CN100402526C - Lysotropic-photodiscolour diaryl ethylene and preparation and application thereof - Google Patents
Lysotropic-photodiscolour diaryl ethylene and preparation and application thereof Download PDFInfo
- Publication number
- CN100402526C CN100402526C CNB021006830A CN02100683A CN100402526C CN 100402526 C CN100402526 C CN 100402526C CN B021006830 A CNB021006830 A CN B021006830A CN 02100683 A CN02100683 A CN 02100683A CN 100402526 C CN100402526 C CN 100402526C
- Authority
- CN
- China
- Prior art keywords
- reaction
- compound
- lysotropic
- application
- bromo
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to lysotropic-photochromic diaryl ethylene, a preparation method thereof and the application thereof. The present invention relates to an organic lysotropic-photochromic material, a preparation method thereof and the application thereof, particularly to lysotropic-photochromic diaryl ethylene, the preparation method thereof and the application thereof. The lysotropic-photochromic diaryl ethylene has a general formula (I) of 1, 2-bis(2-methylthiophene-3-yl) perfluorocyclopentene, wherein the R1 and the R2 are betaine groups with lysotropic-photochromic properties. The compound of the present invention can be used as an eraseable optical information storage material with super high density and a photoswitch material.
Description
Technical field
The present invention relates to the organic Lysotropic-photodiscolour material of a class and manufacture method and application, particularly relate to the organic Lysotropic-photodiscolour vinyl compound of a class and manufacture method and application.
Background technology
Along with fast development of computer technology, the digitizing information storage has been proposed more and more higher requirement, should satisfy high storage density, high data rate, high storage life and high erasable number of times, have the equipment of simple economy and the advantage of low price information digit again.Compare with the magnetic storage technology, advantages such as optical storage technology has that storage life is long, contactless read/write and wiping, the information carrier-to-noise ratio is high and the position price ratio is low, optical disc has been obtained and has been developed rapidly and become mainstream technology in recent years.
Concerning the Optical Disc Data Storage with Ultrahigh Density technology, storage medium is its center integral part, but its development becomes the bottleneck in this field very slowly and, and the optical disk medium of therefore exploring new super-high density remains crucial.At present, inorganic optical memory material such as magneto-optic and phase change material are used widely, and organic optical storage media also is in the primary stage of research and development.In the heat pattern of magneto-optic or phase change medium record,, thereby cause resolution limit of this class recording medium existence because the irregular fever character of medium makes that the minimum hot spot that is recorded also is to be irregularly shaped.Advantage such as organic optical memory material has the storage density height, can realize molecular memory, heat conductance is little, signal to noise ratio is big, fusing point and softening temperature adjustability low, that higher recording sensitivity, molecular structure are arranged are big, therefore the organic medium of developing the super-high density optical storage that is suitable for photon mode is trend of the times, has broad application prospects.
At present, the organic dye that is used as optical information storage medium has azo, Hua Jing, phthalocyanine, fulgide, spiro-pyrans etc., but these molecules all can not satisfy the needs of high density compact disc of future generation owing to its inherent character defective.In recent years, the photic material of photochromic diaryl alkene that one class is novel, because advantages such as its good chemistry and thermostability, significant fatigue resistance, high cyclisation quantum yield and sensitivity, in erasable optical memory material and light-operated molecular switch material, have good application prospects and become the focus of research.Photochromic molecules is in the photoisomerization process, except absorption spectrum changes, its geometric configuration, specific refractory power, specific inductivity, oxidation/reduction potential etc. all can change, thereby are used for can using when optical information is stored the multiple character of light, realize the photon type storage.These character also can be used to prepare various opto-electronic devices, as super-high density erasable and rewritable optical storage material and light-operated molecule switching element.
The key that photochromic compound is used for the photon type storage is the nondestructive readout problem.Because photochromic reactions is read light can't prevent photochromic reactions when reading generation, thereby can be damaged recorded information for the linear response of photon.Addressing this problem is a great problem in the storage of present photon type.
Summary of the invention
The purpose of this invention is to provide a kind of novel diarylethene Lysotropic-photodiscolour compound.
Diarylethene Lysotropic-photodiscolour compound of the present invention is 1 of a following general formula (I), two (2-thiotolene-3-yl) Perfluorocyclopentenes of 2-:
Wherein R1, R2 have the molten trimethyl-glycine group that causes variable color character.
For example, R1, R2 can be selected from one of following groups:
R wherein
3For-NO
2Or-CN; R
4And R
5For-H ,-CH
3Or-Ph.
Second purpose of the present invention provides a kind of production 1, the method for two (2-thiotolene-3-yl) Perfluorocyclopentenes of 2-, and this method consists essentially of following steps:
1) 2-thiotolene bromination obtains 3,5-two bromo-2-thiotolenes;
2) with the tributyl borate reaction, generate 2-methyl-3-bromo-5-boronate thiophene;
3) will have the molten trimethyl-glycine group that causes variable color character by linked reaction is connected with thiphene ring;
4) generate target molecule with the Perfluorocyclopentene reaction.
In aforesaid method, described is that the liquid bromine that will be added with acetate under condition of ice bath slowly is added dropwise in the 2-thiotolene with 2-thiotolene bromination, and reaction back water separatory extracts the product in the organic phase.
Described 3,5-two bromo-2-thiotolenes and tributyl borate reaction are carried out under condition of ice bath.
The described trimethyl-glycine group that is connected with thiphene ring by linked reaction can be selected from one of following groups:
Described linked reaction is at Pd (PPh
3)
4Carry out under the catalysis.
More than Xu Shu production 1, the reaction formula of the method for two (2-thiotolene-3-yl) Perfluorocyclopentenes of 2-is:
The principle of The compounds of this invention photochromic reactions is as follows:
Attitude a has different absorption spectrums with attitude b, at two kinds of different wave length (λ
1, λ
2) light action reversible transition takes place down, utilize the difference of two kinds of attitude absorption spectrums or reflection spectrum just can carry out optical recording and read like this, reach the purpose of information storage.Therefore the main application of The compounds of this invention is to mix up macromolecular material or make diaphragm, is useful for super-high density, erasable organic photon type information storage material.
The key issue that photochromic compound is used for the optical information storage is how to realize nondestructive readout.Because reversible conversion takes place under light action between two attitudes of generation photochromic reactions, reads photo potential like this and must produce destruction to recorded information.What compound of the present invention was different with other diarylvinylene compounds is that therefore compound of the present invention can utilize these characteristics to carry out nondestructive readout owing to have the molten variable color group that causes.The open loop attitude of this compounds has a strong absorption peak in the above zone of 600nm, and this peak is corresponding to the molten absorption that causes the variable color group of trimethyl-glycine.In open loop and closed loop attitude, the position difference of this absorption peak is utilized this character, just can realize the nondestructive readout of photon type storage.Its principle as shown in Figure 1, the molten variable color trimethyl-glycine group that causes of oval representative among Fig. 1, circle is represented photochromic diaryl base vinyl group.At λ
1And λ
2Diarylethene group generation photochromic reactions under the light action; Because molten to cause variable color trimethyl-glycine group absorption spectrum very responsive to environment, causes its absorbing wavelength (λ
3) change.If use λ
3Laser is just read can not cause photochromic reactions, thereby can realize nondestructive readout.
Compound of the present invention can both keep the good photochromic reaction property in solution, film and crystal, and open loop attitude (colourless attitude) and closed loop attitude (colour generation attitude) all have good chemistry and thermostability, significant fatigue resistance and higher cyclisation quantum yield.The absorbing band of its colour generation attitude is positioned at 600～800nm, and the colour generation attitude is returned colourless attitude under the light action of this wavelength region, can mate with the laser apparatus of respective wavelength, as high-density optical storage medium.
Description of drawings
Fig. 1 contains the molten nondestructive readout synoptic diagram that causes variable color group photochromic compound
Fig. 2 is 1, the abosrption spectrogram of two (2-methyl-5-(4-(2-benzimidazolyl-) pyridyl) thiene-3-yl-) Perfluorocyclopentenes of 2-
Embodiment
Embodiment 1,1, two (2-methyl-5-(4-(2-benzimidazolyl-) pyridyl) thiene-3-yl-) Perfluorocyclopentenes of 2-synthetic
1, the synthetic route of two (2-methyl-5-(4-(2-benzimidazolyl-) pyridyl) thiene-3-yl-) Perfluorocyclopentenes of 2-is shown below:
Concrete synthesis step is:
1,8g (81.6mmol) 2-thiotolene is dissolved in 33.4ml acetate, the ice bath cooling.9.6ml liquid bromine and 14ml acetate slowly are added dropwise in the above-mentioned thiophene solution after mixing, and drip approximately 2 hours.Continued the ice bath stirring reaction 16 hours, and reaction solution was poured in about 100ml water into separatory.The about 30g Na of water
2CO
3Neutralization, and with extracted with diethyl ether (20ml * 4).Merge organic phase, with about 10ml Na
2CO
3Molecular sieve drying is used in the saturated solution washing.Revolve and boil off solvent, underpressure distillation gets 3, and 5-two bromo-2-thiotolenes (b.p.99-100 ℃/10mmHg, n
d 20=1.6080.NMR (DCCl
3): δ
CH3=2.94, δ
H=7.61).Productive rate about 80%.
2,6g (23.5mmol) 3,5-two bromo-2-thiotolenes are dissolved in about 100ml ether (remove superoxide, dewater), at N
2Protection is the ice bath cooling down.Drip n-BuLi (23.5mmol) with syringe.In ice bath, continue reaction after 30 minutes, add tributyl borate 7ml, rise to room temperature, add the 4%HCl stopped reaction, separatory, aqueous phase discarded.Organic phase extracts with 4%NaOH, water 10%HCl acidifying.Suction filtration, with rare HCl washing, vacuum-drying gets faint yellow solid 2-methyl-3-bromo-5-boronate thiophene (IR (cm
-1) 690.0,789.9,832.3,1009.9,1132.4,1340.3,1473.5,1528.3,1290.8,3201.5).Productive rate about 65%.
3,3.5g (20.0mmol) 2-chloro benzimidazole and 3.15g (20.0mmol) 4-bromopyridine are miscible in about 100ml dimethyl sulfoxide (DMSO), reacted 2 hours down for 140 ℃ in oil bath, obtain N-(2-benzimidazolyl-)-about 3g of 4-bromopyridine (MP:88 ℃), productive rate about 55%.
4,3.3g (15.0mmol) 2-methyl-3-bromo-5-boronate thiophene is dissolved in 15ml 2M Na
2CO
3In the aqueous solution; 4.2g the Pd (PPh of N-(2-benzimidazolyl-)-4-bromopyridine and 0.5g new system
3)
4Sneak in the 30ml tetrahydrofuran (THF) (THF removes superoxide, dewaters), stirred 5 minutes.The aqueous solution of boronic acid compounds is joined in the THF solution, at N
2Stirring and refluxing is 8 hours under the protection.Be cooled to room temperature, separatory, water merges with organic phase with THF extraction back, uses the saturated NaCl aqueous solution and H respectively
2MgSO is used in the O washing
4Drying is revolved and is boiled off solvent, vacuum-drying.Separate with silica gel chromatographic column, get faint yellow product 2-methyl-3-bromo-5-(N-(2-benzimidazolyl-) pyridin-4-yl) thiophene, productive rate about 70% after the crystallization.
5,2-methyl-3-bromo-5-(N-(2-benzimidazolyl-) pyridin-4-yl) thiophene 3.92g (10.6mmol) is dissolved among about 60ml THF (remove superoxide, dewater).At N
2Under the protection, cryosel is bathed and is cooled to-15 ℃ approximately.Drip n-BuLi 14mmol with syringe, stirred 30 minutes.Add Perfluorocyclopentene 0.72ml (about 5.3mmol), continue reaction 2 hours, rise to room temperature, add about 10ml H
2The O stopped reaction.Vacuum-drying, with silica gel chromatographic column separate product 1, two (2-methyl-5-(4-(2-benzimidazolyl-) pyridyl) thiene-3-yl-) Perfluorocyclopentenes of 2-(
1HNMR (CDCl
3): δ 2.24 (6H), δ 6.75 (4H), δ 6.86 (4H), δ 7.06 (4H), δ 7.28 (2H), δ 7.64 (4H), productive rate about 50%.
As shown in Figure 2, be the product 1 of this embodiment, the abosrption spectrogram of two (2-methyl-5-(4-(2-benzimidazolyl-) pyridyl) thiene-3-yl-) Perfluorocyclopentenes of 2-, solid line is the open loop attitude among the figure, dotted line is the closed loop attitude, as can be seen from the figure at λ
1And λ
2Diarylethene group generation photochromic reactions under the light action; Because molten to cause variable color trimethyl-glycine group absorption spectrum very responsive to environment, causes its absorbing wavelength (λ
3) change.Use λ
3Laser readable just goes out can not cause photochromic reactions.
Claims (9)
1. the compound of following general formula (I):
Wherein R1, R2 have the molten trimethyl-glycine group that causes variable color character.
2. compound according to claim 1 is characterized in that: described R1, and R2 is selected from one of following groups:
R wherein
3For-NO
2Or-CN; R
4And R
5For-H ,-CH
3Or-Ph.
3. method of producing the described compound of claim 1 may further comprise the steps:
1) 2-thiotolene bromination obtains 3,5-two bromo-2-thiotolenes;
2) with the tributyl borate reaction, generate 2-methyl-3-bromo-5-boronate thiophene;
3) will have the molten trimethyl-glycine group that causes variable color character by linked reaction is connected with thiphene ring;
4) generate target molecule with the Perfluorocyclopentene reaction.
4. method according to claim 3 is characterized in that: with 2-thiotolene bromination is that the liquid bromine that will be added with acetate under condition of ice bath slowly is added dropwise in the 2-thiotolene, and reaction back water separatory extracts the product in the organic phase.
5. method according to claim 3 is characterized in that: described 3,5-two bromo-2-thiotolenes and tributyl borate reaction are carried out under condition of ice bath.
6. method according to claim 3 is characterized in that: the described trimethyl-glycine group that is connected with thiphene ring by linked reaction is one of following groups:
R wherein
3For-NO
2Or-CN; R
4And R
5For-H ,-CH
3Or-Ph.
7. method according to claim 3 is characterized in that: described linked reaction is at Pd (PPh
3)
4Carry out under the catalysis.
8. the compound of claim 1 is as the application of super-high density, erasable and rewritable optical storage material.
9. the compound of claim 1 is as the application of photoswitch material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021006830A CN100402526C (en) | 2002-02-22 | 2002-02-22 | Lysotropic-photodiscolour diaryl ethylene and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021006830A CN100402526C (en) | 2002-02-22 | 2002-02-22 | Lysotropic-photodiscolour diaryl ethylene and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1439640A CN1439640A (en) | 2003-09-03 |
| CN100402526C true CN100402526C (en) | 2008-07-16 |
Family
ID=27792969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021006830A Expired - Fee Related CN100402526C (en) | 2002-02-22 | 2002-02-22 | Lysotropic-photodiscolour diaryl ethylene and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100402526C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333674B (en) * | 2013-07-16 | 2016-01-13 | 天津城建大学 | There is diaryl ethylene photochromic compound and the synthetic method of Electric Field Modulated function |
| CN104292234B (en) * | 2014-10-13 | 2017-03-22 | 江西科技师范大学 | Asymmetric perfluorocyclopentene photochromic fluorescent probe compound containing benzimidazole group as well as preparation method and application of asymmetric perfluorocyclopentene photochromic fluorescent probe compound |
| CN105254622B (en) * | 2015-08-14 | 2018-02-27 | 江西科技师范大学 | There is photochromic perfluoro-cyclopentene compound of aluminium ion identification function and its preparation method and application containing antipyrine monomer |
| CN105254533B (en) * | 2015-11-04 | 2017-08-25 | 陕西师范大学 | A kind of molten mutagens color fluorescent chemicals and its synthetic method and application |
| CN109734670B (en) * | 2018-12-16 | 2022-03-22 | 桂林理工大学 | Preparation method and application of biphenyl bridged bis-benzimidazolium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08119963A (en) * | 1994-10-21 | 1996-05-14 | Masahiro Irie | Dithienylethene-based compound and photochromic material comprising the same compound |
| JPH09311355A (en) * | 1996-05-22 | 1997-12-02 | Masahiro Irie | Display medium and device for photochromic material |
| JPH11311813A (en) * | 1998-04-28 | 1999-11-09 | Kyocera Corp | Optical function element |
-
2002
- 2002-02-22 CN CNB021006830A patent/CN100402526C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08119963A (en) * | 1994-10-21 | 1996-05-14 | Masahiro Irie | Dithienylethene-based compound and photochromic material comprising the same compound |
| JPH09311355A (en) * | 1996-05-22 | 1997-12-02 | Masahiro Irie | Display medium and device for photochromic material |
| JPH11311813A (en) * | 1998-04-28 | 1999-11-09 | Kyocera Corp | Optical function element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1439640A (en) | 2003-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20030174560A1 (en) | Photochromic compounds for molecular switches and optical memory | |
| Frigoli et al. | Modulation of the Absorption, Fluorescence, and Liquid‐Crystal Properties of Functionalised Diarylethene Derivatives | |
| US4499165A (en) | Amorphous compositions of dyes and binder-mixtures in optical recording elements and information recorded elements | |
| CN1978444B (en) | Photochromic thiophene pyrrole mixed linkage type dithienylethene compounds, and their synthesizing and use | |
| CN102399456B (en) | Use of appended dyes in optical data storage media | |
| CN100491373C (en) | Photochromic thiophene pyrazole heterocyclic mixed linkage type asymmetrical dithienylethene compounds, and their preparing method and use | |
| CA2477201A1 (en) | Polymer bound donor-acceptor-donor compounds and their use in a 3-dimensional optical memory | |
| CN104098555A (en) | Method for synthesizing ultrashort-wavelength photochromic diarylethene compound by using imidazole-thiophene aromatic heterocycle and application of compound | |
| EP1130063A1 (en) | Styryl dye | |
| CN100402526C (en) | Lysotropic-photodiscolour diaryl ethylene and preparation and application thereof | |
| CN103130846A (en) | Photochromic bi-thiophene six-sugar water-solubility symmetrical octafluorocyclopentene compound and preparation method and application | |
| CN101591334B (en) | Photochromic thiophene-thiazole heterocycle hybrid asymmetric perfluorocyclopentene compound, preparation method and application | |
| CN101602743B (en) | Photochromic thiazole hexatomic ring series-parallel asymmetric perfluoro-cyclopentene compound and preparation method and application thereof | |
| Chun et al. | The effect of the molecular structure of the chromophore on the photorefractive properties of the polymer systems with low glass transition temperatures | |
| JP2006077239A (en) | Photoresponsive heterocyclic azo compound and method for producing the same and optical information recording medium | |
| US4626361A (en) | Binder-mixtures for optical recording layers and elements | |
| CN100391949C (en) | SW diaryl ethylene compounds and preparation and application thereof | |
| CN101851232B (en) | Photochromic isoxazole thiophene hybrid-type perfluorinated cyclopentene compound as well as synthesis method and application thereof | |
| JP2004339460A (en) | Bis-styryl dye and method for manufacturing the same and its use for high density optical recording medium | |
| CN1206308C (en) | Photochromic diaryl ethylene compound and its prepn and use | |
| CN101845041B (en) | Photochromic benzofuran thiophene series-parallel perfluoro-cyclopentene compound as well as synthesizing method and application thereof | |
| JP2007039588A (en) | Subporphyrin compound, process for its production and its application | |
| JPH07173151A (en) | Diarylethene-based compound and optical recording-regeneration of optical recording medium containing the same compound | |
| CN1186341C (en) | Diaryl perfluoro cycolpenfene photochrmism compounds and its preparing method and use | |
| KR20010070126A (en) | Cyanine dyes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080716 |