CN104130192A - Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof - Google Patents
Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and a preparation method thereof. The preparation method comprises: firstly taking imidazol and derivatives and p-fluorobenzaldehyde as raw materials to prepare 4-imidazolyl benzaldehyde or imidazol-derivative benzaldehyde; and then taking the product and p-phenylenediamine as raw materials to obtain a series of bis-Schiff bases with a conjugated structure and a rigid plane through a condensation reaction of an aldehyde group and a primary amine. The technological synthesis is low in cost, high in yield, easily controllable in reaction conditions and simple in product purification. The new compounds have extremely good fluorescent performance, also have selectivity on metal ions, and are applicable to material field or sensor field.
Description
Technical field
The present invention relates to two Schiff's base of a kind of imidazoles phenyl aldehyde contracting Ursol D and preparation method thereof, this compound has rigid planar structure, show good fluorescence property, there is the C=N functional group containing lone-pair electron simultaneously, there is very strong coordination ability with metal ion, there is good ion selectivity.
Background technology
Imidazoles is a kind of five member ring heterocyclic compound that contains two nitrogen-atoms, as a kind of important heterogeneous ring compound, is extensively present in natural product.Imidazoles has very high biological activity, can be widely used in the aspects such as medicine, agricultural chemicals, dyestuff and photographic developer.In addition, glyoxaline compound, as organic nitrogen-containing heterogeneous ring compound, also has good coordination ability, occupies very important status in coordination chemistry.
Because imidazole molecule has a closed large π key, and the not sp of Cheng Jian of one of them nitrogen-atoms
2on track, have a pair of lone-pair electron, therefore it has aromaticity, and both aobvious slightly acidic, can show again weakly alkaline.This has just determined the diversity of imidazoles generation chemical reaction (particularly substitution reaction), generate the diversity of derivative, also determined that glyoxaline compound has such as ligand complex, the premium propertiess such as the transitivity of electronics, proton, have more determined that this compounds is with a wide range of applications.Glyoxaline compound has conjugate acid and base performance and complex coordination performance, enjoys the good reputation of " biological catalyst " " bio-ligand ".
Schiff base compounds, as a kind of important industrial chemicals, is applied very extensive.Have the physical material performances such as good optical, electrical, magnetic due to Schiff's base, the physiologically actives such as good ligancy and unique antibacterial, anticancer, weeding, make it be subject to extensive concern.At present carry out a lot of reports about imidazolium compounds in medicine, agricultural chemicals, field of fine chemical, but at present two the synthetic of Schiff's base of imidazoles have not been reported.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide the imidazoles phenyl aldehyde contracting Ursol D that a class is new two Schiff's base, this Schiff's base has good fluorescence property and ion selectivity energy, and this technique have easy to operate, cost is low, condition is easily controlled, productive rate advantages of higher.
Another object of the present invention is to provide the preparation method of the two Schiff's base of described imidazoles phenyl aldehyde contracting Ursol D.
Another object of the present invention is to provide the application of the two Schiff's base of described imidazoles phenyl aldehyde contracting Ursol D.
In order to realize such object, technical scheme of the present invention is as follows:
The two Schiff's base of a kind of imidazoles phenyl aldehyde contracting Ursol D, its structural formula is as follows:
R
1for methoxyl group, hydrogen, R
2for hydrogen, fluorine, chlorine, R
3for hydrogen, carboxyl, nitro, hydroxyl, cyano group.
Preferred R
1for methoxyl group, R
2for chlorine, R
3for nitro;
Wherein methoxyl group is outstanding electron-donating group, and chlorine atom has very strong electronegativity, and nitro has good electron attraction;
This compound is mainly used in Material Field or sensor field;
A preparation method for the two Schiff's base of imidazoles phenyl aldehyde contracting Ursol D, its preparation method is as follows:
1) take imidazoles or imdazole derivatives and p-Fluorobenzenecarboxaldehyde and be dissolved in solvent;
The mol ratio of described imidazoles or imdazole derivatives and p-Fluorobenzenecarboxaldehyde is 1:1～3:1; The mol ratio of described imidazoles or imdazole derivatives and solvent is 1:15～1:90; Described imdazole derivatives is 5-nitroimidazole, 2-methoxyl group imidazoles, the chloro-5-nitroimidazole of 4-; Described solvent is DMF, dimethyl sulfoxide (DMSO), ethanol;
The mol ratio of preferred imidazoles or imdazole derivatives and p-Fluorobenzenecarboxaldehyde is 1.5:1;
2) take salt of wormwood and join step 1) described solution, the mol ratio of imidazoles or imdazole derivatives and salt of wormwood is 1:1～1:4, at 50～120 DEG C, constant temperature stirs 10～20h, be cooled to after room temperature, pour in 100mL frozen water, have yellow solid to separate out, suction filtration, with ethyl alcohol recrystallization, obtain sterling, vacuum-drying obtain 4-imidazolyl benzaldehyde or imdazole derivatives phenyl aldehyde;
3) taking step 2) 4-imidazolyl benzaldehyde or imdazole derivatives phenyl aldehyde and Ursol D be dissolved in solvent;
Described 4-imidazolyl benzaldehyde or the mol ratio of imdazole derivatives phenyl aldehyde and Ursol D are 2:1～5:1;
The mol ratio of preferred 4-imidazolyl benzaldehyde or imdazole derivatives and Ursol D is 2:1;
Described 4-imidazolyl benzaldehyde or the mol ratio of imdazole derivatives phenyl aldehyde and solvent are 1:5～1:90;
Described solvent is DMF, dimethyl sulfoxide (DMSO), ethanol;
4) take hydrochloric acid and join step 3) in described mixing solutions, the mol ratio of 4-imidazolyl benzaldehyde or imdazole derivatives phenyl aldehyde and hydrochloric acid is 1:1～1:5, isothermal reaction 1～12h at 25～90 DEG C, underpressure distillation is except desolventizing, obtain yellow powder shape solid, purify by ethanol, methyl alcohol or re-crystallizing in ethyl acetate, vacuum-drying obtain the finished product;
Described recrystallization solvent used is ethanol, methyl alcohol or ethyl acetate.
The present invention reacts imidazole and its derivants with p-Fluorobenzenecarboxaldehyde, be prepared into 4-imidazolyl benzaldehyde or imdazole derivatives phenyl aldehyde, it is reacted to obtain to the two Schiff's base of a series of imidazoles phenyl aldehyde contracting Ursol D based on imidazoles with Ursol D, after tested, this compound has good fluorescence property and ion selectivity (the results are shown in accompanying drawing 5-10).
New compound of the present invention can be used as probe application in ion detection field, also can be used as fluorescent material for Material Field.
Brief description of the drawings:
(1) Fig. 1,2,3,4 is respectively the hydrogen nuclear magnetic resonance spectrogram of compound 1,2,3 and 4.
(2) Fig. 5,6 is respectively uv absorption spectra and the fluorescence spectrum figure of compound.
(3) Fig. 7,8,9,10 is respectively the fluorogram of compound to metalloform-selective.
Embodiment:
Technical scheme for a better understanding of the present invention, below is described in further detail by specific embodiment.
Embodiment 1
Take imidazoles 0.680g (10mmol), take p-Fluorobenzenecarboxaldehyde 1.240g (10mmol) and Anhydrous potassium carbonate 1.380g (10mmol), be dissolved in the N of 25mL, in dinethylformamide, join in the four-hole boiling flask of the 50mL that thermometer, whipping appts are housed.Isothermal reaction 20h at 60 DEG C, is cooled to after room temperature, pours in 100mL frozen water, has yellow solid to separate out, suction filtration, and with ethyl alcohol recrystallization, vacuum-drying 8h at 50 DEG C, obtains 4-imidazolyl benzaldehyde.
Take 4-imidazolyl benzaldehyde 0.172g (1mmol), take Ursol D 0.054g (0.500mmol), be dissolved in the DMF of 5mL, join in the single port flask of the 10mL that thermometer, whipping appts are housed.Then in above-mentioned mixed solution, add hydrochloric acid 0.073g (2mmol), constant temperature stirring reaction 12h at 25 DEG C, underpressure distillation is except desolventizing, obtain yellow powder shape solid, with ethyl alcohol recrystallization, 50 DEG C of vacuum-drying 6h, obtain final purpose product: compound 1 (the two Schiff's base of imidazoles phenyl aldehyde contracting Ursol D).Productive rate: 90%.
Ultimate analysis: C
26h
20n
6: %C:75.89 (75.00); %H:4.83 (4.81); %N:19.28 (20.19) (being observed value in bracket).
Compound 1 nmr analysis (nuclear magnetic spectrogram is shown in accompanying drawing 1):
Must table 1 by the structural formula to compound 1 and hydrogen nuclear magnetic resonance spectrum analysis.This compound has 10 kinds of hydrogen, and near the fignal center wherein occurring 7.96-7.76ppm is proton 1,2,10 fignal center, and its peak area is 3.09; The fignal center occurring at 8.75ppm annex is the fignal center of proton 3, and its peak area is 1.00; Near the fignal center occurring 7.40ppm is the fignal center of proton 4,6, and its peak area is 2.00; The fignal center occurring at 8.08ppm annex is the fignal center of proton 5,7, and its peak area is 2.04; Near the fignal center occurring 8.41ppm is the fignal center of proton 8, and its peak area is 0.99; Near the fignal center occurring 7.16ppm is the fignal center of proton 9, and its peak area is 1.01.This shows, the hydrogen nuclear magnetic resonance spectrogram of compound 1 has well met the structure of compound 1, i.e. the two Schiff's base of imidazoles phenyl aldehyde contracting Ursol D.
Table 1 compound 1
1the chemical shiftsum peak ownership of HNMR
S: unimodal; D: doublet; M: multiplet
Embodiment 2
Take 5-nitroimidazole 2.260g (20mmol), take p-Fluorobenzenecarboxaldehyde 1.860g (15mmol) and Anhydrous potassium carbonate 2.760g (20mmol), be dissolved in the N of 30mL, in dinethylformamide, join in the four-hole boiling flask of the 50mL that thermometer, whipping appts are housed.Isothermal reaction 16h at 80 DEG C, is cooled to after room temperature, pours in 100mL frozen water, has yellow solid to separate out, suction filtration, and with ethyl alcohol recrystallization, vacuum-drying 10h at 50 DEG C, obtains 4-(5-nitro-1-imidazolyl) phenyl aldehyde.
Take 4-(5-nitro-1-imidazolyl) phenyl aldehyde 0.217g (1mmol), take Ursol D 0.027g (0.250mmol), be dissolved in the DMF of 4mL, join in the single port flask of the 10mL that thermometer, whipping appts are housed.Then in above-mentioned mixed solution, add hydrochloric acid 0.107g (2.932mmol), constant temperature stirring reaction 10h at 50 DEG C, underpressure distillation is except desolventizing, obtain yellow powder shape solid, with ethyl alcohol recrystallization, 60 DEG C of vacuum-drying 6h obtain final purpose product: compound 2 (the two Schiff's base of 5-nitroimidazole phenyl aldehyde contracting Ursol D).Productive rate: 82%.
Ultimate analysis: C
26h
18n
8o
4: %C:62.08 (61.66); %H:3.57 (3.49); %N:21.68 (22.13); %O:12.67 (12.65) (being observed value in bracket).
Compound 2 nmr analysis (nuclear magnetic spectrogram is shown in accompanying drawing 2):
Must table 2 by the structural formula to compound 2 and hydrogen nuclear magnetic resonance spectrum analysis.This compound has 9 kinds of hydrogen, and near the fignal center wherein occurring 7.75ppm is the fignal center of proton 1,2, and its peak area is 2.00; The fignal center occurring at 8.88ppm annex is the fignal center of proton 3, and its peak area is 1.00; Near the fignal center occurring 7.40ppm is the fignal center of proton 4,6, and its peak area is 2.04; The fignal center occurring at 8.08ppm annex is the fignal center of proton 5,7, and its peak area is 2.00; Near the fignal center occurring 8.41ppm is the fignal center of proton 8, and its peak area is 1.01; Near the fignal center occurring 7.21ppm is the fignal center of proton 9, and its peak area is 1.01.This shows, the hydrogen nuclear magnetic resonance spectrogram of compound 2 has well met the structure of compound 2, i.e. the two Schiff's base of 5-nitroimidazole phenyl aldehyde contracting Ursol D.
Table 2 compound 2
1the chemical shiftsum peak ownership of HNMR
S: unimodal; D: doublet; M: multiplet
Embodiment 3
Take 2-methoxyl group imidazoles 2.940g (30mmol), take p-Fluorobenzenecarboxaldehyde 1.860g (15mmol) and Anhydrous potassium carbonate 4.140g (30mmol), be dissolved in the N of 40mL, in dinethylformamide, join in the four-hole boiling flask of the 100mL that thermometer, whipping appts are housed.Isothermal reaction 14h at 90 DEG C, is cooled to after room temperature, pours in 100mL frozen water, has yellow solid to separate out, suction filtration, and with ethyl alcohol recrystallization, vacuum-drying 8h at 60 DEG C, obtains 4-(2-methoxyl group-1-imidazolyl) phenyl aldehyde.
Take 4-(2-methoxyl group-1-imidazolyl) phenyl aldehyde 0.606 (3mmol), take Ursol D 0.130g (1.250mmol), be dissolved in the DMF of 4mL, join in the single port flask of the 10mL that thermometer, whipping appts are housed.Then in above-mentioned mixed solution, add hydrochloric acid 0.178g (4.877mmol), constant temperature stirring reaction 6h at 60 DEG C, underpressure distillation is except desolventizing, obtain yellow powder shape solid, with ethyl alcohol recrystallization, 50 DEG C of vacuum-drying 6h obtain final purpose product: compound 3 (the two Schiff's base of 2-methoxyl group imidazoles phenyl aldehyde contracting Ursol D).Productive rate: 84%.
Ultimate analysis: C
28h
26n
6o
2: %C:71.08 (70.29); %H:4.93 (5.44); %N:18.28 (17.57); %O:5.71 (6.69) (being observed value in bracket).
Compound 3 nmr analysis (nuclear magnetic spectrogram is shown in accompanying drawing 3):
Must table 3 by the structural formula to compound 3 and hydrogen nuclear magnetic resonance spectrum analysis.This compound has 10 kinds of hydrogen, and near the fignal center wherein occurring 6.65ppm is the fignal center of proton 1,2, and its peak area is 1.99; The fignal center occurring at 8.14ppm annex is the fignal center of proton 3, and its peak area is 1.00; Near the fignal center occurring 7.43-7.48ppm is proton 4,6,9 fignal center, and its peak area is 3.01; The fignal center occurring at 8.01ppm annex is the fignal center of proton 5,7, and its peak area is 2.00; Near the fignal center occurring 7.27ppm is the fignal center of proton 8, and its peak area is 1.00; Near the fignal center occurring 3.85ppm is the fignal center of proton 10, and its peak area is 2.99.This shows, the hydrogen nuclear magnetic resonance spectrogram of compound 3 has well met the structure of compound 3, i.e. the two Schiff's base of 2-methoxyl group imidazoles phenyl aldehyde contracting Ursol D.
Table 3 compound 3
1the chemical shiftsum peak ownership of HNMR
S: unimodal; D: doublet; M: multiplet
Embodiment 4
Take the chloro-5-nitroimidazole of 4-2.970g (20mmol), take p-Fluorobenzenecarboxaldehyde 0.992g (8mmol) and Anhydrous potassium carbonate 9.960g (70mmol), be dissolved in the N of 35mL, in dinethylformamide, join in the four-hole boiling flask of the 100mL that thermometer, whipping appts are housed.Isothermal reaction 12h at 100 DEG C, is cooled to after room temperature, pours in 100mL frozen water, has yellow solid to separate out, suction filtration, and with ethyl alcohol recrystallization, vacuum-drying 8h at 50 DEG C, obtains 4-(the chloro-5-nitro-1-of 4-imidazolyl) phenyl aldehyde.
Take 4-(the chloro-5-nitro-1-of 4-imidazolyl) phenyl aldehyde 0.758g (3mmol), take Ursol D 0.161g (1.505mmol), be dissolved in the DMF of 5mL, join in the single port flask of the 10mL that thermometer, whipping appts are housed.Then in above-mentioned mixed solution, add hydrochloric acid 0.365g (10mmol), constant temperature stirring reaction 5h at 70 DEG C, underpressure distillation is except desolventizing, obtain yellow powder shape solid, with ethyl alcohol recrystallization, 50 DEG C of vacuum-drying 6h obtain final purpose product: compound 4 (the two Schiff's base of the chloro-5-nitroimidazole of 4-phenyl aldehyde contracting Ursol D).Productive rate: 88%.
Ultimate analysis: C
26h
16n
8o
4cl
2: %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 observed value in bracket).
Compound 4 nmr analysis (nuclear magnetic spectrogram is shown in accompanying drawing 4):
Must table 4 by the structural formula to compound 4 and hydrogen nuclear magnetic resonance spectrum analysis.This compound has 8 kinds of hydrogen, and near the fignal center wherein occurring 7.42ppm is the fignal center of proton 1,2, and its peak area is 2.04; The fignal center occurring at 9.01ppm annex is the fignal center of proton 3, and its peak area is 0.99; Near the fignal center occurring 8.05ppm is the fignal center of proton 4,6, and its peak area is 1.99; The fignal center occurring at 7.68ppm annex is the fignal center of proton 5,7, and its peak area is 1.99; Near the fignal center occurring 8.56ppm is the fignal center of proton 8, and its peak area is 1.00.This shows, the hydrogen nuclear magnetic resonance spectrogram of compound 4 has well met the structure of compound 4, i.e. the two Schiff's base of the chloro-5-nitroimidazole of 4-phenyl aldehyde contracting Ursol D.
Table 4 compound 4
1the chemical shiftsum peak ownership of HNMR
S: unimodal; D: doublet; M: multiplet
Experimental example
1, compound fluorescence property test
The compound 1,2,3,4 of the purification process of learning from else's experience, utilizes DMF to dissolve, dilute, and is configured to 1.0 × 10
-5the sample solution of mol/L.Utilize the uv absorption spectra (the results are shown in accompanying drawing 5) of ultraviolet-visible pectrophotometer working sample, according to the uv-absorption maximum wavelength of the compound recording, utilize the fluorescence exciting wavelength of F-4600 fluorescent spectrophotometer assay compound, and measure the fluorescence spectrum (the results are shown in accompanying drawing 6) of compound.
2, utilize DMF to make solvent and prepare respectively 1.0 × 10
-5the compound 1,2,3,4 of mol/L and the 1:1 mixing solutions of metal ion.The fluorescence spectrum (the results are shown in accompanying drawing 7,8,9,10) of test compounds and metal ion solution.
Result of study shows: compound has fluorescence property, and compound 1 has good selectivity to cupric ion (II) simultaneously; Compound 2 has good selectivity for cadmium ion (II); Compound 3 has good selectivity for zine ion (II); Compound 4 (II) has good selectivity for cadmium ion.
Claims (6)
1. the two Schiff's base of imidazoles phenyl aldehyde contracting Ursol D, is characterized in that: its structural formula is as follows:
R
1for methoxyl group, hydrogen, R
2for hydrogen, fluorine, chlorine, R
3for hydrogen, carboxyl, nitro, hydroxyl, cyano group.
2. the application of compound as claimed in claim 1, is characterized in that: be applied to Material Field or sensor field.
3. the preparation method of the two Schiff's base of a kind of imidazoles phenyl aldehyde contracting Ursol D as claimed in claim 1, is characterized in that: its preparation method is as follows:
1) take imidazoles or imdazole derivatives and p-Fluorobenzenecarboxaldehyde and be dissolved in solvent;
The mol ratio of described imidazoles or imdazole derivatives and p-Fluorobenzenecarboxaldehyde is 1:1～3:1; The mol ratio of described imidazoles or imdazole derivatives and solvent is 1:15～1:90; Described imdazole derivatives is 5-nitroimidazole, 2-methoxyl group imidazoles, the chloro-5-nitroimidazole of 4-; Described solvent is DMF, dimethyl sulfoxide (DMSO), ethanol;
2) take salt of wormwood and join step 1) described solution, the mol ratio of imidazoles or imdazole derivatives and salt of wormwood is 1:1～1:4, at 50～120 DEG C, constant temperature stirs 10～20h, be cooled to after room temperature, pour in 100mL frozen water, have yellow solid to separate out, suction filtration, with ethyl alcohol recrystallization, obtain sterling, vacuum-drying obtain 4-imidazolyl benzaldehyde or imdazole derivatives phenyl aldehyde;
3) taking step 2) 4-imidazolyl benzaldehyde or imdazole derivatives phenyl aldehyde and Ursol D be dissolved in solvent;
Described 4-imidazolyl benzaldehyde or the mol ratio of imdazole derivatives phenyl aldehyde and Ursol D are 2:1～5:1;
Described 4-imidazolyl benzaldehyde or the mol ratio of imdazole derivatives phenyl aldehyde and solvent are 1:5～1:90;
Described solvent is DMF, dimethyl sulfoxide (DMSO), ethanol;
4) take hydrochloric acid and join step 3) in described mixing solutions, the mol ratio of 4-imidazolyl benzaldehyde or imdazole derivatives phenyl aldehyde and hydrochloric acid is 1:1～1:5, isothermal reaction 1～12h at 25～90 DEG C, underpressure distillation is except desolventizing, obtain yellow powder shape solid, purify by ethanol, methyl alcohol or re-crystallizing in ethyl acetate, vacuum-drying obtain the finished product.
4. the two Schiff's base of a kind of imidazoles phenyl aldehyde contracting Ursol D as claimed in claim 1, is characterized in that R in its structural formula
1for methoxyl group, R
2for chlorine, R
3for nitro.
5. the preparation method of the two Schiff's base of a kind of imidazoles phenyl aldehyde contracting Ursol D as claimed in claim 3, is characterized in that, the mol ratio of described imidazoles or imdazole derivatives and p-Fluorobenzenecarboxaldehyde is 1.5:1.
6. the preparation method of the two Schiff's base of a kind of imidazoles phenyl aldehyde contracting Ursol D as claimed in claim 3, is characterized in that, described 4-imidazolyl benzaldehyde or the mol ratio of imdazole derivatives and Ursol D are 2:1.
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Cited By (4)
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| CN105384701A (en) * | 2015-11-26 | 2016-03-09 | 齐鲁工业大学 | Benzotriazole benzaldehyde condensate ursol bis-Schiff base and preparation method thereof |
| CN106966981A (en) * | 2017-04-25 | 2017-07-21 | 陈宗源 | A kind of combined reactor and the method that pyrazolyl benzaldehyde-p-phenylenediamine bi-schiff base is prepared using the combined reactor |
| CN107314991A (en) * | 2017-05-16 | 2017-11-03 | 西北农林科技大学 | Schiff base compound as cyanide ion and copper ion fluorescence probe application |
| 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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| CN106966981A (en) * | 2017-04-25 | 2017-07-21 | 陈宗源 | A kind of combined reactor and the method that pyrazolyl benzaldehyde-p-phenylenediamine bi-schiff base is prepared using the combined reactor |
| CN106966981B (en) * | 2017-04-25 | 2020-08-18 | 陈宗源 | Combined reactor and method for preparing pyrazolyl benzaldehyde p-phenylenediamine bis-Schiff base by using same |
| CN107314991A (en) * | 2017-05-16 | 2017-11-03 | 西北农林科技大学 | Schiff base compound as cyanide ion and copper ion fluorescence probe application |
| 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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| CN104130192B (en) | 2017-05-24 |
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