CN115073412B - Fluorescent group modified indene fused ring naphthopyran photochromic compound and preparation method and application thereof - Google Patents
Fluorescent group modified indene fused ring naphthopyran photochromic compound and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 title abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000003973 paint Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 51
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 239000007810 chemical reaction solvent Substances 0.000 claims description 14
- 229940125782 compound 2 Drugs 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 claims description 11
- 229940125797 compound 12 Drugs 0.000 claims description 11
- 229940126214 compound 3 Drugs 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 7
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- LFABNOYDEODDFX-UHFFFAOYSA-N bis(4-bromophenyl)methanone Chemical compound C1=CC(Br)=CC=C1C(=O)C1=CC=C(Br)C=C1 LFABNOYDEODDFX-UHFFFAOYSA-N 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- -1 4,4' -dibromodiphenyl ketone Chemical class 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical group [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000976 ink Substances 0.000 claims 1
- 238000005562 fading Methods 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 7
- 241000220317 Rosa Species 0.000 abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 238000012512 characterization method Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- UEOGLANRPZAEAC-UHFFFAOYSA-N indeno-naphthopyran Chemical compound O1C=CC=C2C3=C4C=C(C=CC=C5)C5=C4C=CC3=CC=C21 UEOGLANRPZAEAC-UHFFFAOYSA-N 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000006740 morphological transformation Effects 0.000 description 1
- 125000004309 pyranyl group Chemical class O1C(C=CC=C1)* 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a fluorescent group modified indene fused ring naphthopyran photochromic compound, a preparation method and application thereof, wherein the molecular formula is shown as the formula T-I, R 1 and R 2 are the same or different, and each independently represents hydrogen, straight-chain or branched-chain alkyl containing 1-6 carbon atoms, straight-chain or branched-chain alkoxy containing 1-6 carbon atoms, phenyl or substituted phenyl. The photochromic compound T-I has the characteristics of rose or purple color, quick fading, no residual color, excellent fatigue resistance and the like, has fluorescent property, and can be applied to the fields of solar protection glasses, glass windows, decorative articles, clothing, paint ink or anti-counterfeiting materials and the like.
Description
Technical Field
The invention relates to the field of organic light functional materials, in particular to a fluorescent group modified indene fused ring naphthopyran photochromic compound, a preparation method and application thereof.
Background
Photochromic phenomenon refers to the fact that under the induction of light, a chemical substance can achieve two reversible different morphological transformations, accompanied by a distinct change in absorption spectrum and physicochemical properties, where the change in color is one of the main properties. By utilizing the characteristics, the photochromic material is widely applied to the fields of photochromic glasses, molecular switches, photochemical information storage, anti-counterfeiting materials and the like.
The organic photochromic compounds mainly comprise spirooxazine, fulgide, diarylethene, azobenzene, naphthopyran and the like. Among a plurality of organic photochromic compounds, naphthopyran compounds have the advantages of high light response speed, high fatigue resistance, simple synthesis method and the like, and become photochromic materials with application value. However, in practical application, naphthopyran photochromic materials have some limitations, such as slow fading rate and high residual color, which limit the practical application range of the materials. In addition, naphthopyran photochromic compounds having fluorescent properties are rarely reported.
Aiming at the problems of slow fading rate and high residual color of naphthopyran photochromic compounds, japanese scholars Jiro Abe design and synthesize the azacyclic pyran compounds and regulate the fading rate through intramolecular hydrogen bonds (adv. Mater. 2018, 1805661). In addition, the invention discloses a preparation method of indenonaphthopyran photochromic compound (CN 110295037A), and the problem that the material has low fading speed and residual color, poor fatigue resistance and the like, and lacks other optical properties such as fluorescent property, is solved by introducing condensed rings.
The invention introduces a group with fluorescence property on the indenonaphthopyran photochromic compound, so that the material has both photochromic property and fluorescence property.
Disclosure of Invention
The invention aims to develop a novel naphthopyran photochromic compound which has the advantages of quick fading, low residual color, good fatigue resistance and fluorescent property.
The technical scheme adopted for realizing the purpose of the invention is as follows:
A fluorescent group modified indeno-fused ring naphthopyran photochromic compound having the structural formula of formula T-I:
；
Wherein R 1 and R 2 are the same or different and each independently represents: hydrogen, straight-chain or branched alkyl groups having 1 to 6 carbon atoms, straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, phenyl groups or substituted phenyl groups.
Preferably, in the formula, R 1 and R 2 are the same or different and each independently represents: hydrogen, alkyl or alkoxy groups containing 1 to 3 carbon atoms, phenyl.
The invention also provides a preparation method of the fluorescent group modified indeno fused ring naphthopyran photochromic compound, which comprises the following steps:
step 1: the compound 1 and the o-dibromobenzene are subjected to suzuki coupling reaction in a reaction solvent under the catalysis of palladium to obtain a compound 2, wherein the reaction formula is as follows:
；
Step 2: the compound 2 and 4,4' -dibromodiphenyl ketone react under alkaline condition to obtain a compound 3, and the reaction formula is as follows:
；
step 3: compound 3 reacts under acidic conditions to obtain compound 4, the reaction formula is as follows:
；
step 4: compound 4 and compound 11 are subjected to a bell wood coupling reaction in a reaction solvent under the catalysis of palladium to obtain compound 12, wherein the reaction formula is as follows:
；
step 5: the compound 12 is reacted under the catalysis of Lewis acid to obtain an intermediate compound 13, and the reaction formula is as follows:
；
Step 6: the compound 13 and 1,1- (diaryl) -2-propyn-1-alcohol generate a photochromic compound T-I under the catalysis of organic acid, and the reaction formula is as follows:
；
Preferably, in the step 1 reaction, the carbonate used is cesium carbonate, potassium carbonate or sodium carbonate; the palladium catalyst used in the reaction is tetrakis (triphenylphosphine) palladium, palladium acetate or palladium dichloride; the reaction solvent is a mixed solvent of an ether solvent and water, preferably a mixed solvent of 1, 4-dioxane and water, and the volume ratio of the 1, 4-dioxane to the water is preferably 2:1, a step of; the reaction temperature is 80-100 ℃ and the reaction time is 18-24 h; wherein the mol ratio of the compound 1 to the o-dibromobenzene is 1 (1.0-1.2), and the mol ratio of the compound 1 to the carbonate is 1: (4-6), wherein the molar ratio of the compound 1 to the palladium catalyst is 1: (0.05-0.15);
In the step 2, the base is tert-butyllithium or n-butyllithium, the reaction solvent is tetrahydrofuran, the reaction temperature is-78-25 ℃, the reaction time is 6-10 h, wherein the molar ratio of the compound 2 to the 4,4' -dibromobenzophenone is 1 (0.5-0.8), and the molar ratio of the compound 2 to the base is 1 (0.8-1.2);
In the step 3, the acid used is trifluoromethanesulfonic acid, the reaction solvent is dichloromethane, the reaction temperature is 25-30 ℃, the reaction time is 3-6 h, wherein the molar ratio of the compound 3 to the trifluoromethanesulfonic acid is 1 (0.3-0.7);
In the step 4 reaction, the carbonate used is cesium carbonate, potassium carbonate or sodium carbonate; the palladium catalyst used in the reaction is tetrakis (triphenylphosphine) palladium, palladium acetate or palladium dichloride; the reaction solvent is a mixed solvent of an ether solvent and water, preferably a mixed solvent of 1, 4-dioxane and water, and the volume ratio of the 1, 4-dioxane to the water is preferably 2:1, a step of; the reaction temperature is 80-100 ℃, the reaction time is 18-24 h, wherein the molar ratio of the compound 4 to the compound 11 is 1 (2.0-2.4), and the molar ratio of the compound 4 to the carbonate is 1: (4-6), wherein the molar ratio of the compound 1 to the palladium catalyst is 1: (0.05-0.15);
in the step 5 reaction, the Lewis acid is boron tribromide, the reaction solvent is methylene dichloride, the reaction temperature is 25-30 ℃, the reaction time is 4-6 h, wherein the molar ratio of the compound 12 to the boron tribromide is 1 (5-10);
in the step 6, the organic acid is dodecylbenzene sulfonic acid, the reaction solvent is toluene or xylene, the reaction temperature is 40-50 ℃, the reaction time is 3-6 h, wherein the molar ratio of the compound 13 to 1,1- (diaryl) -2-propyn-1-ol is 1 (1-1.3), and the molar ratio of the compound 13 to the dodecylbenzene sulfonic acid is 1: (1.5 to 2.0).
The reagents used in the above reactions are all materials well known in the art and are all commercially available.
The invention also provides application of the fluorescent group modified indene fused ring naphthopyran photochromic compound in the fields of solar protection glasses, glass windows, decorative articles, clothes, paint ink or anti-counterfeiting materials.
Compared with the prior art, the invention has the beneficial effects that: the solution of the compound of the formula T-I can be changed from colorless to rose or purple under the irradiation of ultraviolet rays, and can fade from rose or purple to colorless after the irradiation is stopped, and the fading rate is fast, and T 1/2 is 5 seconds at maximum, and is within 1 min. The compound has the advantages of rapid color changing rate and decoloring rate, low residual color, excellent fatigue resistance, fluorescent property and wide application prospect. The method can be widely applied to the fields of solar protection glasses, glass windows, decorative articles, clothing, paint ink, anti-counterfeiting materials and the like.
Drawings
The fading properties of compounds T-Ib of FIG. 1 in chloroform;
FIG. 2 is a graph of fatigue resistance cycle test of compounds T-Ib in chloroform solution;
FIG. 3 fluorescence excitation spectra of compounds T-Ib in solvents of different ratios of chloroform and water;
FIG. 4 is a schematic representation of the photochromism of compound T-Ib in chloroform solution.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
All reaction conditions, such as pH, temperature, length, flow, including ranges, are approximations. It is to be understood that the term "about" is not always preceded by the explicit recitation of all numerical designations. It is also to be understood that the agents described herein are merely examples and that equivalents thereof are known in the art, although not always explicitly recited.
Example 1: preparation of photochromic compounds T-Ia
Step 1: preparation of compound 2, the reaction formula is as follows:
；
To a 250 mL round bottom flask was added compound 1 (5.00 g,17.60 mmol), o-dibromobenzene (4.15 g,17.60 mmol), tetrakis (triphenylphosphine) palladium (1.02 g,0.88 mmol) and anhydrous potassium carbonate (12.14 g,88.00 mmol). The mixture was sealed and evacuated, protected by N 2, and a1, 4-dioxane/water (70 mL/35 mL) mixture was injected through a needle, and the mixture was heated to 95℃to react at 20 h. After the reaction was completed, the reaction mixture was cooled to room temperature, washed with brine and extracted with ethyl acetate (100 mL ×2). The organic phases were combined and dried over anhydrous Mg 2SO4. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (pure petroleum ether) to give compound 2 as a white solid in 78% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound 2 are that ：1H NMR (400 MHz, CDCl3) δ 8.33 (dd, J = 8.2, 1.4 Hz, 1H), 7.67 (d, J = 8.0 Hz, 1H), 7.47 – 7.35 (m, 3H), 7.30 (d, J = 3.5 Hz, 2H), 7.24 – 7.16 (m, 2H), 6.78 (d, J = 7.8 Hz, 1H), 3.94 (s, 3H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound 2 are that ：13C NMR (101 MHz, CDCl3) δ 155.5, 141.6, 132.8, 132.6, 132.6, 131.7, 129.1, 127.3, 127.2, 126.8, 125.9, 125.6, 125.4, 125.2, 122.4, 103.2, 55.7.
Step 2: preparation of compound 3, the reaction formula is as follows:
；
To a 100 mL three-necked flask was added compound 2 (1.00 g,3.20 mmol), which was closed and evacuated, and N 2 protected, tetrahydrofuran (30 mL) was injected with a needle, the reaction system was cooled to-78 ℃, N-butyllithium (2.5M, 1.28 mL, 3.20 mmol) was slowly added, 1h was stirred at this temperature, and 4,4' -dibromobenzophenone (0.65 g,1.92 mmol) was slowly added to the flask, and 9 h was stirred at room temperature. After the completion of the reaction, the reaction mixture was washed with brine and extracted with ethyl acetate (50 mL ×2). The organic phases were combined and dried over anhydrous Mg 2SO4. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate=50:1) to give compound 3 as a pale yellow solid in 84% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound 3 are that ：1H NMR (400 MHz, CDCl3) δ 8.25 (d, J = 8.0, 1H), 7.43 – 7.27 (m, 9H), 7.13 (d, J = 6.4, 3H), 6.99 (d, J = 6.8 Hz, 2H), 6.94 (d, J = 7.2 Hz, 2H), 6.84 (d, J = 7.2 Hz, 1H), 6.50 (d, J = 8.8 Hz, 2H), 3.93 (s, 3H), 3.03 (s, 1H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound 3 are that ：13C NMR (101 MHz, CDCl3) δ155.5, 146.5, 145.2, 138.5, 134.0, 133.3, 131.0, 130.8, 130.2, 130.0, 129.8, 129.6, 127.8, 127.3, 126.9, 126.9, 126.3, 125.6, 125.5, 122.0, 121.5, 102.6, 82.9, 55.6, 29.8.
Step 3: preparation of compound 4, the reaction formula is as follows:
；
To a 100mL three-necked flask, compound 3 (0.11 g,0.20 mmol) was charged, and the flask was closed, evacuated, and then protected with N 2, tetrahydrofuran (1 mL) and trifluoromethanesulfonic acid (0.01 mL) were slowly injected in this order through a needle, and stirred at room temperature for 4 h. After the completion of the reaction, the reaction mixture was washed with brine and extracted with ethyl acetate (2 mL ×2). The organic phases were combined and dried over anhydrous MgSO 4. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (pure petroleum ether) to give compound 4 as a white solid in 87% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound 4 are that ：1H NMR (400 MHz, CDCl3) δ 8.76 (d,J= 8.5 Hz, 1H), 8.40 (d,J= 8.4 Hz, 1H), 8.31 (d,J= 7.8 Hz, 1H), 7.73 (t,J= 7.7 Hz, 1H), 7.58 (t,J= 7.4 Hz, 1H), 7.47 (t,J= 7.6 Hz, 1H), 7.40 (s, 2H), 7.38 (s, 3H), 7.30 – 7.24 (m, 1H), 7.14 (d,J= 8.6 Hz, 4H), 6.80 (s, 1H), 3.97 (s, 3H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound 4 are that ：13C NMR (101 MHz, CDCl3) δ156.1, 151.1, 149.6, 144.1, 141.5, 131.5, 130.1, 130.3, 127.9, 127.7, 127.1, 125.9, 125.8, 125.5, 125.3, 123.8, 123.3, 122.3, 121.0, 101.4, 64.8, 55.7, 35.4, 31.9, 29.7, 29.7, 29.4, 22.7, 14.1.
Step 4: preparation of compound 12, the reaction formula is as follows:
；
to a 50mL round bottom flask was added compound 4 (0.13 g,0.23 mmol), compound 11 (0.25 g,0.54 mmol), tetrakis (triphenylphosphine) palladium (0.02 g,0.03 mmol) and anhydrous potassium carbonate (0.19 g,1.38 mmol). The mixture was sealed and evacuated, protected by N 2, and a1, 4-dioxane/water (10 mL/5 mL) mixture was injected through a needle, and heated to 95℃to react at 20 h. After the reaction was completed, the reaction mixture was cooled to room temperature, washed with brine and extracted with ethyl acetate (10 mL ×2). The organic phases were combined and dried over anhydrous Mg 2SO4. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate=50:1) to give compound 12 as a white solid in 76% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound 12 is that ：1H NMR (400 MHz, CDCl3) δ 8.66 (d,J= 8.2 Hz, 1H), 8.27 (d,J= 8.3 Hz, 1H), 8.20 (d,J= 7.2 Hz, 1H), 7.74 – 7.51 (m, 2H), 7.49 – 7.41 (m, 2H), 7.34 (d,J= 7.1 Hz, 7H), 7.27 – 6.87 (m, 51H), 6.80 (s, 1H), 3.83 (s, 2H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound 12 are that ：13C NMR (101 MHz, CDCl3) δ155.9, 152.1, 150.6, 144.3, 143.7, 143.7, 143.7, 142.8, 141.6, 141.1, 140.5, 139.0, 138.3, 134.1, 131.8, 131.4, 131.3, 130.7, 130.2, 128.7, 127.7, 127.7, 127.6, 127.6, 127.5, 127.2, 126.7, 126.5, 126.5, 126.4, 126.0, 125.8, 125.8, 125.0, 123.8, 123.3, 122.2, 102.0, 83.7, 65.3, 55.7.
Step 5: preparation of compound 13, the reaction formula is as follows:
；
To a 50 mL three-necked flask was added compound 12 (0.27 g,0.26 mmol), which was closed and evacuated, and N 2 was protected, methylene chloride (4 mL), boron tribromide (0.24 mL,2.56 mmol) was slowly injected in sequence with a needle under ice bath conditions, and stirred at room temperature for 4 h. After the reaction, the mixture was washed with brine and extracted with dichloromethane (5 mL ×2). The organic phases were combined and dried over anhydrous Mg 2SO4. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate=8:1) to give compound 13 as a white solid in 73% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound 13 is that ：1H NMR (400 MHz, CDCl3) δ 8.81 (d,J= 8.3 Hz, 1H), 8.35 (d,J= 8.2 Hz, 2H), 7.72 (t,J= 7.5 Hz, 1H), 7.63 – 7.47 (m, 3H), 7.43 (d,J= 8.4 Hz, 4H), 7.32 (dd,J= 16.2, 8.3 Hz, 9H), 7.14 (m, 34H), 6.85 (s, 1H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound 13 are ：13C NMR (101 MHz, CDCl3) δ152.0, 151.9, 150.7, 144.2, 143.8, 143.8, 143.8, 142.8, 141.5, 141.2, 140.6, 139.0, 138.3, 131.8, 131.5, 131.4, 130.5, 128.7, 128.4, 127.8, 127.8, 127.7, 126.7, 126.6, 126.5, 126.1, 126.0, 125.8, 125.1, 124.7, 124.0, 123.1, 122.3, 106.9, 65.1.
Step 6: the preparation of compound T-Ia is carried out according to the following reaction formula:
；
To a 50 mL round bottom flask was added compound 13 (0.18 g, 0.17 mmol), toluene (4 mL), 1- (diphenyl) -2-propyn-1-ol (0.04 g,0.19 mmol) and 2 drops of dodecylbenzenesulfonic acid (0.32 mmol). Heating to 40 ℃ to react 3 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent. The residue was separated by column chromatography on silica gel (petroleum ether/ethyl acetate=50:1) to give T-Ia as an off-white solid in 63% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound T-Ia are ：1H NMR (400 MHz, CDCl3) δ 8.83 (d,J= 7.3 Hz, 1H), 8.62 (d,J= 7.5 Hz, 1H), 8.34 (d,J= 7.0 Hz, 1H), 7.71 (d,J= 7.0 Hz, 2H), 7.67 – 7.60 (m, 2H), 7.58 – 7.39 (m, 21H), 7.30 – 7.10 (m, 39H), 6.92 (d,J= 9.2 Hz, 1H), 6.72 (t,J= 7.9 Hz, 0H), 5.96 (d,J= 9.0 Hz, 1H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound T-Ia are ：13C NMR (101 MHz, CDCl3) δ193.6, 154.6, 148.7, 146.7, 144.2, 143.8, 143.7, 142.9, 141.4, 141.2, 141.1, 140.6, 138.9, 138.3, 131.9, 131.5, 131.4, 130.8, 130.6, 130.1, 129.5, 129.4, 128.8, 128.7, 128.4, 128.2, 128.1, 127.8, 127.8, 127.7, 127.5, 127.4, 127.1, 126.1, 126.3, 126.1, 125.7, 125.4, 125.1, 124.1, 123.4, 122.9, 122.1, 114.8, 82.4, 64.8.
Example 2: preparation of photochromic Compounds T-Ib
The reaction formula for the preparation of photochromic compounds T-Ib is as follows, wherein the preparation procedure for compound 13 is the same as in example 1:
；
To a 50mL round bottom flask was added compound 13 (0.18 g, 0.18 mmol), toluene (5 mL), 1- (4-biphenyl) -1-phenylpropan-2-yn-1-ol (0.05 g,0.19 mmol) and 2 drops of dodecylbenzenesulfonic acid (0.32 mmol). Heating to 40 ℃ to react 3 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent. The residue was separated by column chromatography on silica gel (petroleum ether/ethyl acetate=25:1) to give T-Ib as an off-white solid in 56% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound T-Ib are as follows ：1H NMR (400 MHz, CDCl3) δ 8.80 (d,J= 8.5 Hz, 1H), 8.60 (d,J= 8.1 Hz, 1H), 8.30 (d,J= 7.9 Hz, 1H), 7.70 (t,J= 7.2 Hz, 1H), 7.65 – 7.59 (m, 1H), 7.55 – 7.30 (m, 26H), 7.24 (t,J= 5.8 Hz, 4H), 7.21 – 7.09 (m, 34H), 6.89 (d,J= 9.8 Hz, 1H), 5.95 (d,J= 9.8 Hz, 1H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound T-Ib are as follows ：13C NMR (101 MHz, CDCl3) δ154.5, 148.7, 146.7, 144.2, 143.8, 143.7, 143.7, 143.7, 143.0, 142.8, 141.5, 141.3, 141.2, 141.0, 140.6, 140.5, 140.5, 140.1, 139.0, 138.8, 138.2, 138.2, 131.9, 131.8, 131.4, 131.4, 131.3, 130.1, 129.4, 129.3, 128.7, 128.2, 128.1, 127.8, 127.7, 127.7, 127.5, 127.5, 127.4, 127.4, 127.2, 127.0, 127.0, 126.6, 126.6, 126.5, 126.4, 126.2, 126.0, 126.0, 125.7, 125.4, 125.0, 124.1, 123.3, 123.0, 122.1, 114.8, 82.3, 64.8.
Example 3: preparation of photochromic Compounds T-Ic
The reaction scheme for the preparation of photochromic compound T-Ic is as follows, wherein the procedure for the preparation of compound 13 is the same as in example 1:
；
To a 50 mL round bottom flask was added compound 13 (0.18 g, 0.18 mmol), toluene (4 mL), 1-bis (4-methoxyphenyl) prop-2-yn-1-ol (0.05 g,0.19 mmol) and 2 drops of dodecylbenzenesulfonic acid (0.32 mmol). Heating to 40 ℃ to react 3 h. After the completion of the reaction, the reaction mixture was concentrated under reduced pressure to remove the solvent. The residue was separated by column chromatography on silica gel (petroleum ether/ethyl acetate=15:1) to give T-Ic as an off-white solid in 50% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound T-Ic is ：1H NMR (400 MHz, CDCl3) δ 8.62 (d,J= 8.5 Hz, 1H), 8.35 (d,J= 8.4 Hz, 1H), 8.14 (d,J= 7.9 Hz, 1H), 7.52 (t,J= 7.5 Hz, 1H), 7.43 (dd,J= 14.3, 6.6 Hz, 2H), 7.34 (t,J= 10.8 Hz, 6H), 7.27 (d,J= 7.8 Hz, 10H), 7.17 – 6.87 (m, 50H), 6.67 (d,J= 9.8 Hz, 1H), 6.55 (d,J= 8.7 Hz, 5H), 5.67 (d,J= 9.8 Hz, 1H), 3.51 (s, 7H).
The nuclear magnetic resonance carbon spectrum characterization data of the compound T-Ic are ：13C NMR (101 MHz, CDCl3) δ158.7, 154.4, 148.8, 147.1, 146.6, 143.7, 143.7, 142.8, 141.5, 141.1, 140.5, 138.8, 138.2, 136.3, 131.8, 131.3, 131.3, 130.0, 129.3, 128.4, 127.9, 127.7, 127.7, 127.6, 127.4, 127.3, 126.4, 126.1, 125.9, 125.7, 125.2, 125.0, 124.4, 123.9, 123.3, 122.5, 122.0, 114.7, 113.2, 82.0, 64.9, 55.1, 31.9, 29.7, 29.4, 22.7, 14.1.
Example 4: photochromic Properties of Compound T series in solution
Taking T-Ib as an example, the photochromic compounds were weighed and prepared into chloroform solutions of 8X 10 -5 mol/L. And (3) irradiating the solution for 25-35 s by adopting a xenon lamp light source (the electric power is 180W, the ultraviolet power is 2.6W and the visible light power is 19.6W) to reach saturated absorbance, and testing the time for reaching saturated absorbance, the maximum absorption wavelength and the saturated optical density by adopting an ultraviolet-visible absorption spectrum.
After reaching saturated absorbance, the ultraviolet absorption curve is tested at intervals of 5 seconds in a dark environment, and the fading half-life t 1/2 of the photochromic compound in the toluene solution can be calculated through a double-index fitting formula. FIG. 1 shows the UV-visible absorption spectrum of the compound T-Ib during the fading process in chloroform solution, table 1 shows the photochromic properties of the compound T series in solution, and FIG. 4 shows the discoloration process of the compound T-Ib in chloroform solution. As can be seen from Table 1, the light changes the colorless solution into rose or purple, the light response is rapid, the saturated absorbance value is 25-35 s, the saturated optical density value is high, the fading rate is rapid, and the fading half-life is generally within 1 min.
TABLE 1 photochromic Properties of photochromic Compounds in chloroform solution (8X 10 -5 mol/L)
| Compounds of formula (I) | λmax/nm | τAmax/s | τ1/2/s |
| T-Ia | 535 | 30 | 20s |
| T-Ib | 541 | 35 | 36s |
| T-Ic | 557 | 25 | 5s |
Example 5: fatigue resistance of Compound T-Ib in solution
Preparing chloroform solution with the concentration of T-Ib of 8 multiplied by 10 -5 mol/L, adopting a xenon lamp Xe-150 to irradiate 35: 35 s to reach the maximum absorbance value, then placing the solution in a dark place for 4: 4 min to fade, and respectively measuring the absorbance value when the maximum absorbance value is reached and after 4: 4 min is faded. The test was repeated 20 times to obtain a color-changing cycle chart (fig. 2). As can be seen from FIG. 2, after 20 cycles, there was little change in the maximum absorbance, indicating that T-Ib has good fatigue resistance.
Example 6: fluorescent Properties of Compounds T-Ib in solution
T-Ib is selected as a template substrate, the concentration of the template substrate is fixed to be 1' -10 -5 mol/L, a series of solutions to be detected with the same solute concentration and gradient increased water content are obtained by changing the proportion of chloroform and water in a solvent, the water content is from 0% to 99%, a monitoring point is arranged every 10%, and fluorescence emission spectra of the solutions under different gradient concentrations before illumination are tested. FIG. 3 shows fluorescence excitation spectra of compounds T-Ib in different solvents of chloroform and water. From the graph, when the water content is less than 60%, the solution to be measured has substantially no fluorescence emission. When the water content of the solution to be measured is more than 60%, the fluorescence emission is gradually enhanced along with the increase of the water content.
The above phenomenon shows that when the water content of the liquid to be detected is less than 60%, most of T2 is still dispersed in the system in a molecular form and does not show strong fluorescence emission; however, when the water content is greater than 60%, the T2 molecules in the system are aggregated into molecular groups due to the hydrophobicity, so that the molecular rotation is limited, and energy is emitted in the form of electromagnetic waves, so that aggregation-induced emission effect occurs, and the aggregation-induced emission effect is continuously enhanced along with the continuous increment of the water content.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (5)
1. A fluorescent group modified indeno-fused ring naphthopyran photochromic compound characterized in that: the compound has a structural formula shown in a formula T-I:
Wherein R 1 and R 2 are the same or different and each independently represents hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
2. The photochromic compound of claim 1 wherein: r 1 and R 2 are the same or different and each independently represents: hydrogen, alkyl or alkoxy groups containing 1 to 3 carbon atoms, phenyl.
3. A process for the preparation of a fluorophore-modified indeno-fused ring naphthopyran photochromic compound according to claim 1 or 2, characterized by comprising the steps of:
Step 1: the compound 1 and the o-dibromobenzene undergo a bell wood coupling reaction under the catalysis of palladium to obtain a compound 2, wherein the reaction formula is as follows:
Step 2: the compound 2 and 4,4' -dibromodiphenyl ketone react under alkaline condition to obtain a compound 3, and the reaction formula is as follows:
step 3: compound 3 reacts under acidic conditions to obtain compound 4, the reaction formula is as follows:
step 4: the compound 4 and the compound 11 are subjected to a bell wood coupling reaction under the catalysis of palladium to obtain a compound 12, wherein the reaction formula is as follows:
step 5: the compound 12 is reacted under the catalysis of Lewis acid to obtain an intermediate compound 13, and the reaction formula is as follows:
Step 6: the compound 13 and 1,1- (diaryl) -2-propyn-1-alcohol generate a photochromic compound T-I under the catalysis of organic acid, and the reaction formula is as follows:
4. a method of preparation according to claim 3, characterized in that:
In the step 1 reaction, the carbonate used is cesium carbonate, potassium carbonate or sodium carbonate; the palladium catalyst is tetra (triphenylphosphine) palladium, palladium acetate or palladium dichloride; the reaction solvent is a mixed solvent of 1, 4-dioxane and water; the reaction temperature is 80-100 ℃, the reaction time is 18-24h, wherein the molar ratio of the compound 1 to the o-dibromobenzene is 1 (1.0-1.2), and the molar ratio of the compound 1 to the carbonate is 1: (4-6), the molar ratio of the compound 1 to the palladium catalyst is 1: (0.05-0.15);
In the step 2, the base is tert-butyllithium or n-butyllithium, the reaction solvent is tetrahydrofuran, the reaction temperature is-78-25 ℃, the reaction time is 6-10h, wherein the molar ratio of the compound 2 to the 4,4' -dibromobenzophenone is 1 (0.5-0.8), and the molar ratio of the compound 2 to the base is 1 (0.8-1.2);
In the step 3, the acid used is trifluoromethanesulfonic acid, the reaction solvent is dichloromethane, the reaction temperature is 25-30 ℃, the reaction time is 3-6h, wherein the molar ratio of the compound 3 to the trifluoromethanesulfonic acid is 1 (0.3-0.7);
In the step 4 reaction, the carbonate used is cesium carbonate, potassium carbonate or sodium carbonate; the palladium catalyst is tetra (triphenylphosphine) palladium, palladium acetate or palladium dichloride; the reaction solvent is a mixed solvent of 1, 4-dioxane and water; the reaction temperature is 80-100 ℃, the reaction time is 18-24h, wherein the molar ratio of the compound 4 to the compound 11 is 1 (2.0-2.4), and the molar ratio of the compound 4 to the carbonate is 1: (4-6), the molar ratio of the compound 11 to the palladium catalyst is 1: (0.05-0.15);
In the step 5 reaction, the Lewis acid is boron tribromide, the reaction solvent is methylene dichloride, the reaction temperature is 25-30 ℃, the reaction time is 4-6h, wherein the molar ratio of the compound 12 to the boron tribromide is 1 (5-10);
In the step 6, the organic acid is dodecylbenzene sulfonic acid, the reaction solvent is toluene or xylene, the reaction temperature is 40-50 ℃, the reaction time is 3-6h, wherein the molar ratio of the compound 13 to 1,1- (diaryl) -2-propyn-1-ol is 1 (1-1.3), and the molar ratio of the compound 13 to the dodecylbenzene sulfonic acid is 1: (1.5-2.0).
5. Use of a photochromic compound according to claim 1 or 2 in the field of sunglasses, glazing, decorative articles, clothing, paint inks or security materials.
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