CN114014886A - Silicon-fused ring naphthopyran photochromic compound and preparation method and application thereof - Google Patents
Silicon-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 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 76
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 43
- 229940125898 compound 5 Drugs 0.000 claims description 20
- 229940125904 compound 1 Drugs 0.000 claims description 15
- 229940125782 compound 2 Drugs 0.000 claims description 15
- 229940126214 compound 3 Drugs 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007810 chemical reaction solvent Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- FEQPHYCEZKWPNE-UHFFFAOYSA-K trichlororhodium;triphenylphosphane Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FEQPHYCEZKWPNE-UHFFFAOYSA-K 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 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
- PQNQMYMGUXGWTG-UHFFFAOYSA-N 4-bromonaphthalen-2-ol Chemical compound C1=CC=CC2=CC(O)=CC(Br)=C21 PQNQMYMGUXGWTG-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 7
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002841 Lewis acid Substances 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 150000007517 lewis acids Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000005046 Chlorosilane Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 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
- PLVCYMZAEQRYHJ-UHFFFAOYSA-N (2-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1Br PLVCYMZAEQRYHJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 methoxy, phenyl Chemical group 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000003973 paint Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000037072 sun protection Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [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 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000000976 ink Substances 0.000 claims 1
- 238000005562 fading Methods 0.000 abstract description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 238000012512 characterization method Methods 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 10
- 238000010898 silica gel chromatography Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical group C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 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
- WQHBAYPEOODGEA-UHFFFAOYSA-N 1-(4-bromophenyl)prop-2-yn-1-ol Chemical compound C#CC(O)C1=CC=C(Br)C=C1 WQHBAYPEOODGEA-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 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
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 229940125890 compound Ia Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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- 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
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- 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
- C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms
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Abstract
The invention relates to a silicon fused ring naphthopyran photochromic compound and a preparation method and application thereof, wherein the molecular formula is shown as formula I, R1 and R2 are the same or different and respectively and independently represent 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 or halogen, R3Represents a straight or branched alkyl group having 1 to 6 carbon atoms. The color body of the photochromic compound I is yellow or orange, and has the characteristics of high color ratio, quick fading, no residual color, excellent fatigue resistance and the like.
Description
Technical Field
The invention relates to the field of organic optical functional materials, in particular to a silicon fused ring naphthopyran photochromic compound and a preparation method and application thereof.
Background
The photochromic material is photoisomerized under the irradiation of visible light and ultraviolet light, and can generate different absorption spectrums and physicochemical properties, wherein the color change is one of the main properties. By utilizing the performance characteristics, the photochromic material is widely applied to the fields of industrial textiles, photochromic glasses, molecular switches, photochemical information storage, anti-counterfeiting materials and the like. The photochromic material mainly comprises an inorganic photochromic material and an organic photochromic material. The organic photochromic compound mainly comprises spirooxazine, spiropyran, azobenzene, fulgide, diarylethene, naphthopyran and the like, and the materials are rich in variety and easy to regulate and control performance through structural modification.
Among a plurality of organic photochromic compounds, the 3H-naphthopyran compound has the characteristics of easy synthesis, good fatigue resistance, fast photoresponse and the like. The color changing mechanism of the photochromic compound is shown as the following formula: under the irradiation of visible light and ultraviolet light, the C-O bond in the pyran ring is cracked, and the pyran ring is converted from a colorless closed ring body (CF) into a colored open ring body. The open ring mainly comprises TC form and TT form, wherein the TC form can be quickly recovered to the CF form under the condition of keeping away from light, but the TT form needs longer time (minutes or even hours) to be recovered to the closed-ring CF form again, so that the naphthopyran photochromic compound has slow fading rate and higher residual color. In addition, the 3H-naphthopyran compound is low in the color yield of the colored body. The disadvantages of slow fading, low color yield, residual color, etc. have been the main reasons limiting the practical application of 3H-naphthopyran photochromic compounds.
Aiming at the performance defects of the 3H-naphthopyran photochromic compound, the invention provides a preparation method (CN110295037A) of the indene thick naphthopyran photochromic compound, and the introduction of a condensed ring is found to be capable of effectively improving the fading performance of the material, but the problems of low color ratio, slow fading, residual color accompanied with the fading and the like are not solved, and the fatigue resistance of the material is required to be further improved.
Disclosure of Invention
Therefore, the object of the present invention is to develop a novel silicon fused ring naphthopyran-based photochromic compound having high color yield, fast fading, low residual color and good fatigue resistance.
The technical scheme of the invention is as follows:
a photochromic compound characterized by: the compound has a structure shown in formula I:
in the formula R1And R2The same or different, each independently represent: hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, phenyl or substituted phenyl or halogen, R3Represents a straight or branched alkyl group having 1 to 6 carbon atoms.
Preferably, in the formula, R1And R2The same or different, each independently represent: hydrogen, alkyl or alkoxy having 1 to 3 carbon atoms, phenyl or halogen, R3Represents a straight or branched alkyl group having 1 to 3 carbon atoms.
In another aspect, the present invention also provides a method for preparing the above compound, comprising the steps of:
step 1: 1-bromo-3-naphthol and tert-butyldiphenylchlorosilane are reacted under an alkaline condition to form a compound 1, wherein the reaction formula is as follows:
step 2: carrying out Suzuki coupling reaction on the compound 1 and 2-bromobenzoic acid under the catalysis of palladium to obtain a compound 2, wherein the reaction formula is as follows:
and 3, step 3: the compound 2 and dialkyl chlorosilane generate a compound 3 under the alkaline condition, and the reaction formula is as follows:
and 4, step 4: the compound 3 is cyclized under the catalysis of triphenylphosphine rhodium chloride to obtain a compound 4, and the reaction formula is as follows:
and 5, step 5: the compound 4 reacts under the catalysis of Lewis acid to obtain an intermediate compound 5, and the reaction formula is as follows:
and 6, step 6: the compound 5 and 1,1- (diaryl) -2-propyne-1-alcohol generate photochromic compound I under the catalysis of organic acid, and the reaction formula is as follows:
in the preparation method as described above, preferably, in the reaction in step 1, the base used is imidazole, the reaction solvent is 1, 4-dioxane or N, N-dimethylformamide, the reaction temperature is 25-30 ℃, and the reaction time is 10-18h, wherein the molar ratio of 1-bromo-3-naphthol to tert-butyldiphenylchlorosilane is 1: (0.8 to 1.0).
In the reaction in the step 2, the carbonate used is cesium carbonate, potassium carbonate or sodium carbonate; the palladium catalyst used in the reaction is palladium tetrakis (triphenyl) phosphine, palladium acetate or palladium dichloride; the reaction solvent is 1, 4-dioxane and water; the reaction temperature is 80-100 ℃, the reaction time is 18-24h, and the molar ratio of the compound 1 to the 2-bromobenzeneboronic acid is 1: (1.0-1.2).
Preferably, in the reaction in the step 3, the dialkylchlorosilane is dimethylchlorosilane, 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, and the molar ratio of the compound 2 to the dimethylchlorosilane is 1: (1.2-1.5).
Preferably, in the reaction of the 4 th step, the catalyst used is triphenylphosphine rhodium chloride, and the reaction solvent is 1, 4-dioxane, tetrahydrofuran or acetone. The reaction temperature is 80-115 ℃, the reaction time is 24-36h, and the molar ratio of the compound 3 to the triphenylphosphine rhodium chloride is 1: (0.03-0.05).
Preferably, in the reaction of the step 5, the lewis acid used is diisobutylaluminum hydride, the reaction solvent is n-hexane, cyclohexane or a mixed solvent, the reaction temperature is 40-60 ℃, the reaction time is 6-8h, and the molar ratio of the compound 4 to the diisobutylaluminum hydride is 1: (2.6-3.4).
Preferably, in the reaction of the step 6, the used organic acid is dodecylbenzene sulfonic acid, the reaction solvent is toluene or xylene, the reaction temperature is 40-50 ℃, and the reaction time is 3-6 h. Wherein the molar ratio of the compound 5 to the 1,1- (diaryl) -2-propyn-1-ol is 1: 1-1.3.
The photochromic compound prepared by the technical scheme has the greatest characteristic that a molecular structure contains a silicon-doped five-membered fused ring structure, and in order to obtain the structure, the intermediate compounds 1-5 and the preparation process thereof are also within the protection range of the patent, and other photochromic compounds which are not limited in the invention can be prepared and obtained through the intermediate compound 5.
Specifically, intermediates include intermediates 1-5, each having the structure:
the preparation method of the intermediate comprises the following steps:
step 1: 1-bromo-3-naphthol and tert-butyldiphenylchlorosilane are reacted under an alkaline condition to form a compound 1, wherein the reaction formula is as follows:
step 2: carrying out Suzuki coupling reaction on the compound 1 and 2-bromobenzoic acid under the catalysis of palladium to obtain a compound 2, wherein the reaction formula is as follows:
and 3, step 3: the compound 2 and dialkyl chlorosilane generate a compound 3 under the alkaline condition, and the reaction formula is as follows:
and 4, step 4: the compound 3 is cyclized under the catalysis of triphenylphosphine rhodium chloride to obtain a compound 4, and the reaction formula is as follows:
and 5, step 5: the compound 4 reacts under the catalysis of Lewis acid to obtain an intermediate compound 5, and the reaction formula is as follows:
the reagents used in the above reaction are all known in the art and are commercially available.
The invention provides application of a compound I shown in a formula as a photochromic material in the fields of sun protection glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like.
The invention has the beneficial effects that the compound solution in the formula I can be changed into yellow or orange from colorless under the irradiation of ultraviolet rays, and can fade from yellow to colorless after the irradiation of the ultraviolet rays is stopped, the fading rate is high, and t1/2The fastest may be less than 1 second. The compound has the advantages of rapid color change rate and color erasing rate, low residual color, high chroma, excellent fatigue resistance and wide application prospect. Can be widely applied to the fields of sun protection glasses, glass windows, decorative articles, clothes, paint and ink, anti-counterfeiting materials and the like.
Drawings
FIG. 1Ib color fading properties in toluene solution;
FIG. 2 is a graph of fatigue cycle test of compound Ib in toluene solution;
Detailed Description
Example 1: preparation of photochromic Compounds Ia
Step 1: preparation of compound 1, reaction formula:
a50 mL round bottom flask was charged with 1-bromo-3-naphthol (1.10g,4.93mmol), N-dimethylformamide (15mL), tert-butyldiphenylchlorosilane (1.08mL,4.14mmol), and imidazole (0.62g, 9.07mmol) and reacted at room temperature for 14 h. After completion of the reaction, the reaction mixture was washed with brine and extracted with ethyl acetate (20 mL. times.2). The organic phases are combined and freed from anhydrous Mg2SO4And (5) drying. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (pure petroleum ether) to obtain compound 1 as a white solid in a yield of 85%.
The nuclear magnetic resonance hydrogen spectrum characterization data of the compound 1 are as follows:1H NMR(400MHz,CDCl3)δ8.32(d,J＝8.3Hz,1H),8.10–7.99(m,4H),7.82(d,J＝2.4Hz,1H),7.66–7.56(m,7H),7.55–7.45(m,2H),7.24(d,J＝2.4Hz,1H),1.43(s,9H).
the nuclear magnetic resonance carbon spectrum characterization data of the compound 1 are as follows:13C NMR(101MHz,CDCl3)δ153.2,135.8,135.7,135.1,132.6,130.5,130.5,128.3,128.3,128.2,128.0,128.0,127.5,127.1,127.0,126.1,126.0,125.4,123.4,115.0,114.9,26.9,26.8,19.8.
step 2: preparation of compound 2, reaction formula:
to a 100mL round bottom flask was added compound 1(0.97g, 2.11mmol), (2-bromophenyl) boronic acid (0.42g, 2.11mmol), (tetrakistriphenyl) phosphine palladium (0.12g, 0.10mmol), and anhydrous potassium carbonate (1.46g, 10.54 mmol). It is hermetically evacuated, N2To protect, useThe mixed solvent of 1, 4-dioxane/water (20mL/10mL) is injected into the needle, and the mixture is heated to 95 ℃ for reaction for 20 h. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with brine, and extracted with ethyl acetate (50 mL. times.2). The organic phases are combined and freed from anhydrous Mg2SO4And (5) drying. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (pure petroleum ether) to obtain compound 2 as a white solid in a yield of 74%.
The nmr hydrogen spectrum characterization data for compound 2 was:1H NMR(400MHz,CDCl3)δ7.92(m,4H),7.78(dd,J＝8.4,1.3Hz,1H),7.66–7.62(m,1H),7.55–7.51(m,2H),7.50–7.46(m,4H),7.42(m,4H),7.32(m,3H),7.16(d,J＝2.4Hz,1H),1.28(s,9H).
the nuclear magnetic resonance carbon spectrum characterization data of the compound 2 are as follows:13C NMR(101MHz,CDCl3)δ152.7,140.9,140.6,135.8,135.7,134.7,133.0,132.9,132.8,131.9,130.1,130.1,129.2,128.0,128.0,127.5,127.3,127.2,126.2,125.8,124.3,124.1,123.1,26.8,19.7.
and 3, step 3: preparation of compound 3, reaction formula:
to a 100mL three-necked flask was added Compound 2(2.64g, 4.92mmol), which was sealed and evacuated, N2After protection, tetrahydrofuran (30mL) was injected through a needle, the reaction was cooled to-78 deg.C, n-butyllithium (2.5M,2.40mL,5.90mmol) was slowly added, stirred at this temperature for 1h, dimethylchlorosilane (0.71mL, 6.40mmol) was slowly added to the flask, and stirred at room temperature for 9 h. After completion of the reaction, the reaction mixture was washed with brine and extracted with ethyl acetate (70 mL. times.2). The organic phases are combined and freed from anhydrous Mg2SO4And (5) drying. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (pure petroleum ether) to obtain compound 3 as a pale yellow solid in 83% yield.
The nmr hydrogen spectrum characterization data for compound 3 was:1H NMR(400MHz,CDCl3)δ8.18(dd,J＝6.6,2.1Hz,2H),8.15–8.10(m,2H),7.99(dd,J＝6.1,2.6Hz,1H),7.75(d,J＝8.2Hz,1H),7.71–7.60(m,10H),7.54(t,J＝7.0Hz,2H),7.50(d,J＝2.4Hz,1H),7.45–7.39(m,2H),4.40(m,1H),1.50(s,9H),0.21(d,J＝3.5Hz,6H).
the nuclear magnetic resonance carbon spectrum characterization data of the compound 3 are as follows:13C NMR(101MHz,CDCl3)δ152.4,146.5,142.5,135.7,135.0,134.5,133.1,132.6,130.0,128.8,128.6,127.9,127.9,127.0,126.8,126.5,126.0,123.7,123.1,114.3,27.3,19.6,-3.0.
and 4, step 4: preparation of compound 4, reaction formula:
into a 50mL three-necked flask was added compound 3(0.40g, 0.78mmol), triphenylphosphine rhodium chloride (35mg, 0.04mmol), which was then evacuated under a sealed condition, and N2Protected, 1, 4-dioxane (10mL) was injected with a needle. Heating to 115 ℃ and reacting for 24 h. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with brine, and extracted with ethyl acetate (20 mL. times.2). The organic phases are combined and freed from anhydrous Mg2SO4And (5) drying. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate 5: 1) to obtain compound 4 as a white solid in 51% yield.
The nmr hydrogen spectrum characterization data for compound 4 was:1H NMR(400MHz,CDCl3)δ7.86–7.81(m,2H),7.80–7.74(m,3H),7.47(d,J＝8.2Hz,1H),7.43–7.37(m,5H),7.36–7.27(m,4H),7.21–7.18(m,1H),7.16(d,J＝7.8Hz,1H),7.11(d,J＝2.5Hz,1H),7.04(d,J＝2.5Hz,1H),1.15(s,9H),-0.01(s,3H),-0.23(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of the compound 4 are as follows:13C NMR(101MHz,CDCl3)δ151.1,144.2,141.6,137.7,134.4,134.3,133.3,133.0,131.7,131.2,128.9,128.9,128.8,127.8,127.4,126.7,126.7,125.9,125.6,125.1,125.0,122.7,121.9,113.2,25.3,18.3,-0.1.
and 5, step 5: preparation of compound 5, reaction formula:
to a 50mL three-necked flask was added compound 4(0.15g, 0.30mmol), which was sealed and evacuated, N2For protection, n-hexane (6mL), diisobutylaluminum hydride (0.72mL, 0.86mmol) were slowly injected in that order through a needle. Heated to 50 ℃ and reacted for 7 h. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with brine, and extracted with ethyl acetate (10 mL. times.2). The organic phases are combined and freed from anhydrous Mg2SO4And (5) drying. The solvent was removed by concentration, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate 2: 1) to give compound 5 as a pale yellow solid in 87% yield.
The nmr hydrogen spectrum characterization data for compound 5 was:1H NMR(400MHz,CDCl3)δ7.73(d,J＝6.0Hz,1H),7.62(s,1H),7.49–7.39(m,2H),7.35(d,J＝8.3Hz,2H),7.24(s,1H),7.17(t,J＝7.6Hz,1H),7.10(s,1H),6.98(s,1H),0.03(s,3H),-0.27(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of the compound 5 are as follows:13C NMR(101MHz,CDCl3)δ151.7,144.8,141.9,137.2,134.0,133.6,129.5,128.4,127.3,126.0,126.0,125.6,125.5,122.7,118.9,109.0,-0.3.
and 6, step 6: preparation of photochromic Compound Ia, the reaction scheme is as follows:
to a 50mL round bottom flask was added compound 5(0.13g,0.46mmol), toluene (8mL), 1- (diphenyl) -2-propyn-1-ol (0.11g, 0.52mmol), and 2 drops of dodecylbenzene sulfonic acid. Heating to 40 ℃ and reacting for 3 h. After the reaction, the reaction solution was concentrated under reduced pressure to remove the solvent. The residue was subjected to silica gel column chromatography (petroleum ether/ethyl acetate 40: 1) to give Ia as a pale yellow solid in 62% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ia are:1H NMR(400MHz,CDCl3)δ7.89(dd,J＝8.5,2.9Hz,1H),7.62(m,1H),7.43–7.35(m,4H),7.33–7.30(m,1H),7.30–7.24(m,3H),7.23(s,3H),7.17(d,J＝7.0Hz,1H),7.15–7.12(m,2H),7.09(d,J＝2.0Hz,1H),7.04(t,J＝7.6Hz,1H),6.97(d,J＝1.9Hz,1H),6.19(dd,J＝9.9,2.7Hz,1H),-0.37(s,3H),-0.79(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ia are as follows:13C NMR(101MHz,CDCl3)δ149.5,145.1,145.1,145.0,144.4,144.4,143.4,139.5,139.5,134.9,134.8,130.0,129.8,129.1,128.5,128.2,128.1,127.9,127.5,127.1,126.7,126.6,123.5,121.4,121.3,119.9,119.7,113.9,113.9,82.5,82.5,2.8,1.4.
example 2: preparation of photochromic Compound Ib, the reaction scheme is as follows:
to a 50mL round bottom flask was added compound 5(0.12g,0.42mmol), toluene (8mL), 1- (4-biphenyl) -1-phenylpropan-2-yn-1-ol (0.13g, 0.47mmol), and 2 drops of dodecylbenzene sulfonic acid. Heating to 40 ℃ and reacting for 3 h. After the reaction, the reaction solution was concentrated under reduced pressure to remove the solvent. The residue was subjected to silica gel column chromatography (petroleum ether/ethyl acetate 10:1) to give Ib as a pale yellow solid in 72% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ib are as follows:1H NMR(400MHz,CDCl3)δ8.08(m,1H),7.83(m,1H),7.69–7.60(m,6H),7.56(t,J＝6.4Hz,2H),7.52–7.46(m,4H),7.42(m,4H),7.36(m,2H),7.30(d,J＝8.6Hz,1H),7.21(m,2H),6.44–6.36(m,1H),-0.13(s,3H),-0.57(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ib are as follows:13C NMR(101MHz,CDCl3)δ148.1,143.7,143.5,142.9,142.9,142.6,142.0,142.0,139.3,138.9,138.1,138.0,138.0,133.4,133.3,128.6,128.5,128.3,127.7,127.3,127.1,126.8,126.7,126.4,126.3,126.2,126.1,126.1,126.1,125.9,125.8,125.7,125.7,125.6,125.6,125.5,125.4,125.2,125.1,122.1,119.9,119.9,118.5,118.4,112.5,112.4,81.0,1.4.
example 3: preparation of photochromic Compound Ic, the reaction scheme is as follows:
to a 50mL round bottom flask was added compound 5(0.12g,0.42mmol), toluene (8mL), 1-bis (4-methoxyphenyl) prop-2-yn-1-ol (0.12g, 0.47mmol), and 2 drops of dodecylbenzenesulfonic acid. Heating to 40 ℃ and reacting for 3 h. After the reaction, the reaction solution was concentrated under reduced pressure to remove the solvent. The residue was separated by silica gel column chromatography (petroleum ether/ethyl acetate 8:1) to give Ic as a yellow solid in 75% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ic are:1H NMR(400MHz,CDCl3)δ7.99(dd,J＝8.5,2.8Hz,1H),7.76–7.69(m,1H),7.47–7.29(m,9H),7.20(d,J＝8.0Hz,1H),7.14(m,1H),7.03(d,J＝3.7Hz,1H),6.86(d,J＝8.9Hz,2H),6.81–6.75(m,2H),6.23(d,J＝9.9Hz,1H),3.79(s,3H),3.71(s,3H),-0.21(s,3H),-0.63(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ic are:13C NMR(101MHz,CDCl3)δ157.4,148.1,143.7,141.8,138.0,135.9,135.3,135.3,133.3,128.5,128.3,127.6,127.0,126.9,126.9,126.9,126.8,126.0,125.1,125.0,121.9,119.8,118.5,118.4,117.9,112.3,112.0,111.9,80.7,80.7,53.8,53.7,1.3,-0.7.
example 4: preparation of the photochromic compound Id, the reaction scheme is as follows:
to a 50mL round bottom flask was added compound 5(0.24g,0.84mmol), toluene (12mL), 1-bis (4-bromophenyl) prop-2-yn-1-ol (0.31g, 0.94mmol), and 2 drops of dodecylbenzene sulfonic acid. Heating to 40 ℃ and reacting for 3 h. After the reaction, the reaction solution was concentrated under reduced pressure to remove the solvent. The residue was separated by silica gel column chromatography (petroleum ether/ethyl acetate 10:1) to give Id as a yellow solid in 67% yield.
Example 5: preparation of photochromic Compound Ie, the reaction scheme is as follows:
to a 50mL round bottom flask was added compound 5(0.18g,0.63mmol), toluene (10mL), 1-di-p-tolylpropyl-2-yn-1-ol (0.22g, 0.70mmol), and 2 drops of dodecylbenzene sulfonic acid. Heating to 40 ℃ and reacting for 3 h. After the reaction, the reaction solution was concentrated under reduced pressure to remove the solvent. The residue was subjected to silica gel column chromatography (20: 1 petroleum ether/ethyl acetate) to give Ie as a pale yellow solid in 62% yield.
Example 6: photochromic Properties of Compounds Ia, Ib, Ic in solution
Weighing photochromic compounds, and preparing into 8 × 10-5A toluene solution of mol/L. And (3) irradiating the solution by using a xenon lamp light source (the electric power is 180W, the ultraviolet power is 2.6W, and the visible light power is 19.6W) for 20-35 seconds to enable the solution to reach the saturated absorbance, and testing the time for reaching the saturated absorbance, the maximum absorption wavelength and the saturated optical density through an ultraviolet visible absorption spectrum. Notably, the silicon fused ring naphthopyran photochromic compounds synthesized by this patent have greater molar extinction coefficients and saturated optical densities under the same test conditions than the indene fused ring photochromic compounds synthesized by the subject composition (CN110295037A), due to the larger volume of the silicon fused ring than the indene fused ring structure, resulting in enhanced polarizability and photosensitivity of the photochromic molecules.
After the saturated absorbance is reached, testing an ultraviolet absorption curve at intervals of 5 seconds in a dark environment, and calculating the fading half-life t of the photochromic compound in the toluene solution by using a double-exponential fitting formula1/2. FIG. 1 shows the UV-VIS absorption spectrum of compound Ib in toluene solution for fading, and Table 1 shows the photochromic performance of compounds Ia, Ib and Ic in solution. As shown in Table 1, the toluene solutions of the target compounds Ia, Ib and Ic have maximum absorption wavelengths of 431nm, 446nm and 469nm respectively, the colorless solution turns yellow or orange by illumination, the photoresponse is rapid, the saturated absorbance value reaches 25-35 s, the saturated optical density value is higher, the fading rate is fast, the fading half-life period is generally 3-6s, and it is worth pointing out that when the substituent on the benzene ring is-OCH3When the light irradiation was stopped, the fading rate of the corresponding photochromic compound Ic was very fast, and the solution rapidly changed from orange colorThe color is colorless, the fading half life is less than 1s, and the test range of the ultraviolet visible absorption spectrometer under the existing experimental condition is exceeded.
TABLE 1 Compounds Ia, Ib and Ic in toluene solution (8X 10)-5mol/L) photochromic properties
Note: [a] a photochromic optical density; [b] the fading rate is less than 1s and exceeds the testing range of the existing ultraviolet-visible spectrometer.
Example 7: fatigue resistance of compound Ib in solution
The Ib concentration is prepared to be 8 multiplied by 10-5Irradiating the toluene solution of mol/L for 30s by using a xenon lamp Xe-150 to reach the maximum absorbance value, then placing the solution in the dark for 2min for fading, and respectively measuring the absorbance values when the solution reaches the maximum absorbance value and after the solution fades for 2 min. The test was repeated 20 times to obtain a color change cycle graph (FIG. 2). As can be seen from FIG. 2, after 20 cycles, the maximum absorbance had almost no change, indicating that Ib has good fatigue resistance.
The above description is made in detail for the preferred embodiments of the present invention, but the above description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A silicon fused ring naphthopyran photochromic compound having the structural formula shown in formula I:
in the formula R1And R2Identical or different, each independently of the others represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, phenyl or substituted phenyl or halogen, R3Represents a straight or branched alkyl group having 1 to 6 carbon atoms.
2. A silicon fused ring naphthopyran photochromic compound having the structural formula shown in formula I:
in the formula R1And R2Identical or different, each independently represents hydrogen, alkyl or alkoxy having 1 to 3 carbon atoms, phenyl or substituted phenyl, R3Represents a straight or branched alkyl group having 1 to 3 carbon atoms.
3. A silicon fused ring naphthopyran photochromic compound having the structural formula shown in formula I:
in the formula R1And R2The same or different, each independently represent hydrogen, bromine, methyl, methoxy, phenyl, R3Represents a methyl group.
4. A process for the preparation of photochromic compounds according to claims 1 to 3, characterized in that: the method comprises the following steps:
step 1: 1-bromo-3-naphthol and tert-butyldiphenylchlorosilane are reacted under an alkaline condition to form a compound 1, wherein the reaction formula is as follows:
step 2: carrying out Suzuki coupling reaction on the compound 1 and 2-bromobenzoic acid under the catalysis of palladium to obtain a compound 2, wherein the reaction formula is as follows:
and 3, step 3: the compound 2 and dialkyl chlorosilane generate a compound 3 under the alkaline condition, and the reaction formula is as follows:
and 4, step 4: the compound 3 is cyclized under the catalysis of triphenylphosphine rhodium chloride to obtain a compound 4, and the reaction formula is as follows:
and 5, step 5: the compound 4 reacts under the catalysis of Lewis acid to obtain an intermediate compound 5, and the reaction formula is as follows:
and 6, step 6: the compound 5 and 1,1- (diaryl) -2-propyne-1-alcohol generate photochromic compound I under the catalysis of organic acid, and the reaction formula is as follows:
5. the method of preparing a silicon fused ring naphthopyran photochromic compound of claim 4 wherein:
in the reaction in the step 1, imidazole is used as an alkali, 1, 4-dioxane or N, N-dimethylformamide is used as a reaction solvent, the reaction temperature is 25-30 ℃, the reaction time is 10-18h, and the molar ratio of 1-bromo-3-naphthol to tert-butyldiphenylchlorosilane is 1 (0.8-1.0);
in the reaction in the step 2, the carbonate used is cesium carbonate, potassium carbonate or sodium carbonate; the palladium catalyst used in the reaction is palladium tetrakis (triphenyl) phosphine, palladium acetate or palladium dichloride; the reaction solvent is 1, 4-dioxane and water; the reaction temperature is 80-100 ℃, the reaction time is 18-24h, and the molar ratio of the compound 1 to the 2-bromobenzeneboronic acid is 1 (1.0-1.2);
in the reaction in the step 3, the used alkali is tert-butyl lithium or n-butyl lithium, the reaction solvent is tetrahydrofuran, the reaction temperature is-78-25 ℃, the reaction time is 6-10h, and the molar ratio of the compound 2 to the dialkylchlorosilane is 1 (1.2-1.5);
in the reaction in the step 4, the catalyst used is triphenylphosphine rhodium chloride, and the reaction solvent is 1, 4-dioxane, tetrahydrofuran or acetone. The reaction temperature is 80-115 ℃, the reaction time is 24-36h, and the molar ratio of the compound 3 to the triphenylphosphine rhodium chloride is 1 (0.03-0.05).
In the reaction in the step 5, the Lewis acid is diisobutylaluminum hydride, the reaction solvent is n-hexane, cyclohexane or a mixed solvent, the reaction temperature is 40-60 ℃, the reaction time is 6-8h, and the molar ratio of the compound 4 to the diisobutylaluminum hydride is 1 (2.6-3.4).
In the reaction of the step 6, the used organic acid is dodecyl benzene sulfonic acid, the reaction solvent is toluene or xylene, the reaction temperature is 40-50 ℃, and the reaction time is 3-6 h. Wherein the molar ratio of the compound 5 to the 1,1- (diaryl) -2-propyn-1-ol is 1 (1-1.3).
6. Use of the photochromic compounds according to claims 1 to 3 as photochromic materials in the field of sun protection glasses, glazing, decorative articles, clothing, paint inks or anti-counterfeiting materials.
7. An intermediate compound 5 for use in the preparation of silicon fused ring naphthopyran photochromic compounds having the formula:
wherein R is3Represents a straight or branched alkyl group having 1 to 6 carbon atoms.
8. The process of claim 7 for preparing intermediate compound 5 for preparing a silicon fused ring naphthopyran photochromic compound, wherein: comprises the following steps:
step 1: 1-bromo-3-naphthol and tert-butyldiphenylchlorosilane are reacted under an alkaline condition to form a compound 1, wherein the reaction formula is as follows:
step 2: carrying out Suzuki coupling reaction on the compound 1 and 2-bromobenzoic acid under the catalysis of palladium to obtain a compound 2, wherein the reaction formula is as follows:
and 3, step 3: the compound 2 and dialkyl chlorosilane generate a compound 3 under the alkaline condition, and the reaction formula is as follows:
and 4, step 4: the compound 3 is cyclized under the catalysis of triphenylphosphine rhodium chloride to obtain a compound 4, and the reaction formula is as follows:
and 5, step 5: the compound 4 reacts under the catalysis of Lewis acid to obtain an intermediate compound 5, and the reaction formula is as follows:
9. use of the intermediate of claim 7 for the preparation of photochromic compounds.
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| CN116987109A (en) * | 2023-08-03 | 2023-11-03 | 南开大学 | Preparation method and application of boron cluster naphthopyran photochromic compound |
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