CN103333674A - Diarylethene photochromic compound with electric field modulation function and synthesis method - Google Patents
Diarylethene photochromic compound with electric field modulation function and synthesis method Download PDFInfo
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Abstract
The invention provides a diarylethene photochromic compound with an electric field modulation function and a synthesis method. The method comprises the steps as follows: firstly, an aromatic heterocyclic intermediate containing an electronic transmission group is synthesized; then an aromatic heterocyclic intermediate containing a charge transfer group is synthesized; the two intermediates are combined to fluorine atoms of two double-bond carbons of an octafluorocyclopentene molecule respectively, so that an asymmetric type diarylethene photochromic compound containing two types of charge transfer groups is formed; and the intermediate compound containing the electronic transmission group is firstly required to be prepared into single substitutional octafluorocyclopentene intermediate, and then the target product can be smoothly obtained. The diarylethene photochromic compound with the electric field modulation function and the synthesis method have the benefits that the compound has better photochromism and fatigue resistance, and more importantly, photochromism interfered by the electric field can be introduced into the compound; and by virtue of characteristics of the asymmetric type diarylethene photochromic compound molecule, a novel controllable photochromic material can be manufactured, and the compound has a wide application prospect in the field of optical information storage and novel optical devices.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly a kind of diaryl ethylene photochromic compound and synthetic method with electric field modulation function.
Background technology
Photochromic compounds is that a class can under UV-light or radiation of visible light color change take place, and returns to the material of primary colors after stopping to shine again.In the molecular structure of this class material, there are two kinds of metastable states that absorption spectrum has marked difference, under the stimulation of light or heat, reversible photoisomerization process can take place.By the structural modification of molecule, the functional performance of various color distinction or giving property can appear.The photochromic compounds that has been found that mainly contains types such as diarylethene, fulgide, spiro-pyrans, Luo oxazine, nitrogen benzide
[2] " functional materials " 1998,29 (2) 113-120), what these photochromic compounds had is applied, for example, and photochromic clothes printed patterns, photochromic optical mirror slip etc.Deep and extensive along with what study, it is found that the increasing Application Areas of this compounds, cause great interest.Become organic functional material field research focus for a long time.
In the photochromic compounds of studying so far, two aromatic heterocyclic ethylene compounds [4] show excellent characteristic in following several respects, and being considered to is being near a compounds of application request aspect super-high density optical information memory material and the molecular switch.(1) photochromic process has heat irreversible, and it is stable that the open/close isomer still keeps under 100 ℃; Fatigue resistance is good, and the open/close cycle index can reach〉10
4, there is not significantly decay, can guarantee the reliability of the information of storing.(2) very high response speed reaches～the 1ps level, can improve the storage speed of information.(3) absorption spectrum of its closed loop can be easily selected than being easier to reach Wavelength matched with existing irradiating source by changing substituent characteristic electron.(4) still be the form of monocrystalline to connect that Zhi Gongju, dissolving disperse no matter, generally have good solid phase photochromic properties.
Modification main purpose to the diarylethene system was absorption Spectrum characteristic, better resistance to fatigue and the thermodynamic stability that the regulation and control photochromic properties is intended to obtain meeting service requirements in the past.Yet, it is found that to be more suitable for the constitutional features of diaryl ethylene photochromic compound light isomate process in the Application Areas as molecular switch.Design to have synthesized for this reason and have photoinduced paramagnetism photoswitch molecule and photoinduced fluorescent switch molecule.Utilize the change of the multiple character of refractive index that the light isomate process produces, specific inductivity, redox-potential, in field of optoelectronic devices, there is epochmaking potential using value in erasable optical information storage medium and photoswitch field repeatedly as high-density.Now have the diarylethene photochromic compound of bibliographical information, the common ground of its functional performance is, photoinduced isomerization process causes the variation of light, electricity, magnetic property, thereby produces the photoswitch effect of light, electricity, magnetic property.Only to optical radiation sensitivity-namely only have simple photoinduction activity, the light isomery is not subjected to the influence in electric field and magnetic field.
Summary of the invention
The purpose of this invention is to provide a kind of diaryl ethylene photochromic compound and synthetic method with electric field modulation function, in a molecule, contain asymmetrical type diarylethene photochromic compound and the manufacture method thereof of an electron-transporting type organic semiconductor functional group and a hole-transporting type organic semiconductor functional group simultaneously.Thisly contain the asymmetrical type diarylethene photochromic compound that two kinds of dissimilar electric charges pass to group simultaneously, have the photochromic function characteristic that novel electric field is intervened.
In order to realize this purpose, the technical solution used in the present invention provides a kind of diaryl ethylene photochromic compound with electric field modulation function, and wherein: described photochromic compound is for having the compound of following general formula (I):
In the formula: R
1For having cavity type conducting structure substituting group, comprise that all have the building stone of P-conductivity, have the hole transport structure of triphenylamine type, R
1' be methyl or ethyl or phenyl or methylamino or dimethylamino or diethylamino or diphenyl amino and tree-shaped three arylamine building stones, R
2Be structure or the group with electric transmission function, R
2' have group or the structure of electric transmission function, Cyc for the thiazole of the alkyl of hydrogen or phenyl or substituted-phenyl or methyl or ethyl or 3 to 18 carbon or nitro or halogen or replacement
1And Cyc
2Be alicyclic ring or aromatic nucleus that can be identical or different.
A kind of synthetic method with diaryl ethylene photochromic compound of electric field modulation function is provided simultaneously.
Effect of the present invention is this synthetic compound, and in a diarylethene molecule, photochromic division center both sides connect electron-transporting type semiconductor structure and hole transport semiconductor structure respectively, and molecule has good photochromic and fatigue resistance.The more important thing is, in this compounds, can introduce the photochromism that electric field is intervened.If this compounds is applied to thin-film device, in electroluminescent device, hole and electronics are under the promotion of electric field, the center that the compound and exciton energy that produces of current carrier is imported to photochromic structure by the electric transmission group of molecule both sides and cavity transmission group takes place in device, thereby excites and influence the isomate process of molecule.This has just realized applying electric field, and photochromic process is realized intervening artificially.On the other hand, under the stimulation of light, photochromic process when taking place, to the electroconductibility generation change more significantly of device in the film that this molecule forms.Because this new features of molecule can produce controlled photochromic novel material, in optical information storage and new optical devices field, has tempting application prospect.
Description of drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy before and after compound of the present invention (10) illumination;
Fig. 2 is the ultraviolet-visible absorption spectroscopy of the illumination front and back of compound of the present invention (23);
Fig. 3 is midbody compound of the present invention (5)
1H NMR nuclear magnetic spectrogram;
Fig. 4 is midbody compound of the present invention (9)
1H NMR nuclear magnetic spectrogram;
Fig. 5 is target compound of the present invention (10)
1H NMR nuclear magnetic spectrogram;
Fig. 6 is midbody compound of the present invention (16)
1H NMR nuclear magnetic spectrogram;
Fig. 7 is midbody compound of the present invention (16)
13C nuclear magnetic resonance, carbon spectrum.
Embodiment
Diaryl ethylene photochromic compound with electric field modulation function of the present invention, described photochromic compound is for having the compound of following general formula (I):
R in the formula
1For having cavity type conducting structure substituting group, comprise that all have the building stone of P-conductivity, have the hole transport structure of triphenylamine type, R
1' be methyl or ethyl or phenyl or methylamino or dimethylamino or diethylamino or diphenyl amino and tree-shaped three arylamine building stones, R
2Be structure or the group with electric transmission function, R
2' have group or the structure of electric transmission function, Cyc for the thiazole of the alkyl of hydrogen or phenyl or substituted-phenyl or methyl or ethyl or 3 to 18 carbon or nitro or halogen or replacement
1And Cyc
2Be alicyclic ring or aromatic nucleus that can be identical or different.
As depicted in figs. 1 and 2, diaryl ethylene photochromic compound of the present invention has the good photochromic performance.For target compound (10), mainly be subjected to the ultraviolet excitation greater than the big wavelength of 300nm, produce sensitive coloring reaction, the maximum absorption wavelength of coloured state is 633nm, has bigger absorbancy (Fig. 1).For target compound (17), its photochromism and generalization compound have bigger different.Be mainly reflected in, when coloring reaction took place, ultraviolet absorption part and visible absorption part absorbancy increased simultaneously, and maximum absorption wavelength is 584nm and 308nm(Fig. 2).The structure of key intermediate and target product obtains support and the affirmation of proton nmr spectra or carbon spectrum.The proton nmr spectra of midbody compound (5) as shown in Figure 3; The proton nmr spectra that intermediate is carried compound (9) as shown in Figure 4, the proton nmr spectra of target compound (10) as shown in Figure 5, the proton nmr spectra of midbody compound (16) and carbon spectrum are respectively as shown in Figure 6 and Figure 7.
Synthetic method with diaryl ethylene photochromic compound of electric field modulation function of the present invention, this method may further comprise the steps:
(1) at first synthetic have following structure, contains single Perfluorocyclopentene intermediate that replaces of first kind of electric charge transport group:
In above structure, Cyc can be phenyl ring, also can be not contain this part-structure.R is substituting group or the structural unit with electric charge transfer function.Preferentially select the structure of electron-transporting type among the present invention for use, because the electric transmission structure generally has stronger electrophilic, the F atom that the ethylene double bond carbon atom connects on the Perfluorocyclopentene base in the said structure has stronger nucleophilic reaction activity; Among the present invention, select for use 2,5-two to replace-1,3,4-oxadiazole is as the electric transmission structural unit, is connected to form the intermediate (A) of said structure with thiphene ring or thionaphthene ring.
A. being starting raw material with 5-thiotolene formic acid, is reaction media with acetic acid, is being lower than under-10 ° of C conditions, carries out bromination with the solution of bromine in acetic acid, obtains 5-methyl-4-bromothiophene formic acid;
With the compound 2-methylbenzene thiophthene-5-formic acid of 5-methyl-4-bromothiophene formic acid similar, then need with following two kinds of methods, through the polystep reaction preparation.Method one is to Thiosalicylic acid, under the katalysis of sulfuric acid, with ethanol generation esterification, preparation is to the Thiosalicylic acid ethyl ester, again with 2,3 – dichloropropylenes in acetone, as Fu's acid agent, obtain thioether class midbody compound with the Anhydrous potassium carbonate powder.This compound can be at N, through closing reaction process such as ring, rearrangement, elimination, obtains 2-methylbenzene thiophthene-5-ethyl formate in the N-Diethyl Aniline, obtains 2-methylbenzene thiophthene-5-formic acid through hydrolysis reaction; Method two is to bromo thiophenol, with 2,3 – dichloropropylenes are in acetone, with the Anhydrous potassium carbonate powder as Fu acid agent, obtain thioether class midbody compound, this compound is at N, in the N-Diethyl Aniline through closing reaction process such as ring, rearrangement, elimination, obtain 2-methyl-5-bromobenzene thiophthene, convert 2-methylbenzene thiophthene-5-formic acid to through lithium reagent or Grignard reagent;
B. above-mentioned 5-methyl-4-bromothiophene formic acid or 2-methylbenzene thiophthene-5-formic acid converts it into acyl chlorides with thionyl chloride or phosphorus trichloride earlier, with the aryl formyl hydrazine, any hydrazide kind compound reaction obtains the bishydrazide intermediate as benzoyl hydrazine, biphenyl-4-formyl hydrazine, thiophene-2-formyl hydrazine, 1-naphthoyl hydrazine, 1-naphthoyl hydrazine etc. again;
C. described bishydrazide intermediate through condensation, ring closure reaction, obtains 2 of 3-bit strip bromine, and 5-two replaces-1,3,4-oxadiazole class intermediate or not brominated De oxadiazole class intermediate., can obtain through bromination reaction more not with Xiu De oxadiazole class intermediate for the 3-position;
D. after described brominated De oxadiazole class intermediate changes into lithium reagent, with the Perfluorocyclopentene reaction of mol ratio more than three times, generate the single Perfluorocyclopentene intermediate (A) that replaces that contains the electric charge transport group;
(2) the synthetic 3-Br that contains second kind of electric charge transport group with structure as follows is for fragrant heterocycle intermediate:
In above structure, Cyc can be alicyclic ring or aromatic nucleus, also can not have this structure division.R is cavity type electric charge transport group, R
1' be methyl or ethyl or phenyl or methylamino or dimethylamino or diethylamino or diphenyl amino and tree-shaped three arylamine building stones.
First kind of electric charge transmission structure selecting in the matching step (1), select second kind of dissimilar electric charge transport group for use, if step has been selected the electric transmission group for use in (1), then to select for use triphenylamine class formation unit as the cavity type transport group in this step, constitute above-mentioned midbody compound (B);
A. be starting raw material to replace the 2-thiotolene, obtain 3,5-, two bromo thiophene intermediates through bromination; Or be initiator with the bromo thiophenol, with 2,3-dichloropropylene in acetone, be Fu acid agent with Anhydrous potassium carbonate, obtain the intermediate of a thioether class, described intermediate is at N, through closing reaction process such as ring, rearrangement, elimination, make 2-methyl-5-bromobenzene thiophthene in the N-Diethyl Aniline;
B. the above-mentioned 2-methyl that obtains-5-bromobenzene thiophthene intermediate and tributyl borate reaction obtains 2-methyl-3-bromo-thiophene-5-boric acid; Or change into 2-methylbenzene thiophthene-5-boric acid earlier by 2-methyl-5-bromobenzene thiophthene, pass through bromination again after, make 2-methyl-3-bromobenzene thiophthene-5-boric acid;
C. described 2-methyl-3 bromo thiophene-5-boric acid and 4-iodine triphenylamine reaction reagent are in tetrahydrofuran (THF), with Pa (PPh
3)
4Be catalyzer, the organic semiconductor functional group through linked reaction introducing tri-arylamine group type obtains 2-methyl-3-bromo-5-(diphenyl amino) the phenyl thiophene; Or by 2-methyl-3-bromo-thionaphthene-5-boric acid and 4-iodine triphenylamine in tetrahydrofuran (THF), with Pa (PPh
3)
4Be catalyzer, obtain 2-methyl-3-bromo-5-(diphenyl amino through linked reaction) phenyl thiophene (B).Be reaction reagent with 4-iodine triphenylamine, can improve reactive behavior and selectivity, effectively avoid containing the coupling between the bromide reagent.
(3) described intermediate (B) is changed into organolithium reagent, under the temperature of-85 to-90 ° of C, react with the single Perfluorocyclopentene intermediate (A) that replaces that contains the electric transmission group, can form the asymmetrical type diaryl ethylene photochromic compound (I) that contains two kinds of different electric charge transport groups.In reaction, must adopt the temperature condition of-85 to-90 ° of C.Yin Wei oxadiazole structure itself is responsive to the reagent of alkalescence.Suitable cold condition can reduce the structural damage of Dui oxadiazole.
Embodiment 1
By following reaction, can introduce three arylamine structural units and oxadiazoles structural unit respectively in the 5-position that replaces the 2-thiotolene, form two midbody compounds that have dissimilar electric charge transport groups, finally be combined into two aromatic heterocyclic vinyl compounds of the structure that is shown below:
Target compound (10)
Synthetic route is as follows:
Synthetic route-1
Concrete steps are:
1. prepare 2-methyl-3-bromo-5-(4-diphenyl amino) phenyl thiophene (4)
(1) at first 2-thiotolene (2) is carried out bromination, preparation 2-methyl-3,5-dibromo thiophene (3).Bathe under the cooling at cryosel, 24.0 gram 2-thiotolenes (2) are dissolved in 100 milliliters of acetic acid, drip the solution of 29 milliliters of bromines in 40 milliliters of acetic acid then, continue to stir 2 hours, then reaction mixture is poured in the big water gaging, with the bottom dark oily matter (intermediate 3) that dissociates, dry by twice underpressure distillation, collect the cut of 84-87 ° of C/4mmHg, 42.5 grams (productive rate about 67.8%).
(2) 12 gram 2-methyl-3,5-dibromo thiophene (3), be dissolved in 25 milliliters of tetrahydrofuran (THF)s of handling well, be cooled to-78 ° of C, splash into 19.7 milliliters of n-ButLi(2.5M), stir after 40 minutes, splash into 10.8 gram (12.6 milliliters) tributyl borates at the solution of 10.0 milliliters of tetrahydrofuran (THF)s, stir after 30 minutes, be warmed up to room temperature, sodium hydroxide solution extraction with 20%, extract and also use 10% hcl acidifying, separate out solid 2-methyl-3 bromo thiophene-5-boric acid (intermediate 4), recrystallization in sherwood oil, obtain 8.3 gram white solids, productive rate 80%.
(3) 1.46 gram (6.6 mmole) 2-methyl-3 bromo thiophene-5-boric acid (4), 2.33 gram (6.0 mmole) 4-iodine triphenylamines, 229.0 milligrams of Pa (PPh
3)
4, 1.70 gram salt of wormwood join 50 milliliters of tetrahydrofuran solutions that contain 10% water, stirred overnight at room temperature.Mixture is put into 200 ml waters, and the dark oily matter that dissociates and with 100 milliliters of sherwood oils, divides three extractions.With three washings of 100 milliliters of moisture, anhydrous magnesium sulfate drying, decompression steams solvent.The residuum that obtains has sherwood oil/chloroform (2:1) to separate with silica gel column chromatography, obtains 2.1 gram lilac red fluorescent components, 2-methyl-3-bromo-5-(4-diphenyl amino) phenyl thiophene (5), productive rate 75.7%.
1H?NMR(400MHz,CDCl
3)δ(ppm)=2.40(s,3H),5.30(s,1H),7.00(s,1H),7.04(td,J=7.30,2.98,2.98Hz,4H),7.11(dd,J=8.54,1.02Hz,4H),7.24(t,J=2.02,2.02Hz,1H),7.26(d,J=1.03Hz,2H),7.28(t,J=1.96,1.96Hz,1H),7.35-7.33(m,1H),7.36(t,1.96,1.96Hz,1H)。See Fig. 3 for details.
2. prepare mono-substituted Perfluorocyclopentene intermediate 2-(2-(5-methyl-4-(1-Perfluorocyclopentene base) thienyl)-5-phenyl-1,3,4-oxadiazole (9)
(1) 10 gram 5-methyl-thiophene-2-carboxylic acids (7) is dissolved in 100 milliliter 1, in the 2-ethylene dichloride, add about 0.2 gram reduced iron powder, under reflux temperature, drip 11.2 gram (3.6 milliliters) bromines, drip to finish and be back to colourlessly, the native green solid powder of about 11.0 grams is separated out in cooling, use the ethylene dichloride recrystallization, can get 9.6 gram greyish-green solids.
(2) with above 9.6 gram (43.4 mmole) solid products, join in 70 milliliters of thionyl chlorides, reflux after 2 hours, steam except most thionyl chloride, add 30 milliliters of benzos and distillation then at twice to remove residual thionyl chloride.Add 50 milliliter 1 in residuum, the 2-ethylene dichloride drops into about 8 gram benzoyl hydrazine solids in batches, monitors reaction process (developping agent chloroform/acetone=3:0.5) with thin layer.Can obtain the faint yellow product of about 14.0 grams, not need to enter the next step through purifying.
(3) obtain solid more than getting 12.0 grams, adds the phosphorus oxychloride that 150 milliliters of acetonitriles and 85 milliliters newly distill, back flow reaction 2 hours.Decompression distills out most of phosphorus oxychloride and acetonitrile for reaction down, and mixture is poured in the frozen water, separates out 11.0 gram faint yellow solid powder.Use the dehydrated alcohol recrystallization, can obtain about 8.3 grams of needle crystal solid.Be 2-(2-(4-bromo-5-thiotolene base))-5-phenyl-1,3,4-oxadiazole (8).
(4) with 1.0 gram (3.11 mmole) 2-(2-(4-bromo-5-thiotolene bases))-5-phenyl-1,3,4-oxadiazole (8) is dissolved in 30 milliliters of tetrahydrofuran (THF)s of handling well, be cooled to-85 ° of C, splash into 1.37 milliliters of n-ButLi(2.5M), stir after 30 minutes, add 1.67 milliliters of octafluoro cyclopentenes.Keep low temperature to stir 4 hours, add 2 milliliters of ethanol, termination reaction, mixture is poured in 100 ml waters, uses ethyl acetate extraction, and organic phase is steamed after with anhydrous magnesium sulfate drying and desolventized, the residuum silica gel column chromatography can obtain 0.75 gram white solid powder (9).The nuclear-magnetism characterization data is as follows: 1H NMR (300MHz, CDCl
3) δ (ppm)=2.06 (s, 3H), 7.60-7.48 (m, 3H), 7.78 (s, 1H), 8.11 (ddd, J=5.59,4.23,2.46Hz, 2H).See Fig. 4 for details.
3. target compound (10) is synthetic
97 milligrams of midbody compounds (5) are dissolved in 10.0 milliliters of treated tetrahydrofuran (THF)s, be cooled to-78 ° of C, inject 0.11 milliliter of n-ButLi(2.5M), insulated and stirred 60 minutes, cool the temperature to-90 ° of C approximately, inject 100 milligrams of midbody compounds (9) at the solution of 8 milliliters of tetrahydrofuran (THF)s, keep temperature to stir 40 minutes, inject 0.5 milliliter of ethanol stopped reaction.Mixture is poured in 100 ml waters, divides three extractions with 50 milliliters of ethyl acetate.Organic phase reduces pressure after drying and steams solvent, on silicagel column, with methylene dichloride/sherwood oil (3:2) and methylene dichloride/acetone (100:1) chromatography successively, collect photochromic component and obtain 108.0 milligrams of blackish green solid products (10), fusing point 175-180 ° C.The nmr analysis data are as follows:
1H NMR (300MHz, CDCl
3) δ (ppm)=1.96 (s, 3H), 2.05 (s, 3H), 7.15-6.99 (m, 9H), 7.23 (t, J=2.03,2.03Hz, 2H), and 7.29-7.24 (m, 2H), 7.39-7.34 (m, 2H), 7.58-7.47 (m, 3H), 7.78 (s, 1H), 8.10 (dd, J=7.82,1.76Hz, 2H).See Fig. 5 for details.Its photochromic properties as shown in Figure 1.
Target compound (17)
Synthetic route is as follows:
Synthetic route-1
Concrete steps are:
1.2-the preparation of methyl-3-bromobenzene thiophthene-5-boric acid (14)
(1) 80 grams is dissolved in 250 milliliters of acetone bromo thiophenol, add 90 gram anhydrous sodium carbonates, splash into 52.0 grams 2, the solution of 3-dichloropropylene in 50 milliliters of acetone drips to finish and stirred 60 minutes, filters out pressed powder and uses twice of washing with acetone, the acetone soln that obtains, remove solvent under reduced pressure, get 115 gram weak yellow liquids, enter the next step without purifying.
The above thioether class intermediate crude product that obtains is joined 150 milliliters of (1.08 moles) N, in the N-Diethyl Aniline, under the nitrogen protection, with 195-200 ° of C reaction 24 hours.The hydrochloric acid that reaction mixture is made into 131 milliliters of concentrated hydrochloric acids and water (2:1) extracts N, and the N-Diethyl Aniline is separated out faint yellow solid after the cooling, be 2-methyl-5-bromobenzene thiophthene (12) crude product.Behind 95% dissolve with ethanol, add suitable quantity of water and separate out the nattierblue solid.Filter, stand-by in air drying.
(2) 6.4 gram (28.0 mmole) midbody compounds (12) are dissolved in 60 milliliters of treated tetrahydrofuran (THF)s, be cooled to-78 ° of C, splash into 4.7 milliliters of n-ButLi(2.5M), stir after 40 minutes, splash into 9.8 milliliters of tributyl borates, continued stirring reaction 40 minutes.Add 20 milliliter of 10% dilute hydrochloric acid and 100 ml waters, tell organic phase, water merges organic phase with 100 milliliters of Petroleum ether extraction, and decompression after the drying is steamed solvent, and residuum dissolves with 100 milliliter of 20% aqueous sodium hydroxide solution, the clear liquid of filtration.Separate out solid with the 1:1 hcl acidifying, obtain white solid (midbody compound 13) 4.6 grams, productive rate 85% through washing filtering.
(3) 2.0 gram (10.4 mmole) midbody compounds (13) are dissolved in 50 milliliters of acetic acid, splash into 0.53 milliliter of bromine, reflux disappears to red, and underpressure distillation goes out acetic acid.Residuum dissolves with 50 milliliter of 20% aqueous sodium hydroxide solution, filters out solid impurity, and also white solid product (14) is separated out in dilute hydrochloric acid (1:1) acidifying, after filtration, washing and drying, gets 1.1 gram products, productive rate 39%.
2. the preparation of phenyl thiophene midbody compound (16) 2-methyl-3-bromo-5-(4-diphenyl amino)
With 1.50 gram (5.54 mmole) midbody products (14), 2.06 gram 4-iodine triphenylamines (15), 192 milligrams of Pa (PPh
3)
4, 1.5 gram yellow soda ash join in the solution of 55 milliliters of tetrahydrofuran (THF)/water (10:1), stir at 50 ° of C and spend the night.Reaction mixture is poured in 150 ml waters, tells organic phase.Water divides three extractions with 100 milliliters of methylene dichloride, merges organic phase and handles with anhydrous magnesium sulfate drying.Remove organic solvent under reduced pressure, get a dope.On silicagel column, with chloroform/sherwood oil (1:4) column chromatography, collect whole low-polarity constituentses, secondary chromatography then, the elutriant that obtains has been concentrated into solid and has occurred, and 2.2 gram white solids (midbody compound 16), productive rate 85% are separated out in cooling.The nuclear magnetic resonance spectrum data:
1HNMR (400MHz, CDCl
3) δ (ppm)=2.55 (s, 3H), 7.03 (t, J=7.31,7.31Hz, 2H), 7.19-7.11 (m, 6H), 7.25 (dd, J=14.89,7.48Hz, 4H), 7.57-7.50 (m, 3H), 7.75-7.71 (m, 1H), 7.86 (d, J=1.51Hz, 1H); See Fig. 6 for details.The carbon spectrum sees Fig. 7 for details.
3. target compound (17) is synthetic
200 milligrams of (0.43 mmole) midbody compounds (16) are dissolved in 20 milliliters of treated tetrahydrofuran (THF)s, be cooled to-78 ° of C, drip 0.24 milliliter of n-ButLi(2.5M), stir after 40 minutes, splash into the solution of 181.0 milligrams of midbody compounds (9) in 10 milliliters of tetrahydrofuran (THF)s, keep temperature to stir 2 hours, inject 0.5 milliliter of ethanol stopped reaction.Reaction mixture is poured in 100 ml waters, divide three extractions with 60 milliliters of ethyl acetate, merge organic phase, steam solvent with decompression behind the anhydrous magnesium sulfate drying, residuum is on silicagel column, with that column chromatography of sherwood oil/methylene dichloride (1:1) gold, obtain 102.0 milligrams of white solid product (17), fusing point 202-206 ° C.Photochromism sees Fig. 2 for details.
Claims (3)
1. diaryl ethylene photochromic compound with electric field modulation function is characterized in that: described photochromic compound is for having the compound of following general formula (I):
In the formula: R
1For having cavity type conducting structure substituting group, comprise that all have the building stone of P-conductivity, have the hole transport structure of triphenylamine type, R
1' be methyl or ethyl or phenyl or methylamino or dimethylamino or diethylamino or diphenyl amino and tree-shaped three arylamine building stones, R
2Be structure or the group with electric transmission function, R
2' have group or the structure of electric transmission function, Cyc for the thiazole of the alkyl of hydrogen or phenyl or substituted-phenyl or methyl or ethyl or 3 to 18 carbon or nitro or halogen or replacement
1And Cyc
2Can be identical or different alicyclic ring or aromatic nucleus.
2. according to the synthetic method of the described compound of claim 1, this method may further comprise the steps:
(1) at first synthetic have following structure, contains single Perfluorocyclopentene intermediate that replaces of first kind of electric charge transport group:
In above structure, Cyc can be phenyl ring, also can be not contain this part-structure, R is substituting group or the structural unit with electric charge transfer function, select the structure of electron-transporting type among the present invention for use, because the electric transmission structure generally has stronger electrophilic, the F atom that double-linked carbon connects on the Perfluorocyclopentene base in the said structure has stronger nucleophilic reaction activity; Select for use 2,5-two to replace-1,3,4-oxadiazole is as the electric transmission structural unit, is connected to form the intermediate (A) of said structure with thiphene ring or thionaphthene ring;
A. being starting raw material with 5-thiotolene formic acid, is reaction media with acetic acid, is being lower than under-10 ° of C conditions, carries out bromination with the solution of bromine in acetic acid, obtains 5-methyl-4-bromothiophene formic acid;
Compound 2-methylbenzene thiophthene-5-formic acid with 5-methyl-4-bromothiophene formic acid similar, then need with following two kinds of methods, method one is to Thiosalicylic acid, under the katalysis of sulfuric acid, with ethanol generation esterification, preparation is to the Thiosalicylic acid ethyl ester, again with 2,3 – dichloropropylenes as Fu's acid agent, obtain thioether class midbody compound with the Anhydrous potassium carbonate powder in acetone, this compound is at N, encircle through closing in the N-Diethyl Aniline, reset, eliminate reaction process, obtain 2-methylbenzene thiophthene-5-ethyl formate, obtain 2-methylbenzene thiophthene-5-formic acid through hydrolysis reaction; Method two is to bromo thiophenol, with 2,3 – dichloropropylenes are in acetone, with the Anhydrous potassium carbonate powder as Fu acid agent, obtain thioether class midbody compound, this compound is at N, in the N-Diethyl Aniline through closing ring, resetting, eliminate reaction process, obtain 2-methyl-5-bromobenzene thiophthene, convert 2-methylbenzene thiophthene-5-formic acid to through lithium reagent or Grignard reagent;
B. above-mentioned 5-methyl-4-bromothiophene formic acid or 2-methylbenzene thiophthene-5-formic acid changes into acyl chlorides with thionyl chloride or phosphorus trichloride earlier, obtains the bishydrazide intermediate with the reaction of aryl formyl hydrazine compounds again;
C. described bishydrazide intermediate through condensation, ring closure reaction, obtains 2 of 3-bit strip bromine, and 5-two replaces-1,3,4-oxadiazole class intermediate; Among the step b, adopt 2-methylbenzene thiophthene-5-formic acid to produce the bishydrazide intermediate, lack a 2-Br atom in the bishydrazide intermediate, in order to descend the steps d reaction, need to obtain 2-(2-(5-bromo-2-methylbenzene thienyl through a bromination reaction again))-5-phenyl-1,3, the 4-oxadiazole;
D. described 2-(2-(5-bromo-2-methylbenzene thienyl))-5-phenyl-1,3, after 4-oxadiazole intermediate changes into lithium reagent, with the Perfluorocyclopentene reaction of mol ratio more than three times, generate the single Perfluorocyclopentene intermediate (A) that replaces that contains the electric charge transport group;
(2) the synthetic 3-Br that contains second kind of electric charge transport group with structure as follows is for fragrant heterocycle intermediate:
In above structure, Cyc can be alicyclic ring or aromatic nucleus, also can not have this structure division.R is cavity type electric charge transport group, R
1' be methyl or ethyl or phenyl or methylamino or dimethylamino or diethylamino or diphenyl amino and tree-shaped three arylamine building stones, first kind of electric charge transmission structure selecting in the matching step (1), select second kind of dissimilar electric charge transport group for use, if step has been selected the electric transmission group for use in (1), then to select for use triphenylamine class formation unit as the cavity type transport group in this step, constitute above-mentioned midbody compound (B);
A. be starting raw material to replace the 2-thiotolene, obtain 3,5-, two bromo thiophene intermediates through bromination; Or be initiator with the bromo thiophenol, with 2,3-dichloropropylene in acetone, be Fu acid agent with Anhydrous potassium carbonate, obtain the intermediate of a thioether class, described intermediate is at N, through closing reaction process such as ring, rearrangement, elimination, make 2-methyl-5-bromobenzene thiophthene in the N-Diethyl Aniline;
B. the above-mentioned 2-methyl that obtains-5-bromobenzene thiophthene intermediate and tributyl borate reaction obtains 2-methyl-3-bromo-thiophene-5-boric acid; Or change into 2-methylbenzene thiophthene-5-boric acid earlier by 2-methyl-5-bromobenzene thiophthene, pass through bromination again after, make 2-methyl-3-bromobenzene thiophthene-5-boric acid;
C. described 2-methyl-3 bromo thiophene-5-boric acid and 4-iodine triphenylamine reaction reagent are in tetrahydrofuran (THF), with Pa (PPh
3)
4Be catalyzer, the organic semiconductor functional group through linked reaction introducing tri-arylamine group type obtains 2-methyl-3-bromo-5-(diphenyl amino) the phenyl thiophene; Or by 2-methyl-3-bromo-thionaphthene-5-boric acid and 4-iodine triphenylamine in tetrahydrofuran (THF), with Pa (PPh
3)
4Be catalyzer, obtain 2-methyl-3-bromo-5-(diphenyl amino through linked reaction) phenyl thiophene (B);
(3) with described 2-methyl-3-bromo-5-(diphenyl amino) phenyl thiophene (B) changes into organolithium reagent, under the temperature of-85 to-90 ° of C, react with the single Perfluorocyclopentene intermediate (A) that replaces that contains the electric transmission group, can form the asymmetrical type diaryl ethylene photochromic compound (I) that contains two kinds of different electric charge transport groups, is responsive Yin Wei oxadiazole structure itself to the reagent of alkalescence in reaction, must adopt the temperature condition of-85 to-90 ° of C, to reduce the structural damage of Dui oxadiazole.
3. method according to claim 2, it is characterized in that: described aryl formyl hydrazine is benzoyl hydrazine or biphenyl-4-formyl hydrazine or thiophene-2-formyl hydrazine or any hydrazide kind compounds such as 1-naphthoyl hydrazine or 1-naphthoyl hydrazine.
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| CN113072545A (en) * | 2021-04-15 | 2021-07-06 | 天津孚信阳光科技有限公司 | Compound with photochromic and fluorescent properties, and synthetic method and application thereof |
| CN114907334A (en) * | 2021-02-10 | 2022-08-16 | 中国科学院福建物质结构研究所 | Dithiophene ethylene lactone compound and preparation and light regulation and control methods thereof |
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