CN103172678A - Compound with ferrocene aldehyde-phenylhydrazone structure as well as preparation method and application thereof - Google Patents
Compound with ferrocene aldehyde-phenylhydrazone structure as well as preparation method and application thereof Download PDFInfo
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- CN103172678A CN103172678A CN2013100665513A CN201310066551A CN103172678A CN 103172678 A CN103172678 A CN 103172678A CN 2013100665513 A CN2013100665513 A CN 2013100665513A CN 201310066551 A CN201310066551 A CN 201310066551A CN 103172678 A CN103172678 A CN 103172678A
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- compound
- phenylhydrazone
- ferrocene
- aldehyde
- ferrocene aldehyde
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 89
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 48
- HEWFKXVSWQSSAT-UHFFFAOYSA-M cyclopenta-1,3-diene;cyclopenta-2,4-dien-1-ylidenemethanolate;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.[O-]C=C1C=CC=C1 HEWFKXVSWQSSAT-UHFFFAOYSA-M 0.000 claims abstract description 33
- LGROKZMEHJZWDU-UHFFFAOYSA-N n-amino-n-phenylnitramide Chemical compound [O-][N+](=O)N(N)C1=CC=CC=C1 LGROKZMEHJZWDU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 16
- 230000000007 visual effect Effects 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 230000001476 alcoholic effect Effects 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical group NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 claims description 6
- KMVPXBDOWDXXEN-UHFFFAOYSA-N 4-nitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1 KMVPXBDOWDXXEN-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SAFRFSWGAIUFAY-UHFFFAOYSA-N cyclopenta-1,3-diene-1-carbaldehyde;iron(2+) Chemical compound [Fe+2].O=CC1=CC=C[CH-]1.O=CC1=CC=C[CH-]1 SAFRFSWGAIUFAY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 5
- 239000012085 test solution Substances 0.000 claims 2
- 238000005303 weighing Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000011540 sensing material Substances 0.000 abstract description 2
- 238000005882 aldol condensation reaction Methods 0.000 abstract 1
- 238000001917 fluorescence detection Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 14
- 238000004448 titration Methods 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- -1 carboxylic acid ion Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000003115 supporting electrolyte Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 241001164374 Calyx Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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Abstract
本发明涉及一种二茂铁醛-苯腙结构的化合物及其制备方法与应用，属于电化学传感材料技术领域，解决了现有荧光检测醋酸根离子操作复杂、成本高、不能肉眼检测的技术问题。本发明的二茂铁醛-苯腙结构的化合物是以二茂铁醛和硝基苯肼为原料，经过羟醛缩合反应一步合成。本发明还提供该二茂铁醛-苯腙结构的化合物作为目视比色化学传感器分子检测醋酸根离子的应用。本发明的二茂铁醛-苯腙结构的化合物作为目视比色化学传感器分子应用，实现了醋酸根离子的裸眼检测，且不需要昂贵的光谱仪器，操作简单。
The invention relates to a compound with a ferrocenealdehyde-phenylhydrazone structure and its preparation method and application, which belongs to the technical field of electrochemical sensing materials, and solves the problem of complex operation, high cost and inability to detect with naked eyes in the existing fluorescence detection of acetate ions technical problem. The compound of the ferrocene aldehyde-phenylhydrazone structure of the present invention uses ferrocene aldehyde and nitrophenylhydrazine as raw materials, and is synthesized in one step through an aldol condensation reaction. The invention also provides the application of the ferrocenaldehyde-phenylhydrazone structure compound as a visual colorimetric chemical sensor molecule for detecting acetate ions. The ferrocene aldehyde-phenylhydrazone compound of the invention is used as a visual colorimetric chemical sensor molecule to realize the naked-eye detection of acetate ions without requiring expensive spectroscopic instruments and is easy to operate.
Description
Technical field
The present invention relates to the compound and preparation method thereof and application of a kind of ferrocene aldehyde-phenylhydrazone structure, belong to electrochemical sensing material technology field.
Background technology
Negatively charged ion plays considerable effect in the biological and chemical process.In numerous negatively charged ion, acetate ion is unique carboxylic acid ion with triangular structure, it can form very strong hydrogen bond action, acetic acid is synthetic daily essential daily necessities, such as: nylon, therefore the important source material of paper and coating, is invented a kind of sensor that can identify and more and more is subject to people's attention when acetate ion concentration is low.
Existing acetate ion sensor is mainly identified acetate ion by variation and the Red Shift Phenomena of observation fluorescence intensity, as: Doo Ok Jang discloses the benzoglyoxaline based sensor (Tetrahedron Lett.48 (2007) 8846-8850) that a kind of only Dichlorodiphenyl Acetate radical ion shows fluorescence; Huang et al. synthesized a kind of can selectivity the calyx aromatic hydrocarbons sensor (Tetrahedron Lett.46 (2005) 2155-2158) of identification acetate ion.But, because variation and the red shift of fluorescence intensity need to need expensive spectral instrument so adopt aforesaid method to detect acetate ion by spectroscopic analysis, and complicated operation, can not know by naked eyes the relevant information of acetate ion.
The chemical sensor molecule that can identify electronics or required chemical structure is comprised of the signal site, such as: redox active center, colorimetric center or fluorescence centre etc.(Chem.Soc.Rev.18 (1989) 409-450 according to the literature, Chem.Rev.185-186 (1999) 3-36), because ferrocene has good redox reversible, can be used as a signal element, can be by the derived material of its redox electrical signal for the preparation of electrochemical sensor, as: positively charged ion, negatively charged ion, neutral molecule.
In prior art, also not based on ferrocene and nitro phenylhydrazone structure, can realize that visual colorimetric determination detects the chemical sensor molecule of acetate ion.
Summary of the invention
For solving the technical problem that existing fluoroscopic examination acetate ion complicated operation, cost are high, can not naked eyes detect, the present invention proposes compound of a kind of ferrocene aldehyde-phenylhydrazone structure and preparation method thereof and application.
The invention provides the compound of a kind of ferrocene aldehyde-phenylhydrazone structure, its structural formula is suc as formula (I) or formula (П):
In formula, R
1Be H or NO
2
The present invention also provides the preparation method of the compound of a kind of ferrocene aldehyde-phenylhydrazone structure: take ferrocene aldehyde and nitrophenyl hydrazine, add in reaction unit, reflux in lower than the alcoholic solvent of 90 ℃ at boiling point, cooling after, dry after filtration, namely get the compound of ferrocene aldehyde-nitro phenylhydrazone structure;
Described ferrocene aldehyde is ferrocene formaldehyde or 1,1 '-ferrocene dicarbaldehyde;
Described nitrophenyl hydrazine is 2,4 dinitrophenyl hydrazine or 4-nitrophenyl hydrazine.
Preferably, described ferrocene aldehyde and nitrophenyl hydrazine take by stoichiometric ratio.
Preferably, described ferrocene aldehyde takes by the 105%-115% with stoichiometric reaction institute expense, and described nitrophenyl hydrazine is by taking with stoichiometric reaction institute expense.
Preferably, described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol or Virahol.
Preferably, described reflux temperature is 78 ℃-85 ℃, and return time is 2-5h.
The present invention also provides the application of the compound of above-mentioned ferrocene aldehyde-phenylhydrazone structure as visual colorimetric determination chemical sensor Molecular Detection acetate ion: the compound of ferrocene aldehyde-phenylhydrazone structure is dissolved in pure water, obtain pale yellow solution, liquid to be measured is added in pale yellow solution, observe solution colour and change;
Do not contain F in described liquid to be measured
-
Preferably, in described pale yellow solution the concentration of the compound of ferrocene aldehyde-phenylhydrazone structure greater than 0 less than or equal to 1.0 * 10
-3Mol/l.
Preferably, in described liquid to be measured, the concentration of acetate is 0-3.0 * 10
-3Mol/l, H
2PO
4 -, HSO
4 -, NO
3 -, Cl
-And Br
-Concentration be respectively 0-9.0 * 10
-3Mol/l, the concentration of other negatively charged ion is 0.
Beneficial effect of the present invention:
(1) compound of ferrocene aldehyde of the present invention-phenylhydrazone structure is as visual colorimetric determination chemical sensor molecular application, after acetate ion adds, be dissolved with the solution of compound of ferrocene aldehyde-phenylhydrazone structure by the light yellow purple that is transitioned into, realized the open hole detection of acetate ion;
(2) compound of ferrocene aldehyde of the present invention-phenylhydrazone structure is as visual colorimetric determination chemical sensor molecular application, after acetate ion adds, the UV, visible light maximum absorption band of solution of compound that is dissolved with ferrocene aldehyde-phenylhydrazone structure by the 396nm red shift to 545nm (Δ λ=149nm), differential pulse curve Ep=800mV moves to Ep=885mV (Δ E=85mV), and two kinds of methods are verified mutually;
(3) the present invention detects to identify acetate ion by visual colorimetric determination, does not need expensive spectral instrument, and simple to operate.
Description of drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy of compound of the ferrocene aldehyde-phenylhydrazone structure of the embodiment of the present invention 6;
Fig. 2 is the UV, visible light spectra for titration of compound under different acetate ion concentration of the ferrocene aldehyde-phenylhydrazone structure of the embodiment of the present invention 6;
Fig. 3 be the embodiment of the present invention 6 ferrocene aldehyde-phenylhydrazone structure compound the differential pulse curve;
Fig. 4 is the colour-change of solution after adding different anions of the compound of the ferrocene aldehyde that is dissolved with the embodiment of the present invention 6-phenylhydrazone structure.
Embodiment
The compound of ferrocene aldehyde-phenylhydrazone structure, its structural formula are suc as formula (I) or formula (П):
In formula, R
1Be H or NO
2
The preparation method of the compound of ferrocene aldehyde-phenylhydrazone structure: take ferrocene aldehyde and nitrophenyl hydrazine, add in reaction unit, reflux in lower than the alcoholic solvent of 90 ℃ at boiling point, cooling after, dry after filtration, namely get the compound of ferrocene aldehyde-nitro phenylhydrazone structure;
Described ferrocene aldehyde is ferrocene formaldehyde or 1,1 '-ferrocene dicarbaldehyde;
Described nitrophenyl hydrazine is 2,4 dinitrophenyl hydrazine or 4-nitrophenyl hydrazine.
In preparation method of the present invention, described ferrocene aldehyde and nitrophenyl hydrazine take by stoichiometric ratio usually, namely when raw material is ferrocene formaldehyde and nitrophenyl hydrazine, take ferrocene aldehyde and nitrophenyl hydrazine by molar ratio 1:1, when raw material is 1, when 1 '-ferrocene dicarbaldehyde and nitrophenyl hydrazine, take ferrocene aldehyde and nitrophenyl hydrazine by molar ratio 1:2; Due to ferrocene aldehyde in alcoholic solvent solvability greater than nitrophenyl hydrazine solvability in alcoholic solvent, for nitrophenyl hydrazine is reacted completely, preferred described ferrocene aldehyde takes by the 105%-115% with stoichiometric reaction institute expense, and described nitrophenyl hydrazine is by taking with stoichiometric reaction institute expense; Namely when raw material is ferrocene formaldehyde and nitrophenyl hydrazine, preferably take ferrocene aldehyde and nitrophenyl hydrazine by molar ratio 1.05-1.15:1, when raw material is 1, when 1 '-ferrocene dicarbaldehyde and nitrophenyl hydrazine, preferably take ferrocene aldehyde and nitrophenyl hydrazine by molar ratio 1.05-1.15:2.
In preparation method of the present invention, described alcoholic solvent is methyl alcohol, ethanol, propyl alcohol or Virahol.
In preparation method of the present invention, described reflux temperature is 78 ℃-85 ℃, and return time is 2-5h.
The reaction that preparation method of the present invention occurs is aldol reaction, and take raw material as ferrocene formaldehyde as example, the reaction equation of compound that the present invention prepares ferrocene aldehyde-phenylhydrazone structure is as follows:
The compound of above-mentioned ferrocene aldehyde-phenylhydrazone structure is as the application of visual colorimetric determination chemical sensor Molecular Detection acetate ion.
The invention provides the compound of a kind of ferrocene aldehyde-phenylhydrazone structure as the detailed process of the application of visual colorimetric determination chemical sensor Molecular Detection acetate ion, but the invention is not restricted to this: the compound of ferrocene aldehyde-phenylhydrazone structure is dissolved in pure water, obtain pale yellow solution, liquid to be measured is added in pale yellow solution, observe its colour-change; If contain acetate ion in liquid to be measured, solution is by the light yellow purple that is transitioned into, if there is no acetate ion in liquid to be measured, and the solution nondiscoloration; Do not contain F in described liquid to be measured
-
In the present invention, in described pale yellow solution, the concentration of the compound of ferrocene aldehyde-phenylhydrazone structure is preferably greater than 0 less than or equal to 1.0 * 10
-3Mol/l, more preferably, 1.0 * 10
-5-1.0 * 10
-3Mol/l.
In the present invention, in preferred liquid to be measured, the concentration of acetate ion is in three times of concentration of the compound of ferrocene aldehyde-phenylhydrazone structure in pale yellow solution, more preferably 0-3.0 * 10
-3Mol/l, most preferably 1.0 * 10
-5-3.0 * 10
-3Mol/l.
In the present invention, in described liquid to be measured, preferred H
2PO
4 -, HSO
4 -, NO
3 -, Cl
-And Br
-Concentration respectively in three times of acetate ion concentration, more preferably respectively in 0-9.0 * 10
-3Mol/l.
In the present invention, in described liquid to be measured, preferably except acetate ion, the H that may contain
2PO
4 -, HSO
4 -, NO
3 -, Cl
-And Br
-Do not contain other negatively charged ion outward.
Take the compound of ferrocene aldehyde with formula (I) structure-phenylhydrazone structure as example, the compound of ferrocene aldehyde of the present invention-phenylhydrazone structure is as follows as the mechanism of visual colorimetric determination chemical sensor Molecular Detection acetate ion:
Can find out from the mechanism reaction formula, color reaction be owing to forming chelate ring by hydrogen bond action between the compound of ferrocene aldehyde-phenylhydrazone structure and detected ion, increased the planar conjugate of system, thereby the absorption spectrum of system is moved, color reaction has occured; For metal ion, metal ion belongs to the electron deficiency system, the condition that forms hydrogen bond can not be provided, therefore, metal ion not can with the compound formation chelate ring of ferrocene aldehyde-phenylhydrazone structure, just can not produce obviously impact to absorption spectrum yet, namely color reaction can not occur, on not impact of test result.
The structure of the compound of ferrocene aldehyde of the present invention-phenylhydrazone structure confirms by nucleus magnetic resonance, mass spectroscopy and ultimate analysis.
The compound of ferrocene aldehyde of the present invention-phenylhydrazone structure can be used as visual colorimetric determination chemical sensor Molecular Detection acetate ion, jointly confirm by UV, visible light spectra for titration and differential pulse curve, wherein, the test condition of differential pulse curve: supporting electrolyte is the [(n-C of 0.1mol/l
4H
9)
4N] PF
6(oxygen is abbreviated as TBAPF at tetrabutyl ammonium hexafluorophosphate
6), step-length 50ms, scanning speed 4mVs
-1, pulse height 10mV, electrode are the standard silver electrode; Before each test, electrode all will clean, solution nitrogen bubble ten minutes.
For making those skilled in the art further understand the present invention, the invention will be further described below in conjunction with embodiment and accompanying drawing.
Formula (I) structure (R
1Be H) the preparation of compound of ferrocene aldehyde-phenylhydrazone structure:
Take ferrocene formaldehyde 0.21g by stoichiometric ratio, 4-nitrophenyl hydrazine 0.153g is dissolved in 20ml ethanol, in 78 ℃ of backflow 2h, naturally cool to room temperature, filter to such an extent that red precipitate is also used twice of washing with alcohol, each ethanol 5ml that uses, crude product is through the silicagel column separating-purifying, with the mixing solutions wash-out of petrol ether/ethyl acetate, evaporating solvent, drying obtains red powder, is the compound of ferrocene aldehyde-phenylhydrazone structure.
Formula (П) structure (R
1Be H) the preparation of compound of ferrocene aldehyde-phenylhydrazone structure:
Take 1 by stoichiometric ratio, 1 '-ferrocene dicarbaldehyde 0.242g, 4-nitrophenyl hydrazine 0.306g is dissolved in 30ml ethanol, in 80 ℃ of backflow 3h, naturally cool to room temperature, filter to such an extent that red precipitate is also used washing with alcohol twice, use ethanol 5ml at every turn, crude product is through the silicagel column separating-purifying, with the mixing solutions wash-out of petrol ether/ethyl acetate.Evaporating solvent, drying obtains red powder, is the compound of ferrocene aldehyde-phenylhydrazone structure.
Embodiment 3
Formula (П) structure (R
1Be H) the preparation of compound of ferrocene aldehyde-phenylhydrazone structure:
Take 1,1 '-ferrocene dicarbaldehyde 0.242g, 4-nitrophenyl hydrazine 0.352g is dissolved in 30ml ethanol, in 85 ℃ of backflow 2h, naturally cool to room temperature, filter to such an extent that red precipitate is also used washing with alcohol twice, use ethanol 5ml at every turn, crude product is through the silicagel column separating-purifying, mixing solutions wash-out with petrol ether/ethyl acetate, evaporating solvent, drying obtains red powder, is the compound of ferrocene aldehyde-phenylhydrazone structure.
Embodiment 4
Formula (I) structure (R
1Be NO
2) the preparation of compound of ferrocene aldehyde-phenylhydrazone structure:
Take ferrocene formaldehyde 0.21g by stoichiometric ratio, 2,4 dinitrophenyl hydrazine 0.198g is dissolved in 20ml ethanol, in 82 ℃ of backflow 5h, naturally cool to room temperature, filter to such an extent that red precipitate is also used washing with alcohol twice, use ethanol 5ml at every turn, crude product is through the silicagel column separating-purifying, mixing solutions wash-out with petrol ether/ethyl acetate, evaporating solvent, drying obtains red powder, is the compound of ferrocene aldehyde-phenylhydrazone structure.
Formula (П) structure (R
1Be NO
2) the preparation of compound of ferrocene aldehyde-phenylhydrazone structure:
Take 1 by stoichiometric ratio, 1 '-ferrocene dicarbaldehyde 0.242g, 2,4-dinitrophenylhydrazine 0.396g is dissolved in 30ml ethanol, in 80 ℃ of backflow 3h, naturally cool to room temperature, filter to such an extent that red precipitate is also used twice of washing with alcohol, each ethanol 5ml that uses, crude product is through the silicagel column separating-purifying, with the mixing solutions wash-out of petrol ether/ethyl acetate, evaporating solvent, drying obtains red powder, is the compound of ferrocene aldehyde-phenylhydrazone structure.
Formula (I) structure (R
1Be NO
2) the preparation of compound of ferrocene aldehyde-phenylhydrazone structure:
Take ferrocene formaldehyde 0.21g by stoichiometric ratio, 2,4 dinitrophenyl hydrazine 0.198g is dissolved in 20mol/l ethanol, in 85 ℃ of backflow 2h, naturally cool to room temperature, filter to such an extent that red precipitate is also used washing with alcohol twice, use ethanol 5ml at every turn, crude product is through the silicagel column separating-purifying, mixing solutions wash-out with petrol ether/ethyl acetate, evaporating solvent, drying obtains red powder, is the compound of ferrocene aldehyde-phenylhydrazone structure.
The compound of the ferrocene aldehyde that embodiment 6 is obtained-phenylhydrazone structure carries out nmr analysis, mass spectrum, ultimate analysis, records its nucleus magnetic hydrogen spectrum:
1H NMR (DMSO-d
6) δ (ppm): 11.15 (s, 1H, NH), 9.24 (d, 1H, Ar-H), 8.36 (d, 1H, Ar-H), 8.08 (t, 1H, Ar-H), 7.94 (s, 1H ,-CH=N), 4.74 (st, 2H, C-H), 4.5 (st, 2H, C-H), 4.28 (s, 5H, C-H); Mass spectrum ESI-mass:m/z394.04m
+Ultimate analysis Anal.Caled.for C
17H
14O
4N
4Fe
1: C, 51.80; H, 3.58; N, 14.21; Found:C, 51.72; H, 3.00; N, 14.23; Proof the present invention has prepared the compound of the ferrocene aldehyde that structure is formula (I)-phenylhydrazone structure really.
The compound of the ferrocene aldehyde that embodiment 6 is obtained-phenylhydrazone structure carries out the ultraviolet-visible absorption spectroscopy analysis, and Fig. 1 is the ultraviolet-visible absorption spectroscopy of compound of the ferrocene aldehyde-phenylhydrazone structure of the embodiment of the present invention 6.
Under room temperature, the compound of the ferrocene aldehyde that respectively 9 groups of 0.1g embodiment 6 is obtained-phenylhydrazone structure is dissolved in pure water, and stirring and preparing 9 groups of concentration is 1.0 * 10
-5The compound solution of the ferrocene aldehyde of mol/l-phenylhydrazone structure, adding respectively concentration is 0mol/l, 0.2 * 10
-5Mol/l, 0.4 * 10
-5Mol/l, 0.6 * 10
-5Mol/l, 0.8 * 10
-5Mol/l, 1.0 * 10
-5Mol/l, 1.4 * 10
-5Mol/l, 1.6 * 10
-5Mol/l, 2.0 * 10
-5The acetum of mol/l (by acetic acid and pure water preparation), 9 groups of solution are carried out the analysis of UV, visible light spectra for titration, Fig. 2 is the UV, visible light spectra for titration of compound under different acetate ion concentration of the ferrocene aldehyde-phenylhydrazone structure of the embodiment of the present invention 6, curve 1 is the UV, visible light spectra for titration of the compound of ferrocene aldehyde-phenylhydrazone structure, and curve 2 is that the compound of ferrocene aldehyde-phenylhydrazone structure is 0.2 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion, curve 3 are that the compound of ferrocene aldehyde-phenylhydrazone structure is 0.4 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion, curve 4 are that the compound of ferrocene aldehyde-phenylhydrazone structure is 0.6 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion, curve 5 are that the compound of ferrocene aldehyde-phenylhydrazone structure is 0.8 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion, curve 6 are that the compound of ferrocene aldehyde-phenylhydrazone structure is 1.0 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion, curve 7 are that the compound of ferrocene aldehyde-phenylhydrazone structure is 1.4 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion, curve 8 are that the compound of ferrocene aldehyde-phenylhydrazone structure is 1.6 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion, curve 9 are that the compound of ferrocene aldehyde-phenylhydrazone structure is 2.0 * 10
-5UV, visible light spectra for titration under the mol/l acetate ion; As can be seen from Figure 2, after acetate ion adds, the maximum absorption band of the uv-vis spectra of the compound of ferrocene aldehyde-phenylhydrazone structure by the 396nm red shift to 545nm (Δ λ=149nm).
Under room temperature, the compound of the ferrocene aldehyde that respectively 4 groups of 0.1g embodiment 6 is obtained-phenylhydrazone structure is dissolved in pure water, and stirring and preparing 4 groups of concentration is 1.0 * 10
-3The solution of mol/l leaves one group as blank sample, remains 3 groups and adds respectively 1.0 * 10
-3The CH of mol/l
3COONa solution (CH
3COONa and pure water preparation), 1.0 * 10
-3Mol/lNaHSO
4Solution (NaHSO
4With the pure water preparation) and 1.0 * 10
-3Mol/lNaF solution (NaF and pure water preparation) carries out the differential pulse analysis to 4 groups of solution respectively; Test condition is: supporting electrolyte is 0.1mol/l[(n-C
4H
9)
4N] PF
6(TBAPF
6), step-length 50ms, scanning speed 4mVs
-1, pulse height 10mV, electrode are the standard silver electrode; Fig. 3 is that the compound of ferrocene aldehyde-phenylhydrazone structure of the embodiment of the present invention 6 is at acetate ion, HSO
4 -And F
-Differential pulse curve (X-coordinate of curve is take the standard silver electrode as reference) under existing; Curve 1 is in the differential pulse curve of compound of ferrocene aldehyde-phenylhydrazone structure, and curve 2 is the differential pulse curve of compound under acetate ion exists of ferrocene aldehyde-phenylhydrazone structure, and curve 3 is that the compound of ferrocene aldehyde-phenylhydrazone structure is at HSO
4 -Differential pulse curve under existing, curve 4 are that the compound of ferrocene aldehyde-phenylhydrazone structure is at F
-Differential pulse curve under existing; As can be seen from Figure 3, after adding acetate ion, in the differential pulse curve of the compound of ferrocene aldehyde-phenylhydrazone structure, oxidation peak moves to noble potential, moves to Ep=885mV (Δ E=85mV) by Ep=800mV.
Under room temperature, the compound of the ferrocene aldehyde that respectively 8 groups of 0.1g embodiment 6 is obtained-phenylhydrazone structure is dissolved in pure water, and stirring and preparing 8 groups of concentration is 1.0 * 10
-4The solution of mol/l leaves one group as blank sample, and all the other 7 groups add respectively 3.0 * 10
-4The CH of mol/l
3COONa solution (CH
3The preparation of COONa and pure water), 3.0 * 10
-4The NaF solution of mol/l (NaF and pure water preparation), 3.0 * 10
-4The NaH of mol/l
2PO
4Solution (NaH
2PO
4With pure water preparation), 3.0 * 10
-4The NaHSO of mol/l
4Solution (NaHSO
4With pure water preparation), 3.0 * 10
-4The NaNO of mol/l
3Solution (NaNO
3With pure water preparation), 3.0 * 10
-4The NaCl solution of mol/l (NaCl and pure water preparation) and 3.0 * 10
-4The NaBr solution of mol/l (NaBr and pure water preparation); Fig. 4 is the colour-change after the solution of the compound of the ferrocene aldehyde that is dissolved with the embodiment of the present invention 6-phenylhydrazone structure adds different anions; From left to right, be respectively blank sample, acetate ion, F
-, H
2PO
4 -, HSO
4 -, NO
3 -, Cl
-, Br
-As can be seen from Figure 4, acetate ion adds the compound solution that makes ferrocene aldehyde-phenylhydrazone structure by the light yellow purple that is transitioned into, H
2PO
4 -, HSO
4 -, NO
3 -, Cl
-And Br
-Add the color of the solution changed, be still light yellow, due to F
-The strongest emprotid, so F
-The detection of Dichlorodiphenyl Acetate radical ion exists to be disturbed, F
-Add and make solution by the light yellow purple that is transitioned into.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105301084A (en) * | 2015-10-09 | 2016-02-03 | 桂林理工大学 | Ferrocene side chain-containing benzophenanthrene anion identifying agent and application thereof |
| CN105820195A (en) * | 2016-04-20 | 2016-08-03 | 南京晓庄学院 | Ferrocenyl thiourea derivative as well as synthesis method and application |
| CN106987247A (en) * | 2017-04-19 | 2017-07-28 | 南京晓庄学院 | A kind of multi signal probe and its production and use |
| CN109988335A (en) * | 2019-04-12 | 2019-07-09 | 深圳市通产丽星股份有限公司 | A kind of ferrocenyl Schiff base and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105301084A (en) * | 2015-10-09 | 2016-02-03 | 桂林理工大学 | Ferrocene side chain-containing benzophenanthrene anion identifying agent and application thereof |
| CN105820195A (en) * | 2016-04-20 | 2016-08-03 | 南京晓庄学院 | Ferrocenyl thiourea derivative as well as synthesis method and application |
| CN105820195B (en) * | 2016-04-20 | 2017-03-08 | 南京晓庄学院 | A kind of ferrocene thiourea derivative and its synthesis method and application |
| CN106987247A (en) * | 2017-04-19 | 2017-07-28 | 南京晓庄学院 | A kind of multi signal probe and its production and use |
| CN106987247B (en) * | 2017-04-19 | 2017-12-29 | 南京晓庄学院 | A kind of multi signal probe and its production and use |
| CN109988335A (en) * | 2019-04-12 | 2019-07-09 | 深圳市通产丽星股份有限公司 | A kind of ferrocenyl Schiff base and preparation method and application thereof |
| CN109988335B (en) * | 2019-04-12 | 2021-03-23 | 深圳市通产丽星股份有限公司 | Ferrocenyl Schiff base and preparation method and application thereof |
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