CN1425664A - Double five-membered heterocycle substituted fulgide photochromic compound and its synthesis and use - Google Patents
Double five-membered heterocycle substituted fulgide photochromic compound and its synthesis and use Download PDFInfo
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- CN1425664A CN1425664A CN01144132A CN01144132A CN1425664A CN 1425664 A CN1425664 A CN 1425664A CN 01144132 A CN01144132 A CN 01144132A CN 01144132 A CN01144132 A CN 01144132A CN 1425664 A CN1425664 A CN 1425664A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 59
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title description 16
- 238000003786 synthesis reaction Methods 0.000 title description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 heterocyclic aldehyde Chemical class 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 49
- 230000003287 optical effect Effects 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 16
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 239000012312 sodium hydride Substances 0.000 claims abstract description 13
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 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 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 129
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 111
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 238000001704 evaporation Methods 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 239000003208 petroleum Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 239000012074 organic phase Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 235000019476 oil-water mixture Nutrition 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 238000006467 substitution reaction Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 238000006600 Stobbe condensation reaction Methods 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- 239000008346 aqueous phase Substances 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- FMEYPAIIOVKZRA-UHFFFAOYSA-N 3-ethylideneoxolane-2,5-dione Chemical compound CC=C1CC(=O)OC1=O FMEYPAIIOVKZRA-UHFFFAOYSA-N 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000002024 ethyl acetate extract Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- PUSJAEJRDNPYKM-UHFFFAOYSA-N 3-Acetyl-2,5-dimethylthiophene Chemical compound CC(=O)C=1C=C(C)SC=1C PUSJAEJRDNPYKM-UHFFFAOYSA-N 0.000 description 2
- KBSVBCHYXYXDAG-UHFFFAOYSA-N 3-acetyl-2,5-dimethylfuran Chemical compound CC(=O)C=1C=C(C)OC=1C KBSVBCHYXYXDAG-UHFFFAOYSA-N 0.000 description 2
- BSQKBHXYEKVKMN-UHFFFAOYSA-N 3-methylthiophene-2-carbaldehyde Chemical compound CC=1C=CSC=1C=O BSQKBHXYEKVKMN-UHFFFAOYSA-N 0.000 description 2
- LOLKAJARZKDJTD-UHFFFAOYSA-N 4-Ethoxy-4-oxobutanoic acid Chemical class CCOC(=O)CCC(O)=O LOLKAJARZKDJTD-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- QCRYBEPPXKKXEW-UHFFFAOYSA-N 1,2,5-trimethylpyrrole-3-carbaldehyde Chemical compound CC1=CC(C=O)=C(C)N1C QCRYBEPPXKKXEW-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006349 photocyclization reaction Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention belongs to the technical fields of photochromic and optical information storage, related photonics materials and the like, and particularly relates to a di-pentaheterocycle substituted fulgide photochromic compound and a synthesis method and application thereof. Mixing heterocyclic aldehyde or heterocyclic ketone and diethyl succinate according to the mol ratio of 1: 1-1: 2 by using Stobbe condensation reaction, slowly adding the mixture into a tert-butyl alcohol solution containing potassium tert-butoxide, refluxing, and carrying out a series of steps to obtain an intermediate mono-heterocyclic substituted diethyl succinate; mixing the obtained intermediate and equimolar heterocyclic aldehyde or heterocyclic ketone in a toluene solution, slowly adding the mixed solution into an anhydrous toluene suspension of sodium hydride with the mole number of 2-3 times that of the heterocyclic ketone or heterocyclic aldehyde under the protection of nitrogen, adding anhydrous ethanol for initiating a reaction, and finally obtaining the di-five-membered heterocyclic substituted fulgide photochromic compound; the compound is thermodynamically stable and can be stored for a long time at room temperature in the absence of light.
Description
Technical Field
The invention belongs to the technical fields of photochromic and optical information storage, related photonics materials and the like, and particularly relates to a di-pentaheterocycle substituted fulgide photochromic compound and a synthesis method and application thereof.
Background
The organic photochromic material has wide application prospect, and compared with inorganic materials, the organic photochromic material has the advantages of high storage density, high speed, easy processing, low cost and the like.
Photochromic materials can be described generally as follows:
a certain photochromic compound A, light (hv) of a certain wavelength1) Under irradiation, the molecular structure of the compound B can be changed to form a compound B, so that the color change is generated. B may be at another wavelength of light (hv)2) Or heat (delta), the original color is restored, and this reversible process is called the photochromic phenomenon.
The fulgide compounds are important in a plurality of organic photochromic compounds, and are characterized by wide spectral response range, different molecular structures and the maximum light response wavelength which can be changed between 300 and 800 nm; secondly, the fatigue resistance is good.
In Chinese patent publication No. CN1097453A, Chinese patent application Nos. 97118941.2 and 97118942.0, fulgides are mostly monoheterocycle substituted fulgides, and the synthesis of dithiophene substituted fulgides is only found for diheterocycle substituted fulgides, such as: yokoyama, chemistry letters, 2000, 3, 220-. The diheterocyclic substituted fulgides are useful in increasing the quantum yield of the photocolor-forming reaction without significantly affecting the quantum yield of the photobleaching reaction.
Disclosure of Invention
One of the purposes of the invention is to provide a bi-five-membered heterocycle substituted fulgide photochromic compound with good thermal stability, fatigue resistance and photochromic performance.
It is a further object of the present invention to provide a process for the preparation of such photochromic compounds.
It is another object of the present invention to provide the use of such photochromic compounds for high density, fast response optical storage, optical switching and photoluminescent materials.
The bi-pentaheterocycle substituted fulgide photochromic compound has the following general formula: or
A type and B type
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5An alkyl or terminal alkenyl group of ═ C1-C5 where two R in the formula1The substituents may be the same or different, and their closed ring systems Ca、Cb、CI、CII、CIII、CIV、CVOr CVIIs defined by the above structure.
The bi-pentaheterocycle substituted fulgide photochromic compound of the present invention has several isomers usually, and the specific isomer number is two R1(each herein denoted by R1 aAnd R1 bExpressed, to distinguish the difference in the position of the substituent) the position and the type of substitution of the substituent, if two R' s1(R1 a＝R1 b) The compound (I) exists in three isomers, namely EE formula, EZ formula and ZZ formula, and the general formula is as follows:or
Or
In the formula: r1 aOr R1 bIs that
A type and B type
Wherein EE formula and EZ formula form a closed ring body after the light color-forming reaction, and the general formula is as follows:
R1 aor R1 bClosed ring systems C when substitution of type Bb
Or R1 aOr R1 bClosed ring systems C when substituted of type Aa 
If two R are present1(R1 a≠R1 b) Instead, compound (I) exists in four isomers, EE1 formula, EZ1, EZ2 and ZZ1 formula, respectively, as follows:or
In the formula, R1 aAnd R1 bNot simultaneously, R1 aIs that
A type and B type
R1 bIs that
A type and B type
Wherein the formula of EE1, EZ1 or EZ2 forms a general formula of a closed ring body after undergoing a light color forming reaction
The following were used:
R1 aand R1 bAll being closed ring bodies in case of A-type substitution
OrOr R1 aIs a type A substitution, R1 bClosed ring when substituted in B-form
Or
R1 aAnd R1 bAll being closed loops in case of B-type substitution
Or
In each of the above structural formulae:
X-O, S or N-R5
X1＝OS or N-R5
X2 ═ O, S or N-R5
And X1 and X2 cannot be the same substituent
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of ═ C1-C5
The reaction general formula of the synthesized di-five-membered heterocyclic ring substituted fulgide photochromic compound is as follows, wherein the reaction general formula comprises a cis-trans isomerization reaction of double bonds and a photocyclization reaction of a (4n +2) hexaelectron system, and the processes are reversible.
When ultraviolet light below 400nm is used to irradiate the bipentaary heterocycle substituted fulgide photochromic compound, EE and EZ type compounds can quickly produce cyclization reaction to produce orange-red closed ring Ca、Cb、CI、CII、CIII、CIV、CVOr CVI(the closed ring structure can be one or two, specifically represented by R1 a、R1 bLimited in substituent structure) and the maximum absorption is about 490nm, while the ZZ compound can be quickly isomerized into ZZ-EZ-EE under ultraviolet irradiation and then a closed ring body C is formeda、Cb、CI、CII、CI、CII、CIII、CIV、CVOr CVI. When the compound is irradiated by visible light (lambda is more than 480nm), the ring-closing body C can generate reversible reaction to generate the bipentaary heterocycle substituted fulgide compound.
The synthetic route of the di-pentaheterocycle substituted fulgide photochromic compound of the invention is as follows:
wherein two R are1The substituents may be the same or different; two R2The substituents may be the same or different.
The reaction principle of the synthetic route is a Stobbe condensation reaction, and the specific steps are as follows:
(1) mixing heterocyclic aldehyde or heterocyclic ketone and diethyl succinate according to the molar ratio of 1: 1-1: 2, slowly adding the mixture into a tert-butyl alcohol solution containing potassium tert-butoxide, refluxing for 1-18 hours, and stopping the reaction, wherein the molar ratio of the potassium tert-butoxide to the diethyl succinate is 1: 1-3: 1; after the reaction liquid is cooled, adding strong acid (such as 5N hydrochloric acid, 5N sulfuric acid and the like) to acidify the reaction liquid until the pH value is 5-6, evaporating the solvent under reduced pressure, and dissolving the residual liquid in diethyl ether, wherein the volume ratio of the residual liquid to the diethyl ether is 1: 1-1: 10; separating the aqueous phase, washing the organic phase with saturated sodium carbonate solution for 2-3 times, mixing the extractive solution and the aqueous phase, acidifying the aqueous phase with strong acid (such as 5N hydrochloric acid, 5N sulfuric acid, etc.) to strong acid with pH less than 1, extracting the obtained oil-water mixture with diethyl ether, mixing ether solutions, drying, and evaporating to remove solvent; dissolving the obtained half-ester in absolute ethyl alcohol, wherein the weight-volume ratio of the half-ester to the ethyl alcohol is 1: 10-1: 50, adding concentrated sulfuric acid with the concentration of 98% as a catalyst, wherein the weight-volume ratio of the half-ester to the acid is 10: 1-3: 1, refluxing for 6-8 hours, cooling, pouring the product into ice water, extracting with diethyl ether, separating a water phase, and combining ether solutions. Then saturated sodium bicarbonate is usedWashing the combined ether solution with water in sequence, drying, evaporating to remove the solvent, and separating the remainder by using a silica gel column (ethyl acetate: petroleum ether is 1: 4-1: 8) to obtain an intermediate mono-heterocyclic substituted diethyl succinate;
R1is that
A type and B type
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of ═ C1-C5
(2) Mixing the intermediate obtained in the step (1) with equimolar heterocyclic aldehyde or heterocyclic ketone in a toluene solution, wherein the weight volume ratio of heterocyclic aldehyde or heterocyclic ketone to toluene is 1: 2.5-1: 50, slowly adding the mixed solution into an anhydrous toluene suspension of sodium hydride with the mole number of 2-3 times that of heterocyclic ketone or heterocyclic aldehyde under the protection of nitrogen, wherein the weight volume ratio of the sodium hydride to the toluene is 1: 2-1: 10, adding absolute ethyl alcohol to initiate reaction, wherein the molar ratio of the ethanol to the sodium hydride is 1: 50-1: 100, stirring for 8-120 hours at room temperature, putting the reaction product into ice water, separating a water phase, extracting an organic phase for 2-3 times by using a saturated sodium carbonate aqueous solution, separating the organic phase, combining the water phases, back-extracting the combined water phase by using ethyl acetate, and then acidifying the water phase by using strong acid (such as 5N hydrochloric acid, 5N sulfuric acid and the like) until the pH value is less than 1; extracting the obtained oil-water mixture with ethyl acetate for 3 times, separating water phase, mixing ethyl acetate extractive solutions, drying with anhydrous magnesium sulfate, filtering, and evaporating under reduced pressure to remove ethyl acetate; dissolving the obtained colloidal half ester in an absolute ethanol solution, wherein the weight-volume ratio of the half ester to the ethanol is 1: 5-1: 20, adding potassium hydroxide, wherein the weight-volume ratio of the potassium hydroxide to the ethanol is 1: 5-1: 20, refluxing for 6-8 hours, evaporating to remove the solvent, dissolving the generated solid in water, acidifying the solution with strong acid (such as 5N hydrochloric acid, 5N sulfuric acid and the like) until the pH of the strong acid is less than 1 to obtain diacid precipitate, performing suction filtration, drying, dissolving the obtained diacid in tetrahydrofuran, wherein the weight-volume ratio of the diacid to the tetrahydrofuran is 1: 10-1: 50, adding N, N-dicyclohexylcarbodiimide,wherein the weight ratio of the diacid to the N, N-dicyclohexylcarbodiimide is 1: 1-1: 2; stirring the mixed solution at room temperature for 12-24 hours, filtering, evaporating excessive tetrahydrofuran from the obtained filtrate, and carrying out silica gel column chromatography on residuesAnd (3) performing spectrum separation, namely recrystallizing the ethyl acetate/petroleum ether serving as eluent in an ethyl acetate/petroleum ether mixed solvent to finally obtain the bi-five-membered heterocycle substituted fulgide photochromic compound.
A type and B type
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of ═ C1-C5
The heterocyclic aldehyde or ketone in this synthetic route is taken from the following compounds:
or
Wherein
X-O, S or N-R4
R3H or C1-C5 alkyl
R4Alkyl or terminal alkenyl of ═ C1-C5
R2H or methyl
The bi-five-membered heterocycle substituted fulgide photochromic compound synthesized by the invention can be used for the following aspects:
1. erasable rewrite and three-dimensional optical information storage;
2. an optical switching device;
3. optical information converters, such as photochromic devices, photonic devices, and the like.
The synthesized bi-five-membered heterocycle substituted fulgide photochromic compound can be observed photochromic phenomena in solid, solution and polymer films. For example, the di-furan substituted fulgide of example 1 rapidly changes from light yellow to orange-red after being irradiated with uv light, and the intensity of the absorption peak in the uv region gradually decreases and the absorption in the visible region increases as the uv irradiation time increases, so that the solution gradually darkens. When the ultraviolet light with the wavelength of more than 480nm is irradiated, the color gradually fades, the visible region gradually decreases, and the absorption intensity of the ultraviolet region is enhanced. The absorption spectra before and after ultraviolet irradiation are shown in the attached drawings.
The di-pentaheterocycle substituted fulgide photochromic compound has the following advantages:
1. the two states before and after photochromism are thermodynamically stable and can be stored for a long time at room temperature in a dark place.
2. The ultraviolet absorption peak of the diheterocyclic substituted fulgide compound appears at 350-380nm, and a pulse laser with 780nm wavelength can be used for two-photon absorption test and research so as to develop a photochromic three-dimensional optical information storage device.
3. The compound has good fatigue resistance
Drawings
FIG. 1. Compound 2 of example 1 of the present invention absorbs a change in the spectrum with time in toluene;
FIG. 2. Compound 2 of example 2 of the present invention absorbs a change in the spectrum with time in toluene;
FIG. 3. absorption spectra of the compound of example 5 of the present invention in toluene as a function of time;
Detailed Description
EXAMPLE 1 Synthesis of (E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furandione 1.Synthesis of diethyl 2- (2, 5-dimethylfuran-3-yl) ethylidenesuccinate
4g of potassium metal are dissolved in 100ml of anhydrous tert-butanol, 9.2ml (0.075mol) of 2, 5-dimethyl-3-acetylfuran and 14ml (0.082mol) of diethyl succinate are mixed and added dropwise to the potassium tert-butoxide solution, after the addition, reflux is carried out for 4 hours, cooling is carried out, the cooled solution is acidified to a pH of 5 to 6 with 5N hydrochloric acid, the solvent is evaporated under reduced pressure, the residue is dissolved in 50ml of diethyl ether, the aqueous phase is separated, the ether layer is extracted with a saturated sodium carbonate solution (3X 60ml), the aqueous layer is combined, the aqueous phase is acidified to a strong acid (pH<1) with 5N hydrochloric acid, the resulting oil-water mixture is extracted with diethyl ether (3X 60ml), the ether solution is combined, the diethyl ether is dried over sodium sulfate and removed, and about 9.8 g of mono-2, 5-dimethylfuran-3-yl-substituted monoethyl succinate are obtained.
The obtained monoethyl ester was added to 50ml of anhydrous ethanol, 2ml of 98% concentrated sulfuric acid was added thereto, the mixture was refluxed for 6 hours, ethanol was removed under reduced pressure, the mixture was cooled to room temperature, the residue was taken up in 50ml of ice water, extracted with (3 × 60) diethyl ether, the ether solutions were combined, the ether solution was washed with 60ml of saturated aqueous sodium bicarbonate solution, the ether solution was washed with water to neutrality, the solvent was evaporated after drying, and the residue was subjected to silica gel column chromatography (ethyl acetate: petroleum ether ═ 1: 4) to isolate 10.9 g of the title compound (yield 54%).1HNMR(ppm，CDCl3)：1.245(2t，6H，CH3(CH2O))；2.193(s，3H，MeC＝)；2.282(s，3H，furan-5-Me)；2.376(s，3H，furan-2-Me)；3.183(s，2H，-CH2-)；4.063-4.244(2q，4H，-CH2O-)；6.353(s，1H，furan-4-H)。
Synthesis of (E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furandione
2 g of sodium hydride and 10ml of anhydrous toluene are added under nitrogen protection in a dry three-neck flask, 4g of diethyl 2- (2, 5-dimethylfuran-3-yl) ethylidene succinate and 40ml of anhydrous toluene solution of 1.9g of 2, 5-dimethyl-3-acetylfuran are added dropwise to the sodium hydride suspension, simultaneously adding a drop of absolute ethyl alcohol to initiate reaction, stirring for 5 days at room temperature after the dropwise addition is finished, pouring the reaction mixture into 50ml of water, separating out water phase, extracting the organic phase with 50ml saturated sodium carbonate aqueous solution for 2 times, separating the organic phase, combining the water phases, back-extracting with 50ml ethyl acetate, the aqueous layer was acidified to strong acidity (pH<1) with 5N hydrochloric acid, the resulting oil-water mixture was extracted 3 times with 50ml of ethyl acetate, and the ethyl acetate extracts were combined and dried over anhydrous magnesium sulfate.
Filtering, evaporating to remove solvent, refluxing the obtained colloidal half ester in 50ml anhydrous ethanol containing 5g potassium hydroxide for 7 hr, cooling, evaporating most of solvent under reduced pressure, pouring the residue into water, acidifying with 5N hydrochloric acid to strong acidity (pH less than 1), filtering the obtained diacid, and drying. About 1.5 g of the obtained diacid was obtained, the obtained diacid was dissolved in 15ml of anhydrous tetrahydrofuran, 1.5 g of dicycloethylcarbodiimide was added, stirring was carried out for 12 hours, the solvent was distilled off, the residue was separated by a silica gel column (ethyl acetate: petroleum ether ═ 1: 5), and recrystallization was carried out in an ethyl acetate/petroleum ether mixed solvent to obtain E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furandione compound as pale yellow crystals, 294 mg. Melting point: 163 ℃ and 165 ℃ in a yield of 6.4%.1HNMR(ppm，CDCl3)：1.883(s，6H，Me＝)；2.127(s，6H，furan-2-Me)；2.523(s，6H，furan-5-Me)；5.494(s，2H，furan-4-H)。MS：340(M+)，325(M-15)
The change of the absorption spectrum of the compound (E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furandione in toluene with time is shown in FIG. 1.
The E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furandione compound synthesized in this example can be used in several respects:
1. erasable rewrite and three-dimensional optical information storage;
2. an optical switching device;
3. photochromic devices or photonicdevices.
Example 2.
Synthesis of 3- (3-methylthiophen-2-yl) methylene-4- (2, 5-dimethyl-3-yl) ethylidene-2, 5-furandione
1.2 Synthesis of diethyl 2- (2, 5-dimethylthien-3-yl) ethylidenesuccinate
According to the synthesis method of compound 1 of example 1, 4g of metal potassium is dissolved in 100ml of anhydrous tert-butyl alcohol, 10ml of 2, 5-dimethyl-3-acetylthiophene and 14ml of diethyl succinate are mixed and then added dropwise into the above-mentioned potassium tert-butoxide solution, and after the addition, the mixture is refluxed for 5 hours. Cooling, acidifying with 5N hydrochloric acid to pH 5-6, evaporating under reduced pressure to remove solvent, dissolving the residue in 50ml of diethyl ether, separating the aqueous phase, extracting the ether layer thoroughly 3 times with 3X 60ml of saturated sodium carbonate solution, combining the aqueous layers, acidifying with 5N hydrochloric acid to strong acidity (pH<1), extracting the resulting oil-water mixture with diethyl ether (3X 60ml), combining the ether solutions, drying with sodium sulfate, and removing solvent to obtain about 10.2 g of mono-2, 5-dimethylthiophen-3-yl-substituted-monoethyl succinate.
The obtained monoethyl ester was added to 50ml of anhydrous ethanol, 2ml of 98% concentrated sulfuric acid was added, heating and refluxing were carried out for 6 hours, ethanol was removed under reduced pressure, then, cooling to room temperature was carried out, the residue was put into 50ml of ice water, extraction was carried out with (3 × 50) diethyl ether, the diethyl ether solutions were combined, the ether solution was washed with 60ml of saturated aqueous sodium bicarbonate solution, the ether solution was washed to neutrality, and after drying, the solvent was distilled off. The residue was subjected to silica gel column chromatography (ethyl acetate: petroleum ether: 1: 6) toseparate 11 g (yield: 50%) of diethyl 2- (2, 5-dimethylthiophen-3-yl) ethylidenesuccinate.
1HNMR(ppm，CDCl3)： 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)。
Synthesis of 3- (3-methylthiophen-2-yl) methylene-4- (2, 5-dimethyl-3-yl) ethylidene-2, 5-furandione
According to the synthesis of the compound (E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furodione of example 1, 7 g of diethyl 2- (2, 5-dimethylthiophen-3-yl) ethylidene succinate and an equal mole of 3-methyl-2-thiophenal are mixed in 20ml of anhydrous toluene, slowly dropped into 10ml of anhydrous toluene of 3 g of sodium hydride under the protection of nitrogen, a drop of anhydrous ethanol is added to initiate the reaction, after the completion of the addition, the reaction mixture is stirred at room temperature for 72 hours, poured into 30ml of water, the aqueous phase is separated, the organic phase is extracted 2 times with 30ml of saturated aqueous sodium carbonate solution, the organic phases are separated, the aqueous phases are combined, back extracted with 30ml of ethyl acetate, the aqueous phase is acidified with 5N hydrochloric acid to a strongly acidic pH (pH<1), the resulting oil-water mixture was extracted 3 times with 30ml of ethyl acetate, and the ethyl acetate extracts were combined and dried over anhydrous magnesium sulfate.
Filtration, evaporation of the solvent, refluxing of the resulting colloidal half-ester in 50ml of absolute ethanol with 5g of potassium hydroxide for 6 hours, cooling, evaporation of the solvent under reduced pressure, pouring of the residue into water, acidification to strong acidity (pH<1) with 5N hydrochloric acid, suction filtration of the diacid obtained,and drying gives about 2.8 g of diacid. The resulting diacid was dissolved in 28ml of anhydrous tetrahydrofuran, 2.8 g of dicycloethylcarbodiimide were added, stirred for 12 hours, the solvent was distilled off and the residue was separated by means of a chromatographic column, 6: 1 petroleum ether/ethyl acetate being the eluent. Recrystallizing with ethyl acetate/petroleum ether mixed solvent to obtain 3- (3-methylthiophene-2-yl) methylene-4- (2, 5-dimethyl-3-yl) ethylidene-2, 5-furandione orange red crystal with the yield of 10%.1HNMR(ppm，CDCl3)：1.9475(s，3H)；2.2285(s，3H)；2.4546(s，3H)；2.6341(s，3H)；6.4872(s，H)；6.8982(s，H)；7.1785(s，H)；7.5757(s，H)MS：344(M+，100％)
The change of the absorption spectrum of the compound 3- (3-methylthiophen-2-yl) methylene-4- (2, 5-dimethyl-3-yl) ethylidene-2, 5-furandione in toluene with time is shown in FIG. 2.
The 3- (3-methylthiophen-2-yl) methylene-4- (2, 5-dimethyl-3-yl) ethylidene-2, 5-furandione synthesized in this example can be used in several aspects:
1. erasable rewrite and three-dimensional optical information storage;
2. an optical switching device;
3. photochromic devices, photonic devices.
EXAMPLE 3 Synthesis of (E), (E) -3, 4-bis (3-methylthiophen-2-yl) methylene-2, 5-furandione
Synthesis of 1.2- (3-methylthiophen-2-yl) methylenesuccinic acid diethyl ester
According to the synthesis of the compound (E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furandione, example 1, 4g of metal potassium was dissolved in 100ml of anhydrous t-butanol, 10.2ml of 3-methyl-2-thiophenylaldehyde was mixed with 15ml of diethyl succinate and added dropwise to the above potassium t-butoxide solution, after addition, refluxingfor 1 hour, then cooling to room temperature and acidifying to pH 5-6 with 5N hydrochloric acid, evaporating off the solvent under reduced pressure, dissolving the residue in 50ml of diethyl ether, separating the aqueous phase, extracting the ether layer 3 times with 3X 50ml of saturated sodium carbonate solution, combining the aqueous layers, acidifying to strong acidity (pH<1) with 5N hydrochloric acid, extracting the resulting oil-water mixture with diethyl ether (3X 50ml), combining the ether solutions, drying over sodium sulfate, the solvent was removed to obtain 12 g of crude monoethyl 2- (3-methylthiophen-2-yl) methylenesuccinate.
The resulting half ester was dissolved in 50ml of absolute ethanol, 2ml of concentrated sulfuric acid was added, refluxed for 6 hours, cooled to room temperature, and ethanol was removed under reduced pressure. The residue was taken up in 50ml of ice water and extracted with (3X 60) diethyl ether, the ethereal solutions were combined and washed with 60ml of saturated aqueous sodium bicarbonate solution until neutral, the product was separated by means of a chromatographic column, 6: 1 petroleum ether/ethyl acetate was used as eluent and the crude product was recrystallized from petroleum ether to give 8 g of white crystals with a melting point of 48-49 ℃ and a yield of 32%.
1HNMR(ppm，CDCl3)：1.2443-1.3615(2t，6H)；3.7831(s，2H)；4.1730-
4.2928(2q，4H)；
6.9322(s，H)；7.301 2(s，H)；8.0580(s，H)
Synthesis of (E), (E) -3, 4-bis (3-methylthiophen-2-yl) methylene-2, 5-furandione
According to the synthesis method of the compound (E), (E) -3, 4-bis (2, 5-dimethylfuran-3-yl) ethylidene-2, 5-furandione which is the compound of example 1, 6.3 g of diethyl 2- (3-methyl-2-thienyl) methylenesuccinate and equimolar 3-methyl-2-thiophenal are mixed in 50ml of anhydrous toluene, slowly dropped into 10ml of anhydrous toluene of 3 g of sodium hydride under the protection of nitrogen, added with a drop of anhydrous ethanol to initiate the reaction, and after the completion of the addition, stirred at room temperature for 8 hours. The reaction mixture was poured into 60ml of water, the aqueous phase was separated, the organic phase was extracted 2 times with 60ml of a saturated aqueous sodium carbonate solution, the organic phases were separated, the aqueous phases were combined, back-extracted with 60ml of ethyl acetate, the aqueous layer was acidified to strong acidity (pH<1) with 5N hydrochloric acid, the resulting oil-water mixture was extracted 3 times with 60ml of ethyl acetate, the ethyl acetate solutions were combined and dried over anhydrous magnesium sulfate.
Filtration, evaporation of the solvent, refluxing of the resulting colloidal half-ester in 50ml of absolute ethanol with 5g of potassium hydroxide for 6 hours, cooling, evaporation of the solvent under reduced pressure, pouring of the residue into water, acidification to strong acidity (pH<1) with 5N hydrochloric acid gives a precipitate of the diacid, suction filtration of the diacid obtained, drying to give about 4g of diacid. The resulting diacid was dissolved in 40ml of anhydrous tetrahydrofuran, 4g of dicycloethylcarbodiimide was added, stirring was carried out for 12 hours, the solvent was distilled off, the product was separated by chromatography column, and recrystallized in ethyl acetate/petroleum ether mixed solvent with 5: 1 petroleum ether/ethyl acetate as eluent to give 1.6 g of red crystals with a yield of 22.6%.
1HNMR(ppm，CDCl3)：2.3917(s，6H)；6.8290(d，2H)；7.3782(d，2H)；
7.9639(s，2H)
MS：316(M+，100％)
The (E), (E)-3, 4-bis (3-methylthiophen-2-yl) methylene-2, 5-furandione synthesized in this example can be used in several respects:
1. erasable rewrite and three-dimensional optical information storage;
2. an optical switching device;
3. optical information converters, such as photochromic devices, photonic devices, and the like.
Example 4
Synthesis of (Z), (Z) -3, 4-bis (2, 5-dimethylthiophen-3-yl) ethylidene-2, 5-furandione
The intermediate is the compound 1 in the example 2, and is obtained by the synthetic steps of the compound 1 in the example 2.
According to the synthesis of compound 2 in example 1, 7 g of diethyl 2- (2, 5-dimethylthiophen-3-yl) ethylbutanedioate and equimolar 2, 5-dimethyl-3-acetylthiophene are mixed in 20ml of anhydrous toluene, slowly added dropwise to 10ml of anhydrous toluene containing 3 g of sodium hydride under the protection of nitrogen, a drop of anhydrous ethanol is added to initiate the reaction, after the dropwise addition, the mixture is stirred at room temperature for 5 days, the reaction mixture is poured into 30ml of water, the aqueous phase is separated off, and the organic phase is extracted with 30ml of saturated aqueous sodium carbonate solution2 times, the organic phases are separated, the aqueous phases are combined and, after back extraction with 30ml of ethyl acetate, the aqueous layer is acidified to strong acidity (pH<1) with 5N hydrochloric acid, the resulting oil-water mixture is extracted 3 times with 30ml of ethyl acetate, the ethyl acetate extracts are combined and dried over anhydrous magnesium sulfate. Filtering and evaporating the solvent. The resulting colloidal half-ester was refluxed in 50ml of absolute ethanol with 5g of potassium hydroxide for 5 hours, cooled, most of the solvent was evaporated under reduced pressure, the residue was poured into water, acidified to strong acidity (pH<1) with 5N hydrochloric acid to give a precipitate of the diacid, the diacid obtained was filtered off with suction and dried to give about 1.2 g of the diacid. Dissolving the obtained diacid in 12ml of anhydrous tetrahydrofuran, adding 1.2 g of dicycloethylcarbodiimide, stirring for 12 hours, evaporating to remove the solvent, separating the product by a chromatographic column, and recrystallizing in an ethyl acetate/petroleum ether mixed solvent by taking petroleum ether/ethyl acetate at a ratio of 8: 1 as eluent to obtain orange red crystals with the yield of 5%.1HNMR(ppm，CDCl3)：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％)
The (Z), (Z) -3, 4-bis (2, 5-dimethylthiophen-3-yl) ethylidene-2, 5-furandione synthesized in this example can be used in several respects:
1. erasable rewrite and three-dimensional optical information storage;
2. an optical switching device;
3. optical information converters, such as photochromic devices, photonic devices, and the like.
Example 5
Synthesis of 3- (1, 2, 5-trimethylthiophen-3-yl) methylene-4- (2, 5-dimethyl-3-yl) ethylidene-2, 5-furandione
The intermediate is the compound 1 in the example 2, and is obtained by the synthetic steps of the compound 1 in the example 2.
According to the synthesis method of compound 2 of example 1, 7 g of diethyl 2- (2, 5-dimethylthiophen-3-yl) ethylidene succinate and equimolar 1, 2, 5-trimethyl-3-pyrrol-aldehyde are mixed in 20ml of anhydrous toluene, slowly dropped into 10ml of anhydrous toluene with 3 g of sodium hydride under the protection of nitrogen, added with one drop of anhydrous ethanol to initiate reaction, and after dropping, the mixture is placed in a chamberAfter stirring at room temperature for 5 days, the reaction mixture was poured into 30ml of water, the aqueous phase was separated, the organic phase was extracted 2 times with 30ml of a saturated aqueous sodium carbonate solution, the organic phases were separated, the aqueous phases were combined, back-extracted with 30ml of ethyl acetate, the aqueous layer was acidified to a strong acidity (pH<1) with 5N hydrochloric acid, the resulting oil-water mixture was extracted 3 times with 30ml of ethyl acetate, the ethyl acetate extracts were combined and dried over anhydrous magnesium sulfate. Filtering, evaporating to remove solvent, refluxing the obtained colloidal half ester in 50ml anhydrous ethanol containing 5g potassium hydroxide for 6 hr, cooling, evaporating under reduced pressure to remove most of solvent, pouring the residue into water, acidifying with 5N hydrochloric acid to strong acidity (pH less than 1) to obtain diacid precipitate, filtering, and drying. About 2.3 g of diacid is obtained, the obtained diacid is dissolved in 23ml of anhydrous tetrahydrofuran, 2.3 g of dicycloethylcarbodiimide is added, the stirring is carried out for 12 hours, the solvent is evaporated, the product is separated by a chromatographic column, and the product is recrystallized in an ethyl acetate/petroleum ether mixed solvent by taking 8: 1 petroleum ether/ethyl acetate as eluent to obtain 0.96 g of orange red crystals with the yield of 12 percent.1HNMR(ppm，CDCl3)：1.8795(s，3H)；2.1819(s，3H)；2.2055(s，3H)；2.4400(s，3H)；2.5746(s，3H)；3.3783(s，3H)；6.50(s，1H)；6.7948(s，2H)MS：355(M+，100％)；340(M+-15，56％)
The 3- (1, 2, 5-trimethylthiophen-3-yl) methylene-4- (2, 5-dimethyl-3-yl) ethylidene-2, 5-furandione synthesized in this example can be used in several aspects:
1. erasable rewrite and three-dimensional optical information storage;
2. an optical switching device;
3. optical information converters, such as photochromic devices, photonic devices, and the like.
Claims (10)
1. A bipentaheterocycle substituted fulgide photochromic compound is characterized in that: the compounds have the general formula: or
A type and B type
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of C1-C5.
2. The compound of claim 1, wherein: the number of isomers of the compound is defined by two R1The position and type of substitution of the substituent, wherein two R are1When the same, respectively using R1 aAnd R1 bThe compound (I) exists in three isomers, namely EE formula, EZ formula and ZZ formula, and the general formula is as follows:
or
In the formula: r1 aOr R1 bIs thatOr
A type and B type
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of C1-C5.
3. The compound of claim 2, wherein: the EE, EZ and ZZ compounds form closed ring bodies after undergoing light color-forming reaction, and the general formula is as follows:
R1 aor R1 bIs type BClosed ring body C at the time of substitutionb 
Or R1 aOr R1 bClosed ring systems C when substituted of type Aa
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of C1-C5.
4. The compound of claim 1, wherein: the number of isomers of the compound is defined by two R1The position and type of substitution of the substituent, wherein two R are1At different times, respectively using R1 aAnd R1 bThe compound (I) exists in four isomers, namely EE1, EZ1,
EZ2 and ZZ1, of the formula:or
In the formula, R1 aAnd R1 bNot simultaneously, R1 aIs thatOr
A-type B-type R1 bIs that
Or
A type and B type
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of C1-C5.
5. The compound of claim 4, wherein: the general formula of the closed ring formed after the light color forming reaction of the EE1 formula, the EZ1 formula or the EZ2 formula is as follows:
R1 aand R1 bAll being closed ring bodies in case of A-type substitution
Or
Or R1 aIs a type A substitution, R1 bClosed ring when substituted in B-formOr
R1 aAnd R1 bAll being closed loops in case of B-type substitutionOr
In each of the above structural formulae:
X-O, S or N-R5
X1 ═ O, S or N-R5
X2 ═ O, S or N-R5
And X1 and X2 cannot be the same substituent
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of C1-C5.
6. A process for the preparation of a bipentaheterocycle substituted photochromic fulgide compound as claimed in claims 1 to 5, which comprises: the method comprises the following steps:
(1) mixing heterocyclic aldehyde or heterocyclic ketone and diethyl succinate according to the molar ratio of 1: 1-1: 2, slowly adding the mixture into a tert-butyl alcohol solution containing potassium tert-butoxide, refluxing for 1-18 hours, and stopping the reaction, wherein the molar ratio of the potassium tert-butoxide to the diethyl succinate is 1: 1-3: 1; after the reaction liquid is cooled, adding strong acid to acidify the reaction liquid until the pH value is 5-6, removing the solvent by reduced pressure evaporation, and dissolving the residual liquid in diethyl ether, wherein the volume ratio of the residual liquid to the diethyl ether is 1: 1-1: 10; separating water phase, washing the organic phase with saturated sodium carbonate solution, mixing the extractive solution and water phase, acidifying the water phase with strong acid to strong acid with pH less than 1, extracting the oil-water mixture with diethyl ether, mixing ether solutions,drying and evaporating the solvent; dissolving the obtained half-ester in absolute ethyl alcohol, wherein the weight-volume ratio of the half-ester to the ethyl alcohol is 1: 10-1: 50, adding concentrated sulfuric acid with the concentration of 98% as a catalyst, wherein the weight-volume ratio of the half-ester to theacid is 10: 1-3: 1, refluxing, cooling, pouring the product into ice water, extracting with diethyl ether, separating a water phase, and combining ether solutions; then washing the combined ether solution by using a saturated sodium bicarbonate aqueous solution and water in sequence, drying, evaporating to remove the solvent, and separating the remainder by using a silica gel column to obtain an intermediate mono-heterocyclic substituted diethyl succinate;R1is that
A type and B type
X-O, S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of ═ C1-C5
(2) Mixing the intermediate obtained in step (1) with equimolar amount of heterocycleMixing heterocyclic aldehyde or heterocyclic ketone and toluene in a toluene solution, wherein the weight-volume ratio of the heterocyclic aldehyde or heterocyclic ketone to the toluene is 1: 2.5-1: 50, slowly adding the mixed solution into an anhydrous toluene suspension of sodium hydride in a mole number of 2-3 times that of the heterocyclic ketone or heterocyclic ketone under the protection of nitrogen, wherein the weight-volume ratio of the sodium hydride to the toluene is 1: 2-1: 10, adding anhydrous ethanol to initiate a reaction, wherein the mole ratio of the ethanol to the sodium hydride is 1: 50-1: 100, stirring at room temperature, adding a reaction product into ice water, separating a water phase, extracting an organic phase with a saturated sodium carbonate aqueous solution, separating an organic phase, combining the water phases, back-extracting the combined water phase with ethyl acetate, and then acidifying the water phase with a strong acid until the pH value is less than 1; extracting the obtained oil-water mixture with ethyl acetate, separating water phase, mixing ethyl acetate extractive solutions, drying with anhydrous magnesium sulfate, filtering, and evaporating ethyl acetate under reduced pressure; dissolving the obtained colloidal half ester in an absolute ethanol solution, wherein the weight-volume ratio of the half ester to the ethanol is 1: 5-1: 20, adding potassium hydroxide, wherein the weight-volume ratio of the potassium hydroxide to the ethanol is 1: 5-1: 20, refluxing, evaporating the solvent, dissolving the generated solid in water, acidifying the solution with a strong acid until the pH value of the strong acid is less than 1, obtaining diacid precipitate, performing suction filtration,drying, dissolving the obtained diacid in tetrahydrofuran, wherein the weight-volume ratio of the diacid to the tetrahydrofuran is 1: 10-1: 50, and then adding N, N-dicyclohexylcarbodiimide, wherein the weight ratio of the diacid to the N, N-dicyclohexylcarbodiimide is 1: 1-1: 2; stirring the mixed solution at room temperature, filtering, evaporating excessive tetrahydrofuran from the obtained filtrate, separating the residue by silica gel column chromatography, and recrystallizing in ethyl acetate/petroleum ether mixed solvent by using ethyl acetate/petroleum ether as eluent to finally obtain the bi-five-membered heterocycle substituted fulgide photochromic compound;
or
A type and B type
X＝O、S or N-R5
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of C1-C5.
7. The method of claim 6, further comprising: the heterocyclic aldehyde or ketone is taken from the following compounds:orWherein
X-O, S or N-R4
R3H or C1-C5 alkyl
R4Alkyl or terminal alkenyl of ═ C1-C5
R2H or methyl
8. The method of claim 6, further comprising: the strong acid is hydrochloric acid or sulfuric acid.
9. The method of claim 6, further comprising: said di-five-membered heterocyclic ring being substitutedWhen the fulgide compound is irradiated by ultraviolet below 400nm, EE and EZ compounds can produce cyclization reaction to produce orange-red closed ring body Ca、Cb、CI、CII、CIII、CIV、CVOr CVIThe maximum absorption is about 490nm, while the ZZ compound can be quickly isomerized into ZZ-EZ-EE under ultraviolet irradiation, and then a closed ring body C is formeda、Cb、CI、CII、CI、CII、CIII、CIV、CVOr CVIWhen irradiated by visible light, lambda is greater than 480nm, and the closed ring body can produce reversible reaction to produce di-pentaheterocycle substituted fulgideThe refined acid anhydride compound is a compound of the class of,
orOrIn the formula: r1 aOr R1 bIs that
A type and B type
In each of the above structural formulae:
X-O, S or N-R5
X1 ═ O, S or N-R5
X2 ═ O, S or N-R5
And X1 and X2 cannot be the same substituent
R2H or methyl
R3H or C1-C5 alkyl
R4、R5Alkyl or terminal alkenyl of C1-C5.
10. Use of a bipentaheterocycle substituted photochromic compound of the fulgide class according to claims 1 to 5, wherein: the double five-membered heterocyclic substituted fulgide photochromic compound is used in erasable rewriting and three-dimensional optical information storage, optical switch device or optical information converter.
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| CNB011441321A Expired - Fee Related CN1199970C (en) | 2001-12-12 | 2001-12-12 | Double five-membered heterocycle substituted fulgide photochromic compound and its synthesis and use |
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| CN (1) | CN1199970C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039855A (en) * | 2019-12-31 | 2020-04-21 | 华侨大学 | Double aromatic ring substituted fulgide ester photochromic compound and preparation method thereof |
| CN111039856A (en) * | 2019-12-31 | 2020-04-21 | 华侨大学 | Benzophenone substituted fulgide ester photochromic compound and preparation method thereof |
-
2001
- 2001-12-12 CN CNB011441321A patent/CN1199970C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039855A (en) * | 2019-12-31 | 2020-04-21 | 华侨大学 | Double aromatic ring substituted fulgide ester photochromic compound and preparation method thereof |
| CN111039856A (en) * | 2019-12-31 | 2020-04-21 | 华侨大学 | Benzophenone 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 |
| CN111039855B (en) * | 2019-12-31 | 2021-08-06 | 华侨大学 | Double aromatic ring substituted fulgide ester photochromic compound and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1199970C (en) | 2005-05-04 |
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