CN105001664B - D-pi-A-type aminoazobenzene dye and preparation method therefor - Google Patents
D-pi-A-type aminoazobenzene dye and preparation method therefor Download PDFInfo
- Publication number
- CN105001664B CN105001664B CN201510402944.6A CN201510402944A CN105001664B CN 105001664 B CN105001664 B CN 105001664B CN 201510402944 A CN201510402944 A CN 201510402944A CN 105001664 B CN105001664 B CN 105001664B
- Authority
- CN
- China
- Prior art keywords
- preparation
- sodium
- reaction
- diazol
- bromoaniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of compound preparation and particularly discloses a D-pi-A-type aminoazobenzene dye and a preparation method therefor. A chemical structural formula of the dye is defined in the specification, wherein R1 is hydrogen, methyl or methoxy; and R2 is hydrogen or bromine substituent. The dye has maximum absorption wavelength being about 405 nm, is remarkable in photochromic property, is matched with a 405-nm blue laser, and has high potential for use as a blue-ray disc storage medium.
Description
Technical field
The present invention relates to technical field of compound preparation, more particularly, to a kind of D- π-A type aminoazabenzol dyestuffs and
Its preparation method.
Background technology
Optical data storage disk is one of data storage medium of current most convenient, as people obtain and machining information amount
Increase, the demand to high-density blue light CD is more and more urgent.Blu-ray Disc using the nm of wavelength 405 blue laser read and
Write-in data, its single surface capacity is 20~50GB, and that DVD is 4.7GB.Blu-ray Disc storage medium can be divided into inorganic by attribute
Optical storage media and organic optical storage media, organic optical storage media have that storage density is high, solubility property is good, cost of manufacture
The advantages of low, environmental pollution is small, diamagnetic ability strong, wavelength can easily be accommodated, it has also become the study hotspot of blu-ray storage medium, wherein
Azo dyes is easily modified due to structure, adjustable spectroscopic absorption wavelength wide ranges, synthesis are simple, by the generally pass of countries in the world
Note.At present, azo dyes is many in the research and application of infrared region, and has realized commercialization, and in indigo plant（It is purple）Light area is current still
In the research and development stage.
The basic structure of azo dyes is A-N=N-B, according to the number of the azo group being embedded into Azo dye
With A, the difference of B structure, the maximum absorption wavelength of azo dyes can be adjusted in larger light abstraction width（λmax=380~
790nm）.The research of blue-ray storage azo dyes is mainly started with from the angle of MOLECULE DESIGN at present, i.e., by changing the knot of A, B
Structure and different substitution bases are introduced on A, B adjust dissolubility and light, the hot property of azo dyes, the blue light idol of existing report
Nitrogen dyestuff is less.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above present on prior art, there is provided a kind of D- π-A
Type aminoazabenzol dyestuff.
Second object of the present invention is to provide the preparation method of the D- π-A type aminoazabenzol dyestuffs.
Third object of the present invention is to provide the Blu-ray Disc record containing above-mentioned D- π-A type aminoazabenzol dyestuffs and is situated between
Matter.
Fourth object of the present invention is to provide above-mentioned D- π-A type aminoazabenzol dyestuffs as Blu-ray Disc recording medium
Application.
The purpose of the present invention is achieved by the following technical programs：
A kind of D- π-A type aminoazabenzol dyestuffs, its chemical structural formula is：
Wherein, R1It is hydrogen or methyl or methoxy, R2It is hydrogen or bromine substituent.
The present invention also provides the preparation method of the D- π-A type aminoazabenzol dyestuffs, comprises the following steps：
S1. the preparation of bromoaniline diazol：After bromoaniline and natrium nitrosum react in acid condition, eliminated
Amount nitrous acid, regulation pH value obtains bromoaniline diazol for 5~6；
S2. the preparation of aromatic amino methanesulfonic sodium：To being added in solution of sodium bisulfite, paraformaldehyde or formaldehyde are water-soluble
Liquid, after 60~65 DEG C of reactions, adds aromatic amine reaction and obtains aromatic amino methanesulfonic sodium；
S3. aromatic amino methanesulfonic sodium solution is added in bromoaniline diazol, 0~5 DEG C of 6~7 h of reaction, plus
Alkali carries out pyrohydrolysis, and it is 8~9 to adjust pH value, obtains final product D- π-A type aminoazabenzols；
Wherein, bromoaniline described in S1 is 3,5- dibromo anilines, 3- bromanilines, and aromatic amine described in S2 is aniline, adjacent methyl
Aniline or o-aminoanisole.
Diazo-reaction is the reaction that one-level amine acts on generation diazol with nitrous acid at low temperature, and aromatic primary amine is diazonium
Component, nitrous acid is diazotization agent, and azobenzene is that diazol is generated with after coupling component reaction again, typically contains strong electrophilic
The aromatic primary amine and coupling component for replacing base are easier to react obtain azobenzene, and inventor has found in experimentation, profit
Be with bromoaniline in raw material, with this patent coupling component reaction generation azobenzene yield it is extremely low, post analysis reason is：
Coupling reaction is the mechanism for following substitution reaction, on the one hand, diazol electropositive is stronger, is more conducive to coupling reaction；The opposing party
Face, coupling component contains electron-donating group so that phenyl ring cloud density increases, so as to be conducive to coupling reaction.In this patent
Diazo component benzene ring substituents be bromine atoms, it is a kind of weaker electron withdraw group, causes the positive electricity of diazol nitrogen-atoms
Property is very weak, therefore coupling reaction activity is relatively low.
Therefore, the present invention is improved the process for obtaining azobenzene as raw material reaction using bromoaniline, that is, closing
Into before azobenzene, the primary amine in coupling component aniline is protected, when reason is aromatic amine directly coupled reaction, aromatic amine
Amido ortho position and contraposition carbon atom can be as coupling reaction site, additionally, imido nitrogen atom also can be with diazonium reactant salt
Three nitrogen compounds are generated, after carrying out amido protection, because the volume of protection group methylene-benzene sodium sulfonate is larger, the space bit of generation
Inhibition effect can cause that the nitrogen-atoms of amido and the reaction probabilities of ortho position carbon atom are greatly reduced, so as to be conducive to amido para-position carbon
The coupling reaction of atom and diazol, the method for carrying out amido protection of the present invention is using sodium hydrogensulfite, paraformaldehyde
（Or formalin）, aromatic amine prepare aromatic amino methanesulfonic sodium, recycle aromatic amino methanesulfonic sodium and diazol component
Reaction obtains azobenzene.
Preferably, during diazo reaction, pH is controlled<2, after diazo reaction terminates, pH is adjusted to 5~6.
Preferably, S1 is conventional diazol preparation process, and the acid condition can use strong acid, such as nitric acid, hydrochloric acid and
Sulfuric acid, or the mixed acid that strong acid and glacial acetic acid are constituted, it is possible to use urea etc. eliminates unnecessary nitrous acid.
Preferably, sodium hydrogensulfite described in S2 and the min of polyformaldehyde reaction 30~35 are advisable, anti-again after addition aromatic amine
Answer 2~3 h.
Preferably, aromatic amino methanesulfonic sodium solution is added to the idol of gained after reacting in bromoaniline diazol in S3
Close liquid and add sodium hydrate aqueous solution, amino protecting group is sloughed in heating hydrolysis, and suction filtration obtains D- π-A type aminoazabenzol dyestuffs
Crude product.
Preferably, add alkaline thermal hydrolysis to be to carry out under nitrogen protection described in S3, be about with acid for adjusting pH value after terminating reaction
8, crude product is obtained final product through TLC separation.
The synthetic route of above-mentioned preparation method is：
Inventor has carried out following explorations when azo reaction is carried out using raw material of the present invention：
1st, the experimental technique optimization that prepared by diazol：Diazo reaction is usual with water as reaction medium, based on 3,5- dibromobenzenes
Amine solid is water insoluble, and dissolubility is larger in ethanol, just using ethanol as the solvent of reaction, but with aqueous hydrochloric acid solution
Add, there are a large amount of solids to separate out immediately, ultimately result in diazo reaction effect on driving birds is not good（The yield of azobenzene only has about 5%）.Experiment hair
It is existing, with 20% aqueous hydrochloric acid solution as the medium for reacting, and salt excessive acid（pH<2）, additionally, reacting preceding mortar by 3,5- dibromos
Aniline is finely ground, and as sodium nitrite in aqueous solution is progressively added dropwise into, suspension just gradually becomes clarification, and reaction is clarified after terminating
Diazonium salt solution, illustrate diazo-reaction ratio more thoroughly, add sodium acetate solid and pH be adjusted to 4~5, be finally coupled anti-
The yield of the azobenzene that should be obtained can reach 32%.
2nd, the experimental technique optimization of amido protection：Bromoaniline diazol is repeated several times experiment with coupling component is directly coupled
After failure, this invention takes the method for amido protecting.On the premise of the consumption of fixed aniline is 1 equivalent, poly first is investigated
Influence of the consumption of aldehyde and sodium hydrogensulfite to reaction yield, it is even when paraformaldehyde consumption is respectively 1,1.1 and 1.2 equivalents
The corresponding yield of pyridine is 25%, 31% and 32%, and sodium hydrogensulfite consumption changes from 1 to 1.1 equivalents, the yield of azobenzene
It is substantially unaffected.
3rd, hydrolysis Deprotection experimental technique optimization：In deprotection reaction is hydrolyzed, hydrolysis temperature influences on reaction yield
Larger, experiment is found when more than 70 DEG C of hydrolysis temperature, and hydrolysis carries out will occurring the sticky shape material of reddish black soon being wrapped in magnetic
Power stirrer, forms one so that hydrolysis is difficult to thoroughly, be finally separating yield and there was only about 10%, if hydrolysis temperature
It is too low（Less than 30 DEG C）, the time of hydrolysis needs to grow very much and be difficult to ensure that hydrolysis is complete.Groped by experiment condition, drawn optimal
Hydrolysis temperature is 40~55 DEG C, and according to the architectural difference of product, hydrolysis temperature is somewhat changed, and electricity is inhaled on diazo component phenyl ring
The stronger compound of sub- effect, the temperature of hydrolysis is appropriate high, otherwise lower, therefore, the temperature ratio of two bromo compound hydrolysis
The height of a corresponding bromo compound.
It is therefore preferred that the mass ratio of aromatic amine, paraformaldehyde and sodium hydrogensulfite described in S2 is 3.1~4.1：1.0~
1.2：3.4~3.8；The mol ratio of the aromatic amine, formalin and sodium hydrogensulfite is 1.0：1.0~1.2：1.0~
1.1。
Preferably, the aromatic amino methanesulfonic sodium described in S3 and the mol ratio of bromoaniline diazol are 1.0~1.2：1.0
~1.1.
The present invention also provides Blu-ray Disc recording medium or nonlinear optical material containing the azobenzene dye.
The present invention also provides application of the azobenzene dye as Blu-ray Disc recording medium.
Compared with prior art, the invention has the advantages that：
The invention provides a kind of preparation method of D- π-A type aminoazabenzol dyestuffs, i.e., before diazol coupling, lead to
Cross the class Mannich reaction synthesis aromatic amino methanesulfonic sodium pair of sodium hydrogensulfite, paraformaldehyde or formalin and aromatic amine
The amino of aromatic amine is protected, and forms the amino protecting group of aromatic amine, and aromatic amino methanesulfonic sodium and diazonium are recycled afterwards
Reactant salt, removes amino protecting group and obtains D- π-A type aminoazabenzol dyestuffs afterwards, and the maximum absorption wavelength of the dyestuff exists
405 nm or so, photochromic properties significantly, match with 405 nm blue lasers, it is expected to as Blu-ray Disc storage medium with
Nonlinear optical material.
Brief description of the drawings
Fig. 1 is the KBr compressing tablet infrared spectrums of the D- π-A type aminoazabenzol dyestuffs that embodiment 1~6 is obtained.
Fig. 2 is that the D- π-A type aminoazabenzol dyestuffs that embodiment 4 is obtained are each with 407 ± 10 nm illumination in ethyl acetate
The ultraviolet-visible spectrogram at individual moment.
Fig. 3 is that the D- π-A type aminoazabenzol dyestuffs that embodiment 4 is obtained are replied in ethyl acetate with 365 ± 10 nm light
The ultraviolet-visible spectrogram at each moment.
Fig. 4 is the thermogravimetric analysis figure of the azobenzene dye that each embodiment is prepared.
Specific embodiment
Present disclosure is further illustrated with reference to Figure of description and specific embodiment, but be should not be construed as to this
The limitation of invention.Without departing from the spirit and substance of the case in the present invention, that the inventive method, step or condition are made is simple
Modification is replaced, and belongs to the scope of the present invention；If not specializing, technological means used is art technology in embodiment
Conventional meanses known to personnel.
Embodiment 1
The present embodiment is the preparation method of 3-bromo- 4- amidos azobenzene, is comprised the following steps：
（1）The preparation of diazol：3.4408 g 3- bromanilines and the hydrochloric acid of 8 mL 20%, 0~5 are added in 100 mL beakers
1.5201 g sodium nitrite in aqueous solution are slowly added dropwise at DEG C, add urea to eliminate excessive nitrite, the regulation of sodium acetate solid after 2 h
PH value to 5, put standby in frozen water by the clarified solution of acquisition.
（2）The preparation of anilino- methanesulfonic sodium：10 mL water and 2.3505 g bisulfites are added in 50 mL round-bottomed flasks
Sodium, adds 0.7251 g paraformaldehydes after sodium hydrogensulfite dissolving, the 1.8611 of redistillation is instilled after 60 DEG C of 35 min of reaction
G aniline, heating is stopped after 2 h of reaction, obtains anilino- methanesulfonic sodium mixed liquor.
（3）The preparation of azobenzene compound：By step（2）After the mixed liquor of acquisition is cooled to room temperature, it is stirred vigorously lower slow
It is slow to instill step（1）In the diazol of acquisition, now, the diazonium salt solution of clarification gradually becomes dark red viscous fluid, and temperature control is 0~5
DEG C reaction 6 h after terminate reaction；The sodium hydrate aqueous solutions of 50 mL 30%, dark red viscous fluid is added to be changed into yellow turbid solution, nitrogen
7 h of lower 45 DEG C of hydrolysis are protected, 8 are about with salt acid for adjusting pH value after terminating reaction, crude product obtains dyestuff 3 through TLC separation
- bromo- the g of 4- amidos azobenzene 1.8225（Yield is 33%）, its chemical structural formula is as shown in Equation 1.1H NMR (CDCl3-TMS,
400MHz): 4.06(s,2H,NH2), 6.66~6.70 (m, 2H), 7.29~7.34 (m, 1H), 7.44~7.49 (m, 1H),
7.74~7.78 (m, 3H), 7.90~7.97 (m, 1H).Infrared spectrogram is as shown in Figure 1.
Embodiment 2
The present embodiment is the preparation method of 3-bromo- 3- methyl-4- amido azobenzenes, is comprised the following steps：
（1）The preparation of diazol：3.4414 g 3- bromanilines and the hydrochloric acid of 8 mL 20%, 0~5 are added in 100 mL beakers
1.5216 g sodium nitrite in aqueous solution are slowly added dropwise at DEG C, add urea to eliminate excessive nitrite, the regulation of sodium acetate solid after 2 h
PH value to 5, put standby in frozen water by the clarified solution of acquisition.
（2）The preparation of o-methyl-benzene amido methanesulfonic sodium：Add 10 mL water and 2.3517 g sub- in 50 mL round-bottomed flasks
Niter cake, adds 0.7264 g paraformaldehydes after sodium hydrogensulfite dissolving, it is adjacent to instill 2.1406 g after 60 DEG C of 35 min of reaction
Methylaniline, heating is stopped after 2 h of reaction, obtains o-methyl-benzene amido methanesulfonic sodium mixed liquor.
（3）The preparation of azobenzene compound：By step（2）After the mixed liquor of acquisition is cooled to room temperature, it is stirred vigorously lower slow
It is slow to instill step（1）In the diazol of acquisition, now, the diazonium salt solution of clarification gradually becomes dark red viscous fluid, and temperature control is 0~5
DEG C reaction 6 h after terminate reaction；The sodium hydrate aqueous solutions of 50 mL 30%, dark red viscous fluid is added to be changed into yellow turbid solution, nitrogen
7 h of lower 40 DEG C of hydrolysis are protected, 8 are about with salt acid for adjusting pH value after terminating reaction, crude product obtains dyestuff 3 through TLC separation
- bromo- the g of 3- methyl -4- amidos azobenzene 1.7608（Yield 31%）, its chemical structural formula is as shown in Equation 2.1H NMR(CDCl3-
TMS,400MHz): 2.23(s,3H,CH3), 4.05 (s, 2H, NH2), 6.73 (d, J=8.0Hz, 2H), 7.34 (t, J=
12.0Hz, 1H), 7.45 (d, J=8.0Hz, 2H), 7.69 (d, J=12.0Hz, 2H), 7.74~7.79 (m, 2H), 7.98 (s,
1H).Infrared spectrogram is as shown in Figure 1.
Embodiment 3
The present embodiment is the preparation method of 3-bromo- 3- methoxyl groups-4- amido azobenzenes, is comprised the following steps：
（1）The preparation of diazol：3.4451g 3- bromanilines and the hydrochloric acid of 8 mL 20%, 0~5 DEG C are added in 100 mL beakers
Under be slowly added dropwise 1.5211 g sodium nitrite in aqueous solution, after 2 h add urea eliminate excessive nitrite, sodium acetate solid regulation pH
Value to 5, put standby in frozen water by the clarified solution of acquisition.
（2）The preparation of o-aminoanisole base methanesulfonic sodium：10 mL water and 2.3528 g are added in 50 mL round-bottomed flasks
Sodium hydrogensulfite, adds 0.7242 g paraformaldehydes after sodium hydrogensulfite dissolving, 2.4608 g are instilled after 60 DEG C of 35 min of reaction
O-aminoanisole, heating is stopped after 2 h of reaction, obtains o-aminoanisole base methanesulfonic sodium mixed liquor.
（3）The preparation of azobenzene compound：By step（2）After the mixed liquor of acquisition is cooled to room temperature, it is stirred vigorously lower slow
It is slow to instill step（1）In the diazol of acquisition, now, clarification diazonium salt solution gradually becomes dark red viscous fluid, and temperature control is at 0~5 DEG C
Terminate reaction after reacting 6 h；The sodium hydrate aqueous solutions of 50 mL 30%, dark red viscous fluid is added to be changed into yellow turbid solution, nitrogen is protected
Protect it is lower 40 DEG C hydrolysis 7 h, terminate reaction after be about 8 with salt acid for adjusting pH value, crude product through TLC separation, obtain dyestuff 3-
The bromo- g of 3- methoxyl groups -4- amidos azobenzene 1.7608（Yield 21%）, its chemical structural formula is as shown in Equation 3.1H NMR(CDCl3-
TMS,400MHz): 3.88(s,3H,OCH3), 4.29 (s, 2H), 6.71 (d, J=8.0Hz, 1H), 7.32 (d, J=8.0Hz,
1H), 7.41 (s, 1H), 7.47~7.52 (m, 2H), 7.78 (d, J=8.0Hz, 1H), 7.99 (s, 1H).Infrared spectrogram such as Fig. 1
It is shown.
Embodiment 4
The present embodiment is the preparation method of 3,5-two bromo- 4- amidos azobenzenes, is comprised the following steps：
（1）The preparation of diazol：5.0121 g 3,5- dibromo anilines and the hydrochloric acid of 8 mL 20%, 0 are added in 100 mL beakers
Slow toward 1.5213 g sodium nitrite in aqueous solution are added dropwise in suspension at~5 DEG C, addition urea was eliminated after suspension becomes clarification
Amount nitrous acid, sodium acetate solid adjusts pH value to 5, and the clarified solution of acquisition is put standby in frozen water.
（2）The preparation of anilino- methanesulfonic sodium：10 mL water and 2.3529 g bisulfites are added in 50 mL round-bottomed flasks
Sodium, adds 0.7231 g paraformaldehydes after sodium hydrogensulfite dissolving, 1.8609 g redistillations are instilled after 60 DEG C of 35 min of reaction
Aniline, reaction 2 h after stop heating, obtain anilino- methanesulfonic sodium mixed liquor.
（3）The preparation of azobenzene compound：By step（2）After the mixed liquor of acquisition is cooled to room temperature, it is stirred vigorously lower slow
It is slow to instill step（1）In the diazol of acquisition, now, clarification diazonium salt solution gradually becomes dark red viscous fluid, and temperature control is at 0~5 DEG C
Terminate reaction after reacting 6 h.The sodium hydrate aqueous solutions of 50 mL 30%, dark red viscous fluid is added to be changed into yellow turbid solution, nitrogen is protected
7 h of lower 55 DEG C of hydrolysis are protected, 8 are about with salt acid for adjusting pH value after terminating reaction, crude product obtains dyestuff 3,5 through TLC separation
- two bromo- g of 4- amidos azobenzene 2.2713（Yield 32%）, its chemical structural formula is as shown in Equation 4.1H NMR(CDCl3-TMS,
400MHz): 4.17(s,2H,NH2), 6.74 (d, J=8.0Hz, 2H), 7.67 (s, 1H), 7.80 (d, J=8.0Hz, 2H),
7.92(s,2H).Infrared spectrogram is as shown in Figure 1.
Bromo- a length of 407 nm of 4- amidos azobenzene maximum absorption wave in ethyl acetate of dyestuff 3,5-two, will be prepared
D- π-A type aminoazabenzol dyestuffs be configured to 8.0 × 10-5 Mol/L ethyl acetate solutions, take appropriate in band circle plug quartz ratio
In color ware, with 405 ± 10 nm ultraviolet light solution, and each moment is recorded by ultraviolet-uisible spectrophotometer（t=0,
0.2,0.4,0.6,0.8,1.0,1.4,1.8,2.4 s）Uv-vis spectra, until photostationary state, the purple at each moment of illumination
As a result outer visible ray spectrogram as shown in Fig. 2 show：L before illuminationmax=407 nm strong absworption peaks are p-p*And n-p*Two energy level weights
Folded absworption peak, after 405 ± 10 nm light irradiations, strong peak absorbance reduces rapidly,tDuring=0.6 s, occur one at the nm of wavelength 355
Individual new absworption peak, is n-p*Transition absorption peak, strong peak absorbance continues to reduce at subsequent 407 nm, the peak absorbance at 355 nm
Somewhat increase,tStable state is reached during=2.4 s, two are waited suction point respectively at 362,488 nm.
And then replied with the light of 365 ± 10 nm, determine reply each moment respectively（t=0,0.2,0.4,0.6,
0.8,1.0,1.2,1.6,2.0,3.2,4.2,5.6 s）Uv-vis spectra, as shown in figure 3, now p-p*The strong peak extinction of transition
Degree rises and blue shift occurs rapidly, n-p*Transition peak absorbance declines and red shift occurs, whentDuring=2.0 s, absorbed at 355 nm
Peak complete-superposing is absorbed at peak and 407 nm.The appearance for inhaling point is waited according to two, though there is new absworption peak increase, light can be occurred and returned
It is multiple, it may be determined that list of target compound only occurs cis-trans isomerism and turns in the case where 407 ± 10 nm and 365 ± 10 nm light alternately irradiate
Become, the side reactions such as photo-crosslinking or light degradation do not occur.
Embodiment 5
The present embodiment is the preparation method of 3,5-two bromo- 3- methyl-4- amido azobenzenes, is comprised the following steps：
（1）The preparation of diazol：5.0132 g 3,5- dibromo anilines and the hydrochloric acid of 8 mL 20%, 0 are added in 100 mL beakers
Slow toward 1.5241 g sodium nitrite in aqueous solution are added dropwise in suspension at~5 DEG C, addition urea was eliminated after suspension becomes clarification
Amount nitrous acid, sodium acetate solid adjusts pH value to 5, and the clarified solution of acquisition is put standby in frozen water.
（2）The preparation of o-methyl-benzene amido methanesulfonic sodium：Add 10 mL water and 2.3534 g sub- in 50 mL round-bottomed flasks
Niter cake, adds 0.7219 g paraformaldehydes after sodium hydrogensulfite dissolving, it is adjacent to instill 2.1413 g after 60 DEG C of 35 min of reaction
Methylaniline, heating is stopped after 2 h of reaction, obtains o-methyl-benzene amido methanesulfonic sodium mixed liquor.
（3）The preparation of azobenzene compound：By step（2）After the mixed liquor of acquisition is cooled to room temperature, it is stirred vigorously lower slow
It is slow to instill step（1）In the diazol of acquisition, now, clarification diazonium salt solution gradually becomes dark red viscous fluid, and temperature control is at 0~5 DEG C
Terminate reaction after reacting 6 h.The sodium hydrate aqueous solutions of 50 mL 30%, dark red viscous fluid is added to be changed into yellow turbid solution, nitrogen is protected
7 h of lower 50 DEG C of hydrolysis are protected, 8 are about with salt acid for adjusting pH value after terminating reaction, crude product obtains dyestuff 3,5 through TLC separation
- two bromo- 3- methyl -4- amido azobenzenes 2.1402g（Yield 30%）, its chemical structural formula is as shown in Equation 5.1H NMR(CDCl3-
TMS,400MHz): 2.20(s,3H, CH3), 4.09 (s, 1H, NH2), 6.68~6.70 (m, 2H), 7.63 (t, J=4.0Hz,
1H), 7.66~7.67 (m, 2H), 7.89 (d, J=4.0Hz, 2H).Infrared spectrogram is as shown in Figure 1.
Embodiment 6
The present embodiment is the preparation method of 3,5-two bromo- 3- methoxyl groups-4- amido azobenzenes, is comprised the following steps：
（1）The preparation of diazol：5.0114 g 3,5- dibromo anilines and the hydrochloric acid of 8 mL 20%, 0 are added in 100 mL beakers
Slow toward 1.5232 g sodium nitrite in aqueous solution are added dropwise in suspension at~5 DEG C, addition urea was eliminated after suspension becomes clarification
Amount nitrous acid, sodium acetate solid adjusts pH value to 5, and clarified solution is put standby in frozen water.
（2）The preparation of o-aminoanisole base methanesulfonic sodium：10 mL water and 2.3553 g are added in 50 mL round-bottomed flasks
Sodium hydrogensulfite, adds 0.7221 g paraformaldehydes after sodium hydrogensulfite dissolving, 2.4610 g are instilled after 60 DEG C of 35 min of reaction
O-aminoanisole, heating is stopped after 2 h of reaction, obtains o-aminoanisole base methanesulfonic sodium mixed liquor.
（3）The preparation of azobenzene compound：By step（2）After the mixed liquor of acquisition is cooled to room temperature, it is stirred vigorously lower slow
It is slow to instill step（1）In the diazol of acquisition, now, clarification diazonium salt solution gradually becomes dark red viscous fluid, and temperature control is at 0~5 DEG C
Terminate reaction after reacting 6 h.The sodium hydrate aqueous solutions of 50 mL 30%, dark red viscous fluid is added to be changed into yellow turbid solution, nitrogen is protected
7 h of lower 50 DEG C of hydrolysis are protected, 8 are about with salt acid for adjusting pH value after terminating reaction, crude product obtains dyestuff 3,5 through TLC separation
- two bromo- 3- methoxyl groups -4- amido azobenzenes 2.237g（Yield 29%）, its chemical structural formula is as shown in Equation 6.1H NMR
(CDCl3-TMS,400MHz): 3.89(s,1H,OCH3), 4.35 (s, 1H, NH2), 6.71 ~ 6.74 (m, 1H), 7.37~7.38
(s, 1H), 7.50 (t, J=12.0Hz, 1H), 7.62~7.63 (s, 1H), 7.90 (s, 2H).Infrared spectrogram is as shown in Figure 1.
Comparative example 1
This comparative example uses the synthetic method of traditional azobenzene, and detailed process is as follows：
（1）The preparation of diazol：5.0112 g 3,5- dibromo anilines and the hydrochloric acid of 8 mL 20%, 0 are added in 100 mL beakers
Slow toward 1.5207 g sodium nitrite in aqueous solution are added dropwise in suspension at~5 DEG C, addition urea was eliminated after suspension becomes clarification
Amount nitrous acid, sodium acetate solid adjusts pH value to 5, and the clarified solution of acquisition is put standby in frozen water.
（2）Coupling reaction：The g of aniline 1.8618 for taking new distillation is cooled to 0~5 DEG C in frozen water, in the bar of magnetic agitation
It is slowly dropped under part（1）In the diazol of middle preparation, reaction stops reaction after about 5 hours, adds NaOH regulation pH value
To 8~9, TLC separation does not obtain target compound.
Through many experiments and parameter optimization, show：Traditional method, idol of the present invention is cannot get using bromoaniline
Pyridine.
Embodiment 7
The preparation method of the present embodiment 4- amidos azobenzene bromo- to 3,5- bis- is optimized, and draws serial azo dyes system
Standby optimum condition.
1st, the experimental technique optimization that prepared by diazol：Diazo reaction is usual with water as reaction medium, based on 3,5- dibromobenzenes
Amine solid is water insoluble, and dissolubility is larger in ethanol, just using ethanol as the solvent of reaction, but with aqueous hydrochloric acid solution
Add, there are a large amount of solids to separate out immediately, ultimately result in diazo reaction effect on driving birds is not good（The yield of azobenzene only has about 5%）.Experiment hair
It is existing, use 20% aqueous hydrochloric acid solution（Consumption is 7~9 mL）As the medium of reaction, and salt excessive acid（pH<2）, additionally, before reaction
With mortar that 3,5- dibromo anilines is finely ground, as sodium nitrite in aqueous solution is progressively added dropwise into, suspension just gradually becomes clarification, instead
The diazonium salt solution clarified after should terminating, illustrates diazo-reaction ratio more thoroughly, adds sodium acetate solid and adjusts pH
To 4~5, the yield of the azobenzene that last coupling reaction is obtained can reach 32%.
2nd, the experimental technique optimization of amido protection：Bromoaniline diazol is repeated several times experiment with coupling component is directly coupled
After failure, this invention takes the method for amido protecting.On the premise of the consumption of fixed aniline is 1 equivalent, poly first is investigated
Influence of the consumption of aldehyde and sodium hydrogensulfite to reaction yield, it is even when paraformaldehyde consumption is respectively 1,1.1 and 1.2 equivalents
The corresponding yield of pyridine is 25%, 31% and 32%, and sodium hydrogensulfite consumption changes from 1 to 1.1 equivalents, the yield of azobenzene
It is substantially unaffected.
3rd, hydrolysis Deprotection experimental technique optimization：In deprotection reaction is hydrolyzed, hydrolysis temperature influences on reaction yield
Larger, experiment is found when more than 70 DEG C of hydrolysis temperature, and hydrolysis carries out will occurring the sticky shape material of reddish black soon being wrapped in magnetic
Power stirrer, forms one so that hydrolysis is difficult to thoroughly, be finally separating yield and there was only about 10%, if hydrolysis temperature
It is too low（Less than 30 DEG C）, the time of hydrolysis needs to grow very much and be difficult to ensure that hydrolysis is complete.Groped by experiment condition, drawn optimal
Hydrolysis temperature is 40~55 DEG C, and according to the architectural difference of product, hydrolysis temperature is somewhat changed, and electricity is inhaled on diazo component phenyl ring
The stronger compound of sub- effect, the temperature of hydrolysis is appropriate high, otherwise lower, therefore, the temperature ratio of two bromo compound hydrolysis
The height of a corresponding bromo compound.
Claims (7)
1. a kind of D- π-A type aminoazabenzol dyestuffs, it is characterised in that its chemical structural formula is：
；Or；Or；Or；Or。
2. a kind of preparation method of D- π-A type aminoazabenzol dyestuffs for Blu-ray Disc recording medium, it is characterised in that bag
Include following steps：
S1. the preparation of bromoaniline diazol：After bromoaniline and natrium nitrosum react in acid condition, eliminate excessive sub-
Nitric acid, regulation pH value obtains bromoaniline diazol for 5~6；
S2. the preparation of aromatic amino methanesulfonic sodium：To addition paraformaldehyde or formalin, 60 in solution of sodium bisulfite
After~65 DEG C of reactions, add aromatic amine reaction and obtain aromatic amino methanesulfonic sodium；
S3. aromatic amino methanesulfonic sodium solution is added in bromoaniline diazol, 0~5 DEG C of 6~7 h of reaction, plus alkali exists
40~55 DEG C carry out pyrohydrolysis, and it is 8~9 to adjust pH value, obtains final product D- π-A type aminoazabenzols；
Wherein, bromoaniline described in S1 is 3,5- dibromo anilines, 3- bromanilines, and aromatic amine described in S2 is aniline, o-toluidine
Or o-aminoanisole.
3. preparation method according to claim 2, it is characterised in that aromatic amine, paraformaldehyde and bisulfite described in S2
The mass ratio of sodium is 3.1~4.1：1.0~1.2：3.4~3.8；The aromatic amine, formalin and sodium hydrogensulfite rub
You are than being 1.0：1.0~1.2：1.0~1.1.
4. preparation method according to claim 2, it is characterised in that aromatic amino methanesulfonic sodium and bromobenzene described in S3
The mol ratio of amine diazol is 1.0~1.2：1.0~1.1.
5. the Blu-ray Disc recording medium containing azobenzene dye described in claim 1.
6. azobenzene dye described in claim 1 as Blu-ray Disc recording medium application.
7. azobenzene dye described in claim 1 as nonlinear optical material application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510402944.6A CN105001664B (en) | 2015-07-10 | 2015-07-10 | D-pi-A-type aminoazobenzene dye and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510402944.6A CN105001664B (en) | 2015-07-10 | 2015-07-10 | D-pi-A-type aminoazobenzene dye and preparation method therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105001664A CN105001664A (en) | 2015-10-28 |
| CN105001664B true CN105001664B (en) | 2017-05-24 |
Family
ID=54374542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510402944.6A Active CN105001664B (en) | 2015-07-10 | 2015-07-10 | D-pi-A-type aminoazobenzene dye and preparation method therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105001664B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120259B (en) * | 2022-12-09 | 2024-03-12 | 吉林大学 | D-pi-A azobenzene piezochromic material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424155A (en) * | 1980-03-15 | 1984-01-03 | Basf Aktiengesellschaft | Aminoazo compounds |
| CN1032877A (en) * | 1987-10-13 | 1989-05-10 | 三井石油化学工业株式会社 | Optical data recording medium and optical recording system |
| CN1187898A (en) * | 1995-04-06 | 1998-07-15 | 艾里安特技术系统公司 | Liquid crystal optical storage medium with gray scale |
| CN1287355A (en) * | 1999-06-23 | 2001-03-14 | 索尼株式会社 | Optical recording medium and recording and/or playback method and apparatus using optical recording medium |
| CN1408113A (en) * | 2000-01-04 | 2003-04-02 | 法国电信公司 | Method for optical data recording |
-
2015
- 2015-07-10 CN CN201510402944.6A patent/CN105001664B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4424155A (en) * | 1980-03-15 | 1984-01-03 | Basf Aktiengesellschaft | Aminoazo compounds |
| CN1032877A (en) * | 1987-10-13 | 1989-05-10 | 三井石油化学工业株式会社 | Optical data recording medium and optical recording system |
| CN1187898A (en) * | 1995-04-06 | 1998-07-15 | 艾里安特技术系统公司 | Liquid crystal optical storage medium with gray scale |
| CN1287355A (en) * | 1999-06-23 | 2001-03-14 | 索尼株式会社 | Optical recording medium and recording and/or playback method and apparatus using optical recording medium |
| CN1408113A (en) * | 2000-01-04 | 2003-04-02 | 法国电信公司 | Method for optical data recording |
Non-Patent Citations (2)
| Title |
|---|
| D-π-A型偶氮苯衍生物合成、表征及其光致变色性能;宋秀美等;《功能材料》;20150521;第46卷(第9期);09114-09119 * |
| Synthesis and QSAR modeling of 2-acetyl-2-ethoxycarbonyl-1-[4(4’-arylazo)-phenyl]-N,N-dimethylaminophenyl aziridines as potential antibacterial agents;Pratibha Sharma.et al;《European Journal of Medicinal Chemistry》;20080229;第44卷;251-259 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105001664A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ušćumlić et al. | Substituent and solvent effects on the UV/Vis absorption spectra of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridones | |
| Karcı et al. | Hetarylazo disperse dyes derived from 3-methyl-1-(3′, 5′-dipiperidino-s-triazinyl)-5-pyrazolone as coupling component | |
| Song et al. | Synthesis of novel dyes derived from 1-ethyl-3-cyano-6-hydroxy-4-methyl-5-amino-2-pyridone | |
| EP0981558B1 (en) | Homopolymers with high photoinduceable double refraction | |
| Yen et al. | A facile syntheses and absorption characteristics of some monoazo dyes in bis-heterocyclic aromatic systems: part II: syntheses of 4-(p-substituted) phenyl-2-(2-pyrido-5-yl and 5-pyrazolo-4-yl) azo-thiazole derivatives | |
| CN105001664B (en) | D-pi-A-type aminoazobenzene dye and preparation method therefor | |
| CN105038316A (en) | Heterocyclic-ring disperse azo dye and preparation method thereof | |
| Geng et al. | From heterocyclic hydrazone to hydrazone-azomethine dyes: Solvent and pH induced hydrazone and azo-keto transformation for a family of pyrazolone-based heterocyclic dyes | |
| Kasture et al. | Synthesis and characterisation of benzothiazole‐based solid‐state fluorescent azo dyes | |
| JP2004524195A (en) | Optical data recording medium containing triazacyanine dye as light absorbing compound in information layer | |
| Otutu et al. | Synthesis and spectral properties of hetaryl monoazo dyes derived from 2-amino-5-nitrothiazole | |
| JP2006306070A (en) | Optical recording medium, metal complex compound and organic dye compound | |
| CN111004146A (en) | Liquid azophenyl molecular solar thermal fuel and synthesis method and application thereof | |
| Patil et al. | Synthesis and optical properties of Near-Infrared (NIR) absorbing azo dyes | |
| US5447823A (en) | Metal chelate compound and optical recording medium using the compound | |
| Zhang et al. | Azo dyes of hexafluoroisopropylidene derivatives: Synthesis and nonlinear optical properties | |
| CN101440221A (en) | Azobenzol dye compound and preparation thereof | |
| CN103059598B (en) | Azo blue-ray optical storage dye and preparation method thereof | |
| EP1776422B1 (en) | Antipyrine based azo metal complex dyes and their use in optical layers for optical data recording | |
| CN103059065B (en) | Azo metal complex and preparation method thereof | |
| MX2007000935A (en) | Amino antipyrine based azo ligands and their metal complexes for use as optical recording media. | |
| KR100398089B1 (en) | New azo based dye, and use thereof | |
| JP3879201B2 (en) | Sulfonamide compounds and azo compounds | |
| KR100398086B1 (en) | Azo dye having heterocyclic ring useful in optical recording media | |
| KR100398087B1 (en) | New azo metal complex having heterocyclic ring, and use thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |