CN107043353A - A kind of imidazoles benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof - Google Patents
A kind of imidazoles benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of imidazoles benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof.First using imidazole and its derivants and 4-Fluorobenzaldehyde as raw material, 4 imidazolyl benzaldehydes or imdazole derivatives benzaldehyde are prepared.It is again raw material with itself and p-phenylenediamine, by the condensation reaction of aldehyde radical and primary amine, obtains a series of Bis-Schiff Bases with conjugated structure and rigid plane.Technique synthesis cost is low, and yield is high, and easy control of reaction conditions, purifying products are simple.Novel compound of present invention has good fluorescence property, while having selectivity to metal ion, can apply to Material Field or sensor field.
Description
Technical field
The present invention relates to a kind of imidazoles benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof, the compound has firm
Property planar structure, shows preferable fluorescence property, while having the C=N functional groups containing lone pair electrons, has very with metal ion
Strong coordination ability, with good ion selectivity.
Background technology
Imidazoles is a kind of five member ring heterocyclic compound containing two nitrogen-atoms, as a kind of important heterocyclic compound, extensively
It is general to be present in natural products.Imidazoles has very high bioactivity, can be widely used in medicine, agricultural chemicals, dyestuff and
In terms of developer.In addition, glyoxaline compound is as organic nitrogen-containing heterocyclic compound, also with good coordination ability,
Occupy very important status in Coordinative Chemistry.
Because imidazole molecule has the big pi bond of a closure, and the sp of the non-bonding of one of nitrogen-atoms2Have one on track
To lone pair electrons, therefore it has armaticity, both shows faintly acid, and can show alkalescent.It is anti-that this just determines that chemistry occurs for imidazoles
The diversity that (should be particularly substitution reaction), that is, generate the diversity of derivative, also determines that glyoxaline compound has such as
Ligand complex, the premium properties such as electronics, the transitivity of proton, has further determined this kind of compound and has been with a wide range of applications.
Glyoxaline compound has conjugate acid and base performance and complex coordination performance, enjoys the good reputation of " biocatalyst " " bio-ligand ".
Schiff base compounds are as a kind of important industrial chemicals, using quite varied.Due to schiff bases have it is excellent
The physical material performance such as light, electricity, magnetic, the physiologically active such as antibacterial, anticancer, the weeding of good coordination property and uniqueness so that
It receives extensive concern.Many reports have been carried out in medicine, agricultural chemicals, field of fine chemical on imidazolium compounds at present
Lead, but the synthesis to imidazoles Bis-Schiff Bases is not reported at present.
The content of the invention
The purpose of the present invention is that there is provided the double seats of the new imidazoles benzaldehyde contracting p-phenylenediamine of a class in view of the shortcomings of the prior art
Husband's alkali, the schiff bases has a good fluorescence property and ion selectivity energy, and the technique has that easy to operate, cost is low, bar
The advantages of part is easily controlled, yield is high.
It is a further object of the present invention to provide the preparation method of described imidazoles benzaldehyde-p-phenylenediamine bi-schiff base.
It is a further object of the present invention to provide the application of described imidazoles benzaldehyde-p-phenylenediamine bi-schiff base.
In order to realize such purpose, technical scheme is as follows：
A kind of imidazoles benzaldehyde-p-phenylenediamine bi-schiff base, its structural formula is as follows：
R1For methoxyl group, hydrogen, R2For hydrogen, fluorine, chlorine, R3For hydrogen, carboxyl, nitro, hydroxyl, cyano group.
It is preferred that R1For methoxyl group, R2For chlorine, R3For nitro；
Wherein methoxyl group is outstanding electron-donating group, and chlorine atom has very strong electronegativity, and nitro has good suction
Electronic action；
The compound is mainly used in Material Field or sensor field；
A kind of preparation method of imidazoles benzaldehyde-p-phenylenediamine bi-schiff base, its preparation method is as follows：
1) imidazoles or imdazole derivatives are weighed and 4-Fluorobenzaldehyde is dissolved in solvent；
The mol ratio of described imidazoles or imdazole derivatives and 4-Fluorobenzaldehyde is 1:1~3:1；Described imidazoles or imidazoles
The mol ratio of derivative and solvent is 1:15~1:90；Described imdazole derivatives are 5- nitroimidazoles, 2- methoxyl groups imidazoles, 4-
Chloro- 5- nitroimidazoles；Described solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
It is preferred that imidazoles or imdazole derivatives and 4-Fluorobenzaldehyde mol ratio be 1.5:1；
2) weigh potassium carbonate and be added to step 1) described in solution, the mol ratio of imidazoles or imdazole derivatives and potassium carbonate is
1:1~1:4, constant temperature stirs 10~20h at 50~120 DEG C, is cooled to after room temperature, pours into 100mL frozen water, there is yellow solid
Separate out, suction filtration, with ethyl alcohol recrystallization, obtain sterling, vacuum drying produces 4- imidazolyl benzaldehydes or imdazole derivatives benzaldehyde；
3) step 2 is weighed) 4- imidazolyl benzaldehydes or imdazole derivatives benzaldehyde and p-phenylenediamine be dissolved in solvent；
Described 4- imidazolyl benzaldehydes or the mol ratio of imdazole derivatives benzaldehyde and p-phenylenediamine are 2:1~5:1；
It is preferred that 4- imidazolyl benzaldehydes or imdazole derivatives and p-phenylenediamine mol ratio be 2:1；
Described 4- imidazolyl benzaldehydes or the mol ratio of imdazole derivatives benzaldehyde and solvent are 1:5~1:90；
Described solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
4) weigh hydrochloric acid and be added to step 3) described in mixed solution in, 4- imidazolyl benzaldehydes or imdazole derivatives benzene first
The mol ratio of aldehyde and hydrochloric acid is 1:1~1:5,1~12h of isothermal reaction at 25~90 DEG C, vacuum distillation remove solvent, obtain Huang
Color pulverulent solids, are purified with ethanol, methanol or re-crystallizing in ethyl acetate, and vacuum drying produces final products；
Solvent used in described recrystallization is ethanol, methanol or ethyl acetate.
The present invention reacts imidazole and its derivants and 4-Fluorobenzaldehyde, is prepared into 4- imidazolyl benzaldehydes or imidazole derivatives
Thing benzaldehyde, a series of imidazoles benzaldehyde-p-phenylenediamine bi-schiff bases based on imidazoles are reacted to obtain by itself and p-phenylenediamine, warp
Test, the compound has good fluorescence property and ion selectivity (result is 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 fluorogram 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
Imidazoles 0.680g (10mmol) is weighed, 4-Fluorobenzaldehyde 1.240g (10mmol) and Anhydrous potassium carbonate 1.380g is weighed
(10mmol), is dissolved in 25mL DMF, is added to four mouthfuls of burnings of the 50mL equipped with thermometer, agitating device
In bottle.Isothermal reaction 20h, is cooled to after room temperature at 60 DEG C, pours into 100mL frozen water, there is yellow solid precipitation, and suction filtration uses second
Alcohol is recrystallized, and in being dried in vacuo 8h at 50 DEG C, produces 4- imidazolyl benzaldehydes.
4- imidazolyl benzaldehydes 0.172g (1mmol) is weighed, p-phenylenediamine 0.054g (0.500mmol) is weighed, is dissolved in 5mL
DMF in, in the single-necked flask for being added to the 10mL equipped with thermometer, agitating device.State then up mixed
Close and constant temperature stirring reaction 12h at hydrochloric acid 0.073g (2mmol), 25 DEG C is added in liquid, vacuum distillation removes solvent, obtains yellow powder
Last shape solid, with ethyl alcohol recrystallization, 50 DEG C of vacuum drying 6h produce final purpose product：(the imidazoles benzaldehyde contracting pair of compound 1
Phenylenediamine Bis-Schiff Bases).Yield：90%.
Elementary analysis：C26H20N6：%C：75.89(75.00)；%H：4.83(4.81)；%N：19.28 (20.19) (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 10 kinds of hydrogen, its
In the signal peak that occurs near 7.96-7.76ppm be proton 1,2,10 signal peak, its peak area is 3.09；In 8.75ppm
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 7.40ppm 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 2.04；The signal peak occurred near 8.41ppm is the signal peak of proton 8, and its peak area is 0.99；In 7.16ppm
The signal peak nearby occurred is the signal peak of proton 9, and its peak area is 1.01.It can thus be seen that the nuclear magnetic resonance of compound 1
Hydrogen spectrogram has met the structure of compound 1, i.e. imidazoles 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
5- nitroimidazoles 2.260g (20mmol) is weighed, 4-Fluorobenzaldehyde 1.860g (15mmol) and Anhydrous potassium carbonate is weighed
2.760g (20mmol), be dissolved in 30mL DMF, is added to equipped with thermometer, the 50mL of agitating device
In four-hole boiling flask.Isothermal reaction 16h, is cooled to after room temperature at 80 DEG C, pours into 100mL frozen water, has yellow solid precipitation, takes out
Filter, with ethyl alcohol recrystallization, in being dried in vacuo 10h at 50 DEG C, produces 4- (5- nitro -1- imidazole radicals) benzaldehyde.
4- (5- nitro -1- imidazole radicals) benzaldehyde 0.217g (1mmol) is weighed, p-phenylenediamine 0.027g is weighed
(0.250mmol), is dissolved in 4mL DMF, is added to the single port of the 10mL equipped with thermometer, agitating device
In flask.State then up and constant temperature stirring reaction 10h at hydrochloric acid 0.107g (2.932mmol), 50 DEG C is added in mixed liquor, decompression
Solvent is distilled off, yellow powdery solid is obtained, with ethyl alcohol recrystallization, 60 DEG C of vacuum drying 6h produce final purpose product：
Compound 2 (5- nitroimidazoles benzaldehyde-p-phenylenediamine bi-schiff base).Yield：82%.
Elementary analysis：C26H18N8O4：%C：62.08(61.66)；%H：3.57(3.49)；%N：21.68(22.13)；%
O：12.67 (12.65) (being measured value in bracket).
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 9 kinds of hydrogen, wherein
The signal peak occurred near 7.75ppm is the signal peak of proton 1,2, and its peak area is 2.00；Occur in 8.88ppm annexes
Signal peak is the signal peak of proton 3, and its peak area is 1.00；The signal peak occurred near 7.40ppm is the signal of proton 4,6
Peak, its peak area is 2.04；The signal peak occurred in 8.08ppm annexes is the signal peak of proton 5,7, and its peak area is 2.00；
The signal peak occurred near 8.41ppm is the signal peak of proton 8, and its peak area is 1.01；The letter occurred near 7.21ppm
Number peak is the signal peak of proton 9, and its peak area is 1.01.It can thus be seen that the hydrogen nuclear magnetic resonance spectrogram of compound 2 is good
The structure of compound 2, i.e. 5- nitroimidazoles benzaldehyde-p-phenylenediamine bi-schiff base are met.
The compound 2 of table 21HNMR chemical shift and peak ownership
s：It is unimodal；d：Doublet；m：Multiplet
Embodiment 3
2- methoxyl group imidazoles 2.940g (30mmol) are weighed, 4-Fluorobenzaldehyde 1.860g (15mmol) and Carbon Dioxide is weighed
Potassium 4.140g (30mmol), be dissolved in 40mL DMF, is added to equipped with thermometer, agitating device
In 100mL four-hole boiling flask.Isothermal reaction 14h, is cooled to after room temperature at 90 DEG C, pours into 100mL frozen water, there is yellow solid analysis
Go out, suction filtration, with ethyl alcohol recrystallization, in being dried in vacuo 8h at 60 DEG C, produce 4- (2- methoxyl group -1- imidazole radicals) benzaldehyde.
4- (2- methoxyl group -1- imidazole radicals) benzaldehyde 0.606 (3mmol) is weighed, p-phenylenediamine 0.130g is weighed
(1.250mmol), is dissolved in 4mL DMF, is added to the single port of the 10mL equipped with thermometer, agitating device
In flask.State then up and constant temperature stirring reaction 6h at hydrochloric acid 0.178g (4.877mmol), 60 DEG C is added in mixed liquor, decompression
Solvent is distilled off, yellow powdery solid is obtained, with ethyl alcohol recrystallization, 50 DEG C of vacuum drying 6h produce final purpose product：
Compound 3 (2- methoxyl group imidazoles benzaldehyde-p-phenylenediamine bi-schiff base).Yield：84%.
Elementary analysis：C28H26N6O2：%C：71.08(70.29)；%H：4.93(5.44)；%N：18.28(17.57)；%
O：5.71 (6.69) (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 10 kinds of hydrogen, its
In the signal peak that occurs near 6.65ppm be proton 1,2 signal peak, its peak area is 1.99；Occur in 8.14ppm annexes
Signal peak be proton 3 signal peak, its peak area be 1.00；The signal peak occurred near 7.43-7.48ppm is proton 4,
6,9 signal peak, its peak area is 3.01；The signal peak occurred in 8.01ppm annexes is the signal peak of proton 5,7, Qi Feng faces
Product is 2.00；The signal peak occurred near 7.27ppm is the signal peak of proton 8, and its peak area is 1.00；It is attached in 3.85ppm
The signal peak closely occurred is the signal peak of proton 10, and its peak area is 2.99.It can thus be seen that the nuclear magnetic resonance of compound 3
Hydrogen spectrogram has met the structure of compound 3, i.e. 2- methoxyl groups imidazoles benzaldehyde-p-phenylenediamine bi-schiff base well.
The compound 3 of table 31HNMR chemical shift and peak ownership
s：It is unimodal；d：Doublet；m：Multiplet
Embodiment 4
The chloro- 5- nitroimidazoles 2.970g (20mmol) of 4- are weighed, 4-Fluorobenzaldehyde 0.992g (8mmol) and anhydrous carbon is weighed
Sour potassium 9.960g (70mmol), be dissolved in 35mL DMF, is added to equipped with thermometer, agitating device
In 100mL four-hole boiling flask.Isothermal reaction 12h, is cooled to after room temperature at 100 DEG C, pours into 100mL frozen water, there is yellow solid
Separate out, suction filtration, with ethyl alcohol recrystallization, in being dried in vacuo 8h at 50 DEG C, produces 4- (the chloro- 5- nitros -1- imidazole radicals of 4-) benzaldehyde.
4- (the chloro- 5- nitros -1- imidazole radicals of 4-) benzaldehyde 0.758g (3mmol) is weighed, p-phenylenediamine 0.161g is weighed
(1.505mmol), is dissolved in 5mL DMF, is added to the single port of the 10mL equipped with thermometer, agitating device
In flask.State then up and constant temperature stirring reaction 5h, vacuum distillation at hydrochloric acid 0.365g (10mmol), 70 DEG C are added in mixed liquor
Solvent is removed, yellow powdery solid is obtained, with ethyl alcohol recrystallization, 50 DEG C of vacuum drying 6h produce final purpose product：Chemical combination
Thing 4 (the chloro- 5- nitroimidazoles benzaldehyde-p-phenylenediamine bi-schiff bases of 4-).Yield：88%.
Elementary analysis：C26H16N8O4Cl2：%C：53.08(54.07)；%H：2.57(2.78)；%N：20.68
(19.41)；%O：10.67(11.09)；%Cl：13.00 (12.65) (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 8 kinds of hydrogen, wherein
The signal peak occurred near 7.42ppm is the signal peak of proton 1,2, and its peak area is 2.04；Occur in 9.01ppm annexes
Signal peak is the signal peak of proton 3, and its peak area is 0.99；The signal peak occurred near 8.05ppm is the signal of proton 4,6
Peak, its peak area is 1.99；The signal peak occurred in 7.68ppm annexes is the signal peak of proton 5,7, and its peak area is 1.99；
The signal peak occurred near 8.56ppm is the signal peak of proton 8, and its peak area is 1.00.It can thus be seen that compound 4
Hydrogen nuclear magnetic resonance spectrogram met the structure of compound 4 well, i.e. the chloro- 5- nitroimidazoles benzaldehyde contracting p-phenylenediamine of 4- is double
Schiff bases.
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.The fluorescence spectrum of test compound and metal ion solution (result is shown in accompanying drawing 7,8,9,10).
Result of study shows：Compound has fluorescence property, while compound 1 has preferable selection to copper ion (II)
Property；Compound 2 has preferable selectivity for cadmium ion (II)；Compound 3 has preferable selection for zinc ion (II)
Property；Compound 4 (II) has preferable selectivity for cadmium ion.
Claims (4)
1. a kind of imidazoles benzaldehyde-p-phenylenediamine bi-schiff base, it is characterised in that：Its structural formula is as follows：
R1For methoxyl group, hydrogen, R2For hydrogen, chlorine, R3For hydrogen, nitro, cyano group.
The preparation method of described imidazoles benzaldehyde contracting phenylenediamine Bis-Schiff Bases, its preparation method is as follows：
1) imidazoles or imdazole derivatives are weighed and 4-Fluorobenzaldehyde is dissolved in solvent；
The mol ratio of described imidazoles or imdazole derivatives and 4-Fluorobenzaldehyde is 1:1~3:1；Described imidazoles or imidazole derivatives
The mol ratio of thing and solvent is 1:15~1:90；Described imdazole derivatives are 5- nitroimidazoles, 2- methoxyl groups imidazoles, 4- chloro-
5- nitroimidazoles；Described solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
2) weigh potassium carbonate and be added to step 1) described in solution, the mol ratio of imidazoles or imdazole derivatives and potassium carbonate is 1:1
~1:4, constant temperature stirs 10~20h at 50~120 DEG C, is cooled to after room temperature, pours into 100mL frozen water, there is yellow solid analysis
Go out, suction filtration, with ethyl alcohol recrystallization, obtain sterling, vacuum drying produces 4- imidazolyl benzaldehydes or imdazole derivatives benzaldehyde；
3) step 2 is weighed) 4- imidazolyl benzaldehydes or imdazole derivatives benzaldehyde and p-phenylenediamine be dissolved in solvent；
Described 4- imidazolyl benzaldehydes or the mol ratio of imdazole derivatives benzaldehyde and p-phenylenediamine are 2:1~5:1；
Described 4- imidazolyl benzaldehydes or the mol ratio of imdazole derivatives benzaldehyde and solvent are 1:5~1:90；
Described solvent is N,N-dimethylformamide, dimethyl sulfoxide (DMSO), ethanol；
4) weigh hydrochloric acid and be added to step 3) described in mixed solution in, 4- imidazolyl benzaldehydes or imdazole derivatives benzaldehyde with
The mol ratio of hydrochloric acid is 1:1~1:5,1~12h of isothermal reaction at 25~90 DEG C, vacuum distillation remove solvent, obtain yellow powder
Last shape solid, is purified with ethanol, methanol or re-crystallizing in ethyl acetate, and vacuum drying produces final products.
2. the application of compound as claimed in claim 1, it is characterised in that：Fluorescent material and ion detection field.
3. imidazoles benzaldehyde-p-phenylenediamine bi-schiff base as claimed in claim 1, it is characterised in that：Described imidazoles benzene first
The mol ratio of the preparation method of aldehyde contracting p-phenylenediamine Bis-Schiff Bases, imidazoles or imdazole derivatives and 4-Fluorobenzaldehyde is 1.5:1.
4. imidazoles benzaldehyde-p-phenylenediamine bi-schiff base as claimed in claim 1, it is characterised in that：Described imidazoles benzene first
The mol ratio of the preparation method of aldehyde contracting p-phenylenediamine Bis-Schiff Bases, 4- imidazolyl benzaldehydes or imdazole derivatives and p-phenylenediamine is
2:1。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107488151A (en) * | 2017-08-28 | 2017-12-19 | 广东工业大学 | A kind of compound for being used to detect copper ion or prepare preventing and treating Alzheimer disease drug and preparation method thereof and product |
| CN112390805A (en) * | 2020-11-27 | 2021-02-23 | 齐鲁工业大学 | Benzimidazole benzaldehyde fluorescein hydrazide Schiff base and preparation method thereof |
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2016
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107488151A (en) * | 2017-08-28 | 2017-12-19 | 广东工业大学 | A kind of compound for being used to detect copper ion or prepare preventing and treating Alzheimer disease drug and preparation method thereof and product |
| CN107488151B (en) * | 2017-08-28 | 2019-10-29 | 广东工业大学 | It is a kind of for detecting the compound and preparation method thereof and product of copper ion or preparation prevention and treatment Alzheimer disease drug |
| CN112390805A (en) * | 2020-11-27 | 2021-02-23 | 齐鲁工业大学 | Benzimidazole benzaldehyde fluorescein hydrazide Schiff base and preparation method thereof |
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