CN113135883B - Metho[1,2,f]pyran photochromic compound and its preparation method and application - Google Patents
Metho[1,2,f]pyran photochromic compound and its preparation method and application Download PDFInfo
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- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 7
- 125000003386 piperidinyl group Chemical group 0.000 claims abstract description 5
- 125000002757 morpholinyl group Chemical group 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- -1 CF 3 Inorganic materials 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003377 acid catalyst Substances 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 4
- 238000010898 silica gel chromatography Methods 0.000 claims description 4
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000000976 ink Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 150000004880 oxines Chemical class 0.000 abstract description 19
- 238000005562 fading Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003921 oil Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 7
- 238000012544 monitoring process Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- UUNIOFWUJYBVGQ-UHFFFAOYSA-N 2-amino-4-(3,4-dimethoxyphenyl)-10-fluoro-4,5,6,7-tetrahydrobenzo[1,2]cyclohepta[6,7-d]pyran-3-carbonitrile Chemical compound C1=C(OC)C(OC)=CC=C1C1C(C#N)=C(N)OC2=C1CCCC1=CC=C(F)C=C12 UUNIOFWUJYBVGQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009471 action 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011981 development test Methods 0.000 description 1
- 150000001988 diarylethenes Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 235000010228 ethyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004403 ethyl p-hydroxybenzoate Substances 0.000 description 1
- 229940043351 ethyl-p-hydroxybenzoate Drugs 0.000 description 1
- NUVBSKCKDOMJSU-UHFFFAOYSA-N ethylparaben Chemical compound CCOC(=O)C1=CC=C(O)C=C1 NUVBSKCKDOMJSU-UHFFFAOYSA-N 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 108020001756 ligand binding domains Proteins 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004292 methyl p-hydroxybenzoate Substances 0.000 description 1
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000010232 propyl p-hydroxybenzoate Nutrition 0.000 description 1
- 239000004405 propyl p-hydroxybenzoate Substances 0.000 description 1
- QELSKZZBTMNZEB-UHFFFAOYSA-N propylparaben Chemical compound CCCOC(=O)C1=CC=C(O)C=C1 QELSKZZBTMNZEB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- 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
- C07D311/78—Ring systems having three or more relevant rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
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- 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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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/0009—Materials therefor
- G02F1/0063—Optical properties, e.g. absorption, reflection or birefringence
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
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Abstract
The invention discloses a
And [1,2, f ]]Pyran photochromic compounds, and preparation methods and applications thereof. In particular to a compound with a structure shown as a formula I
And [1,2, f ]]Pyran compounds in which R 1 ，R 2 Each independently selected from CH 3 O，CH 3 CH 2 O，CH 3 CH 2 CH 2 O，CH 3 ，CH 3 CH 2 ，CH 3 CH 2 CH 2 ，(CH 3 ) 2 N，(CH 3 CH 2 ) 2 N，H，F，Cl，Br，I，CF 3 ，NO 2 Ph, piperidinyl, morpholinyl. The compounds can pass through 6-
Phenol and alkynol compounds. The
And [1,2, f ]]The pyran photochromic compound can be applied to the fields of photochromic glasses, intelligent windows, photochromic clothes and the like, and has the advantages of quick photoresponse, quick fading, excellent fatigue resistance and the like.
Description
The technical field is as follows:
the invention relates to the field of organic optical functional materials, in particular to a novel material
And [1,2, f ]]Pyran photochromic compound and preparation method and application thereof.
The background art comprises the following steps:
the photochromic phenomenon is a phenomenon in which a structure of a compound is changed by irradiation with light having a certain intensity wavelength to form a new compound. Under the action of light or heat with another wavelength, it can be restored to its original state. The ultraviolet absorption spectra of the two isomers are obviously different and are apparent as color changes. In addition, physical parameters of the compound such as dielectric constant, refractive index, oxidation-reduction potential, fluorescence property, etc. are also changed. Currently, developed organic photochromic materials mainly include azobenzene, diarylethene, spirooxazine, naphthopyran and the like, wherein the naphthopyran photochromic materials have the advantages of easy synthesis, high chromaticity, fast color change and the like, and are widely applied to the fields of color-changing glasses, molecular switches, imaging equipment, intelligent windows and the like.
The currently reported organic photochromic materials, especially naphthopyran compounds, still suffer from disadvantages in use, mainly manifested by insufficient fading rate and insufficient fatigue resistance to meet application requirements, and especially the fading rate is always a bottleneck problem to be solved by the materials. Designing and synthesizing novel organic photochromic compounds, improving the fading rate of materials and improving the excellent fatigue resistance is a challenging problem in the field.
For this reason, the invention is easy to synthesize
Aromatic ring as skeleton for synthesizing>
And [1,2, f ]]Pyran compounds, a novel class of photochromic compounds, relative to naphthoPyran compounds, based on the presence of a ligand or a ligand binding domain>
The aromatic ring has larger conjugation degree, can improve the fading rate and is also beneficial to improving the fatigue resistance.
Disclosure of Invention
An object of the present invention is to provide a compound which is quick in photoresponse, quick in discoloration and excellent in fatigue resistance
And [1,2, f ]]A pyran photochromic compound.
It is another object of the present invention to provide a process for preparing the above
And [1,2, f ]]A pyran photochromic compound.
It is another object of the present invention to provide the above
And [1,2, f ]]Application of pyran photochromic compound is disclosed.
The technical scheme adopted by the invention for solving the technical problem is as follows:
has a structure shown in formula I:
wherein R is 1 ，R 2 Each independently selected from CH 3 O，CH 3 CH 2 O，CH 3 CH 2 CH 2 O，CH 3 ，CH 3 CH 2 ，CH 3 CH 2 CH 2 ，(CH 3 ) 2 N，(CH 3 CH 2 ) 2 N，H，F，Cl，Br，I，CF 3 ，NO 2 Ph, piperidinyl, morpholinyl.
Preferably, R 1 ，R 2 Each independently selected from CH 3 O，CH 3 ，(CH 3 ) 2 N，H，F，Cl，Br，I，CF 3 ，NO 2 Ph, piperazine
A pyridyl group.
Further preferably, R 1 ，R 2 Each independently selected from CH 3 O，CH 3 ，H，F，Cl，Br，CF 3 And Ph.
More preferably, R 1 ，R 2 Each independently selected from CH 3 O，CH 3 ，H，F，Cl，CF 3 And Ph.
Most preferably, selected from the following compounds:
of the structure of formula I
And [1,2, f ]]The pyran photochromic compound can be prepared by the following method:
wherein, the compound 1 and the compound 2 are dissolved in an aprotic organic solvent, react in the presence of an acid catalyst, and are extracted, washed, dried and decompressed and concentrated to obtain a crude product, the crude product is subjected to silica gel column chromatography to prepare the compound I, R is R 1 And R 2 Each independently selected from CH 3 O，CH 3 CH 2 O，CH 3 CH 2 CH 2 O，CH 3 ，CH 3 CH 2 ，CH 3 CH 2 CH 2 ，(CH 3 ) 2 N，(CH 3 CH 2 ) 2 N，H，F，Cl，Br，I，CF 3 ，NO 2 Ph, piperidinyl, morpholinyl.
The aprotic organic solvent is selected from the group consisting of toluene, benzene, dimethyl sulfoxide, acetone, tetrahydrofuran and acetonitrile. The acid catalyst is selected from dodecyl benzene sulfonic acid, dodecyl sulfuric acid and dodecyl sulfonic acid.
Preferably, the molar ratio of compound 1 to compound 2 is from 1:1 to 1:1.5, with a molar ratio of 1: 1.2 being more preferred.
Preferably, the reaction temperature is 20 to 60 ℃ and the reaction time is 2 to 5 hours, wherein the reaction temperature is more preferably 40 ℃ and the reaction time is 3 hours.
Preferably, the detergent for silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 10-100: 1.
The compound shown in the formula I can be widely applied to the fields of photochromic glasses, photochromic glass, photochromic decorative articles, photochromic clothes, photochromic paint ink, anti-counterfeiting materials and the like as a photochromic material. Especially has better application prospect in the field of color-changing glasses, color-changing glass and color-changing clothes. The product can be added with photochromic material in the preparation process so as to obtain photochromic performance.
The invention has the advantages that: the invention has a structure of formula I
And [1,2, f ]]The pyran compound as a novel photochromic material has the characteristics of quick photoresponse color change, quick color fading, excellent fatigue resistance and the like.
Drawings
FIG. 1 is
And [1,2, f ]]Ultraviolet absorption spectra in the ring-off states of pyran compounds Ia, ib, ic, id, ie and If.
FIG. 2 shows the ultraviolet light (365nm, 260mW) irradiation
And [1,2, f ]]Transient absorption spectra of pyran compounds Ia, ib, ic, id, ie and If.
FIG. 3 shows UV light (365nm, 260mW)
And [1,2, f ]]Pyran compounds Ia, ib, ic, id, ie and If at the wavelength of maximum absorption (. Lamda.) max ) Time-dependent photochromic curve of (a).
FIG. 4 is
And [1,2, f ]]Pyran compounds Ia, ib, ic, id, ie and If at the wavelength of maximum absorption (. Lamda.) max ) The fading curve of (c).
FIG. 5 is
And [1,2, f ]]Photochromic cycle profile of pyran compound Ie (uv light for 20s, dark for 20 s).
FIG. 6 is a photochromic cycling curve (UV 20s, photophobic 20 s) for the naphthopyran molecule Da.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification. In the present invention, unless otherwise specified, the drugs and reagents used are commercially available or known in the art.
Example 1, 13-Diphenyl-13H-
And [1,2-f ]]Preparation of pyrane (Ia)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2a (0.31g, 1.5mmol), dissolved in benzene (20 mL), then dodecylbenzene sulfonic acid (1-2 drops) was added dropwise, stirred at 40 ℃ for 3h,and monitoring by TLC. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 100: 1), obtain red solid Ia,179mg,33% yield of yield. M.p.208.8-210.4 ℃.
1 H NMR(400MHz，CDCl 3 )δ8.56(m，1H)，8.50(m，1H)，8.39(m，2H)，7.84-7.76(m，1H)，7.67(d，J＝8.9Hz，1H)，7.64-7.51(m，6H)，7.51-7.42(m，2H)，7.39(d，J＝9.4Hz，1H)，7.21(m，4H)，7.15-7.07(m，2H)，6.09(d，J＝9.5Hz，1H).
13 C NMR(101MHz，CDCl 3 )δ148.46，144.83，133.48，131.49，130.79，129.81，128.66，128.43，128.26，128.25，128.20，127.65，127.64，127.46，127.08，126.94，126.66，126.06，125.43，125.20，124.96，124.50，123.68，123.15，122.96，120.99，113.64，82.34.
Example 2 13-phenyl-13-biphenyl-13H-
And [1,2-f ]]Preparation of pyran (Ib)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2b (0.36g, 1.25mmol), was dissolved in toluene (20 mL), dodecylsulfuric acid (1-2 drops) was added dropwise, stirred at 20 ℃ for 5h, monitored by TLC. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 10: 1) to yield a red solid Ib,178mg,28% yield y field. M.p.219.9-221.4 ℃.
1 H NMR(400MHz，CDCl 3 )δ8.53(m，2H)，8.41(d，J＝9.0Hz，1H)，8.35(d，J＝8.1Hz，1H)，7.86-7.76(m，1H)，7.71(m，3H)，7.63-7.43(m，9H)，7.39(t，J＝9.3Hz，1H)，7.23(t，J＝7.6Hz，1H)，7.13(m，1H)，7.11(s，1H)，6.05(d，J＝9.4Hz，1H).
13 C NMR(101MHz，CDCl 3 )δ148.83，148.20，143.98，133.52，131.59，129.98，129.74，129.66，128.40，128.34，128.08，128.00，127.84，127.64，127.29，127.20，126.79，126.15，125.68，125.47，125.32，125.29，125.25，125.21，125.18，124.75，124.67，123.23，122.77，120.95，113.60，81.94.
Example 3-phenyl-13-p-trifluoromethylphenyl-13H-
And [1,2-f ]]Preparation of pyran (Ic)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2c (0.52g, 1.88mmol), was dissolved in tetrahydrofuran (20 mL), followed by dropwise addition of sodium dodecylsulfonate (1-2 drops), stirring at 30 ℃ for 4h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 80: 1) to give a dark red solid Ic,119mg,19% yield y field. M.p.185.9-187.6 ℃.
1 H NMR(400MHz，CDCl 3 )δ8.67-8.57(m，1H)，8.50(d，J＝9.0Hz，1H)，8.45(d，J＝8.2Hz，0H)，7.87(d，J＝7.4Hz，1H)，7.77(d，J＝8.9Hz，1H)，7.65(dt，J＝9.8，6.7Hz，3H)，7.55-7.50(m，1H)，7.49-7.42(m，3H)，7.32-7.25(m，2H)，7.20-7.16(m，1H)，6.17(d，J＝9.4Hz，0H).
13 C NMR(101MHz，CDCl 3 )δ148.45，144.72，143.77，140.68，140.46，133.49，131.49，129.80，128.69，128.22，128.19，127.64，127.45，127.34，127.27，127.09，126.90，126.88，126.64，126.04，125.42，125.18，124.94，124.50，123.56，123.12，122.94，120.96，113.62，82.25.
Example 4, 13-bis (4-fluorophenyl) -13H-
And [1,2-f ]]Preparation of pyrans (Id)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2d (0.43g, 1.75mmol), dissolved in acetone (20 mL), was added dropwise with dodecylsulfuric acid (1-2 drops), stirred at 50 ℃ for 5h, monitored by TLC. TLC monitored reaction completion, the reaction was extracted with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 30: 1), to yield a red solid Id,106mg,18% yield, m.p.197.4-198.6 ℃.
1 H NMR(400MHz，CDCl 3 )δ8.74-8.65(m，1H)，8.65(m，2H)，8.52-8.41(m，1H)，8.01-7.93(m，1H)，7.87(d，J＝9.0Hz，1H)，7.79-7.56(m，8H)，7.56-7.48(m，1H)，7.09-6.96(m，4H)，6.21-6.07(m，1H).
13 C NMR(101MHz，CDCl 3 )δ163.48，161.03，148.09，140.33，133.51，129.74，128.71，128.63，128.32，128.03，127.78，127.33，127.29，126.73，126.12，125.62，125.27，124.74，124.61，123.20，123.11，122.72，120.95，115.21，114.99，113.45，81.61.
Example 5, 13-bis-p-methylphenyl-13H-
And [1,2-f ]]Preparation of pyran (Ie)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2e (0.33g, 1.38mmol) were dissolved in dimethyl sulfoxide (20 mL), followed by dropwise addition of dodecylsulfonic acid (1-2 drops), stirring at 30 ℃ for 2h, and TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 60: 1) to give Ie as a pale red solid, 138mg,24% yield, p.225.3-226.8 ℃.
1 H NMR(400MHz，CDCl 3 )δ8.55(m，1H)，8.43(m，1H)，7.83(d，J＝7.3Hz，1H)，7.71(d，J＝8.9Hz，1H)，7.63-7.55(m，2H)，7.48(d，J＝8.0Hz，5H)，7.39(d，J＝9.4Hz，1H)，7.17-7.09(m，1H)，7.03(d，J＝7.9Hz，4H)，6.08(d，J＝9.4Hz，1H)，2.18(s，6H).
13 C NMR(101MHz，CDCl 3 )δ148.52，142.02，137.19，133.49，131.44，130.73，129.84，128.82，128.27，128.20，127.51，126.86，126.79，126.55，125.98，125.29，125.10，125.02，124.41，123.96，123.07，122.98，120.98，113.62，82.26，21.07.
Example 6, 13-bis-p-methoxyphenyl-13H-
And [1,2-f ]]Preparation of pyran (If)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2f (0.43g, 1.63mmol) were dissolved in dichloromethane (20 mL), followed by dropwise addition of dodecylbenzenesulfonic acid (1-2 drops), stirring at 20 ℃ for 3h, TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 30: 1) to give a purple-red solid If,154mg,25% yield (yield) 2. M.p.237.1-238.3 ℃.
1 H NMR(400MHz，CDCl 3 )δ8.52-8.41(m，2H)，8.38(m，2H)，7.78(d，J＝7.8Hz，1H)，7.65(d，J＝8.9Hz，1H)，7.55-7.49(m，2H)，7.49-7.42(m，5H)，7.38-7.30(m，1H)，7.08(s，1H)，6.70(d，J＝8.8Hz，4H)，6.00(d，J＝9.4Hz，1H)，3.57(s，3H).
13 C NMR(101MHz，CDCl 3 )δ159.01，148.46，137.11，133.52，132.30，132.23，131.46，130.32，129.85，128.30，128.26，127.56，127.48，126.75，126.59，126.03，125.35，125.14，125.01，124.43，124.07，123.13，122.96，122.76，121.02，113.58，113.49，82.07，55.22.
Example 7 testing of photochromic Properties of Compounds Ia, ib, ic, id, ie and If
Selecting ethyl acetate as ultraviolet testing solvent, 1 × 10 -4 mol/L is the test concentration. Based on the above standard conditions, UV absorption spectra of Ia, ib, ic, id, ie and If before light irradiation were tested, as shown in FIG. 1.
Transient absorption spectra after 30s irradiation of Ia, ib, ic, id, ie and If were measured under UV light (365nm, 260mW) as shown in FIG. 2. As can be seen from the figure, ia, ib, ic, id, ie and If give rise to new absorption peaks at 460nm after illumination.
Under the irradiation of ultraviolet light (365nm, 260mW),
and [1,2, f ]]The time required for the color of the pyran compounds Ia, ib, ic, id, ie and If to reach saturation is shown in FIG. 3. As can be seen, ia, ib, ic, id, ie and If are all relatively saturated at the wavelength of maximum absorption at about 30s or so under continuous UV lamp illumination. In respect of the rate of change of color, compared with the other->
And [1,2, f ]]The pyran compound, if, has the obvious advantage of reaching saturation in 10 seconds. />
Example 8 test of the fading Properties of Compounds Ia, ib, ic, id, ie and If
The thermal fading curves of Ia, ib, ic, id, ie and If after 30s UV irradiation (365nm, 260mW) were tested, as shown in FIG. 4,
and [1,2, f ]]The absorbance of the pyran compound is decreased from the maximum value to a steady state within a period of 30 to 96 seconds, wherein the residual color of Ia and If is the lowest and the fading property is good.
Example 9 fatigue resistance study of Compound Ie
Taking Ie as an example, dissolving it in an organic solvent at a certain concentration, and testing the absorbance of the solution after the solution develops color after being irradiated by ultraviolet light for 20s and the absorbance of the solution after the solution becomes lighter after being shielded from light for 20 s. The fatigue resistance curve was developed after 10 cycles of the test, as shown in fig. 5. The compound is found to have excellent fatigue resistance, and the peak value of the absorbance is hardly changed under the condition of 10-cycle color development test.
For comparison, the naphthopyran molecules Da were measured in the same manner and tested 10 times in cycles to develop a fatigue resistance curve, as shown in FIG. 6. The curve shows that the absorbance peak value of the Da molecule is gradually reduced along with the increase of the color development times, which shows that the color development depth of the Da molecule is continuously reduced along with the increase of the measurement times. Comparing fig. 5, fig. 6, it is evident that the chromaticity of Ie is much higher than Da, thus demonstrating that: with respect to the naphthopyran compounds,
the aromatic ring has a larger conjugation degree, and contributes to improvement of fatigue resistance of color development.
Example 10-phenyl-13-p-nitrophenyl-13H-
And [1,2-f ]]Preparation of pyrans (Ig)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2g (0.38g, 1.5 mmol), dissolved in chloroform (20 mL), followed by dropwise addition of sodium dodecylbenzenesulfonate (1-2 drops), stirring at 40 ℃ for 3h, and monitoring by TLC. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 50: 1), to obtain a red oily substance Ig, and then, 144mg,24% yield by yield in MS (m/z, ESI +): 480.2[ deg. ] M + H]+。
Examples11 13, 13-bis-p-dimethylaminophenyl-13H- 
And [1,2-f ]]Preparation of pyran (Ih) />
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2h (0.44g, 1.5mmol), dissolved in acetonitrile (20 mL), followed by dropwise addition of sodium dodecylbenzenesulfonate (1-2 drops), stirring at 30 ℃ for 3h, TLC monitoring. TLC monitored reaction completion, extracted reaction with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 90: 1), obtaining a red oily substance Ih,202mg,31% yield in yield. MS (m/z, ESI +): 521.7[ 2 ] M + H]+。
Example 12-phenyl-13-p-chlorophenyl-13H-
And [1,2-f ]]Preparation of pyran (Ii)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2i (0.36g, 1.5 mmol), was dissolved in toluene (20 mL), followed by dropwise addition of sodium dodecylsulfonate (1-2 drops), stirring at 60 ℃ for 3h, and TLC monitoring. TLC was monitored for completion of the reaction, and the reaction system was extracted with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), and dried over anhydrous magnesium sulfateFiltering and vacuum concentrating. The crude product was further purified by column chromatography (PE: EA = 90: 1) to give a red oil Ii,105mg,18% yield in ms (m/z, ESI +): 469.1[ 2 ] M + H] + 。
Example 13, 13-bis-p-bromophenyl-13H-
And [1,2-f ]]Preparation of pyran (Ij)
Sequentially adding 6-
Phenol (0.31g, 1.25mmol), alkynol 2j (0.55g, 1.5mmol), was dissolved in benzene (20 mL), sodium dodecyl sulfate (1-2 drops) was added dropwise, stirred at 60 ℃ for 3h, monitored by TLC. TLC monitored reaction completion, the reaction was extracted with ethyl acetate (3X 20 mL), washed with saturated brine (30 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. The crude product was further purified by column chromatography (PE: EA = 60: 1) to yield a red oil Ij,111mg,5% yield by yield in ms (m/z, ESI +): 593.0[ M ] +H] + 。
Example 14-phenyl-13-p-iodophenyl-13H- 
And [1,2-f ]]Preparation of pyrans (Ik) />
With reference to the procedure of example 1, a red oil Ik was prepared, 63mg,9% yield in yield. MS (m/z, ESI +): 561.1[ 2 ] M + H] + 。
Example 15-phenyl-13-p-diethylaminophenyl-13H-
And [1,2-f ]]Preparation of pyran (Il)
<xnotran> 2 , Il,177mg,28%yield.MS (m/z, ESI +): </xnotran> 506.3[ m ] +H] + 。
Example 16-phenyl-13-p-ethylphenyl-13H-
And [1,2-f ]]Preparation of pyran (Im)
Referring to the procedure of example 3, a red oil Im was prepared, 116mg,20% yield of yield. MS (m/z, ESI +): 463.2[ 2 ] M + H] + 。
Example 17-phenyl-13-n-propoxyphenyl-13H-
And [1,2-f ]]Preparation of pyran (In)
Referring to the procedure of example 4, a red oil In was prepared, 92mg,15% yield In. 493.2[ M ] C + H] + 。
Example 18-p-methylphenyl-13-p-nitrophenyl-13H-
And [1,2-f ]]Preparation of pyran (Io)
Referring to the procedure of example 5, io was prepared as a red oil, 136mg,22% yield in yield. MS (m/z, ESI +): 494.2[ M ] +H] + 。
Example 19-p-Biphenyl-13-p-trifluoromethylphenyl-13H-
And [1,2-f ]]Preparation of pyrans (Ip)
Referring to the procedure of example 6, a red oil Ip was prepared, 130mg,18% yield in yield. MS (m/z, ESI +): 579.2[ 2 ] M + H] + 。
Example 20-p-methoxy-phenyl-13-p-ethylphenyl-13H-
And [1,2-f ]]Preparation of pyran (Iq)
With reference to the procedure of example 10, iq was prepared as a red oil, 154mg,25% yield of yield. MS (m/z, ESI +): 493.2[ M ] C + H] + 。
Example 21-p-methoxy-13-p-dimethylaminophenyl-13H-
And [1,2-f ]]Preparation of pyran (Ir)
With reference to the procedure of example 11, ir was prepared as a red oil, 114mg,18% yield in yield. MS (m/z, ESI +): 508.2[ 2 ] M + H] + 。
Example 22-p-chlorophenyl-13-p-trifluoromethylphenyl-13H-
And [1,2-f ]]Preparation of pyrans (Is)
Referring to the procedure of example 12, a red oil Is was prepared, 134mg,20% yield in yield. MS (m/z, ESI +): 537.1[ M ] +H] + 。
Example 23, 13-Biphenyl-13H-
And [1,2-f ]]Preparation of pyran (It)
Referring to the procedure of example 13, it was prepared as a red oil It,220mg,30% yield in yield. MS (m/z, ESI +): 587.2[ M ] +H] + 。
Example 24-phenyl-13-p-piperidinylphenyl-13H-
And [1,2-f ]]Preparation of pyrans (Iu)
Referring to the procedure of example 1, a red oil Iu was prepared, 162mg,25% yield in blue. MS (m/z, ESI +): 518.3[ M ] +H] + 。
Example 25-phenyl-13-p-morpholinophenyl-13H- 
And [1,2-f ]]Preparation of pyran (Iv) />
With reference to the procedure of example 1, a red oil Iv was prepared, 123mg,19%, yield, MS (m/z, ESI +): 520.2[ M ] +H] + 。
Example 26 contains 13, 13-bis-p-methylphenyl-13H-
And [1,2-f ]]Preparation of pyran (Ie) color-changing spectacle lens
Is provided with
Taking one kilogram of the color changing spectacle lens resin as an example, 1 gram of 13, 13-bis-p-methylphenyl-13H-
And [1,2-f ]]Pyran (Ie) and (fluorine silicon) acrylate 50-55%, styrene 35-40%, cross-linking agent 10%, initiator 1-2 g and light stabilizer 5-10 g are mixed uniformly, then injected into mould, heated and polymerized for 24 hours at 95-100 deg.C, until the resin is hardened, so that the spectacle lens can be made. And soaking the lens in deionized water to obtain the photochromic contact lens.
Example 27 containing 13, 13-bis-p-methoxyphenyl-13H-
And [1,2-f ]]Pyran (If) color-changing raincoat plastic
Preparation of
15g of stearic acid, 1g of glyceryl monostearate, 0.5g of hexadecanol and 6g of glycerol are uniformly mixed and heated to 90 ℃, and then 13, 13-di-p-methoxyphenyl-13H-
And [1,2-f ]]0.1g of the pyran (If) photochromic compound was stirred for 5 hours to allow the color-changing dye to be completely dissolved in the mixture. Adding 80g of distilled water at the temperature of 80-90 ℃, accelerating stirring until complete emulsification is achieved, reducing the temperature to 40-45, adding 0.1g of mixture of methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate and propyl p-hydroxybenzoate, uniformly mixing, and cooling to room temperature. And preparing the photochromic plastic. The plastic can be used for preparing photochromic raincoats.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications derived from the technical solutions of the present invention are within the scope of the present invention.
Claims (9)
1. A\17627 [1,2, f ] pyran photochromic compound is characterized by having a structure shown in a formula I:
wherein R is 1 , R 2 Each independently selected from CH 3 O, CH 3 CH 2 O, CH 3 CH 2 CH 2 O, CH 3 , CH 3 CH 2 , CH 3 CH 2 CH 2 , (CH 3 ) 2 N, (CH 3 CH 2 ) 2 N, H, F, Cl, Br, I, CF 3 , NO 2 Ph, piperidinyl, morpholinyl.
2. 3, 17627]A pyran photochromic compound characterized in that R 1 , R 2 Each independently selected from CH 3 O, CH 3 , (CH 3 ) 2 N, H, F, Cl, Br, I, CF 3 , NO 2 Ph, piperidinyl.
3. The 17627]A pyran photochromic compound characterized in that R 1 , R 2 Each independently selected from CH 3 O, CH 3 , H, F, Cl, Br, CF 3 And Ph.
4. The\17627o [1,2, f ] pyran photochromic compound of claim 3 selected from:
5. the method of making the\17627and [1,2, f ] pyran photochromic compound of any one of claims 1-4, characterized by comprising the steps of:
dissolving a compound 1 and a compound 2 in an aprotic organic solvent, reacting in the presence of an acid catalyst, extracting, washing, drying, and concentrating under reduced pressure to obtain a crude product, and performing silica gel column chromatography on the crude product to obtain a compound I; the aprotic organic solvent is selected from one or more of toluene, benzene, dimethyl sulfoxide, acetone, tetrahydrofuran and acetonitrile; the acid catalyst is selected from one or more of dodecyl benzene sulfonic acid, dodecyl sulfuric acid and dodecyl sulfonic acid.
6. The preparation method according to claim 5, wherein the molar ratio of the compound 1 to the compound 2 is 1 to 1.5.
7. The preparation method according to claim 5, wherein the reaction temperature is 20 to 60 ℃ and the reaction time is 2 to 5 hours.
8. The preparation method of the compound of claim 5, wherein the detergent for silica gel column chromatography is a mixed solution of petroleum ether and ethyl acetate =10 to 100 by volume ratio.
9. The use of the\17627 [1,2, f ] pyran photochromic compound according to any one of claims 1 to 4 in the preparation of photochromic glasses, photochromic decorative articles, photochromic garments, photochromic paint inks and anti-counterfeiting materials.
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