CN102911140A - Synthetic method of dual-furan substituted fulgide photochromic compound - Google Patents
Synthetic method of dual-furan substituted fulgide photochromic compound Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims abstract description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 12
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 12
- KBSVBCHYXYXDAG-UHFFFAOYSA-N 3-acetyl-2,5-dimethylfuran Chemical compound CC(=O)C=1C=C(C)OC=1C KBSVBCHYXYXDAG-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 27
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 25
- 229960000956 coumarin Drugs 0.000 claims description 23
- 235000001671 coumarin Nutrition 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- -1 obtain 2 of oily Chemical compound 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 150000002240 furans Chemical class 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 238000010898 silica gel chromatography Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 150000002148 esters Chemical class 0.000 abstract description 7
- 238000006600 Stobbe condensation reaction Methods 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract 2
- 150000005690 diesters Chemical class 0.000 abstract 2
- 150000002576 ketones Chemical class 0.000 description 9
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 3
- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical compound C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-N 0.000 description 2
- KEIFWROAQVVDBN-UHFFFAOYSA-N 1,2-dihydronaphthalene Chemical class C1=CC=C2C=CCCC2=C1 KEIFWROAQVVDBN-UHFFFAOYSA-N 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OVEHNNQXLPJPPL-UHFFFAOYSA-N lithium;n-propan-2-ylpropan-2-amine Chemical compound [Li].CC(C)NC(C)C OVEHNNQXLPJPPL-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical class CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- AOWPVIWVMWUSBD-RNFRBKRXSA-N [(3r)-3-hydroxybutyl] (3r)-3-hydroxybutanoate Chemical compound C[C@@H](O)CCOC(=O)C[C@@H](C)O AOWPVIWVMWUSBD-RNFRBKRXSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000010719 annulation reaction Methods 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical class OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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Abstract
The invention relates to a synthetic method of dual-furan substituted fulgide photochromic compound, the method comprises the steps of taking potassium tert-butoxide as organic alkali; enabling 2, 5-dimethyl-3-acetylfuran and diethyl succinate to generate monoacid ester by Stobbe condensation reaction; then generating diester by methanol and acetylchloride; enabling diester and 2, 5-dimethyl-3-acetylfuran to generate monoacid ester by Stobbe condensation reaction; finally, saponifying the monoacid ester in alcohol solution of potassium hydroxide to obtain dual-acid; dewatering the dual-acid, obtaining dual-furan substituted fulgide. The dual-furan substituted fulgide photochromic compound can change into pink (closed loop body) from yellow (open loop body) in a solid or liquid state under irradiation of the ultraviolet light with wavelength of 360-370nm. Compared with the mono-furan substituted fulgide photochromic compound, the molecule of the furan substituted fulgide photochromic compound has two functional groups capable of cyclization reaction, which better facilitates photochromism.
Description
Technical field
The invention belongs to chemical field, be specifically related to the photochromic material technology, relate in particular to the synthetic method of Coumarin substituted fulgides photochromic compound.
Background technology
Photochromic compound is the novel functional organic material of a class, its photochromism refers to that this compound is subjected to the irradiation of certain wavelength light, carry out specific chemical reaction and generate another product, its absorption spectrum occurs significantly to change, under the irradiation of the light of another wavelength or under the effect of heat, return to again original form, this specific performance of photochromic compound has brought wide application prospect to it, can be used as optical information recording material, molecular wire, molecular switch etc.
At present, research to photochromic compound mostly concentrates on the azomethine class, azobenzene, spiro-pyrans, Luo oxazine, thiazides, diaryl ethylene photochromic compound and fulgenic anhydride, the photochromic mechanism of inhomogeneity chromic systems are not identical yet.The photochromic principle of azomethine class system is that the intramolecular migration of azomethine base vicinal hydroxyl groups hydrogen forms trans ketone, and trans ketone thermal isomerization is cis ketone, and cis ketone can return cis-alcohol again by the thermophoresis of hydrogen; The photochromic principle of azobenzene system is that the formation cis-trans isomerization causes owing to containing the two keys of nitrogen-nitrogen in the nitrogen benzide system; The photochromism of spiro-pyrans, Luo oxazine, thiazides system is because the redox reaction in the molecule and the fracture of chemical bond cause; The diarylethene system has the hexatriene precursor structure of six electronics of a conjugation, it photochromic based on intramolecular cyclization; The photochromic mechanism of fulgenic anhydride is a kind of Woodward-Hoffmann of meeting rule (4m+2) type electrocyclization process, under ultraviolet lighting, fulgenic anhydride conrotatory closed loop generates the dihydronaphthalene derivative of colour generation, and the dihydronaphthalene derivative under the white light irradiation opposite variation can occur.
20 beginnings of the century, Stobbe etc. utilize succinate and group compounds of aldehydes and ketones condensation, obtained a series of succinyl oxide products, and found that wherein the product of succinate and aromatic aldehyde, ketone condensation has photochromism, he claims that the dimethylene derivative of this class Succinic anhydried is fulgide.Heller was on the basis to the fulgide further investigation in 1978, filtered out thermostability high, the fulgenic anhydride of a series of heterocyclic substituted that fatigue resistance is good, and be applied to first optical recording, extremely people's attention of the from then on research of fulgide.
Fulgide is mainly synthetic by the Stobbe condensation reaction, usually take diethyl succinate as starting raw material, ketone (aldehyde) condensation first general and steric hindrance is less, generation contains the succinate that a methylene derivatives replaces, and then with ketone (aldehyde) condensation of another molecule, generate fulgide through dehydration.Reaction needed is carried out under anhydrous condition, and the alkali of selecting is sodium hydride, potassium tert.-butoxide and lithium diisopropylamine (LDA) normally, and the product that obtains is the mixture of E formula and Z formula, can carry out purifying by the method for fractional crystallization or chromatographic separation.Because there is ester-ester condensation simultaneously in not just ketone-ester condensation in the Stobbe condensation reaction, the ketone-side reactions such as ketone condensation, thereby reaction more complicated, the yield of target compound is lower, is generally 5%～30%.
Compare with single heterocyclic substituted fulgide, the heterocycle that a replacement is arranged on each methene carbon in two heterocyclic substituted fulgide molecules, theoretically, may form 2 systems (similar all-cis formula hexatriene structure) that can carry out electrocyclic reaction, the carrying out that more is conducive to photochromic reactions, yet this quasi-molecule has larger sterically hindered, has brought the difficulty on synthetic.1999, the people such as Kiji [Kiji J, et al.A convenient and general synthetic method for photochromic fulgides by palladium-catalyzed carbonylation of 2-butyne-1,4-diols.Mol.Cryst.Lig.Cryst., 2000,344:235-240] reported by butine-1, the method of the carbonylation of 4-glycol is synthesized two heterocycle fulgide compounds, reaction is under Pa catalysis, under High Temperature High Pressure, carry out, this method has been opened up a new path for two the synthetic of heterocycle fulgide, but synthesis condition is harsh, difficult the popularization.[the Yokoyama Y such as Yokoyama, et al.Highly diastereoselective photochromic cyclization of a bisthienylfulgide.Chem.Lett., 2000,220-221] when report made the two thiophene of the preparation that uses the same method replace fulgide, the primary product that obtains was EE formula isomer.
Summary of the invention
Problem to be solved by this invention is to overcome the defective of prior art, and a kind of synthetic method of Coumarin substituted fulgides photochromic compound is provided.
In order to solve above-mentioned technical problem, technical scheme of the present invention is: the synthetic method of Coumarin substituted fulgides photochromic compound comprises the steps:
(1) with potassium metal, obtain a kind of potassium tert.-butoxide solution after anhydrous tertiary butanol and the dry toluene stirring and dissolving, wherein, potassium metal, the weight ratio of anhydrous tertiary butanol and dry toluene is 1:5 ~ 20:25 ~ 50, again with 2,5-dimethyl-3-acetyl furan, diethyl succinate and dry toluene are that 1:1 ~ 5:5 ~ 10 mix and obtain a kind of mixing solutions according to weight ratio, under 20 ~ 25 ° of C above-mentioned mixing solutions slowly is added drop-wise in the above-mentioned potassium tert.-butoxide solution, the control time for adding is 0.5 ~ 1.5h, after dropwising, continue reaction 12 ~ 96h under 20 ~ 25 ° of C, then underpressure distillation desolventizing, resistates is dissolved in 200 ~ 400mL water, be acidified to strongly-acid PH=1 with acid, the organic phase that occurs reddish-brown behind the standing demix with extracted with diethyl ether 3 times (3 * 50mL), filter with anhydrous sodium sulfate drying, steam under the reduced pressure except the 2-[(2 that obtains reddish-brown behind the ether, 5-dimethyl-3 furyl) ethylidene] single-ethyl succinate that replaces, productive rate is 75 ~ 90%;
(2) take by weighing the 2-[(2 that step (1) obtains, 5-dimethyl-3 furyl) ethylidene] single-ethyl succinate and the methanol mixed that replace be even, wherein, 2-[(2,5-dimethyl-3 furyl) ethylidene] single-ethyl succinate that replaces and the weight ratio of methyl alcohol be 1:2 ~ 5, then under 0 ℃, dropwise be added dropwise to 10 ~ 50mL Acetyl Chloride 98Min., after dropwising, rising temperature to 20 ~ 25 ° C, reacting by heating 6 ~ 36h, then underpressure distillation desolventizing, resistates separates with silica gel column chromatography, and leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, obtains yellow 2-[(2 after drip washing separates, 5-dimethyl-3 furyl) ethylidene] diethyl succinate that replaces, productive rate is 70 ~ 85%;
(3) take by weighing the 2-[(2 that step (2) obtains, 5-dimethyl-3 furans) ethylidene] diethyl succinate, 2,5-dimethyl-3-acetyl furan and dry toluene mix according to 2 ~ 6:1 ~ 3:10 ~ 15 weight ratios and obtain a kind of mixed solution, under 20 ~ 25 ℃, above-mentioned mixed solution is dropwise added potassium tert.-butoxide and dry toluene according in the suspension that 1 ~ 3:20 ~ 40 weight ratios are mixed to get, time for adding is 0.5 ~ 1.5h, after dropwising, continue reaction 12 ~ 96h under 20 ~ 25 ° of C, the underpressure distillation desolventizing, resistates is dissolved in 50 ~ 150mL water, use HCl(6mol/L) be acidified to strongly-acid (PH=1), organic phase extracted with diethyl ether 3 times (3 * 50mL) of reddish-brown appear behind the standing demix, filter with anhydrous sodium sulfate drying, steam except behind the ether under the reduced pressure, namely obtain 2 of oily, 3-two-[(2,5 dimethyl-3-furyl) ethylidene] single-ethyl succinate that replaces, productive rate is 65 ~ 75%;
(4) take by weighing the 2-[(2 that step (3) obtains, 5-dimethyl-3 furans) ethylidene] diethyl succinate, potassium hydroxide and dehydrated alcohol mix according to 1 ~ 5:8 ~ 12:80 ~ 100 weight ratios, temperature rises to 80 ~ 90 ° of C, reflux 3 ~ 8h, the underpressure distillation desolventizing, resistates is dissolved in 50 ~ 150mL water, be acidified to strongly-acid (PH=1) with acid, with extracted with diethyl ether 3 times (3 * 50mL), filter with anhydrous sodium sulfate drying, steam under the reduced pressure except ether, resistates is recrystallization twice in ethanol, namely obtains 2 of white crystal shape, and 3-two [(2,5-dimethyl-3-furyl) ethylidene] Succinic Acid that replaces, productive rate is 65 ~ 75%.
(5) take by weighing that step (4) obtains 2,3-two-[(2,5 dimethyl-3-furyl) ethylidene] Succinic Acid and the methylene dichloride that replace mix according to 1 ~ 3:8 ~ 12 weight ratios, then under 0 ℃, dropwise be added dropwise to 10 ~ 50mL Acetyl Chloride 98Min., after dropwising, be warming up to 20 ~ 25 ° of C, stirring reaction 6 ~ 36h, after reaction finished, unnecessary Acetyl Chloride 98Min. was removed in underpressure distillation, and resistates is through silica gel column chromatography separating purification, leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, separated product is recrystallization twice in ethanol, namely obtains Coumarin substituted fulgides photochromic compound of the present invention, and productive rate is 35 ~ 55%.
Preferably, the acid for acidifying is mineral acid in described step (1) and the step (4).
Preferably, the acid for acidifying is hydrochloric acid or sulfuric acid in described step (1) and the step (4).
Coumarin substituted fulgides photochromic compound of the present invention has following chemical structural formula:
The photochromic reactions of Coumarin substituted fulgides photochromic compound of the present invention can represent with following structural formula:
Wherein UV is UV-light (250-400nm), and Vis-IR is that visible light is to infrared light (600-850nm).
Photochromic compound open loop body becomes the closed loop body under UV-irradiation, the closed loop body can absorb infrared light or near infrared light; When the closed loop body is subjected to ruddiness or near infrared light radiation, then can turn back to photochromic compound open loop body.This working cycle can come and go repeatedly.
Coumarin substituted fulgides photochromic compou nd synthesis method of the present invention; the method at first adopts potassium tert.-butoxide as organic bases; at room temperature with 2; 5-dimethyl-3-acetyl furan and diethyl succinate generate single acid esters through the Stobbe condensation reaction; generate dibasic acid esters with methyl alcohol and Acetyl Chloride 98Min. esterification again; then with dibasic acid esters and 2; 5-dimethyl-3-acetyl furan generates single acid esters through the Stobbe condensation reaction; saponification obtains bisgallic acid in the alcoholic solution of KOH at last, and bisgallic acid is dewatered and obtained Coumarin replacement fulgide.Under the irradiation of the UV-light of wavelength 360 ~ 370nm, the Coumarin substituted fulgides compound that is in solid-state or liquid the present invention's proposition can both change pink into by yellow, and the Coumarin that the present invention proposes replaces fulgide compound (open loop body) and becomes colour solid (closed loop body) along with the increase of solvent polarity presents significant solvatochromism.
Advantage of the present invention is: 1. compare with single heterocyclic substituted fulgide, Coumarin substituted fulgides photochromic compound of the present invention, because but molecule contains the functional group of two annulations, the carrying out that more is conducive to photochromic reactions is a kind of stable and efficient fulgides photochromic compound; 2. the Coumarin that utilizes the present invention to synthesize replaces fulgide under the irradiation of the UV-light of wavelength 360 ~ 370nm, it is solid-state or liquidly can both change pink into by yellow, and the Coumarin that the present invention proposes replaces fulgide compound (open loop body) and becomes colour solid (closed loop body) along with the increase of solvent polarity presents significant solvatochromism, photochromism and stable aspect obvious advantage is arranged; 3. synthetic method of the present invention has the advantages such as high, the with low cost and application prospect of the productive rate of simple process, target product is extensive, the Coumarin substituted fulgides photochromic compound that utilizes the present invention to synthesize is novel, efficient, the stable fulgides photochromic material of a new generation, industrial applications has a extensive future, and can be applicable to the fields such as optical information recording material, camouflage protective material, extraordinary sensitive materials, molecular wire, molecular switch.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
Describe the present invention in detail below in conjunction with embodiment, should be appreciated that described herein giving an example only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
In the 250mL of drying three-necked bottle, add the 15mL anhydrous tertiary butanol; then the 5g potassium metal is dissolved in and wherein obtains potassium tert.-butoxide solution; with 9g 2; the trimethyl carbinol of 5-dimethyl-3-acetyl furan and 28g diethyl succinate and 55mL is mixed to get mixing solutions; with 1h above-mentioned mixing solutions dropwise is added drop-wise in the above-mentioned potassium tert.-butoxide solution under 20 ℃ of agitation conditions; after dropwising; continue backflow 24h; then cool to room temperature; the hcl acidifying that with concentration is 5mol/L is 5-6 to pH value; then underpressure distillation desolventizing; resistates is dissolved in 200 ~ 400mL water, and twice (2 * 50mL), water layer uses hcl acidifying (6mol/L) to strongly-acid (PH=1) with extracted with diethyl ether; organic phase monoesters extracted with diethyl ether 3 times (3 * 100mL) of reddish-brown appear behind the standing demix; filter with anhydrous sodium sulfate drying, steam under the reduced pressure except behind the ether, namely obtain the 2-[(2 of reddish-brown; 5-dimethyl-3 furyl) ethylidene] single-ethyl succinate (7.6g, productive rate are 85%) that replaces.
In the 250mL of drying three-necked bottle, with the above-mentioned 2-[(2 of 6g, 5-dimethyl-3 furyl) ethylidene] single-ethyl succinate that replaces adds in the 10mL anhydrous methanol, then under 0 ℃, dropwise be added dropwise to the 35mL Acetyl Chloride 98Min., after dropwising, rising temperature to 20 ° C, reflux 24h, then underpressure distillation desolventizing, resistates separates with silica gel column chromatography, and leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, obtains yellow 2-[(2 after drip washing separates, 5-dimethyl-3 furyl) ethylidene] diethyl succinate (4.5g, productive rate 79%) that replaces.
In the 250mL of drying three-necked bottle; with the above-mentioned 2-[(2 of 4g; 5-dimethyl-3 furans) ethylidene] diethyl succinate and 1.9g 2; 5-dimethyl-3-acetyl furan and 12mL dry toluene mix; under 20 ℃ of stirring states, dropwise add in the suspension (6.5g) that potassium tert.-butoxide and dry toluene be mixed to get according to the 1:30 weight ratio; time for adding is 1h; after dropwising; continue 20 ℃ of lower reaction 36h, the underpressure distillation desolventizing, resistates is dissolved in the 90mL water; use HCl(6mol/L) be acidified to strongly-acid (PH=1); 3 times (3 * 50mL), with the anhydrous sodium sulfate drying filtration, steaming is except behind the ether under the reduced pressure with extracted with diethyl ether; namely obtain 2 of oily; the single-ethyl succinate (3.7g, productive rate 66%) of 3-pair-[(2,5 dimethyl-3-furyl) ethylidene] replacement.
In the 250mL of drying three-necked bottle, with the above-mentioned 2-[(2 of 1.5g, 5-dimethyl-3 furans) ethylidene] diethyl succinate, 2.5g potassium hydroxide and 20mL dehydrated alcohol mix, temperature rises to 85 ° of C, reflux 8 hours, underpressure distillation desolventizing, resistates are dissolved in the 90mL water, use HCl(6mol/L) be acidified to strongly-acid (PH=1), with extracted with diethyl ether 3 times (3 * 50mL), filter with anhydrous sodium sulfate drying, steam under the reduced pressure and desolventize, resistates twice in recrystallization in ether solvent, obtain 2 of white crystal shape, the Succinic Acid (0.99g, productive rate 71%) that 3-two [(2,5-dimethyl-3-furyl) ethylidene] replaces.
In the 250mL of drying three-necked bottle, with 0.9g above-mentioned 2,3-two-[(2,5 dimethyl-3-furyl) ethylidene] Succinic Acid and the 12mL methylene dichloride that replace mix, then under 0 ℃, dropwise be added dropwise to the 18mL Acetyl Chloride 98Min., after dropwising, be warming up to 20 ° of C, stirring reaction 24h, after reaction finishes, unnecessary Acetyl Chloride 98Min. is removed in underpressure distillation, and resistates is through silica gel column chromatography separating purification, and leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, separated product twice in recrystallization in ethanol, obtain Coumarin substituted fulgides photochromic compound of the present invention (0.38g, productive rate 45%), 166 ° of C of fusing point 164 –.
Coumarin substituted fulgides photochromic compound dissolution obtained above in different solvents, with the different wave length irradiation, is studied its photochromic properties.Table 1 is Coumarin substituted fulgides photochromic compound (open loop body) and the λ that becomes colour solid (closed loop body) thereof
MaxChanging conditions in the opposed polarity solvent.
Embodiment 2
Identical with embodiment 1, but the consumption of step (1) 2,5-dimethyl-3-acetyl furan becomes 11.5g by 9g, the consumption of diethyl succinate becomes 33.6g by 28g, and other are constant.
Embodiment 3
Identical with embodiment 1, but the consumption of step (1) 2,5-dimethyl-3-acetyl furan becomes 8.2g by 9g, the consumption of diethyl succinate becomes 23.8g by 28g, and other are constant.
Embodiment 4
Identical with embodiment 1, but step (3) 2-[(2,5-dimethyl-3 furans) ethylidene] consumption of diethyl succinate becomes 4.8g by 4g, and the consumption of 2,5-dimethyl-3-acetyl furan becomes 2.5g by 1.9g, and other are constant.
Embodiment 5
Identical with embodiment 1, but the consumption of step (5) Acetyl Chloride 98Min. becomes 30mL by 18mL, and other are constant.
Coumarin substituted fulgides compound of the present invention can be used for weighing erasable and the mutually three-dimensional storage medium of two-photon body, photochromic device or photonic device material.
Table 1 Coumarin substituted fulgides photochromic compound (open loop body) and the λ of one-tenth colour solid (closed loop body) in the opposed polarity solvent thereof
MaxChanging conditions
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with technique can understand content of the present invention and according to this enforcement, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (4)
1. the synthetic method of Coumarin substituted fulgides photochromic compound comprises the steps:
(1) with potassium metal, obtain a kind of potassium tert.-butoxide solution after anhydrous tertiary butanol and the dry toluene stirring and dissolving, wherein, potassium metal, the weight ratio of anhydrous tertiary butanol and dry toluene is 1:5 ~ 20:25 ~ 50, again with 2,5-dimethyl-3-acetyl furan, diethyl succinate and dry toluene are that 1:1 ~ 5:5 ~ 10 mix and obtain a kind of mixing solutions according to weight ratio, under 20 ~ 25 ° of C above-mentioned mixing solutions slowly is added drop-wise in the above-mentioned potassium tert.-butoxide solution, the control time for adding is 0.5 ~ 1.5h, after dropwising, continue reaction 12 ~ 96h under 20 ~ 25 ° of C, then underpressure distillation desolventizing, resistates is dissolved in 200 ~ 400mL water, be acidified to strongly-acid PH=1 with acid, the organic phase that occurs reddish-brown behind the standing demix with extracted with diethyl ether 3 times (3 * 50mL), filter with anhydrous sodium sulfate drying, steam under the reduced pressure except the 2-[(2 that obtains reddish-brown behind the ether, 5-dimethyl-3 furyl) ethylidene] single-ethyl succinate that replaces, productive rate is 75 ~ 90%;
(2) take by weighing the 2-[(2 that step (1) obtains, 5-dimethyl-3 furyl) ethylidene] single-ethyl succinate and the methanol mixed that replace be even, wherein, 2-[(2,5-dimethyl-3 furyl) ethylidene] single-ethyl succinate that replaces and the weight ratio of methyl alcohol be 1:2 ~ 5, then under 0 ℃, dropwise be added dropwise to 10 ~ 50mL Acetyl Chloride 98Min., after dropwising, rising temperature to 20 ~ 25 ° C, reacting by heating 6 ~ 36h, then underpressure distillation desolventizing, resistates separates with silica gel column chromatography, and leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, obtains yellow 2-[(2 after drip washing separates, 5-dimethyl-3 furyl) ethylidene] diethyl succinate that replaces, productive rate is 70 ~ 85%;
(3) take by weighing the 2-[(2 that step (2) obtains, 5-dimethyl-3 furans) ethylidene] diethyl succinate, 2,5-dimethyl-3-acetyl furan and dry toluene mix according to 2 ~ 6:1 ~ 3:10 ~ 15 weight ratios and obtain a kind of mixed solution, under 20 ~ 25 ℃, above-mentioned mixed solution is dropwise added potassium tert.-butoxide and dry toluene according in the suspension that 1 ~ 3:20 ~ 40 weight ratios are mixed to get, time for adding is 0.5 ~ 1.5h, after dropwising, continue reaction 12 ~ 96h under 20 ~ 25 ° of C, the underpressure distillation desolventizing, resistates is dissolved in 50 ~ 150mL water, use HCl(6mol/L) be acidified to strongly-acid, PH=1, the organic phase that occurs reddish-brown behind the standing demix with extracted with diethyl ether 3 times (3 * 50mL), filter with anhydrous sodium sulfate drying, steam under the reduced pressure except behind the ether, namely obtain 2 of oily, the single-ethyl succinate of 3-pair-[(2,5 dimethyl-3-furyl) ethylidene] replacement, productive rate is 65 ~ 75%;
(4) take by weighing the 2-[(2 that step (3) obtains, 5-dimethyl-3 furans) ethylidene] diethyl succinate, potassium hydroxide and dehydrated alcohol mix according to 1 ~ 5:8 ~ 12:80 ~ 100 weight ratios, temperature rises to 80 ~ 90 ° of C, reflux 3 ~ 8h, the underpressure distillation desolventizing, resistates is dissolved in 50 ~ 150mL water, use HCl(6mol/L) be acidified to strongly-acid (PH=1), with extracted with diethyl ether 3 times (3 * 50mL), filter with anhydrous sodium sulfate drying, steam under the reduced pressure except ether, resistates is recrystallization twice in ethanol, namely obtains 2 of white crystal shape, and 3-two [(2,5-dimethyl-3-furyl) ethylidene] Succinic Acid that replaces, productive rate is 65 ~ 75%.
(5) take by weighing that step (4) obtains 2,3-two-[(2,5 dimethyl-3-furyl) ethylidene] Succinic Acid and the methylene dichloride that replace mix according to 1 ~ 3:8 ~ 12 weight ratios, then under 0 ℃, dropwise be added dropwise to 10 ~ 50mL Acetyl Chloride 98Min., after dropwising, be warming up to 20 ~ 25 ° of C, stirring reaction 6 ~ 36h, after reaction finished, unnecessary Acetyl Chloride 98Min. was removed in underpressure distillation, and resistates is through silica gel column chromatography separating purification, leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, separated product is recrystallization twice in ethanol, namely obtains Coumarin substituted fulgides photochromic compound of the present invention, and productive rate is 35 ~ 55%.
2. synthetic method according to claim 1 is characterized in that, the acid that is used for acidifying in described step (1) and the step (4) is mineral acid.
3. synthetic method according to claim 2 is characterized in that, the acid that is used for acidifying in described step (1) and the step (4) is hydrochloric acid or sulfuric acid.
4. Coumarin substituted fulgides photochromic compound is characterized in that photochromic compound has following chemical structural formula:
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| CN111039856A (en) * | 2019-12-31 | 2020-04-21 | 华侨大学 | Benzophenone substituted fulgide ester photochromic compound and preparation method thereof |
| CN111039855A (en) * | 2019-12-31 | 2020-04-21 | 华侨大学 | Double aromatic ring substituted fulgide ester photochromic compound and preparation method thereof |
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