CN102911140B - Synthetic method of dual-furan substituted fulgide photochromic compound - Google Patents
Synthetic method of dual-furan substituted fulgide photochromic compound Download PDFInfo
- Publication number
- CN102911140B CN102911140B CN201210370241.6A CN201210370241A CN102911140B CN 102911140 B CN102911140 B CN 102911140B CN 201210370241 A CN201210370241 A CN 201210370241A CN 102911140 B CN102911140 B CN 102911140B
- Authority
- CN
- China
- Prior art keywords
- dimethyl
- ethylidene
- furyl
- photochromic compound
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 23
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims abstract description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 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 26
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 26
- 229960000956 coumarin Drugs 0.000 claims description 22
- 235000001671 coumarin Nutrition 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 15
- -1 2, 5-dimethyl-3-furyl Chemical group 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 10
- 229960004756 ethanol Drugs 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 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
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000013517 stratification Methods 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- 239000013078 crystal Substances 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
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 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
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 150000002576 ketones Chemical class 0.000 description 8
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000126 substance Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 239000002070 nanowire Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003451 thiazide diuretic agent Substances 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001089 thermophoresis Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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 ethyl alcohol 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 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 subject 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, the research of photochromic compound is mostly concentrated on to azomethine class, azobenzene, spiro-pyrans, Luo oxazine, thiazides, diaryl ethylene photochromic compound and fulgenic anhydride, the photochromic mechanism of inhomogeneity chromic systems is 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 to again cis-alcohol by the thermophoresis of hydrogen; The photochromic principle of azobenzene system is that formation cis-trans isomerization causes owing to containing the two keys of nitrogen-nitrogen in nitrogen benzide system; The photochromism of spiro-pyrans, Luo oxazine, thiazides system is because the fracture of the redox reaction in molecule and chemical bond causes; 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 dihydronaphthalene derivative, under white light irradiates, contrary 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.Within 1978, Heller is on the basis that fulgide is furtherd investigate, filter 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 Stobbe condensation reaction, conventionally taking diethyl succinate as starting raw material, ketone (aldehyde) condensation first general and steric hindrance is less, generate the succinate replacing containing a methylene derivatives, 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 obtaining is the mixture of E formula and Z formula, can carry out purifying by the method for fractional crystallization or chromatographic separation.Due to not just ketone-ester condensation in Stobbe condensation reaction, there is the condensation of ester-ester simultaneously, the side reactions such as ketone-one condensation, thereby reaction more complicated, the yield of target compound is lower, is generally 5%～30%.
Compared with single heterocyclic substituted fulgide, in two heterocyclic substituted fulgide molecules, on each methene carbon, there is the heterocycle of a replacement, theoretically, may form 2 systems (similar all-cis formula hexatriene structure) that can carry out electrocyclic reaction, more be conducive to the carrying out of photochromic reactions, but this quasi-molecule has larger sterically hindered, bring 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 of2-butyne-1, 4-diols.Mol.Cryst.Lig.Cryst., 2000, 344:235-240] report 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 is that two heterocycle fulgides synthetic opened up a new path, but synthesis condition harshness, more difficult popularization.[the Yokoyama Y such as Yokoyama, et al.Highly diastereoselective photochromic cyclization of a bisthienylfulgide.Chem.Lett., 2000,220-221] report that when the two thiophene of the preparation that makes to use the same method replace fulgide, the primary product obtaining is EE formula isomer.
Summary of the invention
Problem to be solved by this invention is to overcome the defect 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) by potassium metal, after anhydrous tertiary butanol and dry toluene stirring and dissolving, obtain a kind of potassium tert.-butoxide solution, wherein, potassium metal, the weight ratio of anhydrous tertiary butanol and dry toluene is 1:5～20:25～50, again by 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, at 20～25 DEG C, above-mentioned mixing solutions is slowly added drop-wise in above-mentioned potassium tert.-butoxide solution, control time for adding is 0.5～1.5h, after dropwising, at 20～25 DEG C, continue reaction 12～96h, then underpressure distillation is except desolventizing, resistates is dissolved in 200～400mL water, be acidified to strongly-acid PH=1 with acid, after stratification, there is the organic phase extracted with diethyl ether 3 times (3 × 50mL) of reddish-brown, filter with anhydrous sodium sulfate drying, under reduced pressure, steam except the 2-[(2 that obtains reddish-brown after ether, 5-dimethyl-3 furyl) ethylidene] replace single-ethyl succinate, productive rate is 75～90%,
(2) take the 2-[(2 that step (1) obtains, 5-dimethyl-3 furyl) ethylidene] replace single-ethyl succinate and ethanol mix, wherein, 2-[(2, 5-dimethyl-3 furyl) ethylidene] replace single-ethyl succinate and the weight ratio of ethanol be 1:2～5, then at 0 DEG C, be dropwise added dropwise to 10～50mL Acetyl Chloride 98Min., after dropwising, rising temperature to 20～25 DEG C, reacting by heating 6～36h, then underpressure distillation is except desolventizing, resistates separates with silica gel column chromatography, leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, drip washing obtains yellow 2-[(2 after separating, 5-dimethyl-3 furyl) ethylidene] replace diethyl succinate, productive rate is 70～85%,
(3) take the 2-[(2 that step (2) obtains, 5-dimethyl-3 furans) ethylidene] diethyl succinate, 2, 5-dimethyl-3-acetyl furan and dry toluene mix and obtain a kind of mixed solution according to 2～6:1～3:10～15 weight ratio, at 20～25 DEG C, above-mentioned mixed solution is dropwise added in the suspension that potassium tert.-butoxide and dry toluene be mixed to get according to 1～3:20～40 weight ratio, time for adding is 0.5～1.5h, after dropwising, at 20～25 DEG C, continue reaction 12～96h, underpressure distillation is except desolventizing, resistates is dissolved in 50～150mL water, with HCl(6mol/L) be acidified to strongly-acid (PH=1), after stratification, there is the organic phase extracted with diethyl ether 3 times (3 × 50mL) of reddish-brown, filter with anhydrous sodium sulfate drying, under reduced pressure, steam except after ether, obtain 2 of oily, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace single-ethyl succinate, productive rate is 65～75%,
(4) take that step (3) obtains 2, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace single-ethyl succinate, potassium hydroxide and dehydrated alcohol mix according to 1～5:8～12:80～100 weight ratio, temperature rises to 80～90 DEG C, reflux 3～8h, underpressure distillation is except desolventizing, resistates is dissolved in 50～150mL water, be acidified to strongly-acid (PH=1) with acid, by extracted with diethyl ether 3 times (3 × 50mL), filter with anhydrous sodium sulfate drying, under reduced pressure, steam except ether, resistates twice, recrystallization in ethanol, obtain 2 of white crystal shape, 3-two [(2, 5-dimethyl-3-furyl) ethylidene] replace succinic acid, productive rate is 65～75%.
(5) take that step (4) obtains 2, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace succinic acid and methylene dichloride mix according to 1～3:8～12 weight ratio, then at 0 DEG C, be dropwise added dropwise to 10～50mL Acetyl Chloride 98Min., after dropwising, be warming up to 20～25 DEG C, stirring reaction 6～36h, after reaction finishes, unnecessary Acetyl Chloride 98Min. is removed in underpressure distillation, 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 twice, recrystallization in ethanol, obtain Coumarin substituted fulgides photochromic compound of the present invention, productive rate is 35～55%.
Preferably, in described step (1) and step (4), be mineral acid for the acid of acidifying.
Preferably, in described step (1) and step (4), be hydrochloric acid or sulfuric acid for the acid of acidifying.
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 ray is to infrared light (600-850nm).
Photochromic compound open loop body becomes closed loop body under UV-irradiation, and closed loop body can absorb infrared light or near infrared light; In the time that closed loop body is subject to ruddiness or near infrared light radiation, 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; first the method adopts potassium tert.-butoxide as organic bases; at room temperature by 2; 5-dimethyl-3-acetyl furan and diethyl succinate generate single acid esters through Stobbe condensation reaction; generate dibasic acid esters with ethanol and Acetyl Chloride 98Min. esterification again; then by dibasic acid esters and 2; 5-dimethyl-3-acetyl furan generates single acid esters through Stobbe condensation reaction; finally in the alcoholic solution of KOH, saponification obtains bisgallic acid, 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 proposing in solid-state or liquid the present invention can 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. compared with single heterocyclic substituted fulgide, Coumarin substituted fulgides photochromic compound of the present invention, due to molecule contain two can annulation functional group, more being conducive to the carrying out of photochromic reactions, is a kind of stable and efficient fulgides photochromic compound; 2. utilize the synthetic Coumarin of the present invention to replace fulgide under the irradiation of the UV-light of wavelength 360～370nm, it is solid-state or liquidly can change pink into by yellow, and the Coumarin of the present invention's proposition replaces fulgide compound (open loop body) and become colour solid (closed loop body) along with the increase of solvent polarity presents significant solvatochromism, is having obvious advantage aspect photochromism and stability; 3. synthetic method of the present invention has the advantages such as the productive rate of simple process, target product is high, with low cost and application prospect is extensive, utilizing the synthetic Coumarin substituted fulgides photochromic compound of the present invention 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 the present invention is described.The implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in 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 dry 250mL three-necked bottle, add 15mL anhydrous tertiary butanol, then 5g potassium metal is dissolved in and wherein obtains potassium tert.-butoxide solution, by 9g2, the trimethyl carbinol of 5-dimethyl-3-acetyl furan and 28g diethyl succinate and 55mL is mixed to get mixing solutions, under 20 DEG C of agitation conditions, with 1h, above-mentioned mixing solutions is dropwise added drop-wise in above-mentioned potassium tert.-butoxide solution, after dropwising, continue backflow 24h, then cool to room temperature, the hcl acidifying that is 5mol/L by concentration is 5-6 to pH value, then underpressure distillation is except desolventizing, resistates is dissolved in 200～400mL water, by twice of extracted with diethyl ether (2 × 50mL), hcl acidifying for water layer (6mol/L) is to strongly-acid (PH=1), after stratification, there is the organic phase monoesters extracted with diethyl ether 3 times (3 × 100mL) of reddish-brown, filter with anhydrous sodium sulfate drying, under reduced pressure, steam except after ether, obtain the 2-[(2 of reddish-brown, 5-dimethyl-3-furyl) ethylidene] replace single-ethyl succinate (7.6g, productive rate is 85%).
In dry 250mL three-necked bottle, by above-mentioned 6g 2-[(2, 5-dimethyl-3 furyl) ethylidene] replace single-ethyl succinate add in 10mL dehydrated alcohol, then at 0 DEG C, be dropwise added dropwise to 35mL Acetyl Chloride 98Min., after dropwising, rising temperature to 20 DEG C, reflux 24h, then underpressure distillation is except desolventizing, resistates separates with silica gel column chromatography, leacheate is the mixture (v/v=1/4) of ethyl acetate and sherwood oil, drip washing obtains yellow 2-[(2 after separating, 5-dimethyl-3 furyl) ethylidene] replace diethyl succinate (4.5g, productive rate 79%).
In dry 250mL three-necked bottle, by above-mentioned 4g 2-[(2, 5-dimethyl-3 furans) ethylidene] diethyl succinate and 1.9g2, 5-dimethyl-3-acetyl furan and 12mL dry toluene mix, under 20 DEG C of stirring states, dropwise add in the suspension (6.5g) that potassium tert.-butoxide and dry toluene be mixed to get according to 1:30 weight ratio, time for adding is 1h, after dropwising, at continuing 20 DEG C, react 36h, underpressure distillation is except desolventizing, resistates is dissolved in 90mL water, with HCl(6mol/L) be acidified to strongly-acid (PH=1), by extracted with diethyl ether 3 times (3 × 50mL), filter with anhydrous sodium sulfate drying, under reduced pressure, steam except after ether, obtain 2 of oily, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace single-ethyl succinate (3.7g, productive rate 66%).
In dry 250mL three-necked bottle, by above-mentioned 1.5g 2, 3-two [(2, 5-dimethyl-3-furyl) ethylidene] replace single-ethyl succinate, 2.5g potassium hydroxide and 20mL dehydrated alcohol mix, temperature rises to 85 DEG C, reflux 8 hours, underpressure distillation is except desolventizing, resistates is dissolved in 90mL water, with HCl(6mol/L) be acidified to strongly-acid (PH=1), by extracted with diethyl ether 3 times (3 × 50mL), filter with anhydrous sodium sulfate drying, under reduced pressure, steam and desolventize, resistates twice, recrystallization in ether solvent, obtain 2 of white crystal shape, 3-two [(2, 5-dimethyl-3-furyl) ethylidene] replace succinic acid (0.99g, productive rate 71%).
In dry 250mL three-necked bottle, by above-mentioned 0.9g 2, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace succinic acid and 12mL methylene dichloride mix, then at 0 DEG C, be dropwise added dropwise to 18mL Acetyl Chloride 98Min., after dropwising, be warming up to 20 DEG C, stirring reaction 24h, after reaction finishes, unnecessary Acetyl Chloride 98Min. is removed in underpressure distillation, 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 twice, recrystallization in ethanol, obtain Coumarin substituted fulgides photochromic compound (0.38g of the present invention, productive rate 45%), 166 DEG C of fusing point 164 –.
Coumarin substituted fulgides photochromic compound dissolution obtained above, in different solvents, by the rayed of different wave length, is studied to 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 opposed polarity solvent.
Embodiment 2
Identical with embodiment 1, but the consumption of step (1) 2,5-dimethyl-3-acetyl furan becomes 11.5g from 9g, the consumption of diethyl succinate becomes 33.6g from 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 from 9g, the consumption of diethyl succinate becomes 23.8g from 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 from 4g, and the consumption of 2,5-dimethyl-3-acetyl furan becomes 2.5g from 1.9g, and other are constant.
Embodiment 5
Identical with embodiment 1, but the consumption of step (5) Acetyl Chloride 98Min. becomes 30mL from 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 opposed polarity solvent thereof
maxchanging conditions
Above-mentioned example is only explanation technical conceive of the present invention and feature, and its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalent transformations that spirit is done according to the present invention or modification, within all should being encompassed in protection scope of the present invention.
Claims (1)
1. the synthetic method of Coumarin substituted fulgides photochromic compound, comprises the steps:
(1) by potassium metal, after anhydrous tertiary butanol and dry toluene stirring and dissolving, obtain a kind of potassium tert.-butoxide solution, wherein, potassium metal, the weight ratio of anhydrous tertiary butanol and dry toluene is 1:5～20:25～50, again by 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, at 20～25 DEG C, above-mentioned mixing solutions is slowly added drop-wise in above-mentioned potassium tert.-butoxide solution, control time for adding is 0.5～1.5h, after dropwising, at 20～25 DEG C, continue reaction 12～96h, then underpressure distillation is except desolventizing, resistates is dissolved in 200～400mL water, be acidified to strongly-acid pH=1 with acid, after stratification, there are organic phase 50mL extracted with diethyl ether 3 times of reddish-brown, filter with anhydrous sodium sulfate drying, under reduced pressure, steam except the 2-[(2 that obtains reddish-brown after ether, 5-dimethyl-3-furyl) ethylidene] replace single-ethyl succinate, productive rate is 75～90%,
(2) take the 2-[(2 that step (1) obtains, 5-dimethyl-3-furyl) ethylidene] replace single-ethyl succinate and ethanol mix, wherein, 2-[(2, 5-dimethyl-3-furyl) ethylidene] replace single-ethyl succinate and the weight ratio of ethanol be 1:2～5, then at 0 DEG C, be dropwise added dropwise to 10～50mL Acetyl Chloride 98Min., after dropwising, rising temperature to 20～25 DEG C, reacting by heating 6～36h, then underpressure distillation is except desolventizing, resistates separates with silica gel column chromatography, leacheate is that volume ratio is the ethyl acetate of 1:4 and the mixture of sherwood oil, drip washing obtains yellow 2-[(2 after separating, 5-dimethyl-3-furyl) ethylidene] replace diethyl succinate, productive rate is 70～85%,
(3) take the 2-[(2 that step (2) obtains, 5-dimethyl-3-furans) ethidine] replace diethyl succinate, 2, 5-dimethyl-3-acetyl furan and dry toluene mix and obtain a kind of mixed solution according to 2～6:1～3:10～15 weight ratio, at 20～25 DEG C, above-mentioned mixed solution is dropwise added in the suspension that potassium tert.-butoxide and dry toluene be mixed to get according to 1～3:20～40 weight ratio, time for adding is 0.5～1.5h, after dropwising, at 20～25 DEG C, continue reaction 12～96h, underpressure distillation is except desolventizing, resistates is dissolved in 50～150mL water, be acidified to strongly-acid with 6mol/L HCl, pH=1, after stratification, there are organic phase 50mL extracted with diethyl ether 3 times of reddish-brown, filter with anhydrous sodium sulfate drying, under reduced pressure, steam except after ether, obtain 2 of oily, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace single-ethyl succinate, productive rate is 65～75%,
(4) take that step (3) obtains 2, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace single-ethyl succinate, potassium hydroxide and dehydrated alcohol mix according to 1～5:8～12:80～100 weight ratio, temperature rises to 80～90 DEG C, reflux 3～8h, underpressure distillation is except desolventizing, resistates is dissolved in 50～150mL water, be acidified to strongly-acid pH=1 with 6mol/L HCl, by 50mL extracted with diethyl ether 3 times, filter with anhydrous sodium sulfate drying, under reduced pressure, steam except ether, resistates twice, recrystallization in ethanol, obtain 2 of white crystal shape, 3-two [(2, 5-dimethyl-3-furyl) ethylidene] replace succinic acid, productive rate is 65～75%,
(5) take that step (4) obtains 2, 3-two-[(2, 5 dimethyl-3-furyl) ethylidene] replace succinic acid and methylene dichloride mix according to 1～3:8～12 weight ratio, then at 0 DEG C, be dropwise added dropwise to 10～50mL Acetyl Chloride 98Min., after dropwising, be warming up to 20～25 DEG C, stirring reaction 6～36h, after reaction finishes, unnecessary Acetyl Chloride 98Min. is removed in underpressure distillation, resistates is through silica gel column chromatography separating purification, leacheate is that volume ratio is the ethyl acetate of 1:4 and the mixture of sherwood oil, separated product twice, recrystallization in ethanol, obtain Coumarin substituted fulgides photochromic compound of the present invention, productive rate is 35～55%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210370241.6A CN102911140B (en) | 2012-09-28 | 2012-09-28 | Synthetic method of dual-furan substituted fulgide photochromic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210370241.6A CN102911140B (en) | 2012-09-28 | 2012-09-28 | Synthetic method of dual-furan substituted fulgide photochromic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102911140A CN102911140A (en) | 2013-02-06 |
| CN102911140B true CN102911140B (en) | 2014-11-26 |
Family
ID=47609746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210370241.6A Active CN102911140B (en) | 2012-09-28 | 2012-09-28 | Synthetic method of dual-furan substituted fulgide photochromic compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102911140B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039855B (en) * | 2019-12-31 | 2021-08-06 | 华侨大学 | Double aromatic ring substituted fulgide ester photochromic compound and preparation method thereof |
| CN111039856B (en) * | 2019-12-31 | 2021-08-06 | 华侨大学 | Benzophenone substituted fulgide ester photochromic compound and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039239C (en) * | 1993-07-12 | 1998-07-22 | 中国科学院感光化学研究所 | Pyrrole substituting fulgide photochromic material |
| CN1213687A (en) * | 1997-10-05 | 1999-04-14 | 中国科学院感光化学研究所 | Polymerizable benzpyrrole and pyrrole substituted fulgide photochromic material and its synthetic process and use |
| CN1213686A (en) * | 1997-10-05 | 1999-04-14 | 中国科学院感光化学研究所 | Benzpyrrole substituted flugide photochromic material and its synthetic process and use |
| US6149841A (en) * | 1998-07-10 | 2000-11-21 | Ppg Industries Ohio, Inc. | Photochromic benzopyrano-fused naphthopyrans |
| CN1446878A (en) * | 2002-03-26 | 2003-10-08 | 中国科学院理化技术研究所 | Biheterocycle substituted photochromic compound in fulgide category as well as synthetic method and usage |
-
2012
- 2012-09-28 CN CN201210370241.6A patent/CN102911140B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039239C (en) * | 1993-07-12 | 1998-07-22 | 中国科学院感光化学研究所 | Pyrrole substituting fulgide photochromic material |
| CN1213687A (en) * | 1997-10-05 | 1999-04-14 | 中国科学院感光化学研究所 | Polymerizable benzpyrrole and pyrrole substituted fulgide photochromic material and its synthetic process and use |
| CN1213686A (en) * | 1997-10-05 | 1999-04-14 | 中国科学院感光化学研究所 | Benzpyrrole substituted flugide photochromic material and its synthetic process and use |
| US6149841A (en) * | 1998-07-10 | 2000-11-21 | Ppg Industries Ohio, Inc. | Photochromic benzopyrano-fused naphthopyrans |
| CN1446878A (en) * | 2002-03-26 | 2003-10-08 | 中国科学院理化技术研究所 | Biheterocycle substituted photochromic compound in fulgide category as well as synthetic method and usage |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102911140A (en) | 2013-02-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Moorthy et al. | Helicity as a steric force: Stabilization and helicity-dependent reversion of colored o-quinonoid intermediates of helical chromenes | |
| AU2010296299B2 (en) | Chromene compound | |
| JPH06500100A (en) | Photochromic chromene compound | |
| Thomas et al. | Improved synthesis of indolyl fulgides | |
| CN104098555A (en) | Method for synthesizing ultrashort-wavelength photochromic diarylethene compound by using imidazole-thiophene aromatic heterocycle and application of compound | |
| CN102911140B (en) | Synthetic method of dual-furan substituted fulgide photochromic compound | |
| CN108191624A (en) | A kind of UV-blue light absorbent and UV-blue light absorbing material | |
| Sousa et al. | Naphthopyrans as efficient dual color photoinitiators for volumetric 3D printing | |
| Coelho et al. | Photochemical and thermal behaviour of new photochromic indeno-fused naphthopyrans | |
| CN107522688A (en) | The class photochromic material of triaryl-ethylene containing thiophene derivant and its synthetic method and application | |
| CN101845041B (en) | Photochromic benzofuran thiophene series-parallel perfluoro-cyclopentene compound as well as synthesizing method and application thereof | |
| Wang et al. | Preparation and properties of multifunctional tetraarylethenes and their oxides | |
| CN101851232B (en) | Photochromic isoxazole thiophene hybrid-type perfluorinated cyclopentene compound as well as synthesis method and application thereof | |
| CN104447824A (en) | Fluoro-boron diisoindole compounds and preparation method thereof | |
| Islamova et al. | Improving the stability of photochromic fluorinated indolylfulgides | |
| Oliveira et al. | Synthesis and photochromic behaviour under flash photolysis and continuous irradiation of novel 2H-chromenes derived from hydroxydibenzothiophenes | |
| Erko et al. | Synthesis and photochromic properties of a bis (diarylethene)-naphthopyran hybrid | |
| CN108623543B (en) | Furan derivative-containing triaryl ethylene photochromic material and its synthesis method and use | |
| CN105272918B (en) | Halogenation -1- alkyl -3- vinyl -2,4,5- triarylimidazoles and preparation method and purposes | |
| JPH03503528A (en) | New photoactive compounds, their production methods, and their intermediates | |
| Li et al. | Enantiodifferentiating photoisomerization of cyclooctene included and sensitized by benzoate modified β-cyclodextrin derivatives: switching of product chirality by solvent | |
| Gabbutt et al. | The synthesis and photochromism of a 2, 2-diaryl-6-styryl-2H-[1] benzopyran: Unexpected palladium-mediated ring-contraction of a 6-bromo-2, 2-diaryl-2H-[1] benzopyran | |
| CN104710481B (en) | The molysite class two-photon absorbing material of butylcyclopentadiene containing tolans and preparation method | |
| CN111039856B (en) | Benzophenone substituted fulgide ester photochromic compound and preparation method thereof | |
| Fan et al. | Synthesis, crystal structure and photochromic properties of a new unsymmetrical diarylethene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230628 Address after: 311100 Room 102, Building 2, No. 2626, Yuhangtang Road, Cangqian Street, Yuhang District, Hangzhou City, Zhejiang Province Patentee after: Zhejiang Akemai New Material Co.,Ltd. Address before: Room B218 and 220, Second Teaching Building, No. 150 Ren'ai Road, Industrial Park, Suzhou City, Jiangsu Province, 215123 Patentee before: Jiangsu Chuangji New Material Co.,Ltd. |