CN100391949C - SW diaryl ethylene compounds and preparation and application thereof - Google Patents
SW diaryl ethylene compounds and preparation and application thereof Download PDFInfo
- Publication number
- CN100391949C CN100391949C CNB021006814A CN02100681A CN100391949C CN 100391949 C CN100391949 C CN 100391949C CN B021006814 A CNB021006814 A CN B021006814A CN 02100681 A CN02100681 A CN 02100681A CN 100391949 C CN100391949 C CN 100391949C
- Authority
- CN
- China
- Prior art keywords
- perfluorocyclopentene
- methylthiazol
- base
- reaction
- hour
- 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
- -1 diaryl ethylene compounds Chemical class 0.000 title abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 230000003287 optical effect Effects 0.000 claims abstract description 18
- 239000011232 storage material Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 41
- YBMDPYAEZDJWNY-UHFFFAOYSA-N 1,2,3,3,4,4,5,5-octafluorocyclopentene Chemical compound FC1=C(F)C(F)(F)C(F)(F)C1(F)F YBMDPYAEZDJWNY-UHFFFAOYSA-N 0.000 claims description 33
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 23
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 230000031709 bromination Effects 0.000 claims description 6
- 238000005893 bromination reaction Methods 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 150000001988 diarylethenes Chemical class 0.000 claims description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000005977 Ethylene Substances 0.000 abstract 2
- 238000003860 storage Methods 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- 241000931526 Acer campestre Species 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- QFRBTSDMPVCWOA-UHFFFAOYSA-N 2-benzyl-5-bromo-4-methyl-1,3-thiazole Chemical compound S1C(Br)=C(C)N=C1CC1=CC=CC=C1 QFRBTSDMPVCWOA-UHFFFAOYSA-N 0.000 description 1
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4MTO Natural products CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 1
- NSXCMCDBNNASAL-UHFFFAOYSA-N 5-bromo-2-ethyl-4-methyl-1,3-thiazole Chemical compound CCC1=NC(C)=C(Br)S1 NSXCMCDBNNASAL-UHFFFAOYSA-N 0.000 description 1
- 125000006278 bromobenzyl group Chemical group 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000382 optic material Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention relates to a short wavelength diaryl ethylene compound, a preparation method and application thereof. The present invention relates to organic photochromic material, a preparation method and application thereof, particularly an organic photochromic diaryl ethylene compound, a preparation method and application thereof. The present invention provides the compound disclosed in formula (I). The present invention can be widely used as optical information storage material and a photochromic molecular device.
Description
Technical field
The present invention relates to a class organic photochromic material and manufacture method and application, particularly relate to a class organic photochromic diaryl ethylene compounds and manufacture method and application.
Background technology
The semi-conductor short wavelength laser has important use at numerous areas such as physics, chemistry, biology and information.Along with the continuous increase of semi-conductor short wavelength laser wavelength, the research of the material that matches is become very important.
Development along with society, the quantity of information in the whole world increases day by day, optical storage technology just advances towards the direction of high storage density and faster access speed more, and storage media is the key in highly dense, the quick optical storage technology, and the preparation method who seeks the new high quality recording film of novel high-performance optical recording medium and development has become current vital task.
In the optical recording of far field, the size of measuring point is decided by the diffraction limit of focused light, and the focal diameter of light (d) is directly proportional with optical wavelength (λ), and is inversely proportional to the numerical aperture (NA) of camera lens, i.e. d=0.56 λ/NA, and storage density is proportional to (NA/ λ)
2So improve the bit density of storage, will shorten optical maser wavelength and increase the numerical aperture of object lens, the short wavelength laser record is one of valid approach that improves optical storage density.
Research to short wavelength's HIGH-DENSITY OPTICAL STORAGE material is in the exploration in the world, and the phase change material that mainly contains systems such as Ag-Ln-Sb-Te, Ge-Sb-Te at present can be used for short wavelength's record.Research to organic optical memory material is carried out for many years, and a few practicability is wherein arranged, as is used for recording the colored cyanines and the phthalocyanines dye of CD CD (CD-R).For the erasable optical disc that has come out, leading storage media remains inorganic magneto-optic and phase change material.Although there are unfavorable factors such as photo and thermal stability is relatively poor in organic materials, but compare with inorganic materials, therefore organic materials has the susceptibility height, processes, is convenient to adjust advantages such as structure properties and CD record format compatibility easily, researchs and develops excellent property, cheap organic optical memory material has very important realistic meaning.
People begin to pay attention to the application of light-induced variable colour pattern molecule in optical memory material in recent years.With traditional magnetic/light type record, inversion of phases and other photo-thermal types record are compared, this class material can be realized the record of " photon type ", they utilize the photon of material to react the purpose that reaches record, thereby the numerous characteristics of light all may be applied in optical storage as wavelength, phase of wave etc., in addition, because the reversibility of photochromic reactions can reach repeatedly erasable purpose.
In various photochromic compound systems, the diarylethene, particularly diaryl perfluoro cyclopentene compound of band hetero-aromatic ring have excellent thermostability, chemical stability, and good fatigue resistance.According to reports, some band heterocyclic diarylvinylene compounds, its open loop attitude and closed loop attitude all have well thermally-stabilised, even also can stablize more than three months at 80 ℃, and cyclisation/ring-opening reaction circulation can repeat 10
4Also have good photochromic properties more than inferior, so this quasi-molecule is suitable as erasable optical storage media.
Although existing a large amount of diarylvinylene compound is produced, they are often responsive to the light ratio about 600nm.Improve storage density, it is shorter that reading and writing optical maser wavelength will become, and therefore exploitation is significant with the diarylvinylene compound of 400～500nm semiconductor laser coupling.
Summary of the invention
The diaryl ethylene compounds that the purpose of this invention is to provide a kind of short wavelength.
Diaryl ethylene compounds provided by the invention is general formula (I) compound:
Wherein, X
1, X
2Be CH or N;
R
1, R
2Be CH
2R or CH=CH
2R;
R is the alkyl of carbonatoms 1-6, cycloalkyl or the aryl of carbonatoms 3-6.
Another object of the present invention provides a kind of method of preparation symmetric formula (I) compound, may further comprise the steps:
1) with 2-substituting group-4-methylthiazol ring 5-position bromination or get 2-substituting group-4-thiotolene;
2) n-Butyl Lithium with equivalent reacts, and adds identical normal Perfluorocyclopentene then, promptly synthetic symmetric diarylethene product.
If expect X with this method
1=X
2=N, R
1=R
2Formula (I) compound, its specific practice is:
1) with 2-R
1Base-4-methylthiazol is dissolved in the dithiocarbonic anhydride, dripping bromine slowly under condition of ice bath; Then room temperature reaction 2～3 hours, 5-bromo-2-R
1Base-4-methylthiazol;
2) with 5-bromo-2-R
1Base-4-methylthiazol is dissolved in the anhydrous tetrahydro furan, at N
2Protection is cooled to-78 ℃ approximately down, adds the n-BuLi afterreaction 1 hour; Add 0.5 normal Perfluorocyclopentene again, continued low-temp reaction 2～3 hours, rise to room temperature then, stopped reaction obtains product;
X in synthetic formula (I) compound
1=X
2=N, R
1=R
2
If expect X with this method
1=X
2=CH, R
1=R
2Formula (I) compound, its specific practice is:
1) with 2-R
1Base-4-thiotolene is dissolved in the anhydrous diethyl ether, at N
2Protection is cooled to about 0 ℃ down, drips n-BuLi; Refluxed then 1 hour, and be cooled to 0 ℃ again, add 0.5 normal Perfluorocyclopentene, continue reaction 1 hour, add the dilute hydrochloric acid stopped reaction and obtain product;
X in synthetic formula (I) compound
1=X
2=CH, R
1=R
2
The 3rd purpose of the present invention provides a kind of method for preparing asymmetric (I) compound, may further comprise the steps:
1) with 2-substituting group-4-methylthiazol ring 5-position bromination or get 2-substituting group-4-thiotolene;
2) add the Perfluorocyclopentene of equivalent, behind the stoichiometric number hour, single Perfluorocyclopentene that replaces; With 2-substituting group-4-thiotolene or 5-bromo-2-substituting group-4-methylthiazol (different) and the reaction of equivalent n-Butyl Lithium with last step reactant, add single Perfluorocyclopentene that replaces again, promptly synthesize asymmetrical diarylethene product.
If expect X with this method
1=CH, X
2=N, R
1≠ R
2Formula (I) compound, its specific practice is:
1) with 2-R
2Base-4-methylthiazol is dissolved in the anhydrous diethyl ether, dripping bromine slowly under condition of ice bath, then room temperature reaction 2～3 hours, 5-bromo-2-R
2Base-4-methylthiazol (stand-by);
2) with 2-R
1Base-4-thiotolene is dissolved in anhydrous diethyl ether, at N
2Protection is cooled to about 0 ℃ down, behind the dropping n-BuLi; Refluxed 1 hour, and be cooled to room temperature again, add the Perfluorocyclopentene of equivalent, continue reaction 1-2 hour, stopped reaction gets single Perfluorocyclopentene that replaces.
3) with 5-bromo-2-R
2Base-4-methylthiazol is dissolved in anhydrous diethyl ether, at N
2Be cooled to-78 ℃ approximately under the protection, adding n-BuLi, low-temp reaction add single Perfluorocyclopentene that replaces after 1 hour, continue reaction 2-3 hour, rise to room temperature, get product after the stopped reaction;
X in synthetic formula (I) compound
1=CH, X
2=N, R
1≠ R
2
If expect X with this method
1=X
2, R
1≠ R
2Formula (I) compound, its specific practice is:
1) X
1=X
2During=CH, with 2-R
1Base-4-thiotolene is dissolved in anhydrous diethyl ether, at N
2Protection is cooled to about 0 ℃ down, behind the dropping n-BuLi; Refluxed 1 hour, and be cooled to room temperature again, add the equivalent Perfluorocyclopentene, continue reaction 1-2 hour, get single Perfluorocyclopentene that replaces, again with 5-lithium-2-R
2Base-4-thiotolene react product.
2) X
1=X
2During=N, earlier will be at 2-R
1Base-4-methylthiazol, 2-R
2Base-4-methylthiazol bromination; With 5-bromo-2-R
1Base-4-methylthiazol is dissolved in anhydrous diethyl ether, N
2Protect down, be cooled to-78 ℃ approximately, add n-BuLi, low-temp reaction 1 hour, the Perfluorocyclopentene of adding equivalent gets single Perfluorocyclopentene that replaces, again with 5-lithium-2-R
2Base-4-methylthiazol reaction obtains product.
X1=X2 in synthetic formula (I) compound, R1 ≠ R2.
SW diaryl ethylene compounds provided by the present invention has good photo and thermal stability and fatigue resistance, highly sensitive, bigger photochemistry quantum yield is arranged, can dissolve each other with superpolymer such as PMMA, good film-forming property has the good photochromic reactivity in solid film, its closed loop attitude has stronger absorption in the 400-500nm scope, optical absorption characteristics is applicable to the storage of short wavelength's blue light range, is the erasable storage media of ideal.
Diarylvinylene compound of the present invention has good photochromic character in crystalline state and non-crystalline state, and two kinds of photoisomer photo and thermal stabilities are good, and photoresponse is highly sensitive, and response is fast, is suitable as the photochromic molecules device, as the photochromic molecules switch etc.
The diarylethene open loop attitude of the present invention of symmetrical configuration can form two kinds of C
2Symmetric closed loop attitude (S, S)-and (R, R) chiral isomer, the application that can utilize the character of chiral isomer to be used for being correlated with.
Below in conjunction with accompanying drawing embodiments of the invention are described further.
Description of drawings
Fig. 1 is 1-(the UV-Vis absorption spectrum of 2-ethyl-4-methyl-thiazole-5-yl)-2-(5-benzyl-3-methyl-thiophene-2-yl) Perfluorocyclopentene open loop attitude and closed loop attitude
Embodiment
Embodiment 1,1-(2-ethyl-4-methyl-thiazole-5-yl)-2-(5-benzyl-3-methyl-thiophene-2-yl) Perfluorocyclopentene synthetic
Synthetic route is as follows:
Concrete steps are:
1,2-ethyl-4-methylthiazol 5g is dissolved in the 50ml dithiocarbonic anhydride, puts into ice bath, slowly drip the 2ml bromine.Rise to room temperature reaction 2 hours after adding.Add the water stopped reaction, chloroform extraction organic phase, MgSO
4Drying gets colourless oil liquid 5-bromo-2-ethyl 4-methylthiazol 4.14g through underpressure distillation, and productive rate is 51%.
bp113～115℃/100mmHg；Anal.：Calcd：C，34.95；H，3.88；N，6.80％?Found：C，35.02；H，3.85；N，6.75％
2,3 methyl thiophene 3g is dissolved in the 50ml tetrahydrofuran (THF), slowly drips n-BuLi hexane solution 18.4ml (1.6M) under 0 ℃ of nitrogen protection.Add the back backflow after 1 hour, be cooled to 0 ℃, add tributyl borate 9ml, rise to room temperature naturally and continue reaction 1 hour.In the previous step reactant, add 5.2g bromobenzyl, 0.4g Pd (PPh respectively
3)
4, refluxed 5 hours.Be cooled to room temperature then, separatory, water merge with organic phase after with extracted with diethyl ether, use the MgSO4 drying.Revolve and boil off solvent, vacuum-drying separates with silica gel chromatographic column, clear crystal 2-benzyl-4-thiotolene 3.84g, productive rate is 71.2%.
mp?61.2～62.9℃；Anal.：Cal?cd：C，81.82；H，6.82％?Found：C，81.67；H，6.78％
3,2-benzyl-4-thiotolene 6.5g is dissolved in the anhydrous diethyl ether, at N
2Protection is cooled to about 0 ℃ down, drips n-BuLi hexane solution 26ml (1.6M), adds the back and refluxes 1 hour, is cooled to room temperature again, adds the Perfluorocyclopentene of equivalent.React 1 hour postcooling to-78 ℃ approximately, the 5-lithium-2-ethyl-4-methylthiazol with equivalent continued low-temp reaction 3 hours again, rose to room temperature, added the dilute hydrochloric acid stopped reaction.Separatory, the water extracted with diethyl ether.After merging organic phase, use MgSO
4Dry.Desolvate, vacuum-drying, after silica gel chromatographic column separates faint yellow solid 1-(2-ethyl-4-methyl-thiazole-5-yl)-2-(5-benzyl-3-methyl-thiophene-2-yl) Perfluorocyclopentene product 5.03g, productive rate is 28%.
mp?142～143℃；Anal.：Calcd：C，56.67；H，3.90；N，2.87％?Found：C，56.73；H，3.88；N，2.91％。
As shown in Figure 1, be 1-(the UV-Vis absorption spectrum of 2-ethyl-4-methyl-thiazole-5-yl)-2-(5-benzyl-3-methyl-thiophene-2-yl) Perfluorocyclopentene open loop attitude and closed loop attitude, solid line is the absorption spectrum of open loop attitude among the figure, dotted line is the absorption spectrum of closed loop attitude, as can be seen from the figure, the closed loop attitude has a new absorption band between 415-475nm, and is quick on the draw.
Embodiment 2,1, and the synthetic synthetic route of 2-two (4-methyl-2-benzyl thiazole-5-yl) Perfluorocyclopentene is as follows:
Concrete steps are:
1,2-benzyl-4-methylthiazol 7.34g is dissolved among the dithiocarbonic anhydride 50ml, places ice bath, slowly dripping bromine 2ml.Rise to room temperature reaction 2 hours after adding.Add the water stopped reaction, the chloroform extraction organic phase, the MgSO4 drying gets clear crystal 5-bromo-2-benzyl 4-methylthiazol 8.35g after silica gel chromatographic column separates, and productive rate is 80.2%.
mp?65～66℃；
1H?NMR：δ＝2.45(s，3H，Ar-Me)，2.84-3.52(s，-CH2-Ar)，7.40-7.56(m，5H，Ar)；Anal.：Calcd：C，49.25；H，3.73；N，5.22％?Found：C，49.37；H，3.85；N，5.18％
2,5-bromo-2-benzyl 4-methylthiazol 5g is dissolved in anhydrous diethyl ether, is cooled to-78 ℃ approximately with nitrogen protection, add n-BuLi hexane solution 12ml (1.6M), low-temp reaction adds 0.5 normal Perfluorocyclopentene after 1 hour.Continue reaction 3 hours, rise to room temperature, add the dilute hydrochloric acid stopped reaction.Separatory, the water extracted with diethyl ether.After merging organic phase, use the MgSO4 drying.Desolvate, vacuum-drying gets light yellow crystal 3.84g after silica gel chromatographic column separates, and productive rate is 37.5%.
mp?116～1118℃；
1H?NMR：δ＝1.61-2.15(s，6H，2Me)，2.65-3.27(s，-CH2-Ar)，7.42-7.94(m，1H，Ar)；Anal.：Calcd：C，58.91；H，3.64；N，5.09％?Found：C，58.95；H，3.61；N，3.56％。
Claims (9)
1. general formula (I) compound:
Wherein, X
1, X
2Be CH or N;
R
1, R
2Be CH
2R or CH=CH
2R;
R is the alkyl of carbonatoms 1-6, cycloalkyl or the aryl of carbonatoms 3-6.
2. method for preparing the described compound of symmetric claim 1 may further comprise the steps:
1) with 2-substituting group-4-methylthiazol ring 5-position bromination or get 2-substituting group-4-thiotolene;
2) n-Butyl Lithium with equivalent reacts, and adds identical normal Perfluorocyclopentene then, promptly synthetic symmetric diarylethene product.
3. method according to claim 2 is characterized in that its concrete steps are:
1) with 2-R
1Base-4-methylthiazol is dissolved in the dithiocarbonic anhydride, puts into ice bath, dripping bromine slowly, then room temperature reaction 2～3 hours, 5-bromo-2-R
1Base-4-methylthiazol;
2) with 5-bromo-2-R
1Base-4-methylthiazol is dissolved in the anhydrous tetrahydro furan, at N
2Protection is cooled to-78 ℃ approximately down, adds the n-BuLi afterreaction 1 hour; Add 0.5 normal Perfluorocyclopentene, continued low-temp reaction 2～3 hours, rise to room temperature then, stopped reaction obtains product;
X in synthetic formula (I) compound
1=X
2=N, R
1=R
2
4. method according to claim 2 is characterized in that its concrete steps are:
1) with 2-R
1Base-4-thiotolene is dissolved in the anhydrous diethyl ether, at N
2Protection is cooled to about 0 ℃ down, drips n-BuLi; Refluxed then 1 hour, and be cooled to 0 ℃ again, add 0.5 normal Perfluorocyclopentene, continue reaction 1 hour, add the dilute hydrochloric acid stopped reaction and obtain product;
X in synthetic formula (I) compound
1=X
2=CH, R
1=R
2
5. method for preparing the described compound of asymmetrical claim 1 may further comprise the steps:
1) with 2-substituting group-4-methylthiazol ring 5-position bromination or get 2-substituting group-4-thiotolene;
2) add the Perfluorocyclopentene of equivalent, behind the stoichiometric number hour, single Perfluorocyclopentene that replaces; With 2-substituting group-4-thiotolene or 5-bromo-2-substituting group-4-methylthiazol and the reaction of equivalent n-Butyl Lithium, add single Perfluorocyclopentene that replaces again, promptly synthesize asymmetrical diarylethene product.
6. method according to claim 5 is characterized in that its concrete steps are:
1) with 2-R
2Base-4-methylthiazol is dissolved in the anhydrous diethyl ether, dripping bromine slowly under condition of ice bath, then room temperature reaction 2～3 hours, 5-bromo-2-R
2Base-4-methylthiazol;
2) with 2-R
1Base-4-thiotolene is dissolved in anhydrous diethyl ether, at N
2Protection is cooled to 0 ℃ down, drips n-BuLi; Refluxing 1 hour in the back, is cooled to room temperature, adds the Perfluorocyclopentene of equivalent, continues reaction 1-2 hour, and stopped reaction gets single Perfluorocyclopentene that replaces;
3) with 5-bromo-2-R
2Base-4-methylthiazol is dissolved in anhydrous diethyl ether, at N
2Be cooled to-78 ℃ approximately under the protection, adding n-BuLi, low-temp reaction add single Perfluorocyclopentene that replaces after 1 hour, continue reaction 2-3 hour, rise to room temperature, get product after the stopped reaction;
X in synthetic formula (I) compound
1=CH, X
2=N, R
1≠ R
2
7. according to the described method of claim 5, it is characterized in that:
1) X
1=X
2During=CH, with 2-R
1Base-4-thiotolene is dissolved in anhydrous diethyl ether, at N
2Protection is cooled to 0 ℃ down, drips n-BuLi; Refluxing 1 hour in the back, is cooled to room temperature, adds the equivalent Perfluorocyclopentene, continues reaction 1-2 hour, single Perfluorocyclopentene that replaces, again with 5-lithium-2-R
2Base-4-thiotolene react product;
2) X
1=X
2During=N, earlier with 2-R
1Base-4-methylthiazol, 2-R
2Base-4-methylthiazol bromination; With 5-bromo-2-R
1Base-4-methylthiazol is dissolved in anhydrous diethyl ether, N
2Protect down, be cooled to-78 ℃ approximately, add n-BuLi, low-temp reaction 1 hour, the Perfluorocyclopentene of adding equivalent gets single Perfluorocyclopentene that replaces, again with 5-lithium-2-R
2Base-4-methylthiazol reaction obtains product;
X in synthetic formula (I) compound
1=X
2, R
1≠ R
2
8. the compound of claim 1 is as the application of optical storage material.
9. the compound of claim 1 is as the application of photochromic molecules device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021006814A CN100391949C (en) | 2002-02-22 | 2002-02-22 | SW diaryl ethylene compounds and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021006814A CN100391949C (en) | 2002-02-22 | 2002-02-22 | SW diaryl ethylene compounds and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1439635A CN1439635A (en) | 2003-09-03 |
| CN100391949C true CN100391949C (en) | 2008-06-04 |
Family
ID=27792967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021006814A Expired - Fee Related CN100391949C (en) | 2002-02-22 | 2002-02-22 | SW diaryl ethylene compounds and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100391949C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5216954B2 (en) * | 2006-03-10 | 2013-06-19 | 国立大学法人京都大学 | Method for producing diarylethene compound |
| CN102442999A (en) * | 2011-10-18 | 2012-05-09 | 江西科技师范学院 | Photochromic pyrimidine-thiophene mixed octafluorocyclopentene compound, synthesis method and application thereof |
| 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 |
| CN107652279B (en) * | 2017-10-31 | 2020-05-19 | 华中科技大学 | Diaryl ethylene fluorescent molecular switch, and preparation method and application thereof |
| CN108594607A (en) * | 2018-04-26 | 2018-09-28 | 京东方科技集团股份有限公司 | a kind of photoresist and exposure method |
| CN111704626B (en) * | 2020-05-29 | 2022-07-29 | 江南大学 | Diaryl ethylene photochromic organic cage and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0559025A (en) * | 1991-08-30 | 1993-03-09 | Central Glass Co Ltd | Diarylethene compound |
| JPH08245579A (en) * | 1995-03-10 | 1996-09-24 | Masahiro Irie | Diarylethene photochromic compound and optically recording material using the compound |
| JPH11311813A (en) * | 1998-04-28 | 1999-11-09 | Kyocera Corp | Optical function element |
-
2002
- 2002-02-22 CN CNB021006814A patent/CN100391949C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0559025A (en) * | 1991-08-30 | 1993-03-09 | Central Glass Co Ltd | Diarylethene compound |
| JPH08245579A (en) * | 1995-03-10 | 1996-09-24 | Masahiro Irie | Diarylethene photochromic compound and optically recording material using the compound |
| JPH11311813A (en) * | 1998-04-28 | 1999-11-09 | Kyocera Corp | Optical function element |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1439635A (en) | 2003-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nakatani et al. | Introduction: organic photochromic molecules | |
| CN1978444B (en) | Photochromic thiophene pyrrole mixed linkage type dithienylethene compounds, and their synthesizing and use | |
| CN100391949C (en) | SW diaryl ethylene compounds and preparation and application thereof | |
| JP2008274291A (en) | Bis-styryl dye, its production process and its application for high-density optical recording medium | |
| JPH08245579A (en) | Diarylethene photochromic compound and optically recording material using the compound | |
| CN100491373C (en) | Photochromic thiophene pyrazole heterocyclic series-parallel asymmetric perfluorocyclopentene compound and preparation method and application thereof | |
| CN101602743B (en) | Photochromic thiazole hexatomic ring series-parallel asymmetric perfluoro-cyclopentene compound and preparation method and application thereof | |
| CN101591334B (en) | Photochromic thiophene-thiazole heterocycle hybrid asymmetric perfluorocyclopentene compound, preparation method and application | |
| JP2002179672A (en) | New compound and optical element produced by using the compound | |
| JP3963524B2 (en) | Phthalocyanine compound, method for producing the same, and optical recording medium using the same | |
| CN100402526C (en) | Lysotropic-photodiscolour diaryl ethylene and preparation and application thereof | |
| CN1205206C (en) | Asymmetric diaryl ethylene photochromic compound, and its preparing method and use | |
| JP2002275458A (en) | Photochromic amorphous material and high density optical recording medium | |
| JP3538019B2 (en) | Photochromic crystal material | |
| JP4743930B2 (en) | Optical functional element | |
| CN1329391C (en) | Organic photochromic diaryl ethylene compound and its preparation process and application | |
| Song et al. | Study on Photochromic Materials with Photochromic and Optical Storage Composite Properties of a Novel Diarylethene | |
| US8222401B2 (en) | Metallocenyl phthalocyanine compounds and use thereof | |
| Liu et al. | Achieve both multiwavelength and multilevel optical storage on compact disk by diarylethene | |
| Jia et al. | Synthesis and Properties of a New Unsymmetry Diarylethene 1-{2-methyl-[5-(4-methylene-bromine) phenyl]-3-thienyl}-2-[2-methyl-5-(10-phenanthrenyl)-3-thienyl] perfluorocyclopentene | |
| Song et al. | Study on Photochromic Materials with Photochromic and Optical Storage Composite Properties of a Novel Diarylethene | |
| JP2004306587A (en) | Optical recording medium | |
| TWI383896B (en) | Optical recording materials, chalcone compounds and metal complexes | |
| Jing et al. | Photochromic Composite Properties and Application in Optical Memory of a Diarylethene with Benzofuran unit | |
| JP5426158B2 (en) | Methine dyes and their uses |
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: 20080604 |