CN104031652A - Iodine bond liquid crystal with reversible photoinduced phase transition behavior and preparation method thereof - Google Patents
Iodine bond liquid crystal with reversible photoinduced phase transition behavior and preparation method thereof Download PDFInfo
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- CN104031652A CN104031652A CN201410290275.3A CN201410290275A CN104031652A CN 104031652 A CN104031652 A CN 104031652A CN 201410290275 A CN201410290275 A CN 201410290275A CN 104031652 A CN104031652 A CN 104031652A
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- iodine
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- 0 I*1ccc(*=*c(cc2)ccc2OC2CC2)cc1 Chemical compound I*1ccc(*=*c(cc2)ccc2OC2CC2)cc1 0.000 description 1
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Abstract
The invention discloses an iodine bond liquid crystal with reversible photoinduced phase transition behavior and a preparation method thereof. The structural general formula is disclosed in the specification, wherein R is a C10-C24 straight-chain or branched-chain alkyl group. The preparation method comprises the following steps: dissolving I2 and azo pyridine derivative in a solvent, and reacting at room temperature to obtain the iodine bond liquid crystal with photoinduced phase transition behavior. Ultraviolet light can be utilized to adjust the iodine bond liquid crystal from liquid crystal phase to isotropic phase; and the iodine bond liquid crystal has wide potential application range in the fields of adjustable optical filters, adjustable multimode laser protection, forgery prevention, gratings and the like.
Description
Technical field
The present invention relates to liquid crystalline cpd and preparation method thereof, particularly a class be take halogen key liquid crystalline cpd that halogen and azo pyridine derivative prepare as raw material and preparation method thereof.
Background technology
Along with the development of Liquid Crystal, by intermolecular non covalent bond effect, the method for the liquid crystal that self assembly is new has been subject to scientists and has more and more paid attention to.This method of introducing self-assembly in structure can be widened the approach of liquid crystal molecule design.By the different self-assembly effects between body and acceptor of giving, can obtain many new complex bodys with middle phase.Halogen key, as a kind of special Intermolecular Forces similar to hydrogen bond, obtains in fields such as crystal engineering, molecular recognition, Supramolecular Assemblings and applies widely and occupy critical positions, but at present relatively less to the research of halogen key liquid crystal.
When liquid crystal molecule contains light chromophoric group as azo group, by uv irradiation, can there is photochemical reaction, at this moment mesomorphic phase can change isotropic phase under isothermal condition.Azo pyridine derivative is except having the optical activity of azo, the confession of the nitrogen-atoms in its pyridine functional groups is electrically also for our designing material provides unlimited possibility, its pyridine functional groups can also form hydrogen bond with organic acid, form ionic linkage with mineral acid, form metal-complexing key with lanthanon, form halogen key with haloid element.The molecular application of this photoresponse, in the research of halogen key liquid crystal, can be obtained and has the photic halogen key liquid crystal that changes mutually behavior.
Summary of the invention
The object of this invention is to provide a kind of reversible photic halogen key liquid crystal that changes mutually behavior and preparation method thereof that has.
Provided by the invention to have the reversible photic halogen key liquid crystal that changes mutually behavior be a kind of azo pyridine derivative eka iodine key compound, and its general structure is as shown in the formula shown in 1:
Wherein, the straight or branched alkyl that R is C10～C24.
Can be expressed as-C of R
nh
2n+1, the integer that n is 10～24, preferred, n=10～18.
Compound shown in concrete formula 1 is one of following compounds 1c～1e for example:
1c:R=-C
10h
21(being n=10);
1d:R=-C
12h
25(being n=12);
1e:R=-C
14h
29(being n=14).
Iodine key liquid crystal of the present invention prepares by the following method:
1) under the condition that 4-aminopyridine and phenol exist at nitrite anions, there is diazo coupling reaction, obtain intermediate 4-hydroxybenzene azo pyridine;
2) 4-hydroxybenzene azo pyridine and chloroparaffin or brominated alkanes generation etherification reaction, the azo pyridine alkoxy benzene shown in production 2;
Wherein, the straight or branched alkyl that R is C10～C24, is preferably the straight or branched alkyl of C10～C18, and X is Cl or Br;
3) iodine is dissolved in organic solvent, is then added drop-wise in the solution of the azo pyridine alkoxy benzene shown in formula 2, stir, be settled out iodine key liquid crystal.
Preferably, above-mentioned steps 1) first Sodium Nitrite and phenol are placed in to sodium hydroxide or potassium hydroxide aqueous solution, and be cooled to 0 ℃, then this mixing solutions is added drop-wise in the aqueous hydrochloric acid that contains 4-aminopyridine, ice bath stirring reaction, finally by the pH regulator to 6 of reaction mixture～7, filter, by precipitation washing, recrystallization, dry 4-hydroxybenzene azo pyridine solid.
Preferably, above-mentioned steps 2) 4-hydroxybenzene azo pyridine and catalyzer iodate potassium, salt of wormwood are dissolved in organic solvent, to this mixed solution and dripping chloroparaffin or brominated alkanes solution, heating reflux reaction, reacted rear cooling, filtration, water washing and precipitating, recrystallization, the dry solid that to obtain, finally go out the azo pyridine alkoxy benzene shown in formula 2 by column chromatography for separation.
Preferably, above-mentioned steps 3) in iodine is dissolved in the organic solvents such as normal hexane; Azo pyridine alkoxy benzene shown in formula 2 is dissolved in the organic solvents such as chloroform, normal hexane and forms solution; For product iodine key liquid crystalline cpd, these organic solvents are poor solvent, are therefore precipitated out.
Iodine key liquid crystalline cpd of the present invention has the photic behavior that changes mutually, uses UV-light to carry out mesomorphic phase to the regulation and control of isotropic phase to iodine key liquid crystal of the present invention.Iodine key liquid crystal of the present invention is at adjustable optical spectral filter, and there is wide potential application in the fields such as adjustable multi-mode laser protection, false proof, grating, and iodine key liquid crystal preparation method of the present invention is simple, is easy to apply.
Accompanying drawing explanation
Fig. 1 is azo pyridine alkoxy benzene and the DSC test curve of iodine key liquid crystalline cpd and the optical texture figure of iodine key liquid crystalline cpd preparing in embodiment, wherein: (a) the DSC test curve of compd A 10AzPy; (b) the DSC test curve of compound 1c and at the optical texture of 130 ℃; (c) the DSC test curve of A12AzPy; (d) the DSC test curve of compound 1d and at the optical texture of 120 ℃; (e) the DSC test curve of A14AzPy; (f) the DSC test curve of compound 1e and at the optical texture of 122 ℃.
Fig. 2 is the polarizing microscope photo of compound 1d, from left to right for before uv-radiation, after uv-radiation and remove the polarisation picture of UV-light.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further, yet described embodiment should not explain in the mode of restriction.
Embodiment 1: compound 1d's is synthetic
1. intermediate 4-hydroxybenzene azo pyridine is synthetic
4.00g (58mmol) Sodium Nitrite and 5.00g (53mmol) phenol are placed in to 10% (w/w) aqueous sodium hydroxide solution (20mL), and are cooled to 0 ℃.Above-mentioned mixing solutions is dropwise joined in the 45mL hydrochloric acid soln (25mL11N hydrochloric acid and 20mL water) that contains 6.00g (64mmol) 4-aminopyridine.Under ice bath, stir 0.5h.Then, with 10% (w/w) aqueous sodium hydroxide solution, the pH value of reaction mixture is adjusted to 6～7.Filtration obtains yellow precipitation.Washing, recrystallization, the dry yellow solid that obtains.Productive rate: 38.0%.
2. azo pyridine dodecyloxy benzene (being denoted as A12AzPy) is synthetic
4-hydroxybenzene azo pyridine (2.00g, 0.1mol), potassiumiodide (0.005g) and salt of wormwood (6.9g, 0.005mol) are dissolved in DMSO (20mL) solution.In above-mentioned mixing solutions, dropwise drip DMSO (10mL) solution that contains 1-chlorinated dodecane (2.05g, 0.01mol).Be heated to 130 ℃ of back flow reaction 5h.Reacted to be placed in 200mL water and filtered and obtain bisque precipitation.Washing, recrystallization, the dry orange solid that obtains.Then with the mixed solvent that sherwood oil and ethyl acetate volume ratio are 1:1, carry out column chromatography, collect front-end volatiles.Vacuum is spin-dried for solvent in front-end volatiles, obtains light orange toner end.Productive rate: 61.0%.
Structural analysis data are as follows:
IR (KBr, cm
-1): 2918cm
-1and 2849cm
-1place is the charateristic avsorption band of alkyl chain, 1254cm
-1charateristic avsorption band for C-O-C.
1H-NMR(400MHz，CDCI
3):δ8.77(2H,d,Ar-H),δ7.95(2H,d,Ar-H),δ7.71(2H,d,Ar-H),δ7.03(2H,d,Ar-H),δ4.06(2H,t,-O-CH
2-),δ1.85(2H,m,-CH
2-),δ1.46(2H,m,-CH
2-),δ1.27(16H,m,-C
8H
16-),δ0.90(3H,t,-CH
3).
3. iodine key compound (1d) is synthetic
The iodine of 0.1269g (0.5mmol) is dissolved in the normal hexane of 25mL, then is added dropwise in the solution of the azo pyridine dodecyloxy benzene (0.1835g, 0.5mmol) that is dissolved in 5mL chloroform, under room temperature, stir 2h.Filter and the dry precipitation that obtains orange.Productive rate: 91.0%.
Above-mentioned steps 1,2,3 can represent with following reaction formula, and in the present embodiment, XR is 1-chlorinated dodecane, and R is-C
12h
23.
Embodiment 2: compound 1a's is synthetic
Reactions steps, with embodiment 1, just replaces 1-chlorinated dodecane in step 2 with hexyl bromide 1 bromohexane, obtains the own alkoxy benzene of azo pyridine (being denoted as A6AzPy).
Embodiment 3: compound 1b's is synthetic
Reactions steps, with embodiment 1, just replaces 1-chlorinated dodecane in step 2 with 1-bromooctane, obtains the pungent alkoxy benzene of azo pyridine (being denoted as A8AzPy).
Embodiment 4: compound 1c's is synthetic
Reactions steps, with embodiment 1, just replaces 1-chlorinated dodecane in step 2 with 1-bromo-decane, obtains azo pyridine alkoxy benzene in the last of the ten Heavenly stems (being denoted as A10AzPy).
Embodiment 5: compound 1e's is synthetic
Reactions steps, with embodiment 1, just replaces 1-chlorinated dodecane in step 2 with 1-bromo-tetradecane, obtains azo pyridine tetradecyloxyaniline benzene (being denoted as A14AzPy).
The iodine key liquid crystalline cpd that above-described embodiment is made has following feature:
By iodine key compound obtained above (1a to 1e), at 45 ℃ of injection thickness, be the liquid crystal cell of 25 microns, be heated to its liquid crystal temperature, apply UV-light, can realize the transformation of mesomorphic phase-isotropic phase-mesomorphic phase.
Fig. 1 has shown azo pyridine alkoxy benzene (A6AzPy to A14AzPy) and the DSC test curve of iodine key compound (1a to 1e) and the optical texture of iodine key compound of preparing in above-described embodiment, can find out that iodine key compound all has liquid crystal behavior, they have a fusing point (Cr) and a clearing point (I) as can be observed from Figure, between Cr and I, they all present smectic A phase (SmA).
Fig. 2 is the polarizing microscope photo of compound 1d, from left to right for before uv-radiation, after uv-radiation and remove the polarisation picture of UV-light, can find out before ultraviolet lighting, iodine key compound presents smectic A phase texture, after applying UV-light 12s, by smectic phase, change isotropic phase into, present details in a play not acted out on stage, but told through dialogues texture, after removing UV-light, can be returned to initial phase again.
The thermal properties of iodine key compound is summarized in table 1.
The thermal properties of the sample relating in table 1. embodiment
| Material | T/℃ | Material | T/℃ |
| I 2 | 113.5 | ? | ? |
| A6AzPy | 56.7 | 1a | ----- |
| A8AzPy | 67.9 | 1b | ----- |
| A10AzPy | 64.8 | 1c | Cr?123.6?SmA?135.5?I |
| A12AzPy | 72.8 | 1d | Cr?69.6?SmA?129.9?I |
| A14AzPy | 73.3 | 1e | Cr?117.2?SmA?133.8?I |
The above, be only preferred embodiment of the present invention, is not the present invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But, every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (8)
1. an azo pyridine derivative eka iodine key compound, its general structure as shown in Equation 1:
Wherein, the straight or branched alkyl that R is C10～C24.
2. iodine key compound as claimed in claim 1, is characterized in that, the straight or branched alkyl that R is C10～C18.
3. iodine key compound as claimed in claim 1, is characterized in that, described iodine key compound is selected from one of following compounds 1c～1e:
1c:R=-C
10h
21formula 1 compound;
1d:R=-C
12h
25formula 1 compound;
1e:R=-C
14h
29formula 1 compound.
4. the preparation method of the arbitrary described azo pyridine derivative eka iodine key compound of claim 1～3, comprises the following steps:
1) under the condition that 4-aminopyridine and phenol exist at nitrite anions, there is diazo coupling reaction, obtain intermediate 4-hydroxybenzene azo pyridine;
2) 4-hydroxybenzene azo pyridine and chloroparaffin or brominated alkanes generation etherification reaction, the azo pyridine alkoxy benzene shown in production 2;
3) iodine is dissolved in organic solvent, is then added drop-wise in the solution of the azo pyridine alkoxy benzene shown in formula 2, stir, be settled out the iodine key compound shown in formula 1;
Wherein, the straight or branched alkyl that R is C10～C24, X is Cl or Br.
5. preparation method as claimed in claim 4, it is characterized in that, step 1) first Sodium Nitrite and phenol are placed in to sodium hydroxide or potassium hydroxide aqueous solution, and be cooled to 0 ℃, then this mixing solutions is added drop-wise in the aqueous hydrochloric acid that contains 4-aminopyridine, ice bath stirring reaction, finally by the pH regulator to 6 of reaction mixture～7, filter, by precipitation washing, recrystallization, dry 4-hydroxybenzene azo pyridine solid.
6. preparation method as claimed in claim 4, it is characterized in that, step 2) 4-hydroxybenzene azo pyridine and catalyzer iodate potassium, salt of wormwood are dissolved in organic solvent, to this mixed solution and dripping chloroparaffin or brominated alkanes solution, heating reflux reaction, reacted rear cooling, filtration, water washing and precipitating, recrystallization, the dry solid that to obtain, finally go out the azo pyridine alkoxy benzene shown in formula 2 by column chromatography for separation.
7. preparation method as claimed in claim 4, is characterized in that step 3) in iodine is dissolved in normal hexane.
8. preparation method as claimed in claim 4, is characterized in that step 3) the azo pyridine alkoxy benzene shown in Chinese style 2 is dissolved in chloroform and/or normal hexane and forms solution.
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| CN105500857A (en) * | 2015-12-18 | 2016-04-20 | 北京大学 | Light-driven composite with double-layer-film structure and preparation method of light-driven composite |
| CN106045905A (en) * | 2016-06-08 | 2016-10-26 | 北京印刷学院 | Compound assisting metal in enhancing fluorescence and preparation method thereof |
| CN106244043A (en) * | 2016-08-17 | 2016-12-21 | 京东方科技集团股份有限公司 | Sealed plastic box, the manufacture method of display panels and display panels |
| CN112592420A (en) * | 2020-12-11 | 2021-04-02 | Tcl华星光电技术有限公司 | Polarizing material, preparation method thereof, polarizer and display panel |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105500857A (en) * | 2015-12-18 | 2016-04-20 | 北京大学 | Light-driven composite with double-layer-film structure and preparation method of light-driven composite |
| CN106045905A (en) * | 2016-06-08 | 2016-10-26 | 北京印刷学院 | Compound assisting metal in enhancing fluorescence and preparation method thereof |
| CN106045905B (en) * | 2016-06-08 | 2018-11-23 | 北京印刷学院 | A kind of compound and preparation method thereof for assisting metal-enhanced fluorescence |
| CN106244043A (en) * | 2016-08-17 | 2016-12-21 | 京东方科技集团股份有限公司 | Sealed plastic box, the manufacture method of display panels and display panels |
| WO2018032776A1 (en) * | 2016-08-17 | 2018-02-22 | 京东方科技集团股份有限公司 | Sealant, liquid crystal display panel manufacturing method and liquid crystal display panel |
| CN112592420A (en) * | 2020-12-11 | 2021-04-02 | Tcl华星光电技术有限公司 | Polarizing material, preparation method thereof, polarizer and display panel |
| CN112592420B (en) * | 2020-12-11 | 2023-12-05 | Tcl华星光电技术有限公司 | Polarizing material, preparation method thereof, polarizer and display panel |
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Application publication date: 20140910 |