CN113603667B - High-solubility photochromic compound and preparation method thereof - Google Patents
High-solubility photochromic compound and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a high solubility photochromic compound having a junction represented by formula I and a method for preparing the sameThe structure is as follows: wherein R is 1 、R 2 、R 3 、R 4 The same or different, each independently represents: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl alcohol, halogen, trifluoromethyl, phenyl, morpholine, piperidine or indole. R is R 5 Represents C1-C6 alkyl, C1-C6 alkoxy or C1-C6 alkyl alcohol. R is R 6 、R 7 、R 8 Identical or different, at least one of which is-O- (CH) 2 CH 2 O) m-Z, the remainder being: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen, trifluoromethyl, phenyl, morpholine, piperidine or indole; m represents an integer of 0 to 6; z represents hydrogen or- (CH) 2 )p‑CH 3 The method comprises the steps of carrying out a first treatment on the surface of the p represents an integer of 0 to 6. The invention also provides a preparation method of the compound, and the prepared compound has the characteristics of excellent compatibility in an organic solvent system or a high polymer system, quick photoresponse, quick fading speed, good fatigue resistance and the like, and has good application prospect.
Description
Technical Field
The invention relates to the field of organic light functional materials, in particular to a high-solubility photochromic compound and a preparation method thereof.
Background
Photochromic phenomenon refers to a new compound generated by changing the structure of a compound under the irradiation of light with a certain intensity wavelength. Under the action of light with another wavelength or heat, the light can be restored to the original state. The two isomers have obvious difference in ultraviolet absorption spectrum and most intuitively show color change, so that the material is usually a photochromic material. The photochromic material has wide application value in the fields of information storage, optical switches, color-changing glasses, intelligent windows, color-changing clothes, ink paint, anti-counterfeiting materials and the like.
According to the components of the material, the photochromic material mainly comprises two major types of inorganic photochromic materials and organic photochromic materials, wherein the organic photochromic materials are rich in types and comprise azobenzene, diarylethene, spirooxazine, spiropyran, naphthopyran and other types. Among a plurality of organic photochromic materials, naphthopyran compounds are easy to synthesize, have the advantages of rapid light responsiveness, good fatigue resistance and the like, and are practically applied to the fields of color-changing glasses, color-changing clothes, artware and the like.
In practical applications, optical density is one of the basic parameters for evaluating the properties of photochromic materials. The optical density is used for measuring the light absorption quantity of the photochromic substance, is a representation of the shading capability of the material, is related to the wavelength of the incident light and the property of the photochromic material, and is influenced by factors such as solvent, solution concentration, temperature and the like. At present, related to the preparation and application of naphthopyran photochromic compounds, for example, CN105008373A, CN102532088A, CN1671699A has been reported, and the naphthopyran compounds generally have rigid conjugated groups such as benzene rings, naphthalene rings and the like and lack flexible substituent groups, so that the compounds have low solubility in organic solvents such as toluene, ethanol and acetone, poor compatibility in a high polymer system and influence the product quality.
Particularly in optical device applications, such as photochromic spectacles, it is desirable to have as high a light transmittance as possible in the colorless state before receiving uv radiation and a uniform color density in the colored state after receiving uv radiation. Therefore, the present invention provides a naphthopyran photochromic compound which has excellent solubility in an organic solvent and rapid light response and discoloration.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to improve the solubility of naphthopyran photochromic materials in organic solvents and the compatibility of polymer systems, and meanwhile, the invention has the advantages of quick photoresponse, quick fading and the like.
The technical scheme of the invention is as follows:
the flexible ether chain is introduced into the photochromic compound, so that the rigidity of the photochromic molecule is reduced, the non-chemical bond action of the photochromic molecule and the system is increased, and the compatibility is increased.
A photochromic compound characterized by: the compound has a structure shown in formula I:
R 1 、R 2 、R 3 、R 4 the same or different, each independently represents: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl alcohol, halogen, trifluoromethyl, phenyl, morpholine, piperidine or indole.
R 5 Represents C1-C6 alkyl, C1-C6 alkoxy or C1-C6 alkyl alcohol.
R 6 、R 7 、R 8 Identical or different, at least one of which is-O- (CH) 2 CH 2 O) m-Z, the remainder being: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen, trifluoromethyl, phenyl, morpholine, piperidine or indole;
m represents an integer of 0 to 6;
z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 6.
Further, R 1 、R 2 、R 3 、R 4 The same or different, each independently represents: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkyl alcohol, trifluoromethyl; r is R 5 Represents C1-C6 alkyl, C1-C6 alkoxy or C1-C6 alkyl alcohol; r is R 6 、R 7 、R 8 Identical or different, at least one of which is-O- (CH) 2 CH 2 O) m-Z, the remainder being: hydrogen, C1-C6 alkyl, C1-C6 alkoxy, halogen, trifluoromethyl; m represents an integer of 0 to 6; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 6.
Further, R 1 、R 2 、R 3 、R 4 The same or different, each independently represents: hydrogen, C1-C3 alkyl, C1-C3 alkoxy, C1-C3 alkyl alcohol, trifluoromethyl; r is R 5 Represents C1-C3 alkyl, C1-C3 alkoxy or C1-C3 alkyl alcohol; r is R 6 、R 7 、R 8 Identical or different, at least one of which is-O- (CH) 2 CH 2 O) m-Z, the remainder being: hydrogen, C1-C3 alkyl, C1-C3 alkoxy, halogen, trifluoromethyl; m represents an integer of 0 to 3; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 3.
Preferably, in the formula, R 1 、R 2 The same or different, each independently represents hydrogen, methyl or methoxy; r is R 3 、R 4 The same or different, each independently represents hydrogen, methyl, methoxy or trifluoromethyl; r is R 5 Represents methyl; r is R 6 、R 7 、R 8 Identical or different, at least one of which is-O- (CH) 2 CH 2 O) m-Z, Z represents hydrogen or- (CH) 2 )p-CH 3 M and p each represent an integer of 0 to 3.
The scheme of the invention is that R 7 、R 8 、R 6 Comprises the following specific scheme: r is R 7 、R 8 At least one is-O- (CH) 2 CH 2 O) m-Z, m represents an integer of 0-6; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 6.
R 7 、R 8 Both radicals being-O- (CH) 2 CH 2 O) m-Z, m represents an integer of 0-6; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 6.
At R 7 、R 8 On the premise of selection, R 6 is-O- (CH) 2 CH 2 O) m-Z, m represents an integer of 0-6; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 6.
Further, at R 7 、R 8 、R 6 In the scheme of the invention, the following schemes are also included: r is R 7 、R 8 At least one is-O- (CH) 2 CH 2 O) m-Z, m represents an integer of 0-3; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 3.
R 7 、R 8 Both radicals being-O- (CH) 2 CH 2 O) m-Z, m represents an integer of 0-3; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 3.
At R 7 、R 8 On the premise of selection, R 6 is-O- (CH) 2 CH 2 O) m-Z, m represents an integer of 0-3; z represents hydrogen or- (CH) 2 )p-CH 3 P represents an integer of 0 to 3.
In another aspect, the invention also provides a preparation method of the compound, which comprises the following steps:
when only R 7 、R 8 One of them is-O- (CH) 2 CH 2 O) m-Z, prepared by the steps of: by R 7 is-O- (CH) 2 CH 2 O) m-Z is exemplified:
step 1: the benzophenone derivative A and the p-toluenesulfonate derivative B react to generate a benzophenone derivative C, and the reaction formula is as follows:
step 2: the benzophenone derivative C reacts with trimethylsilylacetylene to prepare alkynol D, and the reaction formula is as follows:
step 3: alkynol D and naphthol derivative E are catalyzed by acid to prepare photochromic compound I', and the reaction formula is as follows:
the compound of formula I' is finally obtained.
By R 8 is-O- (CH) 2 CH 2 O) m-Z, the preparation method is the same as described above, except that the position of the substituent is changed.
Preferably, the basic catalyst selected in the step 1 reaction is sodium hydride, and the dosage of the catalyst is 3-10 equivalents. The reaction solvent is one or two of anhydrous DMF and THF. The molar ratio of benzophenone A to p-toluenesulfonate B was 1.0: 1.0-10.0, the reaction temperature is 50-100 ℃, and the reaction time is 50-100h.
Preferably, the catalyst selected in the step 2 reaction is n-butyllithium. The catalyst is used in an amount of 1 to 5 equivalents. The reaction solvent is one or two of anhydrous DMF and THF. The molar ratio of the benzophenone derivative C to the trimethylsilylacetylene is 1.0: 1.0-5.0, the reaction temperature is minus 50-minus 90 ℃ and the reaction time is 3-10h.
Preferably, the catalyst selected in the 3 rd step is dodecylbenzene sulfonic acid. The catalyst is used in an amount of 0.01 to 0.5 equivalent. The reaction solvent is one or two of anhydrous THF and toluene xylene. The molar ratio of alkynol D to naphthol E is 1.0:0.3 to 1.0, the reaction temperature is 30 to 100 ℃ and the reaction time is 1 to 8 hours.
When R is 7 、R 8 Are all-O- (CH) 2 CH 2 O) m-Z, prepared by the steps of:
step 1: the benzophenone derivative A 'and the p-toluenesulfonate derivative B' react to generate a benzophenone derivative C, and the reaction formula is as follows:
the alkali is sodium hydride, cesium carbonate, potassium carbonate or sodium carbonate, and the organic solvent is one or two of N, N-dimethylformamide, tetrahydrofuran and 1, 4-dioxane;
step 2: the benzophenone derivative C' reacts with trimethylsilylacetylene to prepare alkynol D, and the reaction formula is as follows:
step 3: alkynol D ' and naphthol derivative E ' are catalyzed by acid to prepare photochromic compound I ', and the reaction formula is as follows:
R 6 comprising-O- (CH) 2 O) m -Z, the process for the preparation of the photochromic compound comprises the following steps:
naphthopyran F and ether G are prepared into a formula I' under the catalysis of acid, and the reaction formula is as follows
q represents an integer of 0 to 6.
The naphthopyran compound F may be prepared by the method of patent CN108623554A.
Preferably, the naphthopyran F reacts with the ether G, and the selected acid catalyst is p-toluenesulfonic acid or dodecylbenzenesulfonic acid, and the catalyst dosage is 0.01-0.5 equivalent. The reaction solvent is one or two of dichloromethane and tetrahydrofuran. The molar ratio of naphthopyran F to ether G was 1.0:1.0 to 5.0, the reaction temperature is 30 to 100 ℃ and the reaction time is 1 to 8 hours.
The drugs and reagents used in the above reactions are materials well known in the art and commercially available.
The photochromic compound has the advantages of excellent solubility in organic solvents such as toluene, chloroform, tetrahydrofuran and acetone, easy processing into films, quick light response, quick fading, no ground color and high color rendering index.
Drawings
FIG. 1Ia in chloroform (1X 10) -4 mol/L) UV-visible absorption spectrum of the photochromic process;
FIG. 2Ib tetrahydrofuran solution (1X 10) -4 mol/L) UV-visible absorption spectrum of the photochromic process;
FIG. 3Ic chloroform solution (1X 10) -4 mol/L) UV-visible absorption spectrum of the photochromic process;
FIG. 4Id tetrahydrofuran solution (1X 10) -4 mol/L) UV-visible absorption spectrum of the photochromic process;
FIG. 5Ie chloroform solution (1X 10) -4 mol/L) UV-visible absorption of light from a photochromic processA spectrum;
FIG. 6Ia in chloroform (1X 10) -4 mol/L) UV-visible absorption spectrum of the fading process;
FIG. 7Ia ultraviolet absorbance spectra before and after photochromism in PMMA film;
FIG. 8Ia is an ultraviolet visible absorption spectrum of the discoloration process in PMMA film.
Detailed Description
EXAMPLE 1 Synthesis of photochromic Compound Ia
The first step: synthesis of Compound C1
To a 100mL Schlenk tube at 0deg.C was added sodium hydride (0.2 g,64 mmol) and 30mL anhydrous tetrahydrofuran. 4,4' -dihydroxybenzophenone A1 (2.1 g,10 mmol) was dissolved in 30ml anhydrous DMF and added slowly to the reaction flask by syringe and the reaction stirred for 1h. B1 (1.5 g,64 mmol) was added to the reaction system and heated to 60℃to react for 72h. Cooling to room temperature, adding saturated NH into the reaction system 4 The Cl solution, ethyl acetate (3X 50 mL) was extracted three times and the organic phases were combined and washed once with brine (50 mL) and water (50 mL), respectively. Dried over anhydrous sodium sulfate and filtered. The solvent was removed by rotary evaporation to give the crude product, which was purified by column chromatography on silica gel (eluent dichloromethane/methanol=40:1) to give C1 as a yellow oil in 89% yield
Nuclear magnetic resonance hydrogen spectrum of C1: 1 H NMR(400MHz,CDCl 3 )δ(ppm)7.80–7.72(m,4H),7.00–6.94(m,4H),4.28–4.19(m,4H),3.96–3.86(m,4H),3.75–3.72(m,4H),3.64–3.55(m,4H),3.40(s,6H).
nuclear magnetic resonance carbon spectrum of C1: 13 C NMR(101MHz,CDCl 3 )δ(ppm)194.4,162.0,132.2,130.8,114.0,71.93,70.8,69.6,67.6,59.1.
and a second step of: synthesis of Compound D1
at-78deg.C and N 2 To a 500mL Schlenk flask, 100mL anhydrous tetrahydrofuran and trimethylsilylacetylene (2.2 g,20 mmol) were added under protection. To the flask was slowly added n-butyllithium hexane solution (2.5M, 8mL,20 mmol) by syringe and the reaction was stirred for 1h. C1 (4.2 g,10 mmol) was dissolved in 65mL ultra-dry tetrahydrofuran and slowly added to the reaction flask and reacted at room temperature for 5h. 12mL of methanol solution in which 1.2g of potassium hydroxide was dissolved was added to the Schlenk flask, and stirring was continued for 0.5h. After the completion of the reaction, 80mL of NH was added to the reaction mixture 4 The solution was saturated with Cl, extracted three times with ethyl acetate (3X 50 ml) and the organic phase was collected and dried over anhydrous sodium sulfate. The solvent was removed by filtration and rotary evaporator, and the residue was purified by column chromatography on silica gel (dichloromethane/methanol=40:1 as eluent) to give a yellow liquid in 57% yield. Nuclear magnetic resonance hydrogen spectrum of D1: 1 H NMR(400MHz,CDCl 3 )δ(ppm)7.47–7.41(m,4H),6.85–6.77(m,4H),4.09–4.03(m,4H),3.82–3.77(m,4H),3.69–3.63(m,4H),3.61–3.55(m,1H),3.54–3.48(m,4H),3.33(s,6H),2.82(s,1H).
nuclear magnetic resonance carbon spectrum of D1: 13 C NMR(101MHz,CDCl 3 )δ(ppm)158.2,137.4,127.3,114.1,87.0,75.0,73.3,71.9,70.7,69.7,67.4,59.0.
and a third step of: synthesis of photochromic Compound Ia
To a 100mL single vial was added D1 (0.6 g,2 mmol), E1 (0.9 g,2 mmol) and 60mL toluene, and stirred. 2 drops of dodecylbenzene sulfonic acid are added by a rubber head dropper, and the mixture is heated to 40 ℃ for reaction for 3 hours. Cooled to room temperature, extracted three times with dichloromethane (3X 50 ml), and the organic phases were combined and washed once with saturated brine (50 ml) and distilled water (50 ml), respectively. Drying over anhydrous sodium sulfate, filtering, removing the solvent by rotary evaporator, separating and purifying the residue by silica gel column chromatography (dichloromethane/methanol=40:1 as eluent) to obtain dark green oily liquid Ia, standing and converting the liquid into low-melting solid with the yield of 68%.
Nuclear magnetic resonance hydrogen spectrum of Ia: 1 H NMR(400MHz,CDCl 3 )δ(ppm)8.53(d,J＝8.0Hz,1H),8.07(d,J＝8.0Hz,1H),7.76(s,1H),7.46(d,J＝8.0Hz,4H),7.30–7.23(m,2H),7.04(s,1H),6.96–6.83(m,5H),6.22(d,J＝10.0Hz,1H),4.15–4.09(m,4H),3.99(s,3H),3.90(s,3H),3.86–3.80(m,4H),3.74–3.66(m,4H),3.63–3.50(m,4H),3.40(s,6H),1.65(s,6H).
nuclear magnetic resonance carbon spectrum of Ia: 13 C NMR(101MHz,CDCl 3 )δ(ppm)158.1,157.2,156.8,146.6,144.2,137.5,132.9,128.8,128.2,127.0,126.0,125.3,125.0,122.5,120.7,118.9,114.1,113.8,111.9,108.5,101.8,82.0,71.9,70.7,69.7,67.3,59.1,55.5,47.5,26.5.
EXAMPLE 2 Synthesis of photochromic Compound Ib
The first step: synthesis of benzophenone derivative C2
Sodium hydride powder (1.9 g,80 mmol) was weighed into a 250mL Shi Laike bottle and 50mL anhydrous tetrahydrofuran was added under nitrogen. A (25.71 g,25 mmol) was dissolved in 25mL anhydrous N, N-dimethylformamide, and after complete dissolution, the reaction flask was added dropwise. Ice bath, stirring for one hour, B1 (13.7 g,50 mmol) was added to the reaction flask. Heated to 60℃and reacted for 72 hours. Cooling to room temperature, adding saturated NH into the reaction system 4 The Cl solution, ethyl acetate (3X 50 mL) was extracted three times and the organic phases were combined and washed once with brine (50 mL) and water (50 mL), respectively. Dried over anhydrous sodium sulfate and filtered. The solvent was removed by rotary evaporator to give a crude product, which was purified by column chromatography on silica gel (eluent dichloromethane/methanol=40:1) to give colorless transparent oily liquid C2,6.3g, 76% yield. After standing, it turned into a white solid. Melting point: 59.8-60.6 ℃.
Nuclear magnetic resonance hydrogen spectrum of C2: 1 H NMR(400MHz,CDCl 3 )δ7.81–7.74(m,4H),7.00–6.93(m,4H),4.25–4.20(m,2H),3.92–3.86(m,5H),3.76–3.70(m,2H),3.61–3.56(m,2H),3.40(s,3H).
c2 nuclear magnetismResonance carbon spectrum: 13 C NMR(101MHz,CDCl 3 )δ194.5,162.8,162.0,132.2,132.2,130.9,130.7,114.1,113.6,71.9,70.8,69.6,67.6,59.1,55.5.
and a second step of: synthesis of diphenylalkynol derivative D2
at-78deg.C and N 2 To a 250mL three-necked flask, 20mL of anhydrous tetrahydrofuran and trimethylsilylacethylene (2.7 g,27 mmol) were added under protection. To the flask was slowly added n-butyllithium hexane solution (2.5M, 11mL,27 mmol) by syringe and the reaction was stirred for 1h. C2 (4.5 g,13 mmol) was dissolved in 10mL ultra-dry tetrahydrofuran and slowly added to the reaction flask and reacted at room temperature for 5h. 30mL of methanol solution in which 3g of potassium hydroxide was dissolved was added to the three-necked flask, and stirring was continued for 0.5h. 20mL of NH was added to the reaction solution 4 The solution was saturated with Cl, extracted three times with ethyl acetate (3X 30 ml) and the organic phase was collected and dried over anhydrous sodium sulfate. The solvent was removed by filtration and rotary evaporation, and the residue was purified by column chromatography on silica gel (dichloromethane/methanol=40:1 as eluent) to give 4.5g of an orange-yellow oily liquid in 98% yield.
D2 nuclear magnetic resonance hydrogen spectrum: 1 H NMR(400MHz,CDCl 3 )δ7.25(d,J＝8.6Hz,4H),6.63–6.57(m,4H),3.87–3.81(m,2H),3.59–3.54(m,2H),3.50(s,3H),3.45–3.39(m,2H),3.32–3.25(m,2H),3.09(s,3H),2.62(s,1H).
d2 nuclear magnetic resonance carbon spectrum: 13 C NMR(101MHz,CDCl 3 )δ159.0,158.2,137.5,137.3,127.4,114.18,113.5,113.5,113.4,113.4,87.1,75.0,73.4,71.8,70.6,69.6,67.4,59.0,55.3.
and a third step of: synthesis of photochromic Compound Ib
To a 100mL single vial was added D2 (136 mg,0.38 mmol), E2 (100 mg,0.38 mmol) and 10mL toluene, and stirred. By dripping with glue heads1 drop of dodecylbenzenesulfonic acid was added to the tube, and the mixture was heated to 40℃to react for 4 hours. Cooled to room temperature, extracted three times with dichloromethane (3X 10 ml), and the organic phases were combined and washed once with saturated brine (10 ml) and distilled water (10 ml), respectively. Dry over anhydrous magnesium sulfate, filter, remove solvent by rotary evaporator, and purify the residue by column chromatography on silica gel (dichloromethane/methanol=40:1 as eluent) to give pale purple waxy solid Ib,0.17g, 74% yield. Nuclear magnetic resonance hydrogen spectrum of Ib: 1 H NMR(400MHz,CDCl 3 )δ8.63(d,J＝8Hz,1H),8.44(d,J＝8Hz,1H),8.18(d,J＝8Hz,1H),7.59–7.50(m,1H),7.30–7.18(m,2H),6.81(t,J＝8Hz,4H),6.18(d,J＝8Hz,1H),4.04(t,J＝8Hz,2H),3.77(t,J＝8Hz,2H),3.70(s,3H),3.65–3.62(m,2H),3.52–3.48(m,2H),3.33(s,3H),1.62(s,6H).
nuclear magnetic resonance carbon spectrum of Ib: 13 C NMR(101MHz,CDCl 3 )δ158.9,158.1,155.0,148.4,147.5,134.0,137.5,137.2,130.1,128.4,128.3,128.2,127.1,127.1,126.8,125.4,124.9,124.8,123.75,123.3,122.1,121.9,120.6,114.2,113.5,113.2,82.2,72.0,70.7,69.7,67.3,59.1,55.2,47.7,29.8,26.2.
example 3: synthesis of photochromic Compound Ic
D3 synthesis reference examples 1 and 2 steps, which are not repeated
To a 100mL single vial was added D3 (320 mg,1 mmol), E2 (300 mg,1 mmol) and 20mL toluene, and stirred. 2 drops of dodecylbenzene sulfonic acid are added by a rubber head dropper, and the mixture is heated to 40 ℃ for reaction for 3 hours. Cooled to room temperature, extracted three times with dichloromethane (3X 20 ml) and the organic phases were combined and washed once with saturated brine (20 ml) and distilled water (20 ml), respectively. Dry over anhydrous magnesium sulfate, filter, remove solvent by rotary evaporator, and purify the residue by column chromatography on silica gel (dichloromethane/methanol=100:1 as eluent) to give Ic as a pale yellow solid in 79% yield.
Hydrogen nuclear magnetic resonance spectrum of Ic: 1 H NMR(400MHz,CDCl 3 )δ(ppm)8.52(d,J＝8.0Hz,1H),8.07(d,J＝8.0Hz,1H),7.75(d,J＝8.0Hz,1H),7.54–7.42(m,4H),7.30–7.24(m,2H),7.05–7.02(m,1H),6.95–6.90(m,1H),6.88–6.84(m,4H),6.23(d,J＝10.0Hz,1H),3.99(s,3H),3.92(s,3H),3.79(s,6H),1.66(s,6H).
nuclear magnetic resonance carbon spectrum of Ic: 13 C NMR(101MHz,CDCl 3 )δ(ppm)158.9,158.1,157.2,156.8,146.6,144.2,137.4,132.96,132.3,128.7,128.3,127.0,125.9,125.3,125.0,122.4,120.7,118.9,113.7,113.4,111.8,108.5,101.8,82.0,55.5,55.4,55.2,47.5,26.5.
example 4: synthesis of photochromic Compound Ie
Compound Id can be prepared by the method of patent CN108623554a.
In a 100ml single-port flask, compound Id (1 g,1.75 mmol), diethylene glycol monoethyl ether (350 mg,2.62 mmol) and catalytic amount of p-toluene sulfonic acid (100 mg, 10%) were added, solvent dichloromethane 30ml was added, heated to 35℃and TLC monitored for reaction completion. After completion of the reaction, the mixture was cooled to room temperature, washed once with saturated brine (20 ml) and distilled water (20 ml), and the organic phase was collected, dried over anhydrous magnesium sulfate, concentrated, and recrystallized from anhydrous ethanol to give pale green solid Ie in 65% yield.
Nuclear magnetic resonance hydrogen spectrum of Id: 1H NMR (400 MHz, chloroform-d) δ8.30 (d, J=9.2 Hz, 1H), 7.87 (d, J=8.5 Hz, 1H), 7.62 (d, J=2.7 Hz, 1H), 7.52-7.37 (m, 5H), 7.15 (dt, J=5.2, 2.7Hz, 2H), 6.91-6.83 (m, 3H), 6.84-6.76 (m, 2H), 6.20 (d, J=9.9 Hz, 1H), 3.89 (d, J=10.3 Hz, 6H), 3.76 (d, J=16.0 Hz, 6H), 1.77 (s, 3H).
Nuclear magnetic resonance carbon spectrum of Id: 13 C NMR(101MHz,CDCl 3 )δ(ppm)158.9,158.1,157.2,156.8,146.6,144.2,137.4,132.9,132.3,128.7,128.3,127.0,125.9,125.3,125.0,122.4,120.7,118.9,113.7,113.4,111.8,108.5,101.8,82.0,55.5,55.4,55.2,55.1,26.5。
nuclear magnetic resonance hydrogen spectrum of Ie: 1H NMR (400 MHz, DMSO-d 6) delta 8.50 (d, J=9.3 Hz, 1H), 8.08 (d, J=8.5 Hz, 1H), 7.63 (d, J=2.7 Hz, 1H), 7.49-7.34 (m, 5H), 7.29 (dd, J=9.2, 2.7Hz, 1H), 7.06 (d, J=2.5 Hz, 1H), 7.00-6.83 (m, 5H), 6.47 (d, J=9.9 Hz, 1H), 3.94 (s, 3H), 3.83 (s, 3H), 3.70 (d, J=16.0 Hz, 6H), 3.43-3.34 (m, 10H), 1.03 (t, J=7.0 Hz, 3H).
Nuclear magnetic resonance carbon spectrum of Ie: 13 C NMR(101MHz,CDCl 3 )δ(ppm)158.9,158.1,157.2,156.8,146.6,144.2,137.4,132.9,132.3,128.7,128.3,127.0,125.9,125.3,125.0,122.4,120.7,118.9,113.7,113.4,111.8,108.5,101.8,82.0,71.0,70.4,70.1,64.9,66.6,55.5,55.4,55.2,55.1,26.5,15.2.
example 5: synthesis of photochromic Compound If
The synthesis method is described in reference to example 1, example 2 and example 3, and the method is not repeated.
Example 6: synthesis of photochromic compound Ig.
Compound F1 can be prepared by the method of patent CN108623554a.
In a 100ml single-port flask, compound F1 (1 g,1.85 mmol), diethylene glycol monoethyl ether (373 mg,2.78 mmol) and a catalytic amount of p-toluenesulfonic acid (100 mg, 10%) were added, solvent dichloromethane 30ml was added, heated to 35℃and TLC monitored for completion of the reaction. After completion of the reaction, the mixture was cooled to room temperature, washed once with saturated brine (20 ml) and distilled water (20 ml), and the organic phase was collected, dried over anhydrous magnesium sulfate, concentrated, and recrystallized from anhydrous ethanol to give a pale violet solid If.
Example 7: synthesis of photochromic compound Ii.
The synthesis of the compound Ih is described in example 1 and will not be repeated.
The synthesis of compound E5 is described in patent CN108623554a.
The synthesis of the photochromic compound Ii is described in example 4 and will not be repeated.
Example 8: synthesis of photochromic compound Ij.
Ij synthesis reference examples 1 and 2 are not repeated.
Example 9: solubility of photochromic Compounds
At 25 ℃, 1ml of toluene solvent is added into a 5ml volumetric flask, a photochromic compound sample to be detected is added into the volumetric flask, and the mixture is continuously vibrated until the sample is not dissolved any more to reach a saturated state, the mass of the added sample is recorded, and the solubility is calculated as shown in table 1. It can be seen from table 1 that the photochromic compounds Ia, ib, ic all have good solubility in toluene and increase with increasing number and length of flexible carbon-oxygen chains. Id, ie solubility was significantly improved after the introduction of the flexible carbon-oxygen chain. Thus, the incorporation of flexible carbon-oxygen chains in the molecule is an effective method of increasing the solubility of photochromic compounds.
TABLE 1 solubility of photochromic compounds in toluene solvent
Example 10: color change Properties of photochromic Compound solutions
The photochromic compounds Ia, ib and Ic are prepared by using chloroform or tetrahydrofuran as solvent, respectively, with the concentration of 1X 10 -4 The mol/L solution was tested by irradiating the solution with xenon Xe-150 light source for 5s, 10s, 15s, 20s, 25s, 30s, respectivelyIs shown in fig. 1-5. The corresponding photochromic property parameters are listed in table 2. As is clear from Table 2, the photochromic compound prepared according to the present invention has a saturated absorbance time of 20 to 30 seconds, a rapid photoresponse, no color before the discoloration, and blue or purple color after the discoloration.
Table 2 color change performance parameters of the compounds
[a] Time to reach saturation absorbance
Example 11: fade Properties of trichloromethane solution of photochromic Compound Ia
The Ia concentration was 1X 10 by irradiation with a xenon lamp Xe-150 light source -4 The chloroform solution with mol/L is continuously illuminated for 30s, so that the solution reaches saturated absorbance. The solution was then tested for its UV-visible absorbance spectrum, once every 5 seconds, resulting in a UV-visible absorbance spectrum with time change in absorbance, as shown in FIG. 6. The fade half-life τ of Ia in chloroform solution can be calculated according to FIG. 6 1/2 100s.
Example 8: PMMA film preparation of photochromic Compound Ia
Ia (40 mg) and polymethyl methacrylate (2 g) were added to a 100mL round bottom flask, 30mL tetrahydrofuran was added, and the mixture was dissolved with heating and stirring. Taking out 12mL of the obtained solution, pouring the solution into a cylindrical quartz mold (phi=7.5 cm multiplied by 5 cm), placing the quartz mold in an open dark place, removing the mold after the solvent is completely volatilized, and obtaining a colorless transparent film with the thickness of 120-180 mu m.
Example 12: color change Properties of photochromic Compound Ia in PMMA film
The film obtained in example 12 was cut into 2cm×2cm squares, and the ultraviolet absorption spectra of the film before and after ultraviolet irradiation were measured by an ultraviolet spectrophotometer, as shown in fig. 7. Before ultraviolet irradiation, the PMMA film of Ia is not absorbed in the range of 400-800nm, has no ground color, is colorless and transparent, and has a strong absorption peak in the range of 450-750nm after ultraviolet irradiation, and the film is blue and has high chromaticity.
Example 10: fade Properties of photochromic Compound Ia in PMMA film
The film sample of example 12 was irradiated under a Xe-150 xenon lamp for 30s to reach saturated absorbance, and then the uv-vis absorption spectrum was measured every 5s under a dark environment (fig. 8). As can be seen from fig. 8, the photochromic compound Ia has a discoloration half-life of 225s in the PMMA solid film, and has good discoloration properties.
The foregoing describes the preferred embodiments of the present invention in detail, but the description is merely illustrative of the preferred embodiments of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (4)
1. A high solubility photochromic compound characterized by: the compound has two structures of Ia and Ib:
2. a process for the preparation of a photochromic compound according to claim 1, characterized in that: the preparation method of Ia comprises the following steps:
the first step: synthesis of Compound C1
And a second step of: synthesis of Compound D1
And a third step of: synthesis of photochromic Compound Ia
3. The method for producing a photo-induced compound according to claim 1, wherein: the preparation method of Ib comprises the following steps:
the first step: synthesis of benzophenone derivative C2
And a second step of: synthesis of diphenylalkynol derivative D2
And a third step of: synthesis of photochromic Compound Ib
4. Use of a photochromic compound according to claim 1 as a photochromic material in the field of sunglasses, glazing, decorative articles, apparel, paint inks.
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