CN102584623A - Azobenzene compound conjugated Schiff base compound and preparation method thereof - Google Patents
Azobenzene compound conjugated Schiff base compound and preparation method thereof Download PDFInfo
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- CN102584623A CN102584623A CN2011104379545A CN201110437954A CN102584623A CN 102584623 A CN102584623 A CN 102584623A CN 2011104379545 A CN2011104379545 A CN 2011104379545A CN 201110437954 A CN201110437954 A CN 201110437954A CN 102584623 A CN102584623 A CN 102584623A
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Abstract
The invention relates to an azobenzene compound conjugated Schiff base compound. A chemical structural formula of the azobenzene compound conjugated Schiff base compound is shown as the accompanying drawing. In the chemical structural formula, R1 is hydrogen or methyl, and R2 is aromatic substituent groups such as phenyl or naphthyl; and the azobenzene compound conjugated Schiff base compound is formed by p-aminoazobenzene and o-aminoazotoluene to be respectively condensed with aromatic aldehyde. A preparation method comprises the steps that amino substances and aldehyde group substances are subjected to heating back flow reaction for 3 to 8 hours in absolute ethyl alcohol under the proportional condition that the mole ratio of the amino substances to the aldehyde group substances is 1:(1.0-1.2), a large number of brown yellow solid products are separated out from the solution, and the absolute ethyl alcohol is used for recrystallization for 2 to 4 times after the suction filtration drying. The azobenzene compound conjugated Schiff base compound simultaneously contains azobenzol groups and Schiff base groups, compared with the single group molecule generating the relatively single performance, the azobenzene compound conjugated Schiff base compound has the advantages that the molecule processing performance (dispersivity and solubility) is improved, meanwhile, special functions of light, electricity, magnetism, biological medicine and the like are further obtained at the same time, and the azobenzene compound conjugated Schiff base compound can be widely applied to the fields of nonlinear optical materials, photoresponse memory devices, catalysis and the like.
Description
Technical field
The present invention relates to a kind of compound and preparation method thereof, particularly a kind of azobenzene compound and preparation method thereof.
Background technology
Nitrogen benzide is the photochromic molecules along anti-geometrical isomer that has of a quasi-representative; Molecule exists with thermodynamically stable trans (trans) generally speaking, under the effect of UV-light (λ < 370 nm) irradiation, can photoisomerization take place and becomes cis-structure (cis).Because the relative instability of cis molecular structure, can come back to trans state through visible light (λ>430 nm) irradiation or type of heating.Because azobenzene compound has high optical activity and storage density and short characteristics such as switching time; Be considered to rising optical record medium, thereby have application potential widely at aspects such as optical information storage, photoelectron, molecular switch, Electro-optical Modulation, integrated opticss.In addition; The Schiff bases compound is owing to contain the two keys of C=N; N atom on its hybridized orbital has lone-pair electron, has stronger coordination ability, has become the research focus of subjects such as material, chemistry, medicine, biology; Be widely used in Chemical Manufacture and scientific research activity, have important use widely at material and field of biology.
At present; Research about only containing nitrogen benzide or Schiff's base separate base compound is more; 02138674), contain azobenzene photochromicsm compound and the compound method thereof (application number/patent No.: of L-ethyl lactate chiral carbon 200910047192), contain terminal alkyne compound and verivate thereof, the purposes (application number/patent No.: 200510038187) etc. of nitrogen benzide like the preparation method of a kind of 2,2 ＇-dichlorohydrazobenzene (application number/patent No.:.The patent of relevant Schiff's base; 200910200947), contain 1 like a kind of method for preparing Schiff's base (application number/patent No.:; 2,4-triazole Schiff's base pyridazinone verivate and its production and use 201010041815), a kind of method (application number/patent No.: 201010156859) etc. of preparing amino acid schiff base metal complexes without solvent (application number/patent No.:.
In fact, in the production practical application, the organic molecule of functionalization often need contain multiple function substituted radical and the particular chemical structure satisfies various actual needs, and this requires people's complex design and rational functional compounds.At present,, can only produce single performance relatively such as photoisomerization or coordination respectively if only contain nitrogen benzide or only contain single substituted radical such as Schiff's base, this largely limit the rational Design on Plane of organic molecule, composite performance and large-scale application.The complex function schiff base compounds that contains azobenzene group and Schiff's base group simultaneously; Compare with the compound that only contains single substituted radical; When improving organic molecule processibility (like dispersiveness and solvability), can obtain to have light simultaneously, specific function such as electricity, magnetic and biological medicine.
Summary of the invention
The purpose of this invention is to provide a kind of compound conjugation schiff base compounds of nitrogen benzide that contains multi-functional substituted radical and special chemical structure and preparation method thereof.
Particular content of the present invention is:
One, the structural formula of the compound conjugation schiff base compounds of nitrogen benzide is following:
In the formula, R
1=hydrogen, methyl;
R
2=aromatic substituent group.
The compound conjugation schiff base compounds of described nitrogen benzide is formed with the aromatic aldehyde condensation respectively by P-aminoazobenzene, o-aminoazotoluene.
The structural formula of above-mentioned P-aminoazobenzene, o-aminoazotoluene is:
Two, above-mentionedThe preparation method of the compound conjugation schiff base compounds of nitrogen benzide:
Mol ratio in amino substance and aldehyde radical thing is under the ratio condition of 1:1.0-1.2; With its in absolute ethyl alcohol heating reflux reaction 3-8 hour; Solution is separated out a large amount of pale brown look solid products; With absolute ethyl alcohol recrystallization 2-4 time, obtain the compound conjugation schiff base compounds of nitrogen benzide (productive rate 80-95%) after the suction filtration drying.
Cis-trans isomerism can take place in the compound conjugation schiff base compounds of prepared nitrogen benzide in solution, produce photochromic behavior.The above-mentioned conjugation schiff base compounds that contains azobenzene group for preparing is dissolved in the absolute ethyl alcohol, is used for the mensuration of uv-vis spectra.Utilize the UV-irradiation compound solution of 365 nm wavelength, observation is at the ultraviolet-visible spectrogram of different UV-irradiation time.Its medium wavelength is to be near 364 nm that the transconfiguration of nitrogen benzide, wavelength are to be the cis-configuration of nitrogen benzide near 452 nm.Increase along with irradiation time; Wavelength is that near the peak intensity the 364nm weakens gradually, and wavelength is that near the absorption peak the 452nm raises gradually, and trans conformation transition to cis can take place under illumination the expression azo-benzene units; Simultaneously, slight blue shift phenomenon has taken place in the crest of transconfiguration.
The present invention compared with prior art has following advantage: the present invention contains azobenzene group and Schiff's base group simultaneously; Produce single relatively performance with single group molecule; When improving molecule processibility (like dispersiveness and solvability); Further obtain to have specific functions such as light, electricity, magnetic and biological medicine, can be widely used in fields such as nonlinear optical material, photoresponse memory device and catalysis.
Description of drawings
Fig. 1 is the chemical structural drawing of the compound conjugation schiff base compounds of nitrogen benzide that obtained of embodiment of the invention 1-4.
Fig. 2 is the KBr compressing tablet ir spectra of the compound conjugation schiff base compounds of nitrogen benzide that obtained of embodiment of the invention 1-4.
Fig. 3 is the ultraviolet-visible spectrogram of the compound conjugation schiff base compounds of the nitrogen benzide Sal-Azo ethanolic soln that obtained of the embodiment of the invention 1 in the different UV-irradiation time.
Fig. 4 is the ultraviolet-visible spectrogram of the compound conjugation schiff base compounds of the nitrogen benzide Sal-Me-Azo ethanolic soln that obtained of the embodiment of the invention 2 in the different UV-irradiation time.
Embodiment
With 1.00 g P-aminoazobenzene (5.1 mmol) and 0.62 g salicylic aldehyde (5.1 mmol) back flow reaction 3 hours in absolute ethyl alcohol together; Solution is separated out a large amount of yellow solids; After the suction filtration drying with absolute ethyl alcohol recrystallization 2 times; Get product Sal-Azo (1.45 g, 95%) after the drying, its chemical structural formula is as shown in Figure 1.The nuclear magnetic resonance result of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Sal-Azo does
1H NMR (400MHz, CDCl
3): 6.96 (t, 1H); 7.05 (d, 1H); 7.42 (t, 4H); 7.55 (m, 3H); 7.93 (d, 2H); 8.01 (d, 2H); 8.69 (s, 1H, CH=N); 13.06 (s, 1H, OH). and as shown in Figure 2, the KBr compressing tablet ir spectra of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Sal-Azo.The product that nuclear-magnetism and infrared data explanation are obtained is a target compound.As shown in Figure 3, the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Sal-Azo ethanolic soln explains that at the ultraviolet-visible spectrogram of different UV-irradiation time it can cis-trans isomerism take place in solution, produces photochromic behavior.
With 0.50 g o-aminoazotoluene (2.2 mmol) and 0.32 g salicylic aldehyde (2.6 mmol) back flow reaction 8 hours in absolute ethyl alcohol together; Solution is separated out a large amount of yellow solids; After the suction filtration drying with absolute ethyl alcohol recrystallization 4 times; Get product Sal-Me-Azo (0.64 g, 88%) after the drying, its chemical structural formula is as shown in Figure 1.The nuclear magnetic resonance result of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Sal-Me-Azo does
1H NMR (400MHz, CDCl
3): 2.50 (s, 3H); 2.74 (s, 3H); 6.98 (t, 1H); 7.05 (d, 1H); 7.25 (m, 2H); 7.35 (s, 2H); 7.43 (t, 2H); 7.63 (d, 1H); 7.84 (d, 2H); 8.65 (s, 1H, CH=N); 13.24 (s, 1H, OH). and as shown in Figure 2, the KBr compressing tablet ir spectra of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Sal-Me-Azo.The product that nuclear-magnetism and infrared data explanation are obtained is a target compound.As shown in Figure 4, the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Sal-Me-Azo ethanolic soln explains that at the ultraviolet-visible spectrogram of different UV-irradiation time it can cis-trans isomerism take place in solution, produces photochromic behavior.
With 1.00 g P-aminoazobenzene (5.1 mmol) and 0.88 g 2-hydroxyl-1-naphthaldehyde (5.1 mmol) back flow reaction 3 hours in absolute ethyl alcohol together; Solution is separated out a large amount of yellow solids; After the suction filtration drying with absolute ethyl alcohol recrystallization 3 times; Get product Np-Azo (1.61 g, 90%) after the drying, its chemical structural formula is as shown in Figure 1.The nuclear magnetic resonance result of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Np-Azo does
1H NMR (400MHz, CDCl
3): 7.10 (d, 1H); 7.36 (t, 1H); 7.54 (m, 6H); 7.72 (d, 1H); 7.83 (d, 1H); 7.94 (d, 2H); 8.03 (d, 2H); 8.13 (d, 1H); 9.41 (s, 1H, CH=N); 15.37 (s, 1H, OH). and as shown in Figure 2, the KBr compressing tablet ir spectra of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Np-Azo.The product that nuclear-magnetism and infrared data explanation are obtained is a target compound.
With 0.50 g o-aminoazotoluene (2.2 mmol) and 0.45 g 2-hydroxyl-1-naphthaldehyde (2.6 mmol) back flow reaction 8 hours in absolute ethyl alcohol together; Solution is separated out a large amount of yellow solids; After the suction filtration drying with absolute ethyl alcohol recrystallization 4 times; Get product Np-Me-Azo (0.66 g, 80%) after the drying, its chemical structural formula is as shown in Figure 1.The nuclear magnetic resonance result of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Np-Me-Azo does
1H NMR (400MHz, CDCl
3): 2.59 (s, 3H); 2.75 (s, 3H); 7.10 (d, 1H); 7.26 (s, 1H); 7.36 (s, 3H); 7.47 (d, 1H); 7.55 (t, 1H); 7.66 (d, 1H); 7.73 (d, 1H); 7.83 (d, 1H); 7.90 (d, 2H); 8.14 (d, 1H); 9.40 (s, 1H, CH=N); 15.61 (s, 1H, OH). and as shown in Figure 2, the KBr compressing tablet ir spectra of the compound conjugation schiff base compounds of the nitrogen benzide that is obtained Np-Me-Azo.The product that nuclear-magnetism and infrared data explanation are obtained is a target compound.
Claims (3)
1. compound conjugation schiff base compounds of nitrogen benzide, it is characterized in that: contain azobenzene group and Schiff's base group, its chemical structural formula is:
In chemical structural formula, R
1Be hydrogen or methyl, R
2Be aromatic substituent group.
2. the compound conjugation schiff base compounds of nitrogen benzide according to claim 1 is characterized in that: the described conjugation schiff base compounds that contains azobenzene group is formed with the aromatic aldehyde condensation respectively by P-aminoazobenzene, o-aminoazotoluene.
3. the preparation method of the compound conjugation schiff base compounds of nitrogen benzide; It is characterized in that: in amino substance: the ratio of aldehyde radical thing=mol ratio 1:1.0-1.2; With they in absolute ethyl alcohol heating reflux reaction 3-8 hour together; Solution is separated out a large amount of pale brown look solid products, after the suction filtration drying with absolute ethyl alcohol recrystallization 2-4 time.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850262A (en) * | 2012-10-10 | 2013-01-02 | 咸阳师范学院 | Alkylbenzene end group optomagnetic controllable liquid crystal compound containing Schiff base structure and preparation method thereof |
| CN102850263A (en) * | 2012-10-10 | 2013-01-02 | 咸阳师范学院 | Alkyl biphenyl end group optomagnetic controllable liquid crystal compound containing Schiff base structure and synthetic method thereof |
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| JPH01204902A (en) * | 1988-02-12 | 1989-08-17 | Dainippon Ink & Chem Inc | Photocurable resin composition |
| CN1415600A (en) * | 2002-11-23 | 2003-05-07 | 宋伟 | Method for preparing2,2'-dichlorohydrazobenzene |
| CN101492389A (en) * | 2009-03-06 | 2009-07-29 | 东华大学 | Azobenzene photochromicsm compound containing L-ethyl lactate chiral carbon and synthesis thereof |
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2011
- 2011-12-23 CN CN2011104379545A patent/CN102584623A/en active Pending
Patent Citations (3)
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| JPH01204902A (en) * | 1988-02-12 | 1989-08-17 | Dainippon Ink & Chem Inc | Photocurable resin composition |
| CN1415600A (en) * | 2002-11-23 | 2003-05-07 | 宋伟 | Method for preparing2,2'-dichlorohydrazobenzene |
| CN101492389A (en) * | 2009-03-06 | 2009-07-29 | 东华大学 | Azobenzene photochromicsm compound containing L-ethyl lactate chiral carbon and synthesis thereof |
Non-Patent Citations (3)
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| TIFENG JIAO等: "Optical property and photoisomerization of some functional azobenzene derivatives with aromatic substituted groups", 《APPLIED MECHANICS AND MATERIALS》, vol. 121126, 24 October 2011 (2011-10-24), pages 1009 - 1013 * |
| TIFENG JIAO等: "Synthesis and characterization of some functional schiff base derivatives with azobenzene substituted groups", 《ADVANCED MATERIALS RESEARCH》, vol. 187198, 1 February 2011 (2011-02-01), pages 623 - 626 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850262A (en) * | 2012-10-10 | 2013-01-02 | 咸阳师范学院 | Alkylbenzene end group optomagnetic controllable liquid crystal compound containing Schiff base structure and preparation method thereof |
| CN102850263A (en) * | 2012-10-10 | 2013-01-02 | 咸阳师范学院 | Alkyl biphenyl end group optomagnetic controllable liquid crystal compound containing Schiff base structure and synthetic method thereof |
| CN102850263B (en) * | 2012-10-10 | 2014-07-09 | 咸阳师范学院 | Alkyl biphenyl end group optomagnetic controllable liquid crystal compound containing Schiff base structure and synthetic method thereof |
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Application publication date: 20120718 |