CN105001664A - D-pi-A-type aminoazobenzene dye and preparation method therefor - Google Patents
D-pi-A-type aminoazobenzene dye and preparation method therefor Download PDFInfo
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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 specifically, relate to a kind of D-π-A type aminoazobenzene dye well its preparation method.
Background technology
Optical data storage disk is one of data storage medium of current most convenient, along with people obtain and the growth of machining information amount, more and more urgent to the demand of high-density blue light CD.Blu-ray Disc utilizes the blue laser of wavelength 405 nm to read and write data, and its single surface capacity is 20 ~ 50GB, and that DVD is 4.7GB.Blu-ray Disc storage media can be divided into inorganic optical storage media and organic optical storage media by attribute, organic optical storage media has that storage density is high, solubility property good, cost of manufacture is low, environmental pollution is little, diamagnetic ability is strong, wavelength is easy to the advantages such as adjustment, become the study hotspot of blu-ray storage medium, wherein azoic dyestuff due to structure easily modify, adjustable spectroscopic absorption wavelength wide ranges, synthesis be simple, is subject to the common concern of countries in the world.At present, the investigation and application of azoic dyestuff in infrared region is a lot, and realizes commercialization, and is still in the research and development stage at present in blue (purple) light district.
The basic structure of azoic dyestuff is A-N=N-B, according to the number of the azo-group be embedded in Azo dye and the difference of A, B structure, can regulate the maximum absorption wavelength (λ of azoic dyestuff in larger light abstraction width
max=380 ~ 790nm).At present the research of blue-ray storage azoic dyestuff is mainly started with from the angle of molecular designing, namely by changing the structure of A, B and introduce solvability and light, the thermal characteristics that different substituting groups regulates azoic dyestuff on A, B, the blue light azoic dyestuff of existing report is less.
Summary of the invention
Technical problem to be solved by this invention overcomes the above-mentioned defect that prior art exists, and provides a kind of D-π-A type aminoazobenzene dyestuff.
Second object of the present invention is to provide the preparation method of described D-π-A type aminoazobenzene dyestuff.
3rd object of the present invention is to provide the Blu-ray Disc recording medium containing above-mentioned D-π-A type aminoazobenzene dyestuff.
4th object of the present invention is to provide the application of above-mentioned D-π-A type aminoazobenzene dyestuff as Blu-ray Disc recording medium.
The object of the invention is to be achieved by the following technical programs:
A kind of D-π-A type aminoazobenzene dyestuff, its chemical structural formula is:
Wherein, R
1for hydrogen or methyl or methoxy, R
2for hydrogen or bromine substituent.
The present invention also provides the preparation method of described D-π-A type aminoazobenzene dyestuff, comprises the following steps:
S1. the preparation of bromoaniline diazonium salt: after bromoaniline and Sodium Nitrite react in acid condition, eliminate excessive nitrite, adjust ph be 5 ~ 6 bromoaniline diazonium salt;
S2. the preparation of aromatic amino methanesulfonic sodium: add paraformaldehyde or formalin in sodium sulfite solution, after 60 ~ 65 DEG C of reactions, then adds aromatic amine reaction acquisition aromatic amino methanesulfonic sodium;
S3. join in bromoaniline diazonium salt by aromatic amino methanesulfonic sodium solution, 0 ~ 5 DEG C of reaction 6 ~ 7 h, add alkali and carry out thermal hydrolysis, adjust pH is 8 ~ 9, obtains D-π-A type aminoazobenzene;
Wherein, bromoaniline described in S1 is 3,5-dibromo aniline, 3-bromaniline, and aromatic amine described in S2 is aniline, o-toluidine or ORTHO ANISIDINE.
Diazotization reaction is that primary amine and nitrous acid act on the reaction generating diazonium salt at low temperatures, aromatic primary amine is diazo component, nitrous acid is diazotization agent, nitrogen benzide generates after diazonium salt reacts with coupling component again, aromatic primary amine generally containing strong electron-withdrawing substituent and coupling component are easier to carry out being obtained by reacting nitrogen benzide, contriver finds in experimentation, utilize bromoaniline for raw material, to react the productive rate generating nitrogen benzide extremely low with the coupling component in this patent, post analysis reason is: coupled reaction follows the mechanism of substitution reaction, on the one hand, diazonium salt positive polarity is stronger, more be conducive to coupled reaction, on the other hand, coupling component contains electron-donating group, phenyl ring cloud density is increased, thus is conducive to coupled reaction.Diazo component benzene ring substituents in this patent is bromine atoms, and it is the more weak electron-withdrawing group of one, and cause the positive polarity of diazonium salt nitrogen-atoms very weak, therefore coupled reaction activity is lower.
Therefore, the present invention improves the process obtaining nitrogen benzide using bromoaniline as raw material reaction, namely before synthesis nitrogen benzide, primary amine in coupling component aniline is protected, when reason is aromatic amine direct coupled reaction, the amido ortho position of aromatic amine and the carbon atom of contraposition all can be used as coupled reaction site, in addition, imido nitrogen atom also can react generation three nitrogen compound with diazonium salt, after carrying out amido protection, because the volume of protecting group methylene-benzene sodium sulfonate is larger, the space steric effect produced can make the reaction probabilities of the nitrogen-atoms of amido and ortho position carbon atom reduce widely, thus be conducive to the coupled reaction of amido para-position carbon atom and diazonium salt, method of carrying out amido protection of the present invention utilizes sodium bisulfite, paraformaldehyde (or formalin), aromatic amine prepares aromatic amino methanesulfonic sodium, recycling aromatic amino methanesulfonic sodium and diazonium salt component reaction obtain nitrogen benzide.
Preferably, in doazo reaction process, control pH<2, after doazo reaction terminates, pH is adjusted to 5 ~ 6.
Preferably, S1 is conventional diazonium salt preparation process, and described acidic conditions can use strong acid, as nitric acid, hydrochloric acid and sulfuric acid, or the mixing acid of strong acid and Glacial acetic acid composition, urea etc. can be utilized to eliminate unnecessary nitrous acid.
Preferably, sodium bisulfite described in S2 and polyformaldehyde reaction 30 ~ 35 min are advisable, and react 2 ~ 3 h again after adding aromatic amine.
Preferably, the coupling solution in S3, aromatic amino methanesulfonic sodium solution being joined gained after reaction in bromoaniline diazonium salt adds aqueous sodium hydroxide solution, heating hydrolysis deaminize protecting group, suction filtration, obtains D-π-A type aminoazobenzene dyestuff crude product.
Preferably, adding alkaline thermal hydrolysis described in S3 is carry out under nitrogen protection, and be about 8 with acid for adjusting pH value after terminating reaction, thick product is through TLC separation and get final product.
The synthetic route of above-mentioned preparation method is:
Contriver, when utilizing raw material of the present invention to carry out azo reaction, has carried out following exploration:
1, the experimental technique optimization prepared of diazonium salt: doazo reaction is reaction medium usually with water, based on 3,5-dibromo aniline solid is water insoluble, and solvability is larger in ethanol, just the solvent using ethanol as reaction, but along with adding of aqueous hydrochloric acid, there is a large amount of solid to separate out immediately, finally cause doazo reaction poor effect (productive rate of nitrogen benzide only has an appointment 5%).Experiment finds, with the medium of 20% aqueous hydrochloric acid as reaction, and salt excessive acid (pH<2), in addition, react front mortar by 3,5-dibromo aniline porphyrize, along with sodium nitrite in aqueous solution progressively drips into, suspension just becomes clarification gradually, the diazonium salt solution clarified is obtained after reaction terminates, illustrate that diazotization reaction is relatively thorough, then add sodium-acetate solid pH is adjusted to 4 ~ 5, the productive rate of the nitrogen benzide that last coupled reaction obtains can reach 32%.
2, the experimental technique optimization of amido protection: after bromoaniline diazonium salt and the direct coupling of coupling component repeatedly repeat the failure of an experiment, this invention takes the method for amido protecting.The consumption of fixing aniline is under the prerequisite of 1 equivalent, investigate the consumption of paraformaldehyde and sodium bisulfite to the impact of reaction yield, when paraformaldehyde consumption is respectively 1,1.1 and 1.2 equivalent, the productive rate of the correspondence of nitrogen benzide is 25%, 31% and 32%, sodium bisulfite consumption changes from 1 to 1.1 equivalents, and the productive rate of nitrogen benzide is substantially unaffected.
3, the optimization of Deprotection experimental technique is hydrolyzed: in hydrolysis deprotection reaction; hydrolysis temperature is larger on reaction yield impact; experiment finds when hydrolysis temperature more than 70 DEG C; hydrolysis just there will be the sticky shape material of reddish black soon and is wrapped in magnetic stir bar; form one, make hydrolysis reaction be difficult to carry out thoroughly, last isolated yield only has an appointment 10%; if hydrolysis temperature too low (less than 30 DEG C), the time of hydrolysis needs to grow very much and is difficult to ensure that hydrolysis completely.Condition is groped by experiment, show that optimum hydrolysis temperature is 40 ~ 55 DEG C, and according to the textural difference of product, hydrolysis temperature changes a little, the compound that on diazo component phenyl ring, sucting electronic effect is stronger, the temperature of hydrolysis is suitably high, otherwise lower, therefore, the temperature of two bromo compound hydrolysis is more a little than the height of a corresponding bromo compound.
Therefore, preferably, described in S2, the mass ratio of aromatic amine, paraformaldehyde and sodium bisulfite is 3.1 ~ 4.1:1.0 ~ 1.2:3.4 ~ 3.8; The mol ratio of described aromatic amine, formalin and sodium bisulfite 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 diazonium salt are 1.0 ~ 1.2:1.0 ~ 1.1.
The present invention also provides Blu-ray Disc recording medium containing described azobenzene dye or nonlinear optical material.
The present invention also provides described azobenzene dye as the application of Blu-ray Disc recording medium.
Compared with prior art, the present invention has following beneficial effect:
The invention provides a kind of preparation method of D-π-A type aminoazobenzene dyestuff, namely before diazonium salt coupling, pass through sodium bisulfite, the amino of class Mannich reaction synthetic aroma amido methanesulfonic sodium to aromatic amine of paraformaldehyde or formalin and aromatic amine is protected, form the amino protecting group of aromatic amine, recycling aromatic amino methanesulfonic sodium and diazonium salt react afterwards, remove amino protecting group afterwards and obtain D-π-A type aminoazobenzene dyestuff, the maximum absorption wavelength of described dyestuff is at about 405 nm, photochromic properties is remarkable, mate with 405 nm blue lasers, be expected to be used as Blu-ray Disc storage media and nonlinear optical material.
Accompanying drawing explanation
Fig. 1 is the KBr compressing tablet infrared spectra of the D-π-A type aminoazobenzene dyestuff that embodiment 1 ~ 6 obtains.
Fig. 2 be embodiment 4 obtain D-π-A type aminoazobenzene dyestuff in ethyl acetate with the ultraviolet-visible spectrogram in 407 ± 10 each moment of nm illumination.
Fig. 3 is that the ultraviolet-visible spectrogram in each moment replied by the D-π-A type aminoazobenzene dyestuff that embodiment 4 obtains in ethyl acetate with 365 ± 10 nm light.
Fig. 4 is the thermogravimetric analysis figure of the azobenzene dye that each embodiment prepares.
Embodiment
Further illustrate content of the present invention below in conjunction with Figure of description and specific embodiment, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the simple modification do the inventive method, step or condition or replacement, all belong to scope of the present invention; If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
embodiment 1
the present embodiment is the preparation method of 3-bromo-4-amido nitrogen benzide, comprises the following steps:
(1) preparation of diazonium salt: add 3.4408 g 3-bromanilines and 8 mL 20% hydrochloric acid in 100 mL beakers, slowly 1.5201 g sodium nitrite in aqueous solution are dripped at 0 ~ 5 DEG C, add urea after 2 h and eliminate excessive nitrite, sodium-acetate solid adjust ph to 5, the clear liquor of acquisition is put in frozen water for subsequent use.
(2) preparation of anilino methanesulfonic sodium: add 10 mL water and 2.3505 g sodium bisulfites in 50 mL round-bottomed flasks, sodium bisulfite adds 0.7251 g paraformaldehyde after dissolving, 1.8611 g aniline of vapor enrichment are instilled after 60 DEG C of reaction 35 min, stop heating after reacting 2 h, obtain anilino methanesulfonic sodium mixed solution.
(3) preparation of azobenzene compound: after the mixed solution that step (2) obtains is cooled to room temperature, slowly instill in the diazonium salt that step (1) obtains under vigorous stirring, now, the diazonium salt solution dimmed red viscous fluid gradually of clarification, temperature control terminates reaction after 0 ~ 5 DEG C of reaction 6 h; Add 50 mL 30% aqueous sodium hydroxide solutions; dark red viscous fluid becomes yellow turbid solution; lower 45 DEG C of hydrolysis 7 h of nitrogen protection; 8 are about with salt acid for adjusting pH value after terminating reaction; thick product is through TLC separation; obtaining dyestuff 3-bromo-4-amido nitrogen benzide 1.8225 g(productive rate is 33%), its chemical structural formula is as shown in Equation 1.
1H NMR (CDCl
3-TMS, 400MHz): 4.06(s,2H,NH
2)，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 as shown in Figure 1.
embodiment 2
The present embodiment is the preparation method of 3-bromo-3-methyl-4-amido nitrogen benzide, comprises the following steps:
(1) preparation of diazonium salt: add 3.4414 g 3-bromanilines and 8 mL 20% hydrochloric acid in 100 mL beakers, slowly 1.5216 g sodium nitrite in aqueous solution are dripped at 0 ~ 5 DEG C, add urea after 2 h and eliminate excessive nitrite, sodium-acetate solid adjust ph to 5, the clear liquor of acquisition is put in frozen water for subsequent use.
(2) preparation of o-methyl-benzene amido methanesulfonic sodium: add 10 mL water and 2.3517 g sodium bisulfites in 50 mL round-bottomed flasks, sodium bisulfite adds 0.7264 g paraformaldehyde after dissolving, 2.1406 g o-toluidines are instilled after 60 DEG C of reaction 35 min, stop heating after reacting 2 h, obtain o-methyl-benzene amido methanesulfonic sodium mixed solution.
(3) preparation of azobenzene compound: after the mixed solution that step (2) obtains is cooled to room temperature, slowly instill in the diazonium salt that step (1) obtains under vigorous stirring, now, the diazonium salt solution dimmed red viscous fluid gradually of clarification, temperature control terminates reaction after 0 ~ 5 DEG C of reaction 6 h; Add 50 mL 30% aqueous sodium hydroxide solutions; dark red viscous fluid becomes yellow turbid solution; lower 40 DEG C of hydrolysis 7 h of nitrogen protection; 8 are about with salt acid for adjusting pH value after terminating reaction; thick product is through TLC separation; obtain dyestuff 3-bromo-3-methyl-4-amido nitrogen benzide 1.7608 g(productive rate 31%), its chemical structural formula is as shown in Equation 2.
1H NMR(CDCl
3-TMS,400MHz): 2.23(s,3H,CH
3)，4.05(s,2H,NH
2)，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 as shown in Figure 1.
embodiment 3
The present embodiment is the preparation method of 3-bromo-3-methoxyl group-4-amido nitrogen benzide, comprises the following steps:
(1) preparation of diazonium salt: add 3.4451g 3-bromaniline and 8 mL 20% hydrochloric acid in 100 mL beakers, slowly 1.5211 g sodium nitrite in aqueous solution are dripped at 0 ~ 5 DEG C, add urea after 2 h and eliminate excessive nitrite, sodium-acetate solid adjust ph to 5, the clear liquor of acquisition is put in frozen water for subsequent use.
(2) preparation of ORTHO ANISIDINE base methanesulfonic sodium: add 10 mL water and 2.3528 g sodium bisulfites in 50 mL round-bottomed flasks, sodium bisulfite adds 0.7242 g paraformaldehyde after dissolving, 2.4608 g ORTHO ANISIDINE are instilled after 60 DEG C of reaction 35 min, stop heating after reacting 2 h, obtain ORTHO ANISIDINE base methanesulfonic sodium mixed solution.
(3) preparation of azobenzene compound: after the mixed solution that step (2) obtains is cooled to room temperature, slowly instill in the diazonium salt that step (1) obtains under vigorous stirring, now, clarification diazonium salt solution dimmed red viscous fluid gradually, temperature control terminates reaction after 0 ~ 5 DEG C of reaction 6 h; Add 50 mL 30% aqueous sodium hydroxide solutions; dark red viscous fluid becomes yellow turbid solution; lower 40 DEG C of hydrolysis 7 h of nitrogen protection; 8 are about with salt acid for adjusting pH value after terminating reaction; thick product is through TLC separation; obtain dyestuff 3-bromo-3-methoxyl group-4-amido nitrogen benzide 1.7608 g(productive rate 21%), its chemical structural formula is as shown in Equation 3.
1H NMR(CDCl
3-TMS,400MHz): 3.88(s,3H,OCH
3)，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 as shown in Figure 1.
embodiment 4
The present embodiment is 3, and the preparation method of 5-two bromo-4-amido nitrogen benzides, comprises the following steps:
(1) preparation of diazonium salt: add 5.0121 g 3 in 100 mL beakers, 5-dibromo aniline and 8 mL 20% hydrochloric acid, slowly in suspension liquid, 1.5213 g sodium nitrite in aqueous solution are dripped at 0 ~ 5 DEG C, suspension liquid adds urea and eliminates excessive nitrite after becoming clarification, sodium-acetate solid adjust ph to 5, the clear liquor of acquisition is put in frozen water for subsequent use.
(2) preparation of anilino methanesulfonic sodium: add 10 mL water and 2.3529 g sodium bisulfites in 50 mL round-bottomed flasks, sodium bisulfite adds 0.7231 g paraformaldehyde after dissolving, the aniline of 1.8609 g vapor enrichments is instilled after 60 DEG C of reaction 35 min, stop heating after reacting 2 h, obtain anilino methanesulfonic sodium mixed solution.
(3) preparation of azobenzene compound: after the mixed solution that step (2) obtains is cooled to room temperature, slowly instill in the diazonium salt that step (1) obtains under vigorous stirring, now, clarification diazonium salt solution dimmed red viscous fluid gradually, temperature control terminates reaction after 0 ~ 5 DEG C of reaction 6 h.Add 50 mL 30% aqueous sodium hydroxide solutions; dark red viscous fluid becomes yellow turbid solution; lower 55 DEG C of hydrolysis 7 h of nitrogen protection; 8 are about with salt acid for adjusting pH value after terminating reaction; thick product is through TLC separation; obtain dyestuff 3,5-two bromo-4-amido nitrogen benzide 2.2713 g(productive rates 32%), its chemical structural formula is as shown in Equation 4.
1H NMR(CDCl
3-TMS,400MHz): 4.17(s,2H,NH
2)，6.74(d,J= 8.0Hz, 2H)，7.67 (s,1H)，7.80(d,J=8.0Hz,2H)，7.92(s,2H)。Infrared spectrogram as shown in Figure 1.
Dyestuff 3,5-two bromo-4-amido nitrogen benzides maximum absorption wavelength in ethyl acetate is 407 nm, and prepared D-π-A type aminoazobenzene dyestuff is configured to 8.0 × 10
-5mol/L ethyl acetate solution, gets in right amount in band circle plug quartz colorimetric utensil, with 405 ± 10 nm UV-irradiation solution, and by each moment of ultraviolet-visible pectrophotometer record (
t=0,0.2,0.4,0.6,0.8,1.0,1.4,1.8,2.4 uv-vis spectras s), until photostationary state, as shown in Figure 2, result shows the ultraviolet-visible spectrogram in each moment of illumination: l before illumination
maxthe strong absorption peak of=407 nm is p-p
*and n-p
*the absorption peak of two group-overlaps, after 405 ± 10 nm rayed, strong peak absorbancy reduces rapidly,
tduring=0.6 s, wavelength 355 nm place's appearance new absorption peak is n-p
*transition absorption peak, 407 strong peak, nm place absorbancys continue to reduce subsequently, and the peak absorbancy at 355 nm places increases a little,
treach stable state during=2.4 s, two are waited suction point respectively at 362,488 nm places.
And then use the light of 365 ± 10 nm to reply, respectively measure reply each moment (
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 spectras, as shown in Figure 3, now p-p
*transition strong peak absorbancy rises rapidly and occurs blue shift, n-p
*transition peak absorbancy declines and red shift occurs, when
tduring=2.0 s, 355 nm place absorption peaks and 407 nm places absorb peak complete-superposing.Wait the appearance of inhaling point according to two, though there is new absorption peak to increase, light can occurs and reply, can determine that list of target compound under 407 ± 10 nm and 365 ± 10 nm light alternately irradiate, cis-trans isomerism only occurs and changes, the side reaction such as photo-crosslinking or photodegradation does not occur.
embodiment 5
The present embodiment is 3, and the preparation method of 5-two bromo-3-methyl-4-amido nitrogen benzides, comprises the following steps:
(1) preparation of diazonium salt: add 5.0132 g 3 in 100 mL beakers, 5-dibromo aniline and 8 mL 20% hydrochloric acid, slowly in suspension liquid, 1.5241 g sodium nitrite in aqueous solution are dripped at 0 ~ 5 DEG C, suspension liquid adds urea and eliminates excessive nitrite after becoming clarification, sodium-acetate solid adjust ph to 5, the clear liquor of acquisition is put in frozen water for subsequent use.
(2) preparation of o-methyl-benzene amido methanesulfonic sodium: add 10 mL water and 2.3534 g sodium bisulfites in 50 mL round-bottomed flasks, sodium bisulfite adds 0.7219 g paraformaldehyde after dissolving, 2.1413 g o-toluidines are instilled after 60 DEG C of reaction 35 min, stop heating after reacting 2 h, obtain o-methyl-benzene amido methanesulfonic sodium mixed solution.
(3) preparation of azobenzene compound: after the mixed solution that step (2) obtains is cooled to room temperature, slowly instill in the diazonium salt that step (1) obtains under vigorous stirring, now, clarification diazonium salt solution dimmed red viscous fluid gradually, temperature control terminates reaction after 0 ~ 5 DEG C of reaction 6 h.Add 50 mL 30% aqueous sodium hydroxide solutions; dark red viscous fluid becomes yellow turbid solution; lower 50 DEG C of hydrolysis 7 h of nitrogen protection; 8 are about with salt acid for adjusting pH value after terminating reaction; thick product is through TLC separation; obtain dyestuff 3,5-two bromo-3-methyl-4-amido nitrogen benzide 2.1402g(productive rates 30%), its chemical structural formula is as shown in Equation 5.
1H NMR(CDCl
3-TMS,400MHz): 2.20(s,3H, CH
3)，4.09(s,1H,NH
2)，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 as shown in Figure 1.
embodiment 6
The present embodiment is 3, and the preparation method of 5-two bromo-3-methoxyl group-4-amido nitrogen benzides, comprises the following steps:
(1) preparation of diazonium salt: add 5.0114 g 3 in 100 mL beakers, 5-dibromo aniline and 8 mL 20% hydrochloric acid, slowly in suspension liquid, 1.5232 g sodium nitrite in aqueous solution are dripped at 0 ~ 5 DEG C, suspension liquid adds urea and eliminates excessive nitrite after becoming clarification, sodium-acetate solid adjust ph to 5, clear liquor is put in frozen water for subsequent use.
(2) preparation of ORTHO ANISIDINE base methanesulfonic sodium: add 10 mL water and 2.3553 g sodium bisulfites in 50 mL round-bottomed flasks, sodium bisulfite adds 0.7221 g paraformaldehyde after dissolving, 2.4610 g ORTHO ANISIDINE are instilled after 60 DEG C of reaction 35 min, stop heating after reacting 2 h, obtain ORTHO ANISIDINE base methanesulfonic sodium mixed solution.
(3) preparation of azobenzene compound: after the mixed solution that step (2) obtains is cooled to room temperature, slowly instill in the diazonium salt that step (1) obtains under vigorous stirring, now, clarification diazonium salt solution dimmed red viscous fluid gradually, temperature control terminates reaction after 0 ~ 5 DEG C of reaction 6 h.Add 50 mL 30% aqueous sodium hydroxide solutions; dark red viscous fluid becomes yellow turbid solution; lower 50 DEG C of hydrolysis 7 h of nitrogen protection; 8 are about with salt acid for adjusting pH value after terminating reaction; thick product is through TLC separation; obtain dyestuff 3,5-two bromo-3-methoxyl group-4-amido nitrogen benzide 2.237g(productive rates 29%), its chemical structural formula is as shown in Equation 6.
1H NMR(CDCl
3-TMS,400MHz): 3.89(s,1H,OCH
3)，4.35(s,1H,NH
2)，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 as shown in Figure 1.
comparative example 1
This comparative example adopts the synthetic method of traditional nitrogen benzide, and detailed process is as follows:
(1) preparation of diazonium salt: add 5.0112 g 3 in 100 mL beakers, 5-dibromo aniline and 8 mL 20% hydrochloric acid, slowly in suspension liquid, 1.5207 g sodium nitrite in aqueous solution are dripped at 0 ~ 5 DEG C, suspension liquid adds urea and eliminates excessive nitrite after becoming clarification, sodium-acetate solid adjust ph to 5, the clear liquor of acquisition is put in frozen water for subsequent use.
(2) coupled reaction: aniline 1.8618 g getting new distillation is cooled to 0 ~ 5 DEG C in frozen water, slowly be added drop-wise in the diazonium salt of preparation in (1) under the condition of magnetic agitation, react stopped reaction after about 5 hours, add sodium hydroxide adjust ph to 8 ~ 9, TLC separation, does not obtain re-set target compound.
Through many experiments and parameter optimization, show: traditional method, use bromoaniline to can not get nitrogen benzide of the present invention.
embodiment 7
The present embodiment is the preparation method to 3,5-bis-bromo-4-amido nitrogen benzide be optimized, and draws top condition prepared by serial azoic dyestuff.
1, the experimental technique optimization prepared of diazonium salt: doazo reaction is reaction medium usually with water, based on 3,5-dibromo aniline solid is water insoluble, and solvability is larger in ethanol, just the solvent using ethanol as reaction, but along with adding of aqueous hydrochloric acid, there is a large amount of solid to separate out immediately, finally cause doazo reaction poor effect (productive rate of nitrogen benzide only has an appointment 5%).Experiment finds, with the medium of 20% aqueous hydrochloric acid (consumption is 7 ~ 9 mL) as reaction, and salt excessive acid (pH<2), in addition, react front mortar by 3,5-dibromo aniline porphyrize, along with sodium nitrite in aqueous solution progressively drips into, suspension just becomes clarification gradually, the diazonium salt solution clarified is obtained after reaction terminates, illustrate that diazotization reaction is relatively thorough, then add sodium-acetate solid pH is adjusted to 4 ~ 5, the productive rate of the nitrogen benzide that last coupled reaction obtains can reach 32%.
2, the experimental technique optimization of amido protection: after bromoaniline diazonium salt and the direct coupling of coupling component repeatedly repeat the failure of an experiment, this invention takes the method for amido protecting.The consumption of fixing aniline is under the prerequisite of 1 equivalent, investigate the consumption of paraformaldehyde and sodium bisulfite to the impact of reaction yield, when paraformaldehyde consumption is respectively 1,1.1 and 1.2 equivalent, the productive rate of the correspondence of nitrogen benzide is 25%, 31% and 32%, sodium bisulfite consumption changes from 1 to 1.1 equivalents, and the productive rate of nitrogen benzide is substantially unaffected.
3, the optimization of Deprotection experimental technique is hydrolyzed: in hydrolysis deprotection reaction; hydrolysis temperature is larger on reaction yield impact; experiment finds when hydrolysis temperature more than 70 DEG C; hydrolysis just there will be the sticky shape material of reddish black soon and is wrapped in magnetic stir bar; form one, make hydrolysis reaction be difficult to carry out thoroughly, last isolated yield only has an appointment 10%; if hydrolysis temperature too low (less than 30 DEG C), the time of hydrolysis needs to grow very much and is difficult to ensure that hydrolysis completely.Condition is groped by experiment, show that optimum hydrolysis temperature is 40 ~ 55 DEG C, and according to the textural difference of product, hydrolysis temperature changes a little, the compound that on diazo component phenyl ring, sucting electronic effect is stronger, the temperature of hydrolysis is suitably high, otherwise lower, therefore, the temperature of two bromo compound hydrolysis is more a little than the height of a corresponding bromo compound.
Claims (7)
1. a D-π-A type aminoazobenzene dyestuff, it is characterized in that, its chemical structural formula is:
Wherein, R
1for hydrogen or methyl or methoxy, R
2for hydrogen or bromine substituent.
2. the preparation method of azobenzene dye described in claim 1, is characterized in that, comprises the following steps:
S1. the preparation of bromoaniline diazonium salt: after bromoaniline and Sodium Nitrite react in acid condition, eliminate excessive nitrite, adjust ph be 5 ~ 6 bromoaniline diazonium salt;
S2. the preparation of aromatic amino methanesulfonic sodium: add paraformaldehyde or formalin in sodium sulfite solution, after 60 ~ 65 DEG C of reactions, then adds aromatic amine reaction acquisition aromatic amino methanesulfonic sodium;
S3. join in bromoaniline diazonium salt by aromatic amino methanesulfonic sodium solution, 0 ~ 5 DEG C of reaction 6 ~ 7 h, add alkali and carry out thermal hydrolysis at 40 ~ 55 DEG C, adjust pH is 8 ~ 9, obtains D-π-A type aminoazobenzene;
Wherein, bromoaniline described in S1 is 3,5-dibromo aniline, 3-bromaniline, and aromatic amine described in S2 is aniline, o-toluidine or ORTHO ANISIDINE.
3. preparation method according to claim 2, is characterized in that, described in S2, the mass ratio of aromatic amine, paraformaldehyde and sodium bisulfite is 3.1 ~ 4.1:1.0 ~ 1.2:3.4 ~ 3.8; The mol ratio of described aromatic amine, formalin and sodium bisulfite is 1.0:1.0 ~ 1.2:1.0 ~ 1.1.
4. preparation method according to claim 2, is characterized in that, the aromatic amino methanesulfonic sodium described in S3 and the mol ratio of bromoaniline diazonium salt are 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 is as the application of Blu-ray Disc recording medium.
7. azobenzene dye described in claim 1 is as the application of nonlinear optical material.
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| CN116120259A (en) * | 2022-12-09 | 2023-05-16 | 吉林大学 | D-pi-A azobenzene piezochromic material and preparation method thereof |
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