stirred at ambient temperature reacts 1 hour, by reaction solution suction filtration, by the throw out washing after suction filtration, dry, obtain two indole amides acceptor crude product, finally, two indole amides acceptor crude product mixed solvent recrystallization is obtained two indole amides acceptor A1, utilize ultraviolet-visible spectrum to investigate two indole amides acceptor A1 to find after the recognition performance of metallic cation, containing amide group in the two indole amides acceptor A1 molecule of the present invention, its Sauerstoffatom there are lone-pair electron, can coordination good with transition metal ion, and, in A1 molecule, two amide groups are directly connected, and greatly reduce the steric hindrance of acceptor and metal ion bonding, achieve acceptor A1 to Pb
two indole amides acceptor A1 can efficiently, detection and Identification lead ion fast, in fields such as biological, medicine and environment, there is important effect.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of the two indole amides acceptor A1 of the present invention;
Fig. 2 is the DMSO-H of two indole amides acceptor A1 in the embodiment of the present invention
2o (1:1, v/v) neutral buffered liquid adds the absorption spectrum variation diagram of different metal ion;
Fig. 3 is two indole amides acceptor A1 (1.0 × 10 in the embodiment of the present invention
-5m) DMSO-H
2pb is added in O (1:1, v/v) neutral buffer
2+time absorption spectrum variation diagram;
Two indole amides acceptor A1 and the Pb of Fig. 4 the present invention
2+recognition mode schematic diagram.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
1, reagent is related in the embodiment of the present invention:
Indoles, oxalyl chloride are Chemical Reagent Co., Ltd., Sinopharm Group, chemical pure.
Hydrazine hydrate, Tianjin good fortune chemical reagent factory in morning, analytical pure.
Sodium hydroxide, Tianjin Kermel Chemical Reagent Co., Ltd., analytical pure.
PEG-400, Chengdu Ke Long chemical reagent factory, analytical pure.
Nine water iron nitrates, four water cadmium nitrates, cobalt nitrate hexahydrate, zinc nitrate hexahydrate, nine water chromium nitrates, lead nitrate, saltpetre, nitrate trihydrate copper, 1/2 water Mercury pernitrate, Silver Nitrate, eight water nickelous nitrates, x water ferrous perchlorate are Tianjin chemical reagent two factory, analytical pure.
HEPES (C
8h
18n
2o
4s), Acros reagent, purity is 99%.
Solvent: anhydrous diethyl ether, ethyl acetate, DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO) is Tianjin chemical reagent two factory, analytical pure.
Above reagent is not all for further processing, and directly uses.Experimental water is distilled water.
Buffered soln is the buffered soln of HEPES-NaOH, and HEPES concentration is 0.01M, and its pH value is adjusted to 7.0 by the NaOH of 1M.
Instrument:
PHMK 05 micro-meldometer, Germany, thermometer does not correct.
81-2 type constant temperature blender with magnetic force, Shanghai Si Le Instrument Ltd..
SHB-B
95the multiplex vacuum pump of type circulating water type, Zhengzhou Greatwall Scientific Industrial & Trading Co., Ltd..
R-1001 type Rotary Evaporators, Zhengzhou Greatwall Scientific Industrial & Trading Co., Ltd..
Lambda 35 type ultraviolet/visible spectrophotometer, 1cm quartz liquid pool, Perkin-Elmer company.
Inova-400 type nuclear magnetic resonance analyser, Varian company of the U.S..
Infrared spectra (FT-IR) is measured and is above undertaken by KBr pressed disc method at Thermo Nicolet NEXUS TM spectrophotometer (U.S.).Spectrogram obtains after 32 scanning also background correction.
2, the preparation of two indole amides acceptor, as shown in Figure 1, detailed process comprises the following steps synthetic route:
(1) synthesis of intermediate indole acyl chlorides
Take 5g indoles, be dissolved in 100mL round-bottomed flask with 30mL anhydrous diethyl ether, 5.4g oxalyl chloride is slowly added under violent stirring in ice-water bath, stirring reaction 1 hour under ice-water bath, there is bright yellow precipitate to generate, suction filtration, wash three times with 5mL anhydrous diethyl ether, obtain glassy yellow crystal, load in brown airtight bottle for subsequent use.Detecting productive rate is 90%.
(2) synthesis of two indole amides acceptor crude product
Take 4.15g intermediate indole acyl chlorides, with 20mL acetic acid ethyl dissolution in 100mL round-bottomed flask, add 0.32g hydrazine hydrate, add 6 phase-transfer catalyst PEG-400 (0.3mL), stirred at ambient temperature reacts 10 minutes, add the NaOH aqueous solution (mass concentration 5%) of 10mL again, stirred at ambient temperature reacts 1 hour, has and precipitates generation in a large number, suction filtration, remove inorganic salt with 15mL washing, then use 5mL ethyl acetate washing precipitation three times, dry.
(3) two indole amides acceptor is refining
Crude product DMF (5mL)-H
2o (0.5mL) mixed solvent recrystallization obtains two indole amides acceptor A1, and this pair of indole amides acceptor A1 characterization data is as follows:
A1 (C
20h
14n
4o
4): yellow crystals, productive rate: 68%, fusing point: be greater than 300 DEG C.ε:16230M
-1·cm
-1(λ
DMSO318nm).
1H NMR(DMSO-d
6,400MHz,ppm):12.38(s,2H,N(H),10.82(s,2H,N(H),8.74(d,2H,J＝4Hz,Ar-H),8.27(t,2H,J＝8Hz,Ar-H),7.60(t,2H,J＝8Hz,Ar-H),7.30(m,4H,Ar-H).
13C NMR(CDCl
3,100MHz,ppm):181.86,163.12,138.56,136.53,125.80,123.73,122.82,121.28,112.75,112.52.FT-IR(KBr,cm
-1):3224,3126,1595,1513,1431,1335,1313,1235,1143,927,784,742.
3, the metallic cation identification measuring method of acceptor A1, comprises the following steps:
(1) preparation of receptor solution
Weigh a certain amount of acceptor in 10mL test tube, be settled to 10mL with DMSO dilution, be mixed with 5.0 × 10
-4the solution of M, stand-by.
(2) preparation of metal ion solution
Weigh the metal-salt (nitrate or perchlorate) of corresponding weight in 15mL test tube, constant volume is dissolved (due to the problem of solubleness with the HEPES-NaOH buffered soln of pH=7.0, Fe (II) uses perchlorate), being made into concentration of metal ions is 1.0 × 10
-2the neutral buffer of M.
(3) DMSO-H
2the ultraviolet determination of acceptor and different metal cations recognition in O (1:1, v/v) neutral buffer system
The DMSO solution (5.0 × 10 of 80 μ L acceptors is measured respectively with microsyringe
-5m) in a series of test tube.The neutral buffer (1.0 × 10 of the metallic cations such as Fe (III), Cd (II), Co (II), Zn (II), Cr (III), Pb (II), K (I), Cu (II), Hg (II), Ag (I), Ni (II), Fe (II) is measured respectively with microsyringe
-2m) each 4 μ L, are diluted to 2mL with DMSO, then are settled to 4mL with HEPES-NaOH buffered soln.After constant volume, the strength of solution of acceptor is 1.0 × 10
-5m, various metal cation concentration is 1 times of acceptor density, and solution is DMSO-H
2the neutral buffer system of O (1:1, v/v), surveys DEG C its ultraviolet-visible absorption spectroscopy (DMSO-H in 25 after mixing
2reference made by the mixed solvent of O (1:1, v/v)).
(4) DMSO-H
2acceptor A1 and Pb in O (1:1, v/v) neutral buffer system
2+ultraviolet titration experiments
Pipette the DMSO-H of 3mL acceptor A1
2o (1:1, v/v) neutral buffer (1.0 × 10
-5m) in 1cm quartz cuvette liquid pool.The Pb of different volumes is added respectively with microsyringe
2+hEPES neutral buffer (1.0 × 10
-2m), after mixing, obtain acceptor A1 constant concentration (1.0 × 10
-5m), Pb
2+the DMSO-H that concentration increases gradually
2o (1:1, v/v) neutral buffer, surveys DEG C its ultraviolet-visible absorption spectroscopy (DMSO-H in 25
2o (1:1, v/v) neutral buffer makes reference).
4, the metallic cation identification of acceptor A1:
Acceptor A1 has the colorimetric recognition reaction to lead ion.As shown in Figure 2, the DMSO-H of acceptor A1
2o (1:1, v/v) neutral buffer has a stronger absorption peak at 330nm place.When adding the various metallic cation of 1 times of equivalent, Pb
2+can cause the considerable change of system ultra-violet absorption spectrum and solution colour, acceptor A1 obviously weakens at the absorption peak at 330nm place, and red shift is to 345nm place., obviously strengthen in the absorbancy at 400-450nm place meanwhile, become yellow with solution colour from colourless.Cu (II) and Co (II) adds makes acceptor A1 in the faint enhancing of the absorption peak at 330nm place, and faint blue shift all occurs, and is blue shifted to 318 and 315nm respectively.And when adding other metallic cation (Fe (III), Cd (II), Cr (III), Zn (II), K (I), Hg (II), Ag (I), Ni (II), Fe (II)), there is not the change of obvious spectrum and color.
As shown in Figure 3, when not adding metallic cation, acceptor A1 has two absorption peaks in about 268 and 330nm place.Pb is added gradually in acceptor A1
2+time, strengthen gradually at the absorption peak at 268nm place, the absorption peak at 330nm place weakens gradually and red shift occurs, and one group of new absorption peak also appears in red shift herein to 380nm place, solution colour becomes yellow thereupon.Obviously can observe simultaneously and have two isobestic points in 295 and 344nm place, illustrate that new compound generates.The experiment of above-mentioned ultraviolet shows, acceptor A1 not only has higher colorimetric identification selection to Pb (II), and has higher susceptibility, can fast and Pb (II) react.Find in ultraviolet titration experiments, the Pb (II) approximately adding 3.3 times of equivalents just can make acceptor A1 thoroughly disappear at the absorption peak at 330nm place, reaches titration saturated.Therefore, the character of acceptor A1 to the quick response of Pb (II) is that the detection by quantitative of Pb (II) is provided convenience condition.Find out in the Linear Fit Chart that the upper left corner is obtained by Hildebrand-Benesi equation from figure, experimental data linear relationship is good, acceptor A1 and Pb (II) is described with the combination of 1:1 than interacting.Be can be calculated by 381nm linear fit: straight-line equation is: y=5.57713+0.04419x, stability constant K=126.2M
-1, fitting constant R=0.9921.
According to above UV spectrum experimental result, infer that the recognition reaction mechanism of acceptor A1 and Pb (II) may be in conjunction with the document about amides Receptor recognition metal ion: Pb (II) ion has unoccupied orbital, Sauerstoffatom in acceptor A1 on carbonyl group has lone-pair electron, the hole formed and Pb (II) can produce stronger coordination, generate stable metal complexes.Possible recognition mode as shown in Figure 4.
In sum, owing to containing amide group in acceptor A1 molecule, its Sauerstoffatom there are lone-pair electron, can coordination good with transition metal ion.And two amide groups are directly connected in A1 molecule, greatly reduce the steric hindrance of acceptor and metal ion bonding, achieve acceptor A1 to Pb (II) highly selective colorimetric recognition reaction, and can respond fast Pb (II).
Compared to the shortcoming and defect of prior art, the present invention has following beneficial effect: the two indole amides acceptor A1 preparation method of the present invention is simple, and productive rate is higher, is suitable for large-scale production; The two indole amides acceptor A1 of the present invention can efficiently, detection and Identification lead ion fast, in fields such as biological, medicine and environment, there is important effect.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a two indole amides acceptor, it is characterized in that, described acceptor has the chemical structure that is shown below:
2. the preparation method of two indole amides acceptor as claimed in claim 1, is characterized in that, comprise the following steps:
(1) indoles is dissolved in anhydrous diethyl ether, in ice-water bath, under violent stirring, slowly adds oxalyl chloride, react after 1 hour, by reaction solution suction filtration, by the throw out washing after suction filtration, obtain intermediate indole acyl chlorides; Wherein, the molecular volume of described indoles, ether and oxalyl chloride is than being 1mol:(20 ~ 40) mL:(1 ~ 2) mol;
(2) by described intermediate indole acid chloride dissolves in ethyl acetate, add hydrazine hydrate, dropwise add phase-transfer catalyst PEG-400 again, after stirred at ambient temperature reacts 10 minutes, add the NaOH solution of mass concentration 5% again, stirred at ambient temperature reacts 1 hour, by reaction solution suction filtration, by the throw out washing after suction filtration, drying, obtain two indole amides acceptor crude product; Wherein, the molecular volume of described intermediate indole acyl chlorides, ethyl acetate, hydrazine hydrate, PEG-400 and NaOH solution is than being 1mol:(15 ~ 30) mL:(0.5 ~ 1) mol:(0.3 ~ 0.8) mL:(8 ~ 15) mL.
3. the preparation method of two indole amides acceptor as claimed in claim 2, it is characterized in that, in step (1), described washing is for wash three times with 5mL anhydrous diethyl ether.
4. the preparation method of two indole amides acceptor as claimed in claim 3, is characterized in that, in step (1), the molecular volume of described indoles, ether and oxalyl chloride is than being 1mol:30mL:1mol.
5. the preparation method of two indole amides acceptor as claimed in claim 2, is characterized in that, in step (2), described washing is that inorganic salt are removed in the throw out 15mL washing after suction filtration, then washs three times by 5mL ethyl acetate.
6. the preparation method of two indole amides acceptor as claimed in claim 5, it is characterized in that, in step (2), the molecular volume of described intermediate indole acyl chlorides, ethyl acetate, hydrazine hydrate, PEG-400 and NaOH solution is than being 1mol:20mL:0.5mol:0.3mL:10mL.
7. the preparation method of two indole amides acceptor as claimed in claim 6, is characterized in that, in step (2), by dimethyl formamide DMF and H
2after O successively adds and carries out recrystallization in described pair of indole amides acceptor crude product, obtain two indole amides acceptor; Wherein, described DMF, H
2the Molar of O, two indole amides acceptor crude product is than being 5ml:0.5ml:1mol.
8. two indole amides acceptor as claimed in claim 1, is characterized in that, the application in lead ion identification.
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