CN114031594B - Dibenzo chromene compound and application thereof - Google Patents
Dibenzo chromene compound and application thereof Download PDFInfo
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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
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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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Abstract
A dibenzochromene compound and application thereof are provided, wherein the structure of the compound is shown as formula I:
r1, R2, R5, R6 are each selected from hydrogen, methyl, methoxy, methylthio, aryl, halogen, CN, NO 2 、CF 3 Or CF (CF) 2 H is formed; r3, R4, R7, R8 are each selected from hydrogen, methyl, methoxy, methylthio, halogen, CN, NO 2 、CF 3 Or CF (CF) 2 H, and at least one of R3, R4, R7 and R8 is an electron withdrawing group; l is aryl. The compound has high color development sensitivity, excellent durability and extremely short fading half-life. Can be used as memory material, light adjusting material, photochromic lens material, optical filter material, display material, optical information device, optical switch element, photoresist material, light meter or decorative material.
Description
Technical Field
The invention relates to the field of photochromic materials, and provides a dibenzochromene photochromic compound.
Background
Photochromic is a phenomenon in which when light including ultraviolet rays is irradiated to some compounds, the color changes rapidly, and when the light is stopped from being irradiated and placed in a dark place, the original color is restored. The compound with the property is called a photochromic compound, and the photochromic material has wide application prospect in the fields of photochromic glasses, optical information storage, molecular switches, defending and identifying technologies and the like, and is one of research hot spots in the fields of chemistry and material science.
Naphthopyrans are known to be photochromic compounds that are capable of changing color under the influence of polychromatic or monochromatic light, such as UV light. When the irradiation is stopped, or under the influence of temperature and/or polychromatic or monochromatic light different from the initial light, the compound returns to its initial color. Naphthopyrans find application in various fields, for example in the manufacture of ophthalmic lenses, contact lenses, sunglasses, filters, optical cameras or other optical devices, as well as viewing devices, glazing and decorative objects. The 2H-chromene has in some cases a neutral gray or brown colour after UV irradiation, which is of particular interest when used in a dichroic mirror, since it does not require the use of dye mixtures of different colours to obtain the desired hue. In fact, dyes of different colors may have different UV aging resistance characteristics, different fade kinetics or different thermal dependencies, resulting in a change in the hue of the lens during use. For example, for ophthalmic lenses, for visual comfort and safety reasons (e.g., when driving), it is highly desirable that photochromic articles decolorize rapidly in the absence of UV light.
Disclosure of Invention
In studying naphthopyrans, the present inventors have found that compounds have a short discoloration half-life when an electron-withdrawing group is introduced on the benzene ring of 2H naphtho [1,2-b ] pyran (benzochromene). And when two benzo chromene compounds are connected through an electron donating group, the fading half-life period can be obviously shortened, and the ageing resistance can be improved. The compounds have good development prospect.
The technical scheme of the invention is as follows:
a dibenzochromene compound has a structure shown in a formula (I):
r1, R2, R5, R6 are each selected from hydrogen, methyl, methoxy, methylthio, aryl, halogen, CN, NO 2 、CF 3 Or CF (CF) 2 H；
R3, R4, R7, R8 are each selected from hydrogen, methyl, methoxy, methylthio, halogen, CN, NO 2 、 CF 3 Or CF (CF) 2 H, and at least one of R3, R4, R7 and R8 is an electron withdrawing group;
l is aryl.
The dibenzochromene compound as described above, wherein L is phenyl, biphenyl or naphthyl.
The dibenzochromene compound as described above, wherein each of R3 and R7 is H, and each of R4 and R8 is F.
In another aspect, the present invention provides a photochromic composition comprising a dibenzochromene compound as described above.
In yet another aspect, the present invention provides a photochromic material comprising a dibenzochromene compound as described above incorporated into an organic material which is a polymeric material, an oligomeric material and/or a monomeric material.
In yet another aspect, the present invention provides the use of a dibenzochromene compound as described above as a photochromic material.
The dibenzochromene compounds of the present invention can be incorporated into a variety of polymer matrices for ultimate use in the preparation of a variety of different articles. In general, the polymer matrix in which the compound of formula I is incorporated or coated is colorless or slightly colored in its initial state, rapidly forming intense colors when exposed to UV light (365 nm) or under daylight-like light sources. The polymer matrix returns to its original color once irradiation is stopped. The compounds of formula I may be used alone or in combination with other photochromic materials. The use of two or more compounds of formula I for the preparation of articles is also contemplated.
Examples of polymers useful as photochromic materials in the present invention include, but are not limited to: alkyl, cycloalkyl, (poly or oligo) ethylene glycol, aryl or arylalkyl mono-, di-, tri-or tetra-acrylate or mono-, di-, tri-or tetramethyl acrylate, which may optionally be halogenated or comprise at least one ether and/or ester and/or carbonate and/or carbamate and/or thiocarbamate and/or urea and/or amide group, polystyrene, polyether, polyester, polycarbonate (e.g. bisphenol-a polycarbonate, diallyl diglycol polycarbonate), polyurethane, polyepoxide, polyurea, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl (vinyl) polymer, cellulose acetate, cellulose triacetate, cellulose acetate propionate or polyvinyl butyral. Homopolymers and copolymers derived from the above materials may also be used.
As a method for dispersing the compound of the formula I of the present invention in the polymer solid matrix, a general method can be used. Examples include: and a method of kneading the above thermoplastic resin with a photochromic compound in a molten state to disperse the photochromic compound into the resin. Alternatively, a method may be used in which a photochromic compound is dissolved in the polymerizable monomer, and then a polymerization catalyst is added thereto, and the photochromic compound is dispersed in a resin by polymerizing the mixture with heat or light. Further, a method of dispersing a photochromic compound into a resin by dyeing the photochromic compound on the surfaces of the thermoplastic resin and the thermosetting resin is mentioned.
The compounds of formula I according to the invention can be used as photochromic materials in a wide range and as memory materials, light-adjusting materials, photochromic lens materials, optical filter materials, display materials, optical information devices, optical switching elements, photoresist materials, light meters or decorative materials. The memory material may be a copying material, a photoreceptor for printing, a memory material for cathode-ray tube, a photosensitive material for laser, or a photosensitive material for hologram.
The term "alkyl" as used herein refers to a straight or branched chain monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-methyl-1-propyl, 2-butyl, 2-methyl-2-propyl, t-butyl, 1-hexyl, 2-ethylbutyl, and the like.
The term "cyclic alkyl" as used herein refers to cycloalkyl groups of 3 to 8 carbon atoms, but is not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl substituted cycloalkyl.
The term "aryl" as used herein by itself or as part of another substituent refers to a monovalent aromatic hydrocarbon radical derived from the removal of one hydrogen atom from a single carbon atom of the parent aromatic ring system. Aryl encompasses 5-and 6-membered carbocyclic aromatic rings, for example, benzene; bicyclic ring systems wherein at least one ring is carbocyclic and aromatic, e.g., naphthalene, indane, and tetrahydronaphthalene; and tricyclic ring systems, wherein at least one ring is carbocyclic and aromatic, e.g., fluorene. Aryl encompasses polycyclic ring systems having at least one carbocyclic aromatic ring fused to at least one carbocyclic aromatic ring, cycloalkyl ring, or heterocycloalkyl ring.
The term "halogen" as used in the present invention refers to fluorine, chlorine or bromine.
The compounds of formula I of the present invention may be prepared by the following method:
the reaction steps are as shown in formula 1, and the specific steps are as follows:
(1) Cyclizing the compound I-2 with the compound III-1 in the presence of camphoric acid to obtain a compound III-2;
(2) Cyclizing the compound I-6 with the compound III-5 in the presence of camphoric acid to obtain a compound III-6;
(3) Coupling the compounds III-2 and III-3 in the presence of pinacol diboronate, potassium carbonate and tetrakis (triphenylphosphine) palladium to give compound III-4;
(4) The compounds III-4 and III-6 are subjected to metal coupling reaction in the presence of pinacol diboronate, potassium carbonate and tetrakis (triphenylphosphine) palladium to obtain the compound I.
The invention has the beneficial effects that: the compounds of the general formula (I) according to the invention have a high color development sensitivity, excellent durability and an extremely short fade half-life. There are various uses of color-changing materials, for example, a memory material, a dimming material, a photochromic lens material, an optical filter material, a display material, an optical information device, an optical switching element, a photoresist material, a light meter, a decorative material, or the like.
Detailed Description
The following examples illustrate, but do not limit, the synthesis of compounds of formula (I). The temperatures are in degrees celsius. All the evaporation was carried out under reduced pressure, if not otherwise stated. Reagents were purchased from commercial suppliers and used without further purification, if not otherwise indicated. The structure of the end products, intermediates and starting materials is confirmed by standard analytical methods, such as elemental analysis, spectroscopic characterization, such as MS, NMR. Abbreviations used are conventional in the art.
Example 1: preparation of 1, 3-bis (10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ] chromen-5-yl) benzene
1. Preparation of intermediate A-14: 5-bromo-10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ] chromene
1, 1-bis (4-methoxyphenyl) prop-2-yn-1-ol A-3 (450 mg,1.68 mmol) was dissolved in toluene (10 mL), 1-hydroxy-3-bromo-8-fluoronaphthalene A-13 (480 mg,2.01 mmol) and camphorsulfonic acid (89 mg,0.5 mmol) were added, then stirred at 60℃for 2 hours, after completion of the reaction, concentrated, and the crude product was purified by silica gel column chromatography to give 5-bromo-10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ]]Chromene a-14 (120 mg, white solid), yield: 14%. ESI-MS m/z:491[ M+H ]] + 。
2. 5-bromo-10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ]]Chromene A-14 (200 mg,0.41 mmol) was dissolved in toluene (5 mL) and water (0.5 mL), 1, 3-bisphenyldiboronic acid pinacol ester (66 mg,0.2 mmol), potassium carbonate (85 mg,0.61 mmol) and tetrakis (triphenylphosphine) palladium (46 mg,0.04 mmol) were added sequentially and reacted under nitrogen atmosphere with heating to 80℃for 4 hours. After the reaction, cooling to room temperature, extracting with ethyl acetate, washing the organic phase with water, drying with anhydrous sodium sulfate, concentrating, purifying the crude product by silica gel column chromatography to obtain 1, 3-bis (10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ]]Chromen-5-yl) Benzene (30 mg, white solid), yield: 16%. ESI-MS m/z:899[ M+H ]] + 。
1 H-NMR(400MHz，DMSO-d 6 )：δ8.03-7.62(m，3H)，7.57-7.13(m，13H)， 6.91-6.71(m，12H)，6.56(d，J＝7.2Hz，2H)，6.40(d，J＝7.2Hz，2H)，3.51(s，12H).
Example 2:4,4' -bis (10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ] chromen-5-yl) biphenyl
5-bromo-10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ]]Chromene A-14 (200 mg,0.41 mmol) was dissolved in toluene (5 mL) and water (0.5 mL), and bis (pinacolato) (81 mg,0.2 mmol), potassium carbonate (85 mg,0.61 mmol) and tetrakis (triphenylphosphine) palladium (46 mg,0.04 mmol) were added sequentially and heated to 80℃under nitrogen to react for 4 hours. After the reaction, cooling to room temperature, extracting with ethyl acetate, washing the organic phase with water, drying with anhydrous sodium sulfate, concentrating, purifying the crude product by silica gel column chromatography to obtain 4,4' -bis (10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ]]Chromen-5-yl) biphenyl (42 mg, white solid), yield: 21%. ESI-MS m/z:975[ M+H ]] + 。
1 H-NMR(400MHz，DMSO-d 6 )：δ8.08-7.60(m，3H)，7.58-7.11(m，17H)， 6.94-6.72(m，12H)，6.52(d，J＝7.2Hz，2H)，6.41(d，J＝7.2Hz，2H)，3.52(s，12H).
Example 3:2, 7-bis (10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ] chromen-5-yl) naphthalene
5-bromo-10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ]]Chromene A-14 (200 mg,0.41 mmol) was dissolved in toluene (5 mL) and water (0.5 mL) and 2, 7-bis (4, 5-tetramethyl-1, 3, 2-dioxa was added sequentiallyCyclopentaborane-2-yl) naphthalene (76 mg,0.2 mmol), potassium carbonate (85 mg,0.61 mmol) and tetrakis (triphenylphosphine) palladium (46 mg,0.04 mmol) were reacted under nitrogen, heated to 80℃for 4 hours. After the reaction, cooling to room temperature, extracting with ethyl acetate, washing the organic phase with water, drying with anhydrous sodium sulfate, concentrating, purifying the crude product by silica gel column chromatography to obtain 2, 7-bis (10-fluoro-2, 2-bis (4-methoxyphenyl) -2H-benzo [ H ]]Chromen-5-yl) naphthalene (53 mg, white solid), yield: 14%. ESI-MS m/z:949[ M+H ]] + 。
1 H-NMR(400MHz，DMSO-d 6 )：δ8.04-7.61(m，3H)，7.57-7.13(m，15H)， 6.94-6.71(m，12H)，6.52(d，J＝7.2Hz，2H)，6.41(d，J＝7.2Hz，2H)，3.52(s，12H).
Example 4: preparation of photochromic materials
A photochromic curable composition was prepared by thoroughly mixing 0.04 part by mass of the chromene compound obtained in examples 1 to 3, 13 parts by mass of tetraethyleneglycol dimethacrylate, 48 parts by mass of 2, 2-bis [4- (methacryloyloxyethoxy) phenyl ] propane, 2 parts by mass of polyethylene glycol monoallyl ether, 20 parts by mass of trimethylolpropane trimethacrylate, 9 parts by mass of glycidyl methacrylate, 6 parts by mass of α -methylstyrene, 2 parts by mass of a-methylstyrene dimer, and 1 part by mass of t-butyl peroxy 2-ethylhexanoate as a polymerization initiator. Then, the obtained photochromic curable composition was poured into a mold composed of a glass plate and a gasket (gasset) made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization process is as follows: an air oven was used, which was slowly warmed from 30 ℃ to 90 ℃ over 18 hours and held at 90 ℃ for 2 hours. After the polymerization was completed, the polymer was removed from the glass mold of the mold to obtain a photochromic material sample prepared from the compounds of examples 1 to 3.
Experimental example 1: evaluation of photochromic Properties in solution
The photochromic cured product (photochromic optical article) was evaluated by the In mass method. The photochromic properties and half-life were evaluated except that each group of polymers (thickness 2mm, photochromic cured product (optical article)) obtained in example 4 was used as a sample and the light irradiation time was set to 1 second. The results are shown in Table 1.
Maximum absorption wavelength (Amax): the maximum absorption wavelength after color development, which is obtained by a spectrophotometer (instantaneous multichannel photodetector MCPD 2000M) manufactured by the electronic industry of Otsuka, inc., is an index of the color tone at the time of color development.
Color development concentration (ABS): the absorbance after irradiation with light at the maximum absorption wavelength for 0.5 seconds is an indicator of the color development concentration. It can be said that the higher the value, the greater the change in coloration due to light irradiation, and the better the photochromic property.
Fading half-life (T1/2): the time required for the absorbance at the maximum absorption wavelength of the sample to decrease to a half value when the irradiation of light is stopped is an index of the fading speed. The shorter this time, the faster the fade rate.
Degree of Yellowing (YI): for evaluation of yellowing after polymerization curing, the color difference of the sample after polymerization curing was measured by using a color difference meter (SM-4) manufactured by test machine Co., ltd. The smaller the YI value, the higher the transparency of the polymer cured body (including the cured film), or the smaller the degree of deterioration of the evaluation compound.
Survival rate (A) 50 /A 0 X100): in order to evaluate the durability of the color development caused by light irradiation, the following degradation acceleration test was performed. The obtained polymer (sample) was accelerated to deteriorate for 50 hours by a xenon arc weather resistant machine X25 manufactured by test machine Co., ltd. Thereafter, the color development concentration was evaluated before and after the test, and the color development concentration (A0) before the test and the color development concentration (a after the test were measured 50 ) Comparing the ratio (A) 50 /A 0 ) The residual rate was set as an index of the durability of the color development. The higher the residual ratio, the higher the durability of the color development.
Table 1:
comparative example 1
For further comparison, a photochromic cured film was prepared by the same method as in example 4 using the following compounds, and the characteristics of the photochromic plastic lenses obtained were evaluated by the method of experimental example 1, and the results are shown in table 2:
TABLE 2
Experimental results show that the compound of the invention introduces electron withdrawing groups and simultaneously connects different substituted benzochromenes through electron donating groups, and the compound is found to have practical fading half-life and good ageing resistance, and has photochromic property which disappears instantly when the light irradiation is stopped.
Therefore, when a photochromic material such as a photochromic lens is manufactured using the dibenzochromene-based compound of the present invention, a photochromic lens having such a property can be manufactured that rapidly develops color when coming outdoors, rapidly fades and returns to the original color tone when returning from outdoors to indoors, and can be used for a long time.
The dibenzochromene-based compound of the present invention exhibits the above excellent effects and is suitable for various applications, for example, a memory material, a light control material, a photochromic lens material, an optical filter material, a display material, an optical information device, an optical switching element, a photoresist material, a light meter, a decorative material, or the like.
Claims (7)
1. The dibenzochromene compound is characterized in that the structure of the compound is shown as a formula (I):
r1, R2, R5 and R6 are methoxy;
r3, R4, R7 and R8 are respectively selected from hydrogen or halogen, and at least one of R3, R4, R7 and R8 is halogen;
l is phenyl, biphenyl or naphthyl.
2. The dibenzochromene compound according to claim 1, wherein R3 and R7 are each H and R4 and R8 are each F.
3. A photochromic composition comprising the dibenzochromene compound of claim 1 or 2.
4. A photochromic material comprising a dibenzochromene compound according to any one of claims 1-3 incorporated into an organic material which is a polymeric, oligomeric and/or monomeric material.
5. Use of a dibenzochromene compound as claimed in claim 1 or 2 as a photochromic material.
6. The use according to claim 5, wherein the photochromic material is a memory material, a dimming material, a photochromic lens material, an optical filter material, a display material, an optical information device, an optical switching element, a photoresist material, a light meter or a decorative material.
7. The use according to claim 6, wherein the memory material is a copying material, a photoreceptor for printing, a memory material for cathode-ray tubes, a photosensitive material for laser light or a photosensitive material for hologram.
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| US20060228557A1 (en) * | 2005-04-08 | 2006-10-12 | Beon-Kyu Kim | Photochromic materials having extended pi-conjugated systems and compositions and articles including the same |
| EP2294114B1 (en) * | 2008-06-05 | 2012-08-15 | Advanced Polymerik Pty Ltd | Photochromic polymer and composition comprising photochromic polymer |
| GB0815109D0 (en) * | 2008-08-18 | 2008-09-24 | James Robinson Ltd | Polydialkylsiloxane-bridged bi-photochromic molecules |
| KR101097618B1 (en) * | 2010-04-15 | 2011-12-22 | 한남대학교 산학협력단 | Novel indeno-fused naphthopyran-based photochromic compound containing phenylazanediyl group and process for preparing the same |
| EP2705071B1 (en) * | 2011-05-03 | 2017-03-08 | Vivimed Labs Europe Ltd | Photochromic polymer |
| EP2714767B1 (en) * | 2011-06-03 | 2020-07-22 | Vivimed Labs Europe Ltd | Photochromic polymers |
| WO2019013249A1 (en) * | 2017-07-14 | 2019-01-17 | 株式会社トクヤマ | Chromene compound, curable composition comprising same, and optical article comprising cured product formed of curable composition |
| KR20200140819A (en) * | 2018-04-05 | 2020-12-16 | 가부시끼가이샤 도꾸야마 | Photochromic adhesive composition, photochromic laminate, and optical article using the photochromic laminate |
| KR20210004979A (en) * | 2018-04-17 | 2021-01-13 | 가부시끼가이샤 도꾸야마 | Photochromic compound, curable composition and optical article containing the photochromic compound |
| AU2020250724A1 (en) * | 2019-04-03 | 2021-10-28 | Tokuyama Corporation | Photochromic optical article and method for manufacturing same |
| WO2021075456A1 (en) * | 2019-10-17 | 2021-04-22 | 株式会社トクヤマ | Photochromic compound and curable composition including photochromic compound |
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| CN113354629B (en) * | 2021-07-06 | 2022-11-25 | 天津孚信阳光科技有限公司 | Diaryl ethylene-naphthopyran dual photochromic compound and preparation method and application thereof |
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