CN1206309C - Biheterocycle substituted fulgide photochromic compound and its synthesis and use - Google Patents
Biheterocycle substituted fulgide photochromic compound and its synthesis and use Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- -1 heterocyclic ketone Chemical class 0.000 claims abstract description 23
- 150000002148 esters Chemical class 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003287 optical effect Effects 0.000 claims abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical class CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000012312 sodium hydride Substances 0.000 claims abstract description 9
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 8
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000000725 suspension Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000012074 organic phase Substances 0.000 claims description 22
- 125000000623 heterocyclic group Chemical group 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- 238000010025 steaming Methods 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000284 extract Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- 238000003810 ethyl acetate extraction Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000002929 anti-fatigue Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- FMEYPAIIOVKZRA-UHFFFAOYSA-N 3-ethylideneoxolane-2,5-dione Chemical compound CC=C1CC(=O)OC1=O FMEYPAIIOVKZRA-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 238000006862 quantum yield reaction Methods 0.000 description 2
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- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 1
- PUSJAEJRDNPYKM-UHFFFAOYSA-N 3-Acetyl-2,5-dimethylthiophene Chemical compound CC(=O)C=1C=C(C)SC=1C PUSJAEJRDNPYKM-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
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- 229930192474 thiophene Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention belongs to the technical field of photochromic and optical information storage and optical signal conversion materials, and particularly relates to a diheterocycle substituted fulgide photochromic compound and a synthesis method and application thereof. Mixing substituted heterocyclic ketone and diethyl succinate, adding the mixture into a tert-butyl alcohol solution containing potassium tert-butoxide, acidifying the reaction solution, and refluxing the obtained half-ester in an ethanol solution under the action of concentrated sulfuric acid as a catalyst to obtain an intermediate mono-heterocyclic substituted diethyl succinate; mixing the intermediate and equimolar substituted heterocyclic ketone in a toluene solution, adding the mixed solution into an anhydrous toluene suspension of sodium hydride under the protection of nitrogen, adding anhydrous ethanol to initiate a reaction, extracting the precipitated half ester by using ethyl acetate, filtering, drying, dissolving the obtained diacid in tetrahydrofuran, then adding dicyclohexylcarbodiimide, separating and recrystallizing to finally obtain the diheterocycle substituted fulgide photochromic compound; the method is used for erasable and three-dimensional optical information storage and the like.
Description
Technical field
The invention belongs to photochromic and optical information storage and optical signal transition material technical field, particularly the fulgides photochromic compound and the preparation method and use thereof of two heterocyclic substituted.
Background technology
Organic photochromic has broad application prospects, and compares with inorganic materials, advantages such as speed of photoresponse is fast, easily processing, low cost that it has.
Photochromicly roughly can be described below:
A certain photochromic material A is at the light (hv of certain wavelength
1) shine down, can change its molecular structure and form compd B, thereby colour-change takes place.B can be at the light (hv of another wavelength
2) or the effect of heat (△) recover down original color, this reversing process just is called photochromism.
The fulgide compounds is a class important in numerous photochromic compoundses, and its feature is that spectral response range is wide, designs different molecular structures, and its maximum photoresponse wavelength can change between 300-800nm; Next is that anti-fatigue performance is good.
At Chinese patent publication number CN1097453A, in the report of Chinese patent application numbers 97118941.2 and 97118942.0, the fulgide compounds refers to the fulgide compounds of single heterocyclic substituted more, only see the synthetic of pair fulgide of thiophene replacement about the fulgide of two heterocyclic substituted, as: Y.Yokoyama, chemistry letters, 2000,3,220-221.The fulgide of the two heterocyclic substituted of this class helps to improve the quantum yield of light dye-forming reaction, and the quantum yield that reacts for the light colour killing does not then have tangible influence.
Summary of the invention
One of purpose of the present invention provides the fulgides photochromic compound of a kind of thermally-stabilised, antifatigue, two heterocyclic substituted that photochromic properties is good.
Another object of the present invention provides the preparation method of this class photochromic compound.
Another object of the present invention provides this class photochromic compound in the purposes that is used for aspects such as high-density, fast-response optical storage, photoswitch and embedded photoluminescent material.
The fulgides photochromic compound of the two heterocyclic substituted of the present invention has following general formula:
Or
Wherein: substituent R is selected from following substituting group:
Or
The fulgides photochromic compound of the two heterocyclic substituted of the present invention exists with three kinds of isomer usually, is respectively EE formula, EZ formula, ZZ formula, and the photochromic reactions of this compounds can be represented with following general formula:
Wherein: R is selected from following substituting group:
When with the UV-irradiation below the 400nm, ring-closure reaction can take place rapidly in EE formula or EZ formula compound, generates the orange-red colour solid C that is
EEOr C
EZ, maximum absorption is more than 480nm.ZZ-EZ-EE isomerization rapidly takes place in ZZ formula compound under UV-irradiation, carry out the ring of light then and close reaction and generate and to be colour solid.When (λ＞when 480nm) shining, this is colour solid can generate EE formula or EZ formula compound again with visible light.
The synthetic route of the fulgides photochromic compound of the two heterocyclic substituted of the present invention is:
Wherein: R is selected from following substituting group:
Or
This building-up reactions principle is the Stobbe condensation reaction, and concrete step is as follows:
(1) with the heterocyclic ketone and 1: 1 in molar ratio～1: 2 the mixed of diethyl succinate that replace, mixture is joined in the t-butanol solution that contains potassium tert.-butoxide then, wherein, the molar ratio of potassium tert.-butoxide and diethyl succinate is 1～1.5, in the trimethyl carbinol, refluxed 2～18 hours, and be cooled to room temperature then; With 5N hydrochloric acid or sulfuric acid acidation reaction solution to pH value is 5～6, the pressure reducing and steaming solvent, and residual solution is dissolved in the ether, wherein, the volume ratio of residual solution and ether is 1: 1～1: 10, water phase separated, ether liquid more than 1 time, merges water with saturated sodium carbonate solution washing organic phase, uses 5N hydrochloric acid or sulfuric acid acidation water to strongly-acid, pH＜1, reddish-brown oily matter appears in the upper strata, tells organic layer, the water layer extracted with diethyl ether, combined ether liquid and organic layer are used dried over mgso.Remove solvent under reduced pressure, the gained half ester is that 98% the vitriol oil is under the catalyzer in concentration, in ethanolic soln, refluxed 6～8 hours, wherein, the weight of half ester and acid and volume (grams per milliliter) are than being 10: 1～3: 1, half ester and alcoholic acid weight and volume ratio (grams per milliliter) are 1: 10～1: 50, in the resultant impouring frozen water, tell organic layer (lower floor), the water layer extracted with diethyl ether, ether layer after the extraction and organic phase merge, the organic phase after merging with saturated sodium bicarbonate aqueous solution washing again, the washing organic phase is to neutral, and dry back is steamed and desolventized.Resistates is with silica gel column chromatography (ethyl acetate: sherwood oil=1: 4～1: 8) obtain the diethyl succinate of intermediate list heterocyclic substituted.
R takes from following substituting group:
Or
(2) intermediate that step (1) is obtained is mixed in the toluene solution with the heterocyclic ketone that waits the mole replacement; wherein; substituted heterocycle ketone: the weight of toluene and volume ratio (grams per milliliter) are 1: 2.5～1: 50; under nitrogen protection; mixed solution is slowly joined 2～3 times in the dry toluene suspension of the sodium hydride of the heterocyclic ketone mole number that replaces; wherein; sodium hydride: the weight of toluene and volume ratio (grams per milliliter) are 1: 2～1: 10; add the dehydrated alcohol initiation reaction; wherein; ethanol: the mole ratio of sodium hydride is 1: 50～1: 100, stirs 3～7 days.Reaction product is poured in the frozen water, water phase separated, organic phase more than 1 time, is separated organic phase with the saturated aqueous sodium carbonate extraction.Water merges, after stripping with ethyl acetate, again with 5N hydrochloric acid or sulfuric acid acidation to the pH value less than 1.The half ester of separating out uses ethyl acetate extraction more than 1 time, water phase separated, and combining extraction liquid is also used anhydrous magnesium sulfate drying.Filter, boil off ethyl acetate, the gluey half ester of gained is under the catalysis of potassium hydroxide, refluxed in dehydrated alcohol 6～8 hours, wherein, half ester: alcoholic acid weight and volume ratio (grams per milliliter) are 1: 5～1: 20, potassium hydroxide and alcoholic acid weightmeasurement ratio (grams per milliliter) are 1: 5～1: 20, the solid that is generated is soluble in water, uses 5N hydrochloric acid or sulfuric acid acidation solution to strongly-acid, and pH is less than 1.Suction filtration, dry, the gained diacid is dissolved in the tetrahydrofuran (THF), add dicyclohexyl carbon imide then, wherein, the weight of diacid and tetrahydrofuran (THF) and volume ratio (grams per milliliter) are 1: 10～1: 50, and the mol ratio of diacid and dicyclohexyl carbon imide is 1: 1～1: 2, to mixed solution dehydration 12～24 hours, steam and remove excessive tetrahydrofuran (THF).Residue separates through silica gel column chromatography, and the ethyl acetate/petroleum ether of selecting different ratios for use is a leacheate, and recrystallization in the ethyl acetate/petroleum ether mixed solvent finally obtains the fulgides photochromic compound of two heterocyclic substituted.
The heterocyclic ketone of described replacement is:
Or
The fulgides photochromic compound of two heterocyclic substituted that the present invention synthesized can be used for the following aspects:
1. can be as the material for preparing erasable and three dimensional optical information storage products;
2. light shutter device material;
3. optical information converter material is as photochromic device, photonics device material etc.
The fulgide compound that the present invention synthesizes two heterocyclic substituted all can be observed photochromism in solid-state, solution, polymeric film.For example the fulgide that replaces of the two furans among the embodiment 1 with UV-irradiation after, to orange-red colour-change, with the increase of UV-irradiation time, the intensity of ultraviolet region absorption peak weakens gradually by yellowish in generation rapidly, and the visible region absorbs enhancing, thereby solution colour is deepened gradually.During with the radiation of visible light more than the 480nm, color disappears again gradually, and the visible region reduces gradually, the intensity enhancing of ultraviolet region absorption simultaneously.Absorption spectrum before and after the ultraviolet lighting is referring to accompanying drawing 1.
The present invention has the advantage of the following aspects:
1. two of photochromic front and back states all are stable on thermodynamics, under the room temperature lucifuge, but prolonged preservation.
2. the ultraviolet absorption peak of the fulgide compound of two heterocyclic substituted appears at 350-380nm, and the laser apparatus of available 780nm wavelength carries out two-photon absorption test and research, closely develops photochromic three dimensional optical information memory device.
3. the anti-fatigue performance of this compound is good
This compounds to be the colour solid spectral response range wide, can be well be complementary with the emission wavelength of semiconductor laser, help the development of photochromic CD.
Description of drawings
Fig. 1. absorption spectrum is over time in toluene for the compound of the embodiment of the invention 1.
Fig. 2. absorption spectrum is over time in hexanaphthene for the compound of the embodiment of the invention 2
Embodiment
Embodiment 1
(E), (E) two 2, the fulgide that the 5-dimethyl furan replaces synthetic
1. single 2, the diethyl succinate that the 5-dimethyl furan replaces synthetic
4 gram potassium metals are dissolved in the 100ml anhydrous tertiary butanol; 9.2ml (0.075mol) 2; 5-dimethyl-3-acetyl furan; 14ml (0.082mol) diethyl succinate; drip after the mixing in above-mentioned potassium tert.-butoxide solution; keep solution slowly to reflux; adding the back refluxed 4 hours; cool to room temperature is 5-6 with the 5N hcl acidifying to the pH value then; the pressure reducing and steaming solvent is dissolved in the 50ml ether with residual solution, and the sodium carbonate solution saturated with 3 * 60ml thoroughly extracts 3 times, and combining water layer uses the 5N hcl acidifying to strongly-acid (pH＜1); reddish-brown oily matter appears in the upper strata; tell organic layer, (3 * 60ml) extractions merge organic phase to water with ether; obtain the single-ethyl succinate that single 2-(2,5-dimethyl furan-3-yl) replaces with desolvating after the dried over sodium sulfate.
The gained mono ethyl ester is dissolved in the 60ml dehydrated alcohol, adds the vitriol oil of 3ml 98%, reflux 6 hours.After excess ethanol is removed in decompression, be chilled to room temperature, in the impouring 50ml frozen water, tell organic phase (lower floor).Water layer (3 * 60) extracted with diethyl ether, merge with organic phase, organic phase is washed to neutral with the saturated sodium bicarbonate aqueous solution washing organic phase of 60ml in the back, dry back is steamed and is desolventized, and resistates is with silica gel column chromatography (ethyl acetate: sherwood oil=1: 4) isolate title compound (yield 54%)
1HNMR(ppm，CDCl
3)：1.245(2t，6H，2CH
3(CH
2O))；2.193(s，3H，MeC＝)；2.282(s，3H，furan-5-Me)；2.376(s，3H，furan-2-Me)；3.183(s，2H，-CH
2-)；4.063-4.244(2q，4H，2-CH
2O-)；6.353(s，1H，furan-4-H)。
2. (E), (E) two 2, the fulgide that the 5-dimethyl furan replaces synthetic
In an exsiccant three-necked flask, under nitrogen protection, add 2 gram sodium hydride and dry toluene 10ml; with 4g single 2; the diethyl succinate that the 5-dimethyl furan replaces; 1.9g 2; the 40ml anhydrous toluene solution of 5-dimethyl-3-acetyl furan is added drop-wise in the above-mentioned sodium hydride suspension; add a dehydrated alcohol initiation reaction simultaneously, after dropwising, under room temperature, stirred 5 days.Reaction mixture is poured in the 100ml water, told water, organic phase extracts 2 times with the saturated aqueous sodium carbonate of 30ml, separate organic phase, water merges, after stripping with the ethyl acetate of 30ml, to strongly-acid (pH＜1), tell by gained oily half ester with the 5N hcl acidifying for water layer.The ethyl acetate extraction of water usefulness 50ml 3 times merges organic phase and also uses anhydrous magnesium sulfate drying.Filter, steaming desolventizes.The gluey half ester of gained refluxed 5 hours in the 50ml of 5g potassium hydroxide dehydrated alcohol, cooling, and the most of solvent of pressure reducing and steaming, resistates is poured in the water, and the hcl acidifying of using 5N is to strongly-acid (pH＜1), gained diacid suction filtration, drying.The exsiccant diacid is dissolved in the 40ml anhydrous tetrahydro furan, adds 1: 1 two ring ethyl carbon imide of mol ratio, stirs 12 hours, steaming desolventizes, resistates separates (ethyl acetate: sherwood oil=1: 5), obtain title compound, light yellow crystal through silicagel column.Fusing point: 163-165 ℃, productive rate 6.4%.
1HNMR(ppm，CDCl
3)：1.883(s，6H，2Me＝)；2.127(s，6H，2furan-2-Me)；2.523(s，6H，2furan-5-Me)；5.494(s，2H，2furan-4-H).MS：340(M
+)，325(M-15)
The synthetic E of present embodiment institute), (E) two 2, the fulgide that the 5-dimethyl furan replaces can be used for the following aspects:
1. can wipe and rewrite and the three dimensional optical information storage;
2. light shutter device;
3. optical information transmodulator, as photochromic device, photonics device etc.
Embodiment 2
(Z), (Z)-3,4-two (2,5-thioxene-3-yl) ethylidene-2,5-furandione synthetic
1.2-(2,5-thioxene-3-yl) ethylidene diethyl succinate is synthetic
Press the synthetic method of embodiment 1 compound 1, potassium metal 4 gram is dissolved in the 100ml anhydrous tertiary butanol, 2,5-dimethyl-3-acetyl thiophene 10ml with drip in above-mentioned potassium tert.-butoxide solution after diethyl succinate 14ml mixes, after adding, refluxed 5 hours.Cooling, is 5-6 with the 5N hcl acidifying to the pH value, and the pressure reducing and steaming solvent is dissolved in 50ml ether, water phase separated with residual solution, the ether layer thoroughly extracts 3 times with the saturated sodium carbonate solution of 3 * 60ml, to strongly-acid (pH＜1), (3 * 60ml) extract combined ether liquid to the gained oil-water mixture to combining water layer with ether with the 5N hcl acidifying, use dried over sodium sulfate, remove and desolvate, obtain about 10.2 grams of single-ethyl succinate that single 2-(2,5-thioxene-3-yl) replaces.
The gained mono ethyl ester is dissolved in the 50ml dehydrated alcohol, the vitriol oil that adds 2ml 98%, reflux 6 hours is after ethanol is removed in decompression, be chilled to room temperature, resistates is poured in the 50ml frozen water, with (3 * 50) extracted with diethyl ether, ether solution is merged, with the saturated sodium bicarbonate aqueous solution washing ether liquid of 60ml, washing ether liquid is to neutral, and after the drying, steaming desolventizes.Resistates is with silica gel column chromatography (ethyl acetate: sherwood oil=1: 6) isolate 2-(2,5-thioxene-3-yl) ethylidene diethyl succinate compound 11 gram (yield 50%).
1HNMR(ppm，CDCl
3)： 1.161-1.315(2t，6H)；2.180(s，3H)；2.270(s，3H)；2.363(s，3H)；3.172(s，2H)；4.051-4.231(2q，4H)；6.342(s，1H)。
2. (Z), (Z)-3,4-two (2,5-thioxene-3-yl) ethylidene-2,5-furandione synthetic
Press the synthetic method of compound 2 among the embodiment 1; 2-(2; 5-thioxene-3-yl) ethylidene diethyl succinate 7 grams are with equimolar 2; 5-dimethyl-3-acetyl thiophene is blended in the 20ml dry toluene; under protection of nitrogen gas, slowly drip in the dry toluene of 10ml of 3 gram sodium hydrides, add a dehydrated alcohol initiation reaction; after dropwising, at room temperature stirred 5 days.Reaction mixture is poured in the 30ml water, told water, organic phase extracts 2 times with the saturated aqueous sodium carbonate of 30ml, separates organic phase, and water merges, and after stripping with the ethyl acetate of 30ml, water layer uses the 5N hcl acidifying to strongly-acid (pH＜1).The ethyl acetate extraction of gained oil-water mixture usefulness 30ml 3 times, the combined ethyl acetate extraction liquid is used anhydrous magnesium sulfate drying.Filter, steaming desolventizes.The gluey half ester of gained refluxed 5 hours in the 50ml of 5g potassium hydroxide dehydrated alcohol, cooling, and the most of solvent of pressure reducing and steaming, resistates is poured in the water, and the hcl acidifying of using 5N obtains two Acid precipitation to strongly-acid (pH＜1).Gained diacid suction filtration, drying obtains about 1.2 grams of diacid.The diacid of gained is dissolved in the 12ml anhydrous tetrahydro furan, the two ring ethyl carbon imide that add 1.2 grams, stirred 12 hours, steaming desolventizes, product separates through chromatography column, is leacheate with 8: 1 petrol ether/ethyl acetate, at ethyl acetate/petroleum ether mixed solvent recrystallization, obtain yellow crystals, productive rate 5%.
1HNMR(ppm，CDCl
3)：2.1912(s，6H)；2.3640(s，6H)；2.4347(s，6H)；6.5980(s，2H)
MS：372(M
+，91.63％)；357(M
+-15，100％)
Present embodiment institute synthetic (Z), (Z)-3,4-two (2,5-thioxene-3-yl) ethylidene-2, the 5-furandione can be used for the following aspects:
1. can wipe and rewrite and the three dimensional optical information storage;
2. light shutter device;
3. optical information transmodulator, as photochromic device, photonics device etc.
Claims (5)
1. the fulgides photochromic compound of two heterocyclic substituted, it is characterized in that: this compound has following general formula:
Wherein: substituent R is selected from following substituting group:
Or
2. the synthetic method of the fulgides photochromic compound of an as claimed in claim 1 pair of heterocyclic substituted, it is characterized in that: this synthetic method step is:
(1) with the heterocyclic ketone and 1: 1 in molar ratio～1: 2 the mixed of diethyl succinate that replace, mixture is joined in the t-butanol solution that contains potassium tert.-butoxide then, wherein, the molar ratio of potassium tert.-butoxide and diethyl succinate is 1～1.5, in the trimethyl carbinol, reflux, be cooled to room temperature then; With hydrochloric acid or sulfuric acid acidation reaction solution to pH value is 5～6, boils off solvent, and residual solution is dissolved in the ether, wherein, the volume ratio of residual solution and ether is 1: 1～1: 10, water phase separated, ether liquid washs organic phase with saturated sodium carbonate solution, merge water, with hydrochloric acid or sulfuric acid acidation water to strongly-acid, pH＜1, tell organic layer, the water layer extracted with diethyl ether, combined ether liquid and organic layer, drying; Steaming desolventizes, and the gained half ester is under the catalyzer at the vitriol oil, refluxes in ethanolic soln, and wherein, half ester is 10: 1～3: 1 in the weight and the volume ratio of gram and milliliter respectively with acid, and half ester and alcoholic acid weight and volume ratio are 1: 10～1: 50; In the resultant impouring frozen water, tell organic layer, the water layer extracted with diethyl ether, ether layer after the extraction and organic phase merge, the organic phase after merging with saturated sodium bicarbonate aqueous solution washing again, the washing organic phase is to neutral, and dry back is steamed and is desolventized; Obtain the diethyl succinate of intermediate list heterocyclic substituted;
R takes from following substituting group:
(2) intermediate that step (1) is obtained is mixed in the toluene solution with the heterocyclic ketone that waits the mole replacement, wherein, substituted heterocycle ketone and toluene are 1: 2.5～1: 50 in the weight and the volume ratio of gram and milliliter respectively, under nitrogen protection, mixed solution is slowly joined 2～3 times in the dry toluene suspension of the sodium hydride of the heterocyclic ketone mole number that replaces, wherein, sodium hydride and toluene are 1: 2～1: 10 in the weight and the volume ratio of gram and milliliter respectively, add the dehydrated alcohol initiation reaction, wherein, ethanol: the mole ratio of sodium hydride is 1: 50～1: 100, stirs; Reaction product is poured in the frozen water, water phase separated, organic phase extracts with saturated aqueous sodium carbonate, separates organic phase; Water merges, after stripping with ethyl acetate, again with hydrochloric acid or sulfuric acid acidation to the pH value less than 1; The half ester ethyl acetate extraction of separating out, water phase separated, combining extraction liquid is also used anhydrous magnesium sulfate drying; Filter, boil off ethyl acetate, the gluey half ester of gained is under the catalysis of potassium hydroxide, in dehydrated alcohol, reflux, wherein, half ester and ethanol are 1: 5～1: 20 in the weight and the volume ratio of gram and milliliter respectively, and potassium hydroxide and alcoholic acid weightmeasurement ratio are 1: 5～1: 20, and the solid that is generated is soluble in water; To strongly-acid, pH is less than 1 with hydrochloric acid or sulfuric acid acidation solution; Suction filtration, dry, the gained diacid is dissolved in the tetrahydrofuran (THF), add dicyclohexyl carbon imide then, wherein, diacid and tetrahydrofuran (THF) are 1: 10～1: 50 in the weight and the volume ratio of gram and milliliter respectively, and the mol ratio of diacid and dicyclohexyl carbon imide is 1: 1～1: 2, to the mixed solution dehydration, steam and remove excessive tetrahydrofuran (THF); Residue is through separating, and recrystallization finally obtains the fulgides photochromic compound of two heterocyclic substituted; General structure is:
Or
Wherein: substituent R is selected from following substituting group:
3. synthetic method as claimed in claim 1 is characterized in that: the heterocyclic ketone of described replacement is:
Or
4. synthetic method as claimed in claim 1 is characterized in that: the half ester of described step (1) is that 98% the vitriol oil is under the catalyzer in concentration, refluxes in ethanolic soln 6～8 hours.
5. the purposes of the fulgides photochromic compound of an as claimed in claim 1 pair of heterocyclic substituted is characterized in that: the fulgides photochromic compound of the described two heterocyclic substituted that synthesize can be erasable as preparation and the material of three dimensional optical information storage products; The light shutter device material; The optical information converter material.
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