CN107056716A - A kind of triazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof - Google Patents
A kind of triazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof Download PDFInfo
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- CN107056716A CN107056716A CN201611007003.3A CN201611007003A CN107056716A CN 107056716 A CN107056716 A CN 107056716A CN 201611007003 A CN201611007003 A CN 201611007003A CN 107056716 A CN107056716 A CN 107056716A
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- triazole
- benzaldehyde
- phenylenediamine
- triazole derivatives
- triazolyls
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- 239000002262 Schiff base Substances 0.000 title claims abstract description 28
- 150000003852 triazoles Chemical class 0.000 title claims abstract description 24
- UGQWZAZRHUNOKO-UHFFFAOYSA-N C1(=CC=C(C=C1)N)N.C(C1=CC=CC=C1)=O Chemical compound C1(=CC=C(C=C1)N)N.C(C1=CC=CC=C1)=O UGQWZAZRHUNOKO-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 claims abstract description 25
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 14
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000003935 benzaldehydes Chemical class 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 150000000178 1,2,4-triazoles Chemical class 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000001953 recrystallisation Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- -1 methoxyl group Chemical group 0.000 claims description 6
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- QGOUKZPSCTVYLX-UHFFFAOYSA-N 5-chloro-1h-1,2,4-triazole Chemical class ClC1=NC=NN1 QGOUKZPSCTVYLX-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000000523 sample Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 229940125782 compound 2 Drugs 0.000 description 7
- 229940126214 compound 3 Drugs 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229940125904 compound 1 Drugs 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 150000004753 Schiff bases Chemical class 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- IYGFIINCQJDWNJ-UHFFFAOYSA-N 4-chloro-2h-triazole Chemical compound ClC1=CNN=N1 IYGFIINCQJDWNJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000003851 azoles Chemical group 0.000 description 1
- IHYJVMXCOQTNPP-UHFFFAOYSA-N benzene-1,4-diamine;formaldehyde Chemical compound O=C.NC1=CC=C(N)C=C1 IHYJVMXCOQTNPP-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/14—Nitrogen atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The present invention relates to a kind of triazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof.First with 1,2,4 triazoles or triazole derivatives and 4-Fluorobenzaldehyde are raw material, prepare 4 (1 1,2,4 triazolyl) benzaldehydes or triazole derivatives benzaldehyde, it is allowed, by condensation reaction, to obtain a series of Bis-Schiff Bases with rigid planar structure with p-phenylenediamine again.The synthesis technique is simple, and cost is low, and yield is high, easy control of reaction conditions.Novel compound of present invention has good fluorescence property, while having selectivity to metal ion, can also be used for Material Field as fluorescent material as probe application in ion detection field.
Description
Technical field
The present invention relates to a kind of triazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof, the compound has
Rigid planar structure, shows preferable fluorescence property, while the compound can provide abundant coordination mode, with metal from
Son has very strong coordination ability, shows good ion selectivity.
Background technology
Nitrogen heterocyclic ring azole part is the compound of an Electron rich aromatic.Compared with typical aromatic activity molecule,
In the resonance hybrid of azoles ring, ionic resonance structures occupy considerable component, therefore this just considerably increases its chemistry instead
Ying Xing.They can not only react with various electrophilic reagents, and can be with nucleopilic reagent or even free radical reagent reacting；Not only exist
Substitution reaction can occur on ring carbon atom and synthesize many nitrogen heterocyclic ring azole derivatives, and the nitrogen-atoms on ring, due to there is orphan
To electronics, easily complex is combined to form with metal.
Due to there is three nitrogen-atoms on triazole ring, it is more diversified as the coordination mode of bridge ligand, so three
The synthesis that nitrogen azoles and its derivative participate in metal complex as part has very important theory significance and practical significance.Three
Nitrogen azoles not only has the pi-conjugated system of electron rich, while including containing sp2The imidazoles N and sp of hydridization3Hydridization amido N atoms, are one
The individual chromophore for showing excellent luminance property, so it has very wide application prospect in terms of fluorescent material.And
Triazole and its derivative also have very extensive in terms of agricultural chemicals, medical science, information material, luminescent material and molecule base functional material
Application.
Schiff bases refers to the compound containing C=N double bond structures and phosphinylidyne-containing amine group.It synthesizes relatively easy, can be flexibly
Ground selects various amines and the different aldehydes or ketones reactants with carboxyl to be reacted.Change the substituent of connection, change to confession
Body atomic nature and its position, just can open many from chain to cyclization, from monodentate to multiple tooth, performance is totally different, structure is changeable
Schiff base ligand, they can be with most of metal ion formation stability differs in periodic table complex.Although at present
Researcher has carried out many reactions using triazole, but the synthesis of triazole Bis-Schiff Bases and applied to fluorescent material
It yet there are no relevant report.
The content of the invention
The purpose of the present invention is that there is provided the new triazole benzaldehyde contracting p-phenylenediamine of a class is double in view of the shortcomings of the prior art
Schiff bases, the schiff bases has good fluorescence property and ion selectivity energy, and the synthesis technique is simple, cost is low, condition
Controllability is strong, yield is high.
It is a further object of the present invention to provide the preparation method of described triazole benzaldehyde-p-phenylenediamine bi-schiff base.
It is a further object of the present invention to provide the application of described triazole benzaldehyde-p-phenylenediamine bi-schiff base.
In order to realize such purpose, technical scheme is as follows：
A kind of new triazole benzaldehyde-p-phenylenediamine bi-schiff base, its structural formula is as follows：
R1For hydrogen, carboxyl, nitro, hydroxyl, cyano group, R2For hydrogen, fluorine, chlorine, methoxyl group.
It is preferred that R1For cyano group, nitro, R preferably2For methoxyl group；
Cyano group and nitro have very strong electron attraction, and methoxyl group is outstanding electron-donating group.
The compound is mainly used in Material Field or sensor field；
A kind of preparation method of triazole benzaldehyde-p-phenylenediamine bi-schiff base, its preparation method is as follows：
1) 1,2,4- triazoles or triazole derivatives are weighed and 4-Fluorobenzaldehyde is dissolved in solvent；
The mol ratio of described 1,2,4- triazoles or triazole derivatives and 4-Fluorobenzaldehyde is 1:1~4:1；Described
The mol ratio of 1,2,4- triazoles or triazole derivatives and solvent is 1:10~1:100；Described triazole derivatives are 3-
The chloro- 1,2,4- triazoles of cyano group -1,2,4- triazoles, 3- nitros -5- and 5- methoxyl group -1,2,4- triazoles；Described solvent
For N,N-dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
It is preferred that 1,2,4- triazoles or triazole derivatives and 4-Fluorobenzaldehyde mol ratio be 2:1；
2) weigh potassium carbonate and be added to step 1) described in solution, 1,2,4- triazole or triazole derivatives and potassium carbonate
Mol ratio be 1:1~1:4, constant temperature stirs 8~15h at 50~130 DEG C, stops heating, is filtered to remove potassium carbonate, acetic acid second
Ester is extracted, and revolving is removed after solvent, obtains pale solid, with ethyl alcohol recrystallization 3 times, obtains sterling, vacuum drying produces 4- (1-
1,2,4- triazolyls) benzaldehyde or triazole derivatives benzaldehyde.
3) weigh step 2) 4- (1-1,2,4- triazolyls) benzaldehydes or triazole derivatives benzaldehyde and p-phenylenediamine it is molten
In solvent；
Described 4- (1-1,2,4- triazolyls) benzaldehydes or the mol ratio of triazole derivatives benzaldehyde and p-phenylenediamine
For 2:1~5:1；
It is preferred that 4- (1-1,2,4- triazolyls) benzaldehydes or triazole derivatives benzaldehyde and p-phenylenediamine mol ratio
For 3:1；
Described 4- (1-1,2,4- triazolyls) benzaldehydes or the mol ratio of triazole derivatives benzaldehyde and solvent are 1:
10~1:90；
Described solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
4) weigh acetic acid and be added to step 3) described in mixed solution in, 4- (1-1,2,4- triazolyls) benzaldehydes or three nitrogen
The mol ratio of Zole derivatives benzaldehyde and acetic acid is 1:1~1:5,2~12h of isothermal reaction at 30~120 DEG C, vacuum distillation is removed
Solvent is removed, yellow powdery solid is obtained, is purified with methanol, ethanol, dichloromethane or re-crystallizing in ethyl acetate, vacuum drying is
Obtain final products.
The present invention reacts 1,2,4- triazole and its derivative with 4-Fluorobenzaldehyde, is prepared into 4- (1-1,2,4- triazoles
Base) benzaldehyde or triazole derivatives benzaldehyde, a series of triazole benzene based on triazole are reacted to obtain by itself and p-phenylenediamine
Formaldehyde contracting p-phenylenediamine Bis-Schiff Bases, after tested, the compound has good fluorescence property and ion selectivity can (result be shown in
Accompanying drawing 5-10).
Novel compound of present invention can also can be used for as probe application in ion detection field as fluorescent material
Material Field.
Brief description of the drawings：
(1) Fig. 1,2,3,4 are the hydrogen nuclear magnetic resonance spectrogram of compound 1,2,3 and 4 respectively.
(2) Fig. 5,6 are the uv absorption spectra and fluorescence spectra of compound respectively.
(3) Fig. 7,8,9,10 are uv absorption spectra of the compound to metalloform-selective respectively.
Embodiment：
In order to be better understood from technical scheme, it is described in further detail below by way of specific embodiment.
Embodiment 1
1,2,4- triazole 0.691g (10mmol) are weighed, 4-Fluorobenzaldehyde 1.240g (10mmol) and Carbon Dioxide is weighed
Potassium 2.760g (20mmol), is dissolved in 25mL DMF, is added to the 50mL equipped with thermometer, agitating device
Four-hole boiling flask in, stop heating at 80 DEG C after isothermal reaction 10h, be filtered to remove potassium carbonate, ethyl acetate extraction, revolving is removed
After solvent, pale solid is obtained, with ethyl alcohol recrystallization 3 times, sterling is obtained, 50 DEG C of vacuum drying 6h vacuum drying produce 4- (1-
1,2,4- triazolyls) benzaldehyde.
4- (1-1,2,4- triazolyls) benzaldehyde 0.173g (1mmol), p-phenylenediamine 0.054g (0.500mmol) is weighed,
It is dissolved in 4mL DMF, in the single-necked flask for being added to the 10mL equipped with thermometer, agitating device.Then
Acetic acid 0.120g (2mmol) is added into above-mentioned mixed liquor, the isothermal reaction 8h at 50 DEG C, vacuum distillation removes solvent, obtained
Yellow powdery solid, is purified with ethyl alcohol recrystallization, and 50 DEG C of vacuum drying 6h produce (the triazole benzene first of final products compound 1
Aldehyde contracting p-phenylenediamine Bis-Schiff Bases).Yield：89%.
Elementary analysis：C24H18N8：%C：67.89(68.90)；%H：4.73(4.31)；%N：27.38 (26.79) (brackets
Interior is measured value).
The nmr analysis of compound 1 (nuclear magnetic spectrogram is shown in accompanying drawing 1)：
Table 1 is analyzed to obtain by structural formula and hydrogen nuclear magnetic resonance spectrogram to compound 1.The compound has 9 kinds of hydrogen, wherein
The signal peak occurred near 8.04-7.94ppm is the signal peak of proton 1,2, and its peak area is 2.07；In 6.65-6.52ppm
The signal peak that annex occurs is the signal peak of proton 3, and its peak area is 1.00；The signal peak occurred near 8.11ppm is matter
The signal peak of son 4,6, its peak area is 2.00；The signal peak occurred in 8.08ppm annexes is the signal peak of proton 5,7, its peak
Area is 2.07；The signal peak occurred near 9.42ppm is the signal peak of proton 8, and its peak area is 1.08；In 7.16ppm
The signal peak nearby occurred is the signal peak of proton 9, and its peak area is 1.08.It can thus be seen that the nuclear magnetic resonance of compound 1
Hydrogen spectrogram has met the structure of compound 1, i.e. triazole benzaldehyde-p-phenylenediamine bi-schiff base well.
The compound 1 of table 11HNMR chemical shift and peak ownership
s：It is unimodal；d：Doublet；m：Multiplet
Embodiment 2
Weigh 3- cyano group -1,2,4- triazoles 2.820g (30mmol), weigh 4-Fluorobenzaldehyde 1.860g (15mmol) and
Anhydrous potassium carbonate 5.520g (40mmol), is dissolved in 50mL DMF, is added to equipped with thermometer, stirring dress
In the 100mL put four-hole boiling flask.Isothermal reaction 8h at 90 DEG C, is filtered to remove potassium carbonate, and ethyl acetate extraction, revolving removing is molten
After agent, pale solid is obtained, with ethyl alcohol recrystallization 3 times, sterling is obtained, 60 DEG C of vacuum drying 5h vacuum drying produce 4- (3- cyanogen
Base -1,2,4- triazolyls) benzaldehyde.
4- (3- cyano group -1,2,4- triazolyls) benzaldehyde 0.200g (1mmol) is weighed, p-phenylenediamine 0.054g is weighed
(0.5mmol), is dissolved in 4mL DMF, and the single port for being added to the 10mL equipped with thermometer, agitating device burns
In bottle.State then up and constant temperature stirring reaction 12h at acetic acid 0.180g (3mmol), 30 DEG C is added in mixed liquor, vacuum distillation is removed
Solvent is removed, yellow powdery solid is obtained, with ethyl alcohol recrystallization, 60 DEG C of vacuum drying 6h produce final purpose product：Compound 2
((3- cyano group -1,2,4- triazolyls) benzaldehyde-p-phenylenediamine bi-schiff base).Yield：85%.
Elementary analysis：C26H16N10：%C：66.08(66.67)；%H：3.57(3.42)；%N：30.35 (29.91) (are included
It is measured value in number).
The nmr analysis of compound 2 (nuclear magnetic spectrogram is shown in accompanying drawing 2)：
Table 2 is analyzed to obtain by structural formula and hydrogen nuclear magnetic resonance spectrogram to compound 2.The compound has 8 kinds of hydrogen, wherein
The signal peak occurred near 7.98ppm is the signal peak of proton 1,2, and its peak area is 2.08；Occur in 7.00ppm annexes
Signal peak is the signal peak of proton 3, and its peak area is 1.00；The signal peak occurred near 8.08ppm is the signal of proton 4,6
Peak, its peak area is 2.07；The signal peak occurred in 7.98ppm annexes is the signal peak of proton 5,7, and its peak area is 2.00；
The signal peak occurred near 9.40ppm is the signal peak of proton 8, and its peak area is 1.00.It can thus be seen that compound 2
Hydrogen nuclear magnetic resonance spectrogram met the structure of compound 2 well.
The compound 2 of table 21HNMR chemical shift and peak ownership
s：It is unimodal；d：Doublet；m：Multiplet
Embodiment 3
The chloro- triazole 2.228g (15mmol) of 3- nitros -5- are weighed, 4-Fluorobenzaldehyde 1.860g (15mmol) and nothing is weighed
Aqueous carbonate potassium 4.140g (30mmol), is dissolved in 45mL DMF, is added to equipped with thermometer, agitating device
100mL four-hole boiling flask in.Isothermal reaction 12h is filtered to remove potassium carbonate at 60 DEG C, and ethyl acetate extraction, revolving removes solvent
Afterwards, obtain pale solid, with ethyl alcohol recrystallization 3 times, obtain sterling, 50 DEG C of vacuum drying 7h vacuum drying produce 4- (3- nitros-
The chloro- 1,2,4- triazolyls of 5-) benzaldehyde.
4- (3- nitros -5- chloro- 1,2,4- triazolyls) benzaldehyde 0.758g (3mmol) is weighed, p-phenylenediamine is weighed
0.130g (1.250mmol), is dissolved in 3mL DMF, is added to the 10mL equipped with thermometer, agitating device
Single-necked flask in.State then up and constant temperature stirring reaction 5h at acetic acid 0.300g (5mmol), 90 DEG C is added in mixed liquor, subtract
Solvent is distilled off in pressure, obtains yellow powdery solid, and with ethyl alcohol recrystallization, 60 DEG C of vacuum drying 5h produce final purpose production
Thing：Compound 3 ((the chloro- 1,2,4- triazolyls of 3- nitros -5-) benzaldehyde-p-phenylenediamine bi-schiff base).Yield：87%.
Elementary analysis：C24H14N10O4Cl2：%C：50.08(49.91)；%H：2.93(2.43)；%N：23.18
(24.26)；%O：10.71(11.09)；%Cl：13.1 (12.31) (being measured value in bracket).
The nmr analysis of compound 3 (nuclear magnetic spectrogram is shown in accompanying drawing 3)：
Table 3 is analyzed to obtain by structural formula and hydrogen nuclear magnetic resonance spectrogram to compound 3.The compound has 7 kinds of hydrogen, wherein
The signal peak occurred near 7.65ppm is the signal peak of proton 1,2, and its peak area is 2.07；Occur in 8.36ppm annexes
Signal peak is the signal peak of proton 3, and its peak area is 1.00；The signal peak occurred in 7.74ppm annexes is the signal of proton 4,6
Peak, its peak area is 2.07；The signal peak occurred near 7.90ppm is the signal peak of proton 5,7, and its peak area is 2.01.
It can thus be seen that the hydrogen nuclear magnetic resonance spectrogram of compound 3 has met the structure of compound 3 well, i.e., (3- nitros -5- is chloro-
1,2,4- triazolyls) benzaldehyde-p-phenylenediamine bi-schiff base.
The compound 3 of table 31HNMR chemical shift and peak ownership
s：It is unimodal；d：Doublet；m：Multiplet
Embodiment 4
Weigh 5- methoxyl groups -1,2,4- triazoles 2.180g (20mmol), weigh 4-Fluorobenzaldehyde 0.992g (8mmol) and
Anhydrous potassium carbonate 9.960g (70mmol), is dissolved in 55mL DMF, is added to equipped with thermometer, stirring dress
In the 100mL put four-hole boiling flask.Isothermal reaction 15h at 70 DEG C, is filtered to remove potassium carbonate, and ethyl acetate extraction, revolving is removed
After solvent, pale solid is obtained, with ethyl alcohol recrystallization 3 times, sterling is obtained, 50 DEG C of vacuum drying 5h vacuum drying produce 4- (5-
Methoxyl group -1,2,4- triazolyls) benzaldehyde.
4- (5- methoxyl groups -1,2,4- triazolyls) benzaldehyde 0.609g (3mmol) is weighed, p-phenylenediamine 0.216g is weighed
(2mmol), is dissolved in 5mL DMF, is added to the single-necked flask of the 10mL equipped with thermometer, agitating device
In.State then up and constant temperature stirring reaction 3h at acetic acid 0.600g (10mmol), 100 DEG C is added in mixed liquor, vacuum distillation is removed
Solvent is removed, yellow powdery solid is obtained, with ethyl alcohol recrystallization, 50 DEG C of vacuum drying 6h produce final purpose product：Compound 4
((5- methoxyl group -1,2,4- triazolyls) benzaldehyde-p-phenylenediamine bi-schiff base).Yield：86%.
Elementary analysis：C26H22N8O2：%C：65.08(65.27)；%H：4.57(4.61)；%N：23.68(23.43)；%
O：6.67 (6.69) (being measured value in bracket).
The nmr analysis of compound 4 (nuclear magnetic spectrogram is shown in accompanying drawing 4)：
Table 4 is analyzed to obtain by structural formula and hydrogen nuclear magnetic resonance spectrogram to compound 4.The compound has 9 kinds of hydrogen, wherein
The signal peak occurred near 7.98ppm is the signal peak of proton 1,2, and its peak area is 2.07；Occur in 8.70ppm annexes
Signal peak is the signal peak of proton 3, and its peak area is 1.00；The signal peak occurred near 8.10ppm is the signal of proton 4,6
Peak, its peak area is 2.07；The signal peak occurred in 8.31ppm annexes is the signal peak of proton 5,7, and its peak area is 2.01；
The signal peak occurred near 7.18ppm is the signal peak of proton 8, and its peak area is 1.00；The letter occurred near 3.91ppm
Number peak is the signal peak of proton 9, and its peak area is 1.08.It can thus be seen that the hydrogen nuclear magnetic resonance spectrogram of compound 4 is good
The structure of compound 4 is met, i.e. (5- methoxyl groups -1,2,4- triazolyls) benzaldehyde-p-phenylenediamine bi-schiff base.
The compound 4 of table 41HNMR chemical shift and peak ownership
s：It is unimodal；d：Doublet；m：Multiplet
Experimental example
1st, compound fluorescence property is tested
The compound 1,2,3,4 for purification process of learning from else's experience, is dissolved using DMF, diluted, be configured to 1.0
×10-5Mol/L sample solution.Using the uv absorption spectra of ultraviolet-uisible spectrophotometer determination sample, (result is shown in attached
Fig. 5), according to the uv-absorption maximum wavelength of the compound measured, F-4600 fluorescent spectrophotometer assay compounds are utilized
Fluorescence exciting wavelength, and determine the fluorescence spectrum of compound (result is shown in accompanying drawing 6).
2nd, make solvent using N,N-dimethylformamide and prepare 1.0 × 10 respectively-5Mol/L compound 1,2,3,4 and gold
Belong to the 1 of ion:1 mixed solution.Test compound and metal ion solution ultra-violet absorption spectrum (result see accompanying drawing 7,8,9,
10)。
Result of study shows：Compound has fluorescence property, while compound 1 has preferable selection for lead ion (II)
Property；Compound 2 has preferable selectivity for cadmium ion (II)；Compound 3 has preferable selection for lead ion (II)
Property；Compound 4 has preferable selectivity for nickel ion (II).
Claims (4)
1. a kind of triazole benzaldehyde-p-phenylenediamine bi-schiff base, it is characterised in that：Its structural formula is as follows：
R1For hydrogen, nitro, cyano group, R2For hydrogen, chlorine, methoxyl group.
The preparation method of described triazole benzaldehyde contracting phenylenediamine Bis-Schiff Bases, its preparation method is as follows：
1) 1,2,4- triazoles or triazole derivatives are weighed and 4-Fluorobenzaldehyde is dissolved in solvent；
The mol ratio of described 1,2,4- triazoles or triazole derivatives and 4-Fluorobenzaldehyde is 1:1~4:1；Described 1,2,
The mol ratio of 4- triazoles or triazole derivatives and solvent is 1:10~1:100；Described triazole derivatives be 3- cyano group-
The chloro- 1,2,4- triazoles of 1,2,4- triazoles, 3- nitros -5- and 5- methoxyl group -1,2,4- triazoles；Described solvent is N, N-
Dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
2) weigh potassium carbonate and be added to step 1) described in solution, 1,2,4- triazole or triazole derivatives and potassium carbonate rub
You are than being 1:1~1:4, constant temperature stirs 8~15h at 50~130 DEG C, stops heating, is filtered to remove potassium carbonate, ethyl acetate extraction
Take, revolving is removed after solvent, obtains pale solid, with ethyl alcohol recrystallization 3 times, obtain sterling, vacuum drying produce 4- (1-1,2,
4- triazolyls) benzaldehyde or triazole derivatives benzaldehyde.
3) weigh step 2) 4- (1-1,2,4- triazolyls) benzaldehydes or triazole derivatives benzaldehyde and p-phenylenediamine be dissolved in it is molten
Agent；
Described 4- (1-1,2,4- triazolyls) benzaldehydes or the mol ratio of triazole derivatives benzaldehyde and p-phenylenediamine are 2:1
~5:1；
Described 4- (1-1,2,4- triazolyls) benzaldehydes or the mol ratio of triazole derivatives benzaldehyde and solvent are 1:10~
1:90；
Described solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
4) weigh acetic acid and be added to step 3) described in mixed solution in, 4- (1-1,2,4- triazolyls) benzaldehydes or triazole spread out
The mol ratio of biological benzaldehyde and acetic acid is 1:1~1:5,2~12h of isothermal reaction at 30~120 DEG C, vacuum distillation remove molten
Agent, obtains yellow powdery solid, is purified with methanol, ethanol, dichloromethane or re-crystallizing in ethyl acetate, and vacuum drying is produced most
Finished product.
2. the application of compound as claimed in claim 1, it is characterised in that：Fluorescent material and ion detection field.
3. triazole benzaldehyde-p-phenylenediamine bi-schiff base as claimed in claim 1, it is characterised in that：Described triazole
The preparation method of benzaldehyde-p-phenylenediamine bi-schiff base, 1,2,4- triazole or triazole derivatives and 4-Fluorobenzaldehyde rub
You are than being 2:1.
4. triazole benzaldehyde-p-phenylenediamine bi-schiff base as claimed in claim 1, it is characterised in that：Described triazole
The preparation method of benzaldehyde-p-phenylenediamine bi-schiff base, 4- (1-1,2,4- triazolyls) benzaldehydes or triazole derivatives benzene first
The mol ratio of aldehyde and p-phenylenediamine is 3:1.
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| CN108503588B (en) * | 2017-11-27 | 2019-08-09 | 齐鲁工业大学 | A kind of 3- methylpyrazole benzaldehyde contracting 4-AA schiff bases and preparation method thereof |
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