CN106588691A - Photo-responsive azobenzene type compound as well as synthetic method and application thereof - Google Patents
Photo-responsive azobenzene type compound as well as synthetic method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
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Abstract
The invention discloses a photo-responsive azobenzene type compound as well as a synthetic method and an application thereof. The structural formula of the azobenzene type compound is shown in the description, and in the formula, R represents H, -(CH2)mCH3,-O(CH2)mCH3 or -O(CF2)mCF3, m is an integer from 0 to 6, n is an integer from 4 to 12, and R1 represents alkyl of C1-C4. The photo-responsive azobenzene type compound prepared according to the invention has special surface activity (amphipathicity) which can be simply regulated and controlled under the action of illumination and temperature, multiphase emulsion can be prepared by one-step emulsification of oil and water phases by only singly adopting the azobenzene type compound disclosed by the invention as a stabilizer, the multiphase emulsion cannot be subjected to phase separation due to irradiation of ultraviolet light, and the preparation method is simple and is suitable for various oil-water phase systems.
Description
Technical field
The present invention relates to a kind of optical Response azobenzene compound, and the synthetic method of the compound and the compound
Application as stabilizer in multi-phase emulsion is prepared.
Background technology
Azobenzene (azobenzene) class compound is in the photochromic material and important Dyestuff synthesis of a quasi-representative
Mesosome, it is-N=N- the keys due to containing in molecular structure that its photochromic characteristic studies carefully its essence, in ultraviolet-visible or heat
In the presence of occur it is cis- anti-or it is trans- cause along isomery, change some of molecule group in addition, compound it is photochromic
And isomery performance also can change.Under normal circumstances, azobenzene compound is with transconfiguration (trans-) stable existence
, after the azobenzene compound to transconfiguration carries out the ultraviolet light of certain hour, its structure will be changed into cis
Structure (cis-).For transconfiguration, cis-structure is thermodynamic instability configuration, therefore in visible ray or the work of heat
With under, the transconfiguration that what cis-structure can be spontaneous carry out hot wire-CVD, finally become rock-steady structure again.Due to azobenzene compound
This special nature so as in liquid crystal material, textile dyestuff, optical drive molecular switch, optical storage material, biologically active light
Control, surface relief grating and order surface, nonlinear optical material, photonic material, light power receive the fields such as micron machinery all
There is important application.
Amphiphilic compound refers to the compound in molecule simultaneously with polar head group and hydrophobic tail group, including
Biparental organisms molecule phosphatide, surfactant, ionic liquid of surface-active etc., it is closely related with the life of the mankind.Parents
Compound is self-assembly of in the solution various ordered aggregations and plays because having hydrophilic radical and hydrophobic grouping simultaneously
Important function.Ordered aggregation how is built accordingly, with respect to parents' molecule, the such as research of micella, vesica, liquid crystal and solid, extensively
Cause the concern of people generally, and become a focus in current Colloid and interface chemistry field.
And parents' azobenzene compound combines the photochromic and cis-trans isomerization performance of azobenzene compound, after
The good optical activity of azobenzene compound has been held, meanwhile, parents' azobenzene compound is again because intramolecular is simultaneously containing parent
Hydrophobic grouping so as to be provided with special surface-active.So such compound can be used as a kind of surface-active of optical Response
Agent is applied to all kinds of emulsions preparations and the aggregate structure with special transformative is formed, thus constantly causes people's in recent years
Concern.Yukishige Kondo seminars adopt azobenzene derivatives C4AzoTAB and SDS mixtures are used as surfactant system
Standby stable emulsion, then author utilize azobenzene derivatives C4AzoTAB structures in ultraviolet lighting will become from transconfiguration
Performance for cis-structure makes stable emulsion breakdown of emulsion, and emulsion can not be again formed when the two-phase after breakdown of emulsion is emulsified again.
And in actual applications, we are not intended to the transformation of azo surfactant cis-trans isomerism sometimes affects stablizing for emulsion
Property.For example when preparing porous material using emulsion template method, we be both desirable with the rigid benzene of azobenzene surfactant
Structure produces stable emulsion and is difficult to be affected by azo group cis-trans isomerism, and azobenzene surfactant is desirable with again
Molecule cis-trans isomerism can occur in emulsion system and change its assembly behavior and then prepare the material with novel structure pattern.
At present, while the azobenzene compound for meeting this requirement has not been reported.
The content of the invention
The technical problem to be solved is to provide a kind of azobenzene compound with optical Response, and is
The compound provides a kind of synthetic method and new application.
Solve the technical scheme that adopted of above-mentioned technical problem be the optical Response azobenzene compound structural formula such as
Shown in lower：
R represents-H ,-(CH in formula2)mCH3、-O(CH2)mCH3Or-O (CF2)mCF3, m is 0～6 integer, and n is 4～12
Integer, R1Represent C1～C4Alkyl；It is preferred that R represents-H or-OCF3。
The synthetic route and concrete preparation method of above-mentioned optical Response azobenzene compound is as follows：
1st, the compound of formula 2
Shown in formula 1 amino benzenes compounds will be dissolved in distilled water and dense H2SO4Volume ratio be 1:1 mixed solution
In, add NaNO at 0～5 DEG C2The aqueous solution carries out diazo-reaction；By phenol, NaOH, Na2CO3After being dissolved in distilled water, add
In solution after above-mentioned diazo-reaction, react 4～5 hours at 0～5 DEG C, filter, wash, be dried, recrystallize, obtain formula 2
Compound.
2nd, the compound of formula 4
Under nitrogen protection, with tetrahydrofuran as solvent, by dibromoalkane hydrocarbon, K shown in the compound of formula 2, formula 32CO3Press
Mol ratio is 1:4～6:3～5, react 20～24 hours at 70～80 DEG C, isolate and purify, obtain the compound of formula 4.
3rd, the compound of formula 5
Under nitrogen protection, with tetrahydrofuran as solvent, epoxy prapanol, 15- crown ethers -5, NaH are reacted at 0～5 DEG C
30～60 minutes, the compound of formula 4 is subsequently adding, normal-temperature reaction 10～12 hours is isolated and purified, and obtains the compound of formula 5；Wherein formula
4 compounds are 1 with the mol ratio of epoxy prapanol, 15- crown ethers -5, NaH:0.3～1:0.03～0.1:1.5～3.
4th, optical Response azobenzene compound is prepared
In confined conditions, it is in molar ratio 1 by the secondary amine shown in the compound of formula 5, formula 6 with tetrahydrofuran as solvent:1
～1.5, react 3～5 hours at 60～70 DEG C, isolate and purify, obtain optical Response azobenzene compound.
Dibromoalkane hydrocarbon, K in above-mentioned steps 2, shown in the compound of preferred formula 2, formula 32CO3Mol ratio be 1:5:4.
In above-mentioned steps 3, the compound of preferred formula 4, epoxy prapanol, the mol ratio of 15- crown ethers -5, NaH are 1:0.5:0.05:
2。
Application of the optical Response azobenzene compound of the present invention as stabilizer in multi-phase emulsion is prepared, when using
Directly it is mixed with water phase, oil phase, stirring is obtained corresponding multi-phase emulsion.
Beneficial effects of the present invention are as follows：
1st, azobenzene compound of the invention can occur cis-trans isomerism under illumination condition, by anti-under ultraviolet light
Formula structure to cis-structure changes, and is changed from cis-structure to transconfiguration under visible ray or heating condition, the change of structure
Make the compound that there is special surface-active, its surface-active (amphiphilic) can simply be adjusted by illumination and temperature
Control.
Though the 2, adopt the multi-phase emulsion for preparing for stabilizer of azobenzene compound of the present invention under the irradiation of ultraviolet light
So stabilizer there occurs cis-trans isomerism, but emulsion not split-phase, i.e. emulsion intercalation method by azobenzene compound along reef knot
The impact of structure change, can obtain stable multi-phase emulsion system, and this is just that the material for subsequently preparing novel structure pattern is established
Basis.
It is when the 3rd, adopting the azobenzene compound of the present invention to prepare multi-phase emulsion for stabilizer, it is straight with water phase, oil phase
Multi-phase emulsion is prepared into by connecing mixing one-step method.Multiphase breast is prepared with two kinds of surfactants, two steps are needed in prior art
A kind of surfactant (is first prepared by mixing into O/W or W/O internal phase emulsions, then will be made again by the method for liquid with water phase or oil phase
Obtain internal phase emulsions and mix preparation O/W/O or W/O/W multi-phase emulsions with another kind of surfactant, outer oil phase or outer water) compared with,
Preparation method is simple, it is adaptable to various profit phase systems.
Description of the drawings
Fig. 1 is the optical microscope of W/O/W multi-phase emulsions prepared by embodiment 3.
Fig. 2 is the photo of W/O/W multi-phase emulsions prepared by embodiment 3.
Fig. 3 is the optical microscope of O/W/O multi-phase emulsions prepared by embodiment 4.
Fig. 4 is the photo of O/W/O multi-phase emulsions prepared by embodiment 4.
Fig. 5 is the optical microscope of W/O/W multi-phase emulsions prepared by embodiment 5.
Fig. 6 is the photo of W/O/W multi-phase emulsions prepared by embodiment 5.
Fig. 7 is the optical microscope of W/O/W multi-phase emulsions prepared by embodiment 6.
Fig. 8 is the photo of W/O/W multi-phase emulsions prepared by embodiment 6.
Fig. 9 is optical microscope of the W/O/W multi-phase emulsions of the preparation of embodiment 3 after ultraviolet light.
Figure 10 is photo of the W/O/W multi-phase emulsions of the preparation of embodiment 3 after ultraviolet light.
Figure 11 is optical microscope of the W/O/W multi-phase emulsions of the preparation of embodiment 5 after ultraviolet light.
Figure 12 is photo of the W/O/W multi-phase emulsions of the preparation of embodiment 5 after ultraviolet light.
Specific embodiment
With reference to the accompanying drawings and examples the present invention is described in more detail, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
Synthesis optical Response azobenzene compound (CF3- N-OH), synthetic route and synthetic method it is as follows：
1st, formula 2-1 compound
6.27g is added into 14mL distilled water and the dense H of 14mL to trifluoro-methoxyaniline (formula 1-1 compound)2SO4Mixing
In solution, after solid all dissolving, by 4.7g NaNO2It is dissolved in 31.5mL distilled water and above-mentioned mixing is added at 0 DEG C
Diazo-reaction is carried out in liquid, after solution become colorless it is transparent after stop reaction.By 5g phenol, 2g NaOH, 31.35g Na2CO3
180mL distilled water is dissolved in, then the solution is added in the colourless transparent solution after above-mentioned diazo-reaction, at 0 DEG C 5 are reacted
Hour, filtration after react, the yellowish-brown sediment redistilled water that obtains is dried after rinsing, dried product use just oneself
Alkane is recrystallized, and obtains crocus formula 2-1 compound, and its yield is 93%, and structural characterization result is：1H-NMR(400MHz,
CDCl3)δ(ppm):8.02-7.84(m,4H,Ar-H),7.34(d,2H,Ar-H),6.97(d,2H,Ar-H),5.38(s,1H,-
OH)。
2nd, formula 4-1 compound
Under nitrogen protection, 30mL tetrahydrofurans, 4g (30mmol) K are added in there-necked flask2CO3、6.9mL
(37mmol) bromooctanes of 1,8- bis- (formula 3-1 compound), is warming up under agitation 80 DEG C, by 2.1g (7.5mmol) formula 2-1
Compound is dissolved in after 20mL tetrahydrofurans and being added drop-wise in there-necked flask, isothermal reaction 20 hours, naturally cools to after having reacted often
Temperature, is first filtered with sand core funnel, removes K therein2CO3Solid, rotary evaporation removes tetrahydrofuran, with dichloromethane and secondary
Distilled water is extracted 3 times, and organic phase rotary evaporation is spin-dried for, then is heated to reflux, is cooled down recrystallization with n-hexane, removes unnecessary 1,8-
Two bromooctanes, finally with n-hexane and ethyl acetate volume ratio as 10:1 mixed solvent is solvent, with chromatographic column silica gel mistake
Post separation, obtains crocus formula 4-1 compound, and its yield is 88%, and structural characterization result is：1H-NMR(400MHz,CDCl3)δ
(ppm):7.98-7.85(m,4H,Ar-H),7.33(d,2H,Ar-H),7.04-6.97(m,2H,Ar-H),4.05(t,2H,-
OCH2-,),3.42(t,2H,-CH2Br),1.91-1.79(m,4H,-CH2-),1.52-1.34(m,8H,-CH2-)；MS(m/z,
ESI+)C21H24BrF3N2O2,473.1045([M+H+])。
3rd, formula 5-1 compound
Under nitrogen protection, 20mL tetrahydrofurans and 0.283g (12mmol) NaH are added in there-necked flask, is subsequently adding
199.7 μ L (3mmol) epoxy prapanols and 60 μ L (0.3mmol) 15- crown ethers -5, mixed liquor of 5mL tetrahydrofurans, it is anti-at 0 DEG C
Answer 30 minutes；2.8g (6mmol) formula 4-1 compound is dissolved in after 20mL tetrahydrofurans and is added drop-wise in there-necked flask, after dripping off often
Temperature reaction 10 hours, filters, and removes wherein remaining NaH solids, and rotary evaporation removes tetrahydrofuran, with dichloromethane and secondary
Distilled water is extracted 3 times, and organic phase rotary evaporation is spin-dried for, with n-hexane and ethyl acetate volume ratio as 10:1 mixed solvent is exhibition
Agent is opened, with chromatographic column silica gel post separation is crossed, obtain crocus formula 5-1 compound, its yield is 50%, and structural characterization result is：1H-NMR (400MHz, CDCl3)δ(ppm):7.91(dd,4H,Ar-H),7.33(d,2H,Ar-H),7.00(d,2H,Ar-H),
4.04(t,2H,-OCH2-),3.57-3.31(m,4H,-CH2O-,-OCH2-),3.15(dt,1H,-CH-O-),2.83-2.78
(m,1H,-CH2-),2.61(dd,1H,-CH2-),1.88-1.79(m,2H,-CH2-),1.53-1.30(m,10H,-CH2-)；MS
(m/z,ESI+)C24H29F3N2O4,467.2150([M+H+])。
4th, optical Response azobenzene compound (CF is prepared3-N-OH)
0.2g (0.4mmol) formula 5-1 compounds and 10mL tetrahydrofurans are added in there-necked flask, is injected with needle tubing
0.045g mass fractions are 40% dimethylamine agueous solution, are warming up to 65 DEG C, and isothermal reaction 5 hours, rotary evaporation removes tetrahydrochysene
Furans, with water after dichloromethane extraction revolving to colourless, organic phase rotary evaporation is spin-dried for, and obtains crocus optical Response idol
Azobenzene compounds (CF3- N-OH), its yield is 96%, and structural characterization result is：1H-NMR(400MHz,CDCl3)δ(ppm):
7.91(dd,4H,Ar-H),7.33(t,2H,Ar-H),6.99(t,2H,Ar-H),5.35(s,1H,-OH),4.04(t,2H,-
OCH2-),3.96-3.92(m,1H,-CH-),3.44(tt,4H,-CH2O-,-OCH2-),2.61-2.49(m,2H,-CH2-),
2.39(s,6H,-N(CH3)2),1.83-1.77(m,2H,-CH2-),1.50(ddd,10H,-CH2-)；MS (m/z, ESI+)
C26H36F3N3O4,512.2734([M+H+])。
Embodiment 2
Synthesize optical Response azobenzene compound (H-N-OH), synthetic route and synthetic method are as follows：
1st, formula 2-2 compound
3.2g aniline (formula 1-2 compound) is added into 14mL distilled water and the dense H of 14mL2SO4Mixed solution in, treat solid
All after dissolving, by 4.7g NaNO2It is dissolved in 31.5mL distilled water and is added into carrying out diazonium in above-mentioned mixed liquor at 0 DEG C
Change reaction, after solution become colorless it is transparent after stop reaction.By 5g phenol, 2g NaOH, 31.35g Na2CO3It is dissolved in 180mL steamings
Distilled water, then adds the solution in the colourless transparent solution after above-mentioned diazo-reaction, reacts 5 hours at 0 DEG C, has reacted
After filter, the yellowish-brown sediment redistilled water that obtains is dried after rinsing, and dried product is recrystallized with n-hexane, is obtained
To formula Chinese red 2-2 compounds, its yield is 95%, and structural characterization result is：1H-NMR(400MHz,CDCl3)δ(ppm):
7.89(t,4H,Ar-H),7.50(t,2H,Ar-H),7.44(t,1H,Ar-H),6.96(d,2H,Ar-H),5.25(s,1H,-
OH)。
2nd, formula 4-2 compound
Under nitrogen protection, 30mL tetrahydrofurans, 4g (30mmol) K are added in there-necked flask2CO3、6.9mL
(37mmol) bromooctanes of 1,8- bis- (formula 3-2 compound), is warming up under agitation 80 DEG C, by 1.5g (7.5mmol) formula 2-2
Compound is dissolved in after 20mL tetrahydrofurans and being added drop-wise in there-necked flask, isothermal reaction 20 hours, naturally cools to after having reacted often
Temperature, is first filtered with sand core funnel, removes K therein2CO3Solid, rotary evaporation removes tetrahydrofuran, with dichloromethane and secondary
Distilled water is extracted 3 times, and organic phase rotary evaporation is spin-dried for, then is heated to reflux, is cooled down recrystallization with n-hexane, removes unnecessary 1,8-
Two bromooctanes, finally with n-hexane and ethyl acetate volume ratio as 10:1 mixed solvent is solvent, with chromatographic column silica gel mistake
Post separation, obtains Chinese red formula 4-1 compound, and its yield is 80%, and structural characterization result is：1H-NMR(400MHz,CDCl3)δ
(ppm):7.95-7.84(m,4H,Ar-H),7.50(t,2H,Ar-H),7.43(t,1H,Ar-H),7.00(d,2H,Ar-H),
4.04(t,2H,-OCH2-,),3.42(t,2H,-CH2Br),1.90-1.79(m,4H,-CH2-),1.51-1.32(m,8H,-
CH2-)；MS(m/z,ESI+)C20H25BrN2O,389.1220([M+H+])。
3rd, formula 5-2 compound
Under nitrogen protection, 20mL tetrahydrofurans and 0.283g (12mmol) NaH are added in there-necked flask, is subsequently adding
199.7 μ L (3mmol) epoxy prapanols and 60 μ L (0.3mmol) 15- crown ethers -5, mixed liquor of 5mL tetrahydrofurans, it is anti-at 0 DEG C
Answer 30 minutes；2.3g (6mmol) formula 4-2 compound is dissolved in after 20mL tetrahydrofurans and is added drop-wise in there-necked flask, after dripping off often
Temperature reaction 10 hours, filters, and removes wherein remaining NaH solids, and rotary evaporation removes tetrahydrofuran, with dichloromethane and secondary
Distilled water is extracted 3 times, and organic phase rotary evaporation is spin-dried for, with n-hexane and ethyl acetate volume ratio as 10:1 mixed solvent is exhibition
Agent is opened, with chromatographic column silica gel post separation is crossed, obtain Chinese red formula 5-2 compound, its yield is 50%, and structural characterization result is：1H-NMR (400MHz, CDCl3)δ(ppm):7.99-7.83(m,4H,Ar-H),7.50(dd,2H,Ar-H),7.42(dd,1H,
Ar-H),7.30-6.97(m,2H,Ar-H),4.04(t,2H,-OCH2-),3.71(dd,1H,-OCH2-),3.49(ddt,2H,-
CH2O-),3.38(dt,1H,-OCH2-),3.15(m,1H,-CH-O-),2.82-2.76(m,1H,-OCH2-),2.61(dt,
1H,-OCH2-),1.87-1.78(m,2H,-CH2-),1.64-1.58(m,2H,-CH2-),1.52-1.30(m,8H,-CH2-)；
MS(m/z,ESI+)C23H30N2O3,383.2336([M+H+])。
4th, optical Response azobenzene compound (H-N-OH) is prepared
0.15g (0.4mmol) formula 5-2 compounds and 10mL tetrahydrofurans are added in there-necked flask, is injected with needle tubing
0.045g mass fractions are 40% dimethylamine agueous solution, are warming up to 65 DEG C, and isothermal reaction 5 hours, rotary evaporation removes tetrahydrochysene
Furans, with water after dichloromethane extraction revolving to colourless, organic phase rotary evaporation is spin-dried for, and obtains Chinese red optical Response idol
Azobenzene compounds (H-N-OH), its yield is 90%, and structural characterization result is：1H-NMR(400MHz,CDCl3)δ(ppm):7.89
(dd,4H,Ar-H),7.50(t,2H,Ar-H),7.44(d,1H,Ar-H),7.00(t,2H,Ar-H),5.34(s,1H,-OH),
4.04(t,2H,-OCH2-),3.70(m,1H,-CH-),3.52-3.38(m,4H,-CH2O-,-OCH2-),2.73-2.55(m,
8H,-CH2-,-N(CH3)2),1.95-1.45(m,12H,-CH2-)；MS (m/z, ESI+)C25H37N3O3,428.2920([M+H+])。
Embodiment 3
Application of the optical Response azobenzene compound of embodiment 1 in W/O/W multi-phase emulsions are prepared, specifically used method
It is as follows：
0.02g optical Response azobenzene compounds are dissolved in 0.5mL styrene, 0.5mL distilled water are added, normal
The lower mechanical agitation of temperature 2 minutes, rotating speed is 11400 revs/min, obtains W/O/W multi-phase emulsions (see Fig. 1 and Fig. 2), as seen from the figure,
Gained emulsion presents the multi-phase emulsion structure comprising multiple droplets in big drop, and emulsion droplet size is distributed in 8～15 μm
Between.
Embodiment 4
Application of the optical Response azobenzene compound of embodiment 1 in O/W/O multi-phase emulsions are prepared, specifically used method
It is as follows：
0.02g optical Response azobenzene compounds are dissolved in 0.5mL GMAs, are added
0.5mL distilled water, mechanical agitation 2 minutes at normal temperatures, rotating speed is 11400 revs/min, obtains O/W/O multi-phase emulsions (see Fig. 3
And Fig. 4), as seen from the figure, gained emulsion presents the multi-phase emulsion structure comprising multiple droplets in big drop, and emulsion droplet is big
Little uniform, size is about 10 μm.
Embodiment 5
Application of the optical Response azobenzene compound of embodiment 1 in W/O/W multi-phase emulsions are prepared, specifically used method
It is as follows：
0.01g optical Response azobenzene compounds are dissolved in 0.3mL butyl acrylates, 0.3mL distilled water is added,
Mechanical agitation 2 minutes at normal temperatures, rotating speed is 11400 revs/min, obtains W/O/W multi-phase emulsions (see Fig. 5 and Fig. 6), can by figure
See, gained emulsion presents the multi-phase emulsion structure comprising multiple droplets in big drop, emulsion droplet size is more uniform, chi
It is very little to be distributed between 10～18 μm.
Embodiment 6
Application of the optical Response azobenzene compound of embodiment 2 in W/O/W multi-phase emulsions are prepared, specifically used method
It is as follows：
0.01g optical Response azobenzene compounds are dissolved in 0.3mL acrylonitrile, 0.3mL distilled water are added, normal
The lower mechanical agitation of temperature 2 minutes, rotating speed is 11400 revs/min, obtains W/O/W multi-phase emulsions (see Fig. 7 and Fig. 8), as seen from the figure,
Gained emulsion presents the multi-phase emulsion structure comprising droplet in big drop, and emulsion droplet size is more uniform, Size Distribution
Between 10～18 μm.
Inventor by embodiment 3 and 5 prepare multi-phase emulsion irradiate under ultraviolet light 3 hours, find emulsion color by
Yellow originally is changed into crocus, illustrates that optical Response azobenzene compound there occurs from transconfiguration to suitable in emulsion system
The transformation of formula structure, but split-phase emulsion does not occur and emulsion still presents the structure (see Fig. 9～12) of multiphase.
Claims (6)
1. a kind of optical Response azobenzene compound, it is characterised in that the structural formula of the azobenzene compound is as follows：
R represents-H ,-(CH in formula2)mCH3、-O(CH2)mCH3Or-O (CF2)mCF3, m is 0～6 integer, n be 4～12 it is whole
Number, R1Represent C1～C4Alkyl.
2. optical Response azobenzene compound according to claim 1, it is characterised in that：Described R represent-H or-
OCF3。
3. the synthetic method of the optical Response azobenzene compound described in a kind of claim 1, it is characterised in that it is by following
Step is constituted：
(1) compound of formula 2
Shown in formula 1 amino benzenes compounds will be dissolved in distilled water and dense H2SO4Volume ratio be 1:In 1 mixed solution,
NaNO is added at 0～5 DEG C2The aqueous solution carries out diazo-reaction；By phenol, NaOH, Na2CO3After being dissolved in distilled water, add above-mentioned
In solution after diazo-reaction, react 4～5 hours at 0～5 DEG C, filter, wash, be dried, recrystallize, obtain the chemical combination of formula 2
Thing；
(2) compound of formula 4
Under nitrogen protection, with tetrahydrofuran as solvent, by dibromoalkane hydrocarbon, K shown in the compound of formula 2, formula 32CO3By mole
Than for 1:4～6:3～5, react 20～24 hours at 70～80 DEG C, isolate and purify, obtain the compound of formula 4；
(3) compound of formula 5
Under nitrogen protection, with tetrahydrofuran as solvent, epoxy prapanol, 15- crown ethers -5, NaH react at 0～5 DEG C 30～
60 minutes, the compound of formula 4 is subsequently adding, normal-temperature reaction 10～12 hours is isolated and purified, and obtains the compound of formula 5；Wherein formula 4 is changed
Compound is 1 with the mol ratio of epoxy prapanol, 15- crown ethers -5, NaH:0.3～1:0.03～0.1:1.5～3；
(4) optical Response azobenzene compound is prepared
In confined conditions, it is in molar ratio 1 by the secondary amine shown in the compound of formula 5, formula 6 with tetrahydrofuran as solvent:1～
1.5, react 3～5 hours at 60～70 DEG C, isolate and purify, obtain optical Response azobenzene compound；
4. the synthetic method of optical Response azobenzene compound according to claim 3, it is characterised in that：In step
(2) dibromoalkane hydrocarbon, the K in, shown in the compound of the formula 2, formula 32CO3Mol ratio be 1:5:4.
5. the synthetic method of optical Response azobenzene compound according to claim 3, it is characterised in that：In step
(3) in, the compound of the formula 4, epoxy prapanol, the mol ratio of 15- crown ethers -5, NaH are 1:0.5:0.05:2.
6. application of the optical Response azobenzene compound described in claim 1 as stabilizer in multi-phase emulsion is prepared.
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