CN102911111A - Carbazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof - Google Patents
Carbazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof Download PDFInfo
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- CN102911111A CN102911111A CN2012104436858A CN201210443685A CN102911111A CN 102911111 A CN102911111 A CN 102911111A CN 2012104436858 A CN2012104436858 A CN 2012104436858A CN 201210443685 A CN201210443685 A CN 201210443685A CN 102911111 A CN102911111 A CN 102911111A
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- FDTIWOSIDUPTMA-UHFFFAOYSA-N c(cc1c2ccccc22)ccc1[n]2-c(cc1)ccc1Nc(cc1)ccc1Nc(cc1)ccc1-[n]1c(cccc2)c2c2c1cccc2 Chemical compound c(cc1c2ccccc22)ccc1[n]2-c(cc1)ccc1Nc(cc1)ccc1Nc(cc1)ccc1-[n]1c(cccc2)c2c2c1cccc2 FDTIWOSIDUPTMA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to carbazole benzaldehyde-p-phenylenediamine bi-schiff base and a preparation method thereof. Bi-schiff base with a conjugated structure is obtained by the condensation reaction of aldehyde group and primary amine by taking p-phenylenediamine, carbazole and p-fluorobenzaldehyde as raw materials. According to the process, the synthetic cost is low, the yield is high, the reaction condition is moderate, and the product is easy to purify. Therefore the compound has the conjugated and rigid plane structure, so that the strong fluorescence is shown, the fluorescent light of the Cu2+ compound has the strong enhancement action, so that the compound can be used as a Cu2+ fluorescence probe and is applied to the field of fluorescence probes.
Description
Technical field:
The present invention relates to two Schiff's base of a kind of carbazole phenyl aldehyde contracting Ursol D and preparation method thereof, this Schiff's base has good fluorescence property, and can complexation of metal ions, can be used as the metal-ion fluorescent probe.
Background technology:
Carbazole is an electron rich virtue heterocycle, has good electron conjugated plane, is the first-selected parent nucleus of many fluorescent chemicalses therefore.In addition, the carbazole ring is easy to carry out structural modification, and therefore, carbazole and derivative thereof have been furtherd investigate as optical material and Application and Development in addition.
Schiff's base refers to that a class contains the compound of C=N group, has lone-pair electron on the N atom, so that Schiff's base becomes the important organic ligand of a class.If can research and develop a kind of Schiff's base with fluorescence property, since Schiff's base can with metallic ion coordination, so with the Schiff's base of metallic ion coordination because the variation of its space structure, its fluorescence property also can change thereupon, some behavioural characteristic that therefore just can follow the trail of by the variation of Schiff's base fluorescence property metal ion.Here it is in recent years, studies hotter metal-ion fluorescent probe.And about the research of this problem, people have made extensive work.For example, have the investigator to utilize N-ethyl carbazole-3-formaldehyde and quadrol to synthesize N-ethyl carbazole schiff base compounds for raw material, and studied the impact of each metal ion species on its fluorescence property, the result shows Cu
2+Its fluorescence of quencher can be used as and surveys Cu effectively
2+Fluorescent probe [functional materials, 2011,9 (42): 1588-1590].In addition, numerous investigators have also done large quantity research for other some metal-ion fluorescent probes, such as Zn
2+, Ni
2+, Co
2+Etc..
Schiff base metal ion fluorescence probe has a good application prospect because of it, and investigators have done a large amount of research work.But, owing to have the shortcomings such as the fluorescence property of shortage, fluorescence Schiff's base of the fluorescence Schiff's base of novel texture is bad, restricted to a certain extent the use of Schiff's base fluorescent probe.For these problems, the invention provides the two Schiff's base of a kind of new carbazole phenyl aldehyde contracting Ursol D, this Schiff's base has good fluorescent emission in solution.Through retrieval, this schiff base structure has no relevant report.
Summary of the invention:
The objective of the invention is for the deficiencies in the prior art, provide a kind of new carbazole phenyl aldehyde contracting phenylenediamine two Schiff's base, this Schiff's base has the good fluorescence performance, can be used as the metal-ion fluorescent probe.And this technique has, and cost is low, easy and simple to handle, mild condition, productive rate advantages of higher.
Another object of the present invention provides the preparation method of the two Schiff's base of described carbazole phenyl aldehyde contracting Ursol D.
Another object of the present invention provides the application of the two Schiff's base of described carbazole phenyl aldehyde contracting Ursol D.
In order to realize such purpose, adopting carbazole and p-Fluorobenzenecarboxaldehyde in the technical scheme of the present invention is that raw material has prepared the carbazole phenyl aldehyde, utilize again carbazole phenyl aldehyde and cheap Ursol D to be raw material, obtained the two Schiff's base of a kind of carbazole phenyl aldehyde contracting phenylenediamine.
The present invention is achieved by the following measures:
The two Schiff's base of the new carbazole phenyl aldehyde contracting Ursol D that the present invention relates to, its chemical structure is as follows:
The reaction principle of preparation formula of the present invention (I) compound is as follows:
(1) preparation of carbazole phenyl aldehyde
(2) preparation of the two Schiff's base of carbazole phenyl aldehyde contracting phenylenediamine
The method of preparation formula of the present invention (I) compound is as follows:
(1) preparation of carbazole phenyl aldehyde
The carbazole phenyl aldehyde prepares according to bibliographical information.
(2) preparation of the two Schiff's base of carbazole phenyl aldehyde contracting phenylenediamine
Take by weighing a certain amount of carbazole phenyl aldehyde and be dissolved in solvent, start stirring, until the carbazole phenyl aldehyde all dissolves, add a certain amount of Ursol D, add an amount of weak acid, temperature control is at 50 ~ 100 ℃, reaction for some time has obtained yellow Schiff's base powder, and powder is selected suitable solvent recrystallization, obtained pure Schiff's base, vacuum-drying namely gets product.
Concrete steps are as follows:
1) take by weighing the carbazole phenyl aldehyde and be dissolved in solvent, the mol ratio of carbazole phenyl aldehyde and solvent is 1:10 ~ 1:100;
2) take by weighing Ursol D and be dissolved in the described solution of step 1), the mol ratio of Ursol D and carbazole phenyl aldehyde is 1:2 ~ 1:8;
3) measure a certain amount of weak acid and add step 2) in the described solution, the consumption of weak acid is 1 ~ 8d;
4) start stirring and begin reaction, at 50 ~ 75 ℃ of lower isothermal reaction 2 ~ 12h, obtained yellow Schiff's base powder, powder is selected suitable solvent recrystallization, namely gets sterling.
Preferably, solvent is methyl alcohol, ethanol or acetone.
Preferably, weak acid is formic acid or acetic acid.
Preferably, the used solvent of recrystallization is ethanol, chloroform or methylene dichloride.
The present invention reacts carbazole phenyl aldehyde and cheap Ursol D, has obtained a kind of novel compound, and after tested, these compounds all have good fluorescent emission, and can be used as Cu
2+Fluorescent probe (the results are shown in accompanying drawing).
Compound of the present invention can be used as fluorescent probe and is applied to the probe field.
Embodiment:
Technical scheme for a better understanding of the present invention below is described in further detail by specific embodiment.
Embodiment 1:
Taking by weighing carbazole phenyl aldehyde 0.54g (0.002mol) is dissolved in the 30ml methyl alcohol, start stirring, until the carbazole phenyl aldehyde all dissolves, add Ursol D 0.1g (0.001mol), add 1d formic acid, temperature control is at 60 ℃, and reaction 2h has obtained yellow Schiff's base powder, powder is selected Gossypol recrystallized from chloroform, obtained pure Schiff's base, vacuum-drying namely gets compound 1, productive rate: 70%.
P1 (reactant: carbazole phenyl aldehyde, Ursol D)
H
1?NMR(400MHz,d-DMSO)?:δ8.66(s,1H),8.17(t,J=10.0,4H),7.74(d,J=4.0,2H),7.52(d,J=8.0,2H),7.45(t,J=8.0,2H),7.39(s,2H),7.32(t,J=8.0,2H)；
Ultimate analysis: C
44H
30N
4: %C85.97 (85.98); %H4.92 (4.91); 9.10 be measured value in the bracket (9.11);
MS(ESP)m/z:614.30(M)。
Embodiment 2:
Take by weighing carbazole phenyl aldehyde 1.08g (0.004mol) and be dissolved in the 50ml ethanol, start stirring, until the carbazole phenyl aldehyde all dissolves, add Ursol D 0.1g (0.001mol), add the 5d glacial acetic acid, temperature control reacts 6h at 75 ℃, obtained yellow Schiff's base powder, powder is selected Gossypol recrystallized from chloroform, has obtained pure Schiff's base, and vacuum-drying namely gets compound 1, productive rate: 67%, the compound structure characterization data is seen embodiment 1.
Embodiment 3:
Take by weighing carbazole phenyl aldehyde 2.16g (0.008mol) and be dissolved in the 80ml acetone, start stirring, until the carbazole phenyl aldehyde all dissolves, add Ursol D 0.1g (0.001mol), add 8d formic acid, temperature control reacts 8h at 50 ℃, obtained yellow Schiff's base powder, powder is selected the methylene dichloride recrystallization, has obtained pure Schiff's base, and vacuum-drying namely gets compound 1, productive rate: 53%, the compound structure characterization data is seen embodiment 1.
Embodiment 4:
Take by weighing carbazole phenyl aldehyde 1.08g (0.004mol) and be dissolved in the 100ml methyl alcohol, start stirring, until the carbazole phenyl aldehyde all dissolves, add Ursol D 0.1g (0.001mol), add the 3d glacial acetic acid, temperature control reacts 12h at 65 ℃, obtained yellow Schiff's base powder, powder is selected ethyl alcohol recrystallization, has obtained pure Schiff's base, and vacuum-drying namely gets compound 1, productive rate: 50%, the compound structure characterization data is seen embodiment 1.
Experimental example:
1. the fluorescence property of compound 1 research
Embodiment 1 sample of the purification process of learning from else's experience with the DMSO dissolving, is mixed with 1.0x10
-5The sample solution of mol/ml.
Utilize the respectively ultra-violet absorption spectrum of working sample of ultraviolet-visible pectrophotometer, find its uv-absorption maximum wavelength, so with this as fluorescence exciting wavelength, utilize the fluorescence spectrum (the results are shown in accompanying drawing 1) of fluorescent spectrophotometer assay compound.
Result of study shows: compound has good fluorescent emission.
2. metal ion is on the impact of its fluorescence property
Preparation 1.0x10
-5Mol/ml's contains Cu (NO
3)
2, Fe (NO
3)
2, Zn (NO
3)
2, Ni (NO
3)
2DMSO solution, get respectively the above-mentioned 1.0x10 that has prepared
-5The DMSO solution of the compound 1 of mol/ml makes it mix with 1:1 with metal ion solution, the fluorescence spectrum of test mixing solution.(the results are shown in accompanying drawing 2 ~ 3)
Result of study shows: Cu
2+, Fe
2+, Zn
2+, Ni
2+All the fluorescence intensity of compound there is certain increase effect, but Cu
2+The effect of increase the most obvious, can conclude that thus compound 1 can be used as Cu
2+Fluorescent probe.
Description of drawings:
The fluorogram of accompanying drawing 1-compound 1 in DMSO.
The fluorogram of accompanying drawing 2-compound 1 and each metal ion solution mixture.
Claims (6)
1. two Schiff's base of a carbazole phenyl aldehyde contracting Ursol D, it is characterized in that: its structural formula is as follows:
2. the as claimed in claim 1 application of compound is characterized in that: be applied to the fluorescent probe field.
3. the preparation method of the two Schiff's base of a carbazole phenyl aldehyde contracting phenylenediamine claimed in claim 1, it is characterized in that: its preparation method is as follows:
1) take by weighing the carbazole phenyl aldehyde and be dissolved in solvent, the mol ratio of carbazole phenyl aldehyde and solvent is 1:10 ~ 1:100;
2) take by weighing diamine compounds and be dissolved in the described solution of step 1), the mol ratio of Ursol D and carbazole phenyl aldehyde is 1:2 ~ 1:8;
3) measure a certain amount of weak acid and add step 2) in the described solution, the consumption of weak acid is 1 ~ 8d;
4) start stirring and begin reaction, at 50 ~ 75 ℃ of lower isothermal reaction 2 ~ 12h, obtained yellow Schiff's base powder, powder is selected suitable solvent recrystallization, namely gets sterling.
4. the preparation method of compound as claimed in claim 3, it is characterized in that: solvent is methyl alcohol, ethanol or acetone.
5. the preparation method of compound as claimed in claim 3, it is characterized in that: weak acid is formic acid or acetic acid.
6. the preparation method of compound as claimed in claim 3, it is characterized in that: the used solvent of recrystallization is ethanol, chloroform or methylene dichloride.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119286A (en) * | 2014-07-30 | 2014-10-29 | 齐鲁工业大学 | Condensed triazole benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof |
| CN104130192A (en) * | 2014-07-30 | 2014-11-05 | 齐鲁工业大学 | Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof |
| CN105541809A (en) * | 2016-03-14 | 2016-05-04 | 济南正骐生物科技有限公司 | Melamine condensed carbazole benzaldehyde tris-Schiff base and preparation method thereof |
| CN105585560A (en) * | 2016-03-14 | 2016-05-18 | 济南正骐生物科技有限公司 | Melamine shrinkage carbazole formaldehyde single Schiff base and preparation method thereof |
| CN105622586A (en) * | 2016-03-14 | 2016-06-01 | 济南正骐生物科技有限公司 | Melamine carbazole formaldehyde Schiff base and preparation method thereof |
| CN105646460A (en) * | 2016-03-21 | 2016-06-08 | 济南正骐生物科技有限公司 | Melamine condensed carbazole formaldehyde bis-schiff base and preparation method thereof |
| CN105669656A (en) * | 2016-03-14 | 2016-06-15 | 济南正骐生物科技有限公司 | Melamine carbazole benzaldehyde bis-schiff base and preparation method thereof |
| CN105712980A (en) * | 2016-03-14 | 2016-06-29 | 济南正骐生物科技有限公司 | Melamine and shrinkage carbazole benzaldehyde single schiff base and preparation method thereof |
| CN113549004A (en) * | 2021-06-28 | 2021-10-26 | 淮阴师范学院 | 1-pyrene formaldehyde condensation 3-amino-9-ethyl carbazole Schiff base compound and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119286A (en) * | 2014-07-30 | 2014-10-29 | 齐鲁工业大学 | Condensed triazole benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof |
| CN104130192A (en) * | 2014-07-30 | 2014-11-05 | 齐鲁工业大学 | Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof |
| CN104130192B (en) * | 2014-07-30 | 2017-05-24 | 齐鲁工业大学 | Imidazolyl-benzaldehyde p-phenylenediamine bis-Schiff base and preparation method thereof |
| CN104119286B (en) * | 2014-07-30 | 2017-06-20 | 淄博职业学院 | A kind of triazole benzaldehyde-p-phenylenediamine bi-schiff base and preparation method thereof |
| CN105541809A (en) * | 2016-03-14 | 2016-05-04 | 济南正骐生物科技有限公司 | Melamine condensed carbazole benzaldehyde tris-Schiff base and preparation method thereof |
| CN105585560A (en) * | 2016-03-14 | 2016-05-18 | 济南正骐生物科技有限公司 | Melamine shrinkage carbazole formaldehyde single Schiff base and preparation method thereof |
| CN105622586A (en) * | 2016-03-14 | 2016-06-01 | 济南正骐生物科技有限公司 | Melamine carbazole formaldehyde Schiff base and preparation method thereof |
| CN105669656A (en) * | 2016-03-14 | 2016-06-15 | 济南正骐生物科技有限公司 | Melamine carbazole benzaldehyde bis-schiff base and preparation method thereof |
| CN105712980A (en) * | 2016-03-14 | 2016-06-29 | 济南正骐生物科技有限公司 | Melamine and shrinkage carbazole benzaldehyde single schiff base and preparation method thereof |
| CN105646460A (en) * | 2016-03-21 | 2016-06-08 | 济南正骐生物科技有限公司 | Melamine condensed carbazole formaldehyde bis-schiff base and preparation method thereof |
| CN113549004A (en) * | 2021-06-28 | 2021-10-26 | 淮阴师范学院 | 1-pyrene formaldehyde condensation 3-amino-9-ethyl carbazole Schiff base compound and preparation method and application thereof |
| CN113549004B (en) * | 2021-06-28 | 2023-09-08 | 淮阴师范学院 | 1-pyrene formaldehyde condensed 3-amino-9-ethyl carbazole Schiff base compound as well as preparation method and application thereof |
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