CN101440221A - Azobenzol dye compound and preparation thereof - Google Patents
Azobenzol dye compound and preparation thereof Download PDFInfo
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- CN101440221A CN101440221A CNA2008102401519A CN200810240151A CN101440221A CN 101440221 A CN101440221 A CN 101440221A CN A2008102401519 A CNA2008102401519 A CN A2008102401519A CN 200810240151 A CN200810240151 A CN 200810240151A CN 101440221 A CN101440221 A CN 101440221A
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Abstract
The invention provides an azobenzene dyestuff compound and a preparation method thereof, which belong to the field of optical switch and optical storage. The structure of the azobenzene dyestuff compound is shown as a formula (I), wherein n is an integer of between 0 and 8, and m is an integer of between 0 and 3. The azobenzene dyestuff compound has obvious phototropy under ultraviolet irradiation, and can improve the controllability of an azobenzene chromophore in the process of phototropy. The invention also provides the preparation method of the compound. The azobenzene dyestuff compound and the preparation method thereof have excellent development prospect in the field of optical switch and optical storage. In the formula (I), n is the integer of between 0 and 8, and m is the integer of between 0 and 3.
Description
Technical field
The present invention relates to a kind of preparation and application thereof of azobenzol dye compound, especially be with a wide range of applications in fields such as photoswitch and optical storages.
Background technology
The photic cis-trans isomerism of reversible, can take place and change, be i.e. photochromism under UV-light or visible light radiation as dye composition in azobenzene derivatives.The research of azo dyestuff cpds in information storage and optical recording material field enjoys people's favor, is applied in fields such as optical information material, molecular wire, molecular switches in succession.Azoic dyestuff is not only and is about to the listing capacity is the first-selected object of DVD-R (the digital versatile disc recordable) optical disk medium of 4.7GB, and might become the storage media of third generation compact disc recordable HD-DV-R (high density DVD-R).In addition, the photochromic property of azo-compound uniqueness, has huge application potential aspect the storage media that can wipe re-write optical disk, so, azo-compound has caused people's great attention as the important high-density of a class, multifunctional optical disk storage medium, will become the another new research focus of optical disk medium.
Because azobenzene dye has photo and thermal stability preferably, solvability and the characteristics that prepare easily, the aspects such as photochromic behavior of azobenzene derivatives in solvent obtained extensive studies.Replacing azobenzene compound also becomes the focus of people's research.Discover that no matter the para-orientation azobenzene derivatives is power supply or electron withdrawing group always quickens isomerization reaction, this makes that this class azobenzene derivatives photoresponse speed is fast, and photic along anti-change process easy-regulating not, application is met difficulty.Simultaneously, have and discover that intramolecularly reactive force such as hydrogen bond etc. also have the significant effects effect to azobenzene compound photochromic, can be so that the stability of cis-azobenzene derivative improves greatly.For this reason, the ortho position that we have prepared a kind of azo group is respectively the azobenzol dye compound of hydroxyl and alkyl, the intramolecularly reactive force of hydroxyl and alkyl group makes its cis-structure more stable, thereby can improve the not shortcoming of easy-regulating of the photochromic process of azo chromophore to a certain extent.
If the azobenzol dye compound that this type of ortho position replaces is introduced in the polymer materials, can improve the stability and the adjustable ability of optical information material greatly, have broad application prospects in fields such as the optical communication in future and light guides.
Summary of the invention
The technical solution used in the present invention is:
A kind of azobenzol dye compound, structure is suc as formula shown in (I):
In the formula (I), n is 0～8 integer, and m is 0～3 integer.
The invention still further relates to the preparation method of the described azobenzol dye compound of preparation, described method is as follows: below step is
Two steps:
(1) compound shown in the formula (II) is carried out diazotization reaction at diazo reagent in-5～0 ℃ ice-water bath and obtained diazonium salt in 2 hours; Compound shown in the formula (II) with the amount of substance ratio of diazo reagent is: 1:1.0～1.10;
In the formula (II), n is 0～8 integer; Diazo reagent is the mixing solutions of hydrochloric acid and acetate and Sodium Nitrite, perhaps the mixing solutions of sulfuric acid and acetate and Sodium Nitrite;
(2) compound shown in step (1) gained diazonium salt and the formula (III) is carried out coupled reaction; Compound amount of substance ratio shown in diazonium salt and the formula (III) is: 1.0～1.15:1; Coupled reaction is at the Na of 1～2mol/L
2CO
3Carry out in the solution, control pH ≈ 7.5, temperature of reaction is 35 ℃ and reacted 5 hours down, reacted 2 hours down at 35 ℃～70 ℃ again, to pH=2, wash with hcl acidifying, filter, after the vacuum-drying, be the mixed solvent recrystallization of the ethanol of 1.0～1.5:1 and water with volume ratio after, promptly get described azobenzol dye compound;
In the formula (III), m is 0～3 integer.
The compound of The compounds of this invention shown in can through type (II) carries out doazo reaction with the known method of those skilled in the art and obtains diazonium salt, carries out with the known method of those skilled in the art with the compound shown in the formula (III) that coupled reaction is synthetic to obtain the compound shown in the formula (I) again.
Described diazotization reaction and coupled reaction are this area common reactant, and its popular response condition also is applicable to the preparation of The compounds of this invention, adopt following reaction conditions among the present invention:
Diazo reagent is the mixing solutions of hydrochloric acid and acetate and Sodium Nitrite in the step (1), and wherein the volume ratio of hydrochloric acid and acetate is: 1.67～2:1, and concentration is 36% (mass concentration), and sodium nitrite solution concentration is 30% (mass concentration); The perhaps mixing solutions of sulfuric acid and acetate and Sodium Nitrite, wherein the volume ratio of sulfuric acid and acetate is: 0.8～1:1, concentration is 36% (mass concentration), and sodium nitrite solution concentration is 30% (mass concentration).
Diazotization reaction is carried out in-5 ℃～0 ℃ ice-water bath in the step (1).
Coupled reaction is the Na of 1～2mol/L in concentration in the step (2)
2CO
3Carry out in the solution, temperature of reaction is 35 ℃, reacts 2 hours down at 35 ℃～70 ℃ after 5 hours again.Be acidified to pH=2 with dilute hydrochloric acid, washing is filtered, after 80 ℃ of vacuum-drying, be the mixed solvent recrystallization of the ethanol of 1.0～1.5:1 and water with volume ratio after, promptly get described azobenzol dye compound formula (II).
Compound shown in step (1) Chinese style (II) with diazo reagent amount of substance ratio is: 1:1.0～1.10.
The compound amount of substance ratio shown in diazonium salt and the formula (III) is in the step (2): 1.0～1.15:1.
The present invention can improve the stability and the adjustable ability of optical information material greatly, has broad application prospects in fields such as the optical communication in future and light guides.
Description of drawings
Fig. 1 is the infrared spectrogram of compound (I-1);
Fig. 2 is the nuclear magnetic spectrogram of compound (I-1);
Fig. 3 is that the ultra-violet absorption spectrum of compound (I-1) is with the irradiation time change curve;
Fig. 4 is that the ultra-violet absorption spectrum of compound (I-2) is with the irradiation time change curve.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this.
The preparation of embodiment 1:2-methyl-2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzene
1, the preparation of diazonium salt
In the 250mL three-necked bottle of agitator, thermometer is housed, add the 10.6g o-toluidine, 25mL36% hydrochloric acid, 15mL36% acetate and 75mL water place cryosel to bathe three-necked bottle, drip the sodium nitrite in aqueous solution of 25mL30% in the 20min, keep temperature of reaction to be no more than 5 ℃, reaction 1.5h, excessive Sodium Nitrite is removed with urea, gets the red-purple diazonium salt solution.
2, coupled reaction
Add o-tert-butyl p-methyl phenol 1.69g and 25mL water in the 500mL three-necked bottle, 35 ℃ drip diazonium salt solution and 1mol/L Na simultaneously
2CO
3Aqueous solution 150mL controls pH ≈ 7.5, and reaction 5h is warming up to 70 ℃ again, and reaction 2h is acidified to pH=2 with dilute hydrochloric acid, and washing is filtered, and 80 ℃ of vacuum-dryings, gets thick product.With volume ratio is 2-methyl-2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzene that the mixed solvent recrystallization of the second alcohol and water of 1:1 can obtain red powdery solid.
The infrared spectrogram of 2-methyl-2 '-hydroxyl-3 '-tertiary butyl-5 ' that previous reaction obtains-methyl-benzene and nuclear magnetic spectrogram respectively as depicted in figs. 1 and 2, wherein to test employed solvent be deuterochloroform to nuclear-magnetism.The characteristic peak of infrared spectrogram and the characteristic peak of nuclear magnetic spectrogram are consistent with the theoretical value contrast, thereby verified doazo reaction thing and coupled reaction thing really as the theoretical generation of estimating correct linked reaction, get the gained compound and carry out the ultimate analysis test, the result who obtains is as shown in table 1, further confirms to have obtained suc as formula the target compound shown in (I-1).
Table 1 is compound (I-1) ultimate analysis data sheet.
Percentage composition (%)
N C H
Theoretical value 9.92 76.56 7.85
Test value 10.14 75.89 7.65
Get the azobenzol dye compound that 0.01492g makes, be dispersed in 50 milliliters of dry ethanol of crossing, obtain the mother liquor of azobenzol dye compound, get above-mentioned solution 0.4 ml soln and be diluted to 10 milliliters to obtain concentration be 4.227 * 10
-5The azobenzol dye compound solution of mol/L is 365nm with wavelength, and light intensity is that the ultraviolet source of 50mW shines azobenzol dye compound solution every 1 minute the timed interval, and measures its absorption spectrum in the time of 25 ℃, lucifuge during mensuration.Obtain the azobenzol dye compound ultra-violet absorption spectrum as shown in Figure 3 with the irradiation time change curve.
The preparation of embodiment 2:2-nonyl-2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzene
1, the preparation of diazonium salt
In the 250mL three-necked bottle of agitator, thermometer is housed, add 21.9g2-nonyl aniline, 15mL36% sulfuric acid, 15mL36% acetate and 75mL water place cryosel to bathe three-necked bottle, drip the sodium nitrite in aqueous solution of 28mL30% in the 20min, keep temperature of reaction to be no more than 5 ℃, reaction 1.5h, excessive Sodium Nitrite is removed with urea, gets the red-purple diazonium salt solution.
2, coupled reaction
Add o-tert-butyl p-methyl phenol 1.94g and 25mL water in the 500mL three-necked bottle, 35 ℃ drip diazonium salt solution and 2mol/L Na simultaneously
2CO
3Aqueous solution 150mL controls pH ≈ 7.5, and reaction 5h is warming up to 70 ℃ again, and reaction 2h is acidified to pH=2 with dilute hydrochloric acid, and washing is filtered, and 80 ℃ of vacuum-dryings, gets thick product.With volume ratio is 2-nonyl-2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzene that the mixed solvent recrystallization of the second alcohol and water of 1:1 can obtain red powdery solid.Through the analysis of infrared spectra and nuclear magnetic spectrogram, confirm that its structural formula is (I-2).
Get the azobenzol dye compound that 0.02086g makes, be dispersed in 50 milliliters of dry ethanol of crossing, obtain the mother liquor of azobenzol dye compound, get above-mentioned solution 0.4 ml soln and be diluted to 10 milliliters to obtain concentration be 4.227 * 10
-5The azobenzol dye compound solution of mol/L is 365nm with wavelength, and light intensity is that the ultraviolet source of 50mW shone azobenzol dye compound solution every 30 seconds, and measures its absorption spectrum in the time of 25 ℃, lucifuge during mensuration.Obtain the azobenzol dye compound ultra-violet absorption spectrum as shown in Figure 4 with the irradiation time change curve.
The preparation of embodiment 3:2-methyl-2 '-hydroxyl-3 '-methyl-5 '-methyl-benzene
1, the preparation of diazonium salt
In the 250mL three-necked bottle of agitator, thermometer is housed, add the 10.6g o-toluidine, 30mL36% hydrochloric acid, 15mL36% acetate and 75mL water place cryosel to bathe three-necked bottle, drip the sodium nitrite in aqueous solution of 23mL30% in the 20min, keep temperature of reaction to be no more than 5 ℃, reaction 1.5h, excessive Sodium Nitrite is removed with urea, gets the red-purple diazonium salt solution.
2, coupled reaction
Add adjacent methyl p-methyl phenol 1.28g and 25mL water in the 500mL three-necked bottle, 35 ℃ drip diazonium salt solution and 2mol/L Na simultaneously
2CO
3Aqueous solution 150mL, control pH ≈ 7.5, reaction 7h is acidified to pH=2 with dilute hydrochloric acid, and washing is filtered, and 80 ℃ of vacuum-dryings, gets thick product.With volume ratio is 2-methyl-2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl-benzene that the mixed solvent recrystallization of the second alcohol and water of 1:1.5 can obtain red powdery solid.Through the analysis of infrared spectra and nuclear magnetic spectrogram, confirm that its structural formula is (I-3).
The preparation of embodiment 4:2-amyl group-2 '-hydroxyl-3 '-sec.-propyl-5 '-methyl-benzene
1, the preparation of diazonium salt
In the 250mL three-necked bottle of agitator, thermometer is housed, add the adjacent amyl aniline of 16.3g, 12mL36% hydrochloric acid, 15mL36% acetate and 75mL water place cryosel to bathe three-necked bottle, drip the sodium nitrite in aqueous solution of 25mL30% in the 20min, keep temperature of reaction to be no more than 5 ℃, reaction 1.5h, excessive Sodium Nitrite is removed with urea, gets the red-purple diazonium salt solution.
2, coupled reaction
Add o-isopropyl p-methyl phenol 1.69g and 25mL water in the 500mL three-necked bottle, 35 ℃ drip diazonium salt solution and 1.5mol/L Na simultaneously
2CO
3Aqueous solution 150mL controls pH ≈ 7.5, and reaction 5h is warming up to 55 ℃ again, and reaction 2h is acidified to pH=2 with dilute hydrochloric acid, and washing is filtered, and 80 ℃ of vacuum-dryings, gets thick product.With volume ratio is 2-amyl group-2 '-hydroxyl-3 '-sec.-propyl-5 '-methyl-benzene that the mixed solvent recrystallization of the second alcohol and water of 0.5:1 can obtain red powdery solid.Product confirms that through the analysis of infrared spectra and nuclear magnetic spectrogram its structural formula is (I-4).
The preparation of embodiment 5:2-ethyl-2 '-hydroxyl-3 '-methyl-5 '-methyl-benzene
With the o-toluidine among the o ethyl aniline replacement embodiment 1 of equimolar amount, the adjacent methyl p-methyl phenol of equimolar amount replaces the o-tert-butyl p-methyl phenol among the embodiment 1.Preparation method and analytical procedure according to embodiment 1 are carried out, and product confirms that through the analysis of infrared spectra and nuclear magnetic spectrogram its structural formula is (I-5).
The preparation of embodiment 6:2-ethyl-2 '-hydroxyl-3 '-sec.-propyl-5 '-methyl-benzene
With the o-toluidine among the o ethyl aniline replacement embodiment 1 of equimolar amount, the o-isopropyl p-methyl phenol of equimolar amount replaces the o-tert-butyl p-methyl phenol among the embodiment 1.Preparation method and analytical procedure according to embodiment 1 are carried out, and product confirms that through the analysis of infrared spectra and nuclear magnetic spectrogram its structural formula is (I-6).
The foregoing description only is explanation technical conceive of the present invention and characteristics; its purpose is to allow this area personage who is familiar with this technology can recognize content of the present invention and enforcement according to this; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (2)
1. azobenzol dye compound, structure is suc as formula shown in (I):
In the formula (I), n is 0～8 integer, and m is 0～3 integer.
2. prepare the method for azobenzol dye compound as claimed in claim 1, it is characterized in that, step is following two steps:
(1) compound shown in the formula (II) is carried out diazotization reaction at diazo reagent in-5～0 ℃ ice-water bath and obtained diazonium salt in 2 hours; Compound shown in the formula (II) with the amount of substance ratio of diazo reagent is: 1:1.0～1.10;
In the formula (II), n is 0～8 integer; Diazo reagent is the mixing solutions of hydrochloric acid and acetate and Sodium Nitrite, perhaps the mixing solutions of sulfuric acid and acetate and Sodium Nitrite;
(2) compound shown in step (1) gained diazonium salt and the formula (III) is carried out coupled reaction; Compound amount of substance ratio shown in diazonium salt and the formula (III) is: 1.0～1.15:1; Coupled reaction is at the Na of 1～2mol/L
2CO
3Carry out in the solution, control pH ≈ 7.5, temperature of reaction is 35 ℃ and reacted 5 hours down, reacted 2 hours down at 35 ℃～70 ℃ again, to pH=2, wash with hcl acidifying, filter, after the vacuum-drying, be the mixed solvent recrystallization of the ethanol of 1.0～1.5:1 and water with volume ratio after, promptly get described azobenzol dye compound;
In the formula (III), m is 0～3 integer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220474A (en) * | 2016-06-27 | 2016-12-14 | 衢州学院 | A kind of new method preparing paracresol |
| CN108034278A (en) * | 2017-12-27 | 2018-05-15 | 沈阳化工研究院有限公司 | A kind of method that coupling prepares azo dyes |
-
2008
- 2008-12-19 CN CNA2008102401519A patent/CN101440221A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220474A (en) * | 2016-06-27 | 2016-12-14 | 衢州学院 | A kind of new method preparing paracresol |
| CN108034278A (en) * | 2017-12-27 | 2018-05-15 | 沈阳化工研究院有限公司 | A kind of method that coupling prepares azo dyes |
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Application publication date: 20090527 |