CN111171048A - Spirooxazine photochromic compound and preparation method thereof - Google Patents
Spirooxazine photochromic compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a spirooxazine photochromic compound and a preparation method thereof, belonging to the technical field of organic functional materials. Its molecular structure is as follows:
wherein R is1，R2Is hydrogen, C1‑C6Alkyl radical (C)mH2m+1M =1,2,3,4,5, 6), benzyl; r3，R4Is hydrogen, halogen, C1‑C6Alkyl radical (C)mH2m+1M =1,2,3,4,5, 6). The invention introduces the photo-thermal stable fluorenol structure and uses different groups for substitution, thereby providing the advantages of the novel spirooxazine photochromic material, namely, the photo-response speed is high, the color fading is rapid, the photo-thermal stability is good, the open loop state and the closed loop state can exist stably for a long time, and the problem of spirooxazine is solvedThe difficult problem of unstable ring-opening state of the oxazine photochromic compound provides guidance, the photochromic compound with various colors from colorless to red, yellow, green, blue or purple is realized, namely, the color change is more abundant, the market diversification requirement is finally met, the synthetic raw materials are cheap and easy to obtain, and the synthetic process is easy to realize industrialization.
Description
Technical Field
The invention relates to a spirooxazine photochromic compound and a preparation method thereof, belonging to the technical field of organic functional materials.
Background
Photochromism is a chemical-physical phenomenon. The compound undergoes a reversible color change process under the action of light. Research on photochromism has focused mainly on the synthesis of photochromic materials and the mechanism of discoloration. Photochromic materials mainly include fulgides, spiropyrans, spirooxazines, naphthopyrans, perfluorocyclopentenes, and the like. The photochromic material is applied to optical information storage and optical recording materials, organic photochromic resin lenses, anti-counterfeiting materials, photochromic textiles, building glass, automobile glass, national defense application and the like.
Spirooxazine photochromic materials have attracted much attention because of their high color-changing speed and high color-erasing speed. However, under the irradiation of ultraviolet light, the spirooxazine photochromic material has a stable colorless closed-loop state and an unstable colored open-loop state. Therefore, the improvement of the stability of the open ring state of the spirooxazine photochromic material through the structural design plays an important role in the practical application of the spirooxazine photochromic material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the spirooxazine photochromic compound and the preparation method thereof are provided, and the problems that a colorless closed-loop state of a spirooxazine photochromic material is stable and a colored open-loop state of the spirooxazine photochromic material is unstable under ultraviolet irradiation are solved.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a spirooxazine photochromic compound has the following molecular structure:
wherein R is1，R2Is hydrogen, C1-C6Alkyl radical (C)mH2m+1，m=1,2,3,4,5,6）Benzyl; r3，R4Is hydrogen, halogen, C1-C6Alkyl radical (C)mH2m+1，m=1,2,3,4,5,6）。
A preparation method of spirooxazine photochromic compounds mainly comprises the following steps:
s1: the raw material fluorene M1 and N-bromosuccinimide (NBS) are subjected to electrophilic substitution to generate a bromofluorene M2 compound, and the reaction formula is as follows:
R1 |
s2: the compound M2 is subjected to substitution reaction with halogenated hydrocarbon under the action of alkali to prepare M3, wherein the reaction formula is as follows:
R2 |
s3: compound M3 was hydrolyzed under basic conditions to prepare compound M4, of the formula:
R3 |
s4: compound M5 is prepared by the substitution reaction of compound M4 under acidic condition, and the reaction formula is as follows:
s5: compound M5 and indoline in a solvent to prepare target compound I, the reaction formula is as follows:
R5 |
as a preferable example, the brominating agent used in S1 is NBS, used in an amount of 1.0 to 1.2 equivalents, the solvent is glacial acetic acid, used in an amount of 10 to 20 times the mass of the compound M1, the reaction temperature is 25 to 60 ℃, and the reaction time is 3 to 10 hours.
As a preferable example, the hydrogen abstraction agent used in S2 is sodium hydride, calcium hydride or potassium tert-butoxide, the amount of the hydrogen abstraction agent is 1.0 to 2.5 equivalents, the reaction solvent is one or more of N, N-dimethylformamide, 1, 4-dioxane, toluene or tetrahydrofuran, and the halogenated hydrocarbon used is C1-C6One or more of alkyl chloride, bromide and iodide, the reaction temperature is 0-80 ℃, and the reaction time is 2-12 h.
As a preferable example, the base used for hydrolyzing the compound M3 in S3 is one of sodium hydroxide and potassium hydroxide, the using amount is 1.1 to 1.5 equivalents, the solvent can be one of water, a mixed solvent of water and ethanol or a mixed solvent of water and methanol, the reaction temperature is 80 to 120 ℃, and the reaction time is 5 to 16 hours.
As a preferred example, the acidic catalyst used in S4 is dilute sulfuric acid having a concentration of 20% to 50%, the nitrosating agent is sodium nitrite, and the amount used and the molar ratio of compound M4 are (1.0 to 1.3): 1, the reaction temperature is-10-0 ℃, and the reaction time is 1-8 h.
As a preferred example, the molar ratio of compound M5 and indoline in S5 is 1: (1.0-1.5), the used solvent is one of methanol, ethanol or isopropanol, the reacted protective gas is one of nitrogen or argon, the reaction temperature is 60-110 ℃, and the reaction time is 2-24 h.
An application of spirooxazine photochromic compound in the fields of preparing photochromic glasses, building window films and automobile and train window films.
The invention has the beneficial effects that: the invention introduces the photo-thermal stable fluorenol structure and uses different groups for substitution, thereby providing the advantages of the novel spirooxazine photochromic material, namely, the photo-thermal stable fluorenol structure has high photo-response speed, rapid fading and good photo-thermal stability, and the open loop state and the closed loop state can stably exist for a long time, thereby providing guidance for solving the problem of unstable open loop state of the spirooxazine photochromic compound, realizing the photochromic compound with various colors from colorless to red, yellow, green, blue or purple, namely realizing richer color types of discoloration, finally meeting the diversified demands of the market, having cheap and easily obtained synthetic raw materials and easily realizing industrialization of the synthetic process.
Drawings
FIG. 1 is a diagram showing the color change of a compound I before and after irradiation with ultraviolet light in a toluene solution in example one, example two and example three;
FIG. 2 shows the concentration of compound I in the first, second and third examples at 1X 10-4A general diagram of changes of ultraviolet visible light absorption spectra before and after ultraviolet light irradiation in mol/L ethyl acetate solution;
FIG. 3 is the NMR spectrum of I in example I;
FIG. 4 is the NMR spectrum of I in example one;
FIG. 5 is the NMR spectrum of I in example II;
FIG. 6 is the NMR spectrum of I in example II;
FIG. 7 is the NMR spectrum of I in example III;
FIG. 8 is the NMR spectrum of I in example III.
Wherein, the lines with squares and dots in fig. 2 are respectively the ultraviolet-visible light absorption spectrum change chart before and after photochromism of compound I in example one; lines with a positive triangle and an inverted triangle are respectively an ultraviolet visible light absorption spectrum change chart of the compound I before and after photochromism in the second embodiment; the lines with the left triangle and the right triangle are respectively the ultraviolet-visible light absorption spectrum change graphs of the compound I before and after photochromism in example three.
Detailed Description
In order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easily understood, the invention is further described with reference to the specific embodiments and the drawings.
Example one
The synthesis steps of the photochromic target compound I are as follows:
s1: synthesis of M2, reaction formula:
8c184a18095a63526c302baf3d87670 |
adding fluorene M1 (8.310 g, 0.050 mol) into a 250ml four-mouth bottle, adding 100ml glacial acetic acid solvent, magnetically stirring, heating to 40 ℃, completely dissolving, then slowly adding NBS (10.680 g, 0.060 mol) in three batches, continuously stirring and reacting for 5 hours at 40 ℃ after the addition is finished (TCL monitoring), pouring the reaction solution into a large amount of water after the reaction is finished, separating out a product, performing suction filtration, washing with water, and recrystallizing petroleum ether/ethyl acetate to obtain M2 with the yield of 71%;
s2: synthesis of M3, reaction formula:
4d23ded2dee4971b18df64b11a9b731 |
adding M2 (7.350 g, 0.030 mol) into a 100ml four-mouth bottle, then adding 40ml tetrahydrofuran solvent, magnetically stirring at normal temperature for 30min, then cooling to 0 ℃, then adding potassium tert-butoxide (7.850 g, 0.070 mol), finally slowly dripping methyl iodide (9.940 g, 0.070 mol), after the addition is finished, continuing stirring and reacting at 0 ℃ for 6h (TCL monitoring), after the reaction is finished, carrying out suction filtration on the reaction solution, carrying out rotary evaporation on the filtrate, and recrystallizing petroleum ether/dichloromethane to obtain M3 with the yield of 75%;
s3: synthesis of M4, reaction formula:
d2c83a7f26ee48f998dadde75fd76e5 |
adding 80ml of deionized water into a 100ml four-mouth bottle, adding NaOH (1.200 g, 0.030 mol) under magnetic stirring, heating to 100 ℃ to completely dissolve, then slowly adding M3 (5.460 g, 0.020 mol), continuing stirring at 100 ℃ after the addition is finished, carrying out reflux reaction for 8 hours (TCL monitoring), pouring the reaction solution into 500ml of 5% diluted hydrochloric acid solution after the reaction is finished, fully and uniformly stirring, precipitating a product, adjusting the pH value to 5.5-6, carrying out suction filtration, washing for three times, and carrying out vacuum drying to obtain M4 with the yield of 90%;
s4: synthesis of M5, reaction formula:
0ff1d1110db7c9c0948fc8b9cfab7be |
adding M4 (2.100 g, 0.010 mol) into a 50ml four-mouth bottle, adding a 5% sodium hydroxide aqueous solution, magnetically stirring, completely dissolving, cooling to-5 ℃, then adding NaNO2 (0.760 g, 0.011 mol), slowly dripping 42% dilute sulfuric acid solution under vigorous stirring for about 1.5h, continuously stirring at-5 ℃ for reaction for 4.5h (TCL monitoring) after the addition is finished, naturally heating to room temperature after the reaction is finished, directly filtering the reaction solution, washing with water to be neutral, and drying in vacuum to obtain M5 with the yield of 70%;
s5: the synthesis of I, reaction formula is as follows:
8ad050d9418a61db60c3a168175a705 |
adding M5 (1.910 g, 0.008 mol) into a 50ml four-neck bottle, adding 20ml ethanol solvent, magnetically stirring, heating to 80 ℃, completely dissolving, keeping a reflux state, slowly dropwise adding indoline (2.012 g, 0.010 mol) under the protection of nitrogen, after finishing dropwise adding, continuing reflux reaction for 4h at 80 ℃ after finishing adding (TCL monitoring), after finishing the reaction, spin-drying ethanol of the reaction solution, then performing petroleum ether/ethyl acetate column chromatography, and spin-drying to obtain the target product I with the yield of 60%.
The results of the obtained product I after the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum are as follows:
the nuclear magnetic resonance hydrogen spectrum characterization data of I are as follows: 1H NMR (400 MHz, CDCl 3): δ (ppm)7.8 (d, J =7.6Hz, 1H), 7.7 (s, 1H), 7.6 (s, 1H), 7.4 (s, 1H), 7.3 (s, 1H), 6.9 (d, J =7.4Hz, 1H), 6.79 (s, 1H), 6.19 (d, J =7.6Hz, 1H), 2.85(d, J =7.6Hz, 3H), 2.41-2.59 (d, 6H), 1.72(s, 6H), 1.65(s, 1H), 1.39(s, 6H);
the nuclear magnetic resonance carbon spectrum characterization data of I are as follows: 13C NMR (400 MHz, CDCl 3): 151.7, 141.9, 138.1, 136.5, 136.5, 136.1, 135.1, 129.4, 128.9, 128.6, 127.9, 127.9, 127.5, 127.1, 126.7, 126.5, 113.5, 113.3, 103.8, 82.94, 44.2, 33.4, 31.4, 31.4, 29.2, 18.4, 18.4, 14.7, 14.4.
Example two
The synthesis steps of the photochromic target compound I are as follows:
s1: synthesis of M2, reaction formula:
0c27eac0037204ad4300eb584f41ad3 |
adding fluorene M1 (8.310 g, 0.050 mol) into a 100ml four-mouth bottle, adding 100ml glacial acetic acid solvent, magnetically stirring, keeping the temperature at 25 ℃, completely dissolving, then slowly adding NBS (8.890 g, 0.050 mol) in three batches, continuously stirring and reacting for 4 hours at 25 ℃ after the addition is finished (TCL monitoring), pouring the reaction solution into a large amount of water after the reaction is finished, separating out a product, performing suction filtration, washing with water, and recrystallizing petroleum ether/ethyl acetate to obtain M2 with the yield of 69%;
s2: synthesis of M3, reaction formula:
dc22bc6934a0d5ce870ae575dfdcf37 |
adding M2 (8.000 g, 0.033 mol) into a 100ml four-neck bottle, adding 42ml of N, N-dimethylformamide solvent, magnetically stirring at normal temperature for 15min, completely dissolving, heating to 60 ℃, then adding sodium hydride (0.960 g, 0.040 mol), finally slowly dropwise adding ethyl bromide (3.596 g, 0.033 mol), continuously stirring at 60 ℃ for reaction for 8h (TCL monitoring) after the addition is finished, pouring the reaction solution into 500ml of water after the reaction is finished, performing suction filtration and water washing for three times, and performing petroleum ether/ethyl acetate column chromatography to obtain M3 with the yield of 83%;
the third step: synthesis of M4, reaction formula:
e4a12bfd6d3ba1c0dc99a5f65d2691c |
adding 70ml of deionized water and 10ml of ethanol into a 100ml four-neck bottle, adding KOH (1.624 g, 0.029 mol) under magnetic stirring, heating to 90 ℃ to completely dissolve, then slowly adding M3 (7.000 g, 0.026 mol), after the addition is finished, continuing stirring at 90 ℃, carrying out reflux reaction for 6 hours (TCL monitoring), after the reaction is finished, dropwise adding 20ml of 10% diluted hydrochloric acid into the reaction solution, fully and uniformly stirring, after a product is separated out, adjusting the pH value to 5-6, carrying out suction filtration, washing with water for three times, and carrying out vacuum drying to obtain M4 with the yield of 92%;
the fourth step: synthesis of M5, reaction formula:
428787e22017c6f75c756bba2e560a1 |
adding M4 (5.200 g, 0.025 mol) into a 100ml four-mouth bottle, adding a 5% sodium hydroxide aqueous solution, magnetically stirring, completely dissolving, cooling to 0 ℃, then adding NaNO2 (2.070 g, 0.030 mol), slowly dripping 30% dilute sulfuric acid solution under vigorous stirring for about 1h, continuously stirring at 0 ℃ for reaction for 4h (TCL monitoring) after the addition is finished, naturally heating to room temperature after the reaction is finished, directly filtering the reaction solution, washing with water to neutrality, and vacuum drying to obtain M5 with the yield of 75%;
the fifth step: the synthesis of I, reaction formula is as follows:
51dcea83b8c9ba43c81a8337e783f31 |
adding M5 (5.123 g, 0.021 mol) into a 100ml four-neck bottle, adding 50ml of isopropanol solvent, magnetically stirring, heating to 83 ℃, completely dissolving, keeping a reflux state, slowly dropwise adding indoline (3.985 g, 0.023 mol) under the protection of argon, after finishing dropwise adding, continuing reflux reaction at 83 ℃ for 6 hours (TCL monitoring), after finishing the reaction, spin-drying methanol of the reaction solution, then performing petroleum ether/ethyl acetate column chromatography, and spin-drying to obtain the target product I with the yield of 72%.
The results of the obtained product I after the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum are as follows:
the nuclear magnetic resonance hydrogen spectrum characterization data of I are as follows: 1H NMR (400 MHz, CDCl 3): δ (ppm)7.8 (d, J =7.6Hz, 1H), 7.7 (s, 1H), 7.6 (s, 1H), 7.4 (s, 1H), 7.3 (s, 1H), 6.9 (d, J =7.4Hz, 1H), 6.88 (s, 1H), 6.79 (s, 1H), 6.52 (s, 1H), 6.19 (d, J =7.6Hz, 1H), 2.85(d, J =7.6Hz, 1H, 3H), 1.72(s, 2H), 1.65(s, 1H), 1.39(s, 6H), 0.96(s, 3H);
the nuclear magnetic resonance carbon spectrum characterization data of I are as follows: 13C NMR (400 MHz, CDCl 3): 151.7, 141.9, 138.1, 136.5, 136.5, 136.1, 135.1, 129.4, 128.9, 128.6, 127.9, 127.9, 127.5, 127.1, 126.7, 126.5, 113.5, 113.3, 103.8, 82.94, 44.2, 33.4, 31.4, 31.4, 29.2, 18.4, 18.4,8.3.
EXAMPLE III
Synthesis of photochromic target compound I:
the first step is as follows: synthesis of M2, reaction formula:
96d7f487d67aa79f2f5f49a2ce059c1 |
adding fluorene M1 (8.31 g, 0.05 mol) into a 100ml four-neck bottle, adding 100ml glacial acetic acid solvent, magnetically stirring, keeping the temperature at 25 ℃, completely dissolving, then slowly adding NBS (8.89 g, 0.05 mol) in three batches, continuously stirring and reacting for 5 hours at 25 ℃ after the addition is finished (TCL monitoring), pouring the reaction solution into a large amount of water after the reaction is finished, separating out a product, performing suction filtration, washing with water, and recrystallizing petroleum ether/ethyl acetate to obtain M2 with the yield of 71%;
the second step is that: synthesis of M3, reaction formula:
ee24a5715397482805e29cb68d24a5f |
adding M2 (8.000 g, 0.033 mol) into a 100ml four-neck bottle, adding 42ml of N, N-dimethylformamide solvent, magnetically stirring at normal temperature for 15min, completely dissolving, heating to 60 ℃, then adding sodium hydride (0.960 g, 0.040 mol), finally slowly dropwise adding ethyl bromide (3.596 g, 0.033 mol), after the addition is finished, continuously stirring and reacting at 60 ℃ for 8h (TCL monitoring), after the reaction is finished, pouring the reaction solution into 500ml of water, performing suction filtration, and performing petroleum ether/ethyl acetate column chromatography for three times by water washing to obtain M3 with the yield of 83%;
the third step: synthesis of M4, reaction formula:
3a8ccd74f84c9d9b4ab8ade04ffd6be |
adding 70ml of deionized water and 10ml of ethanol into a 100ml four-neck bottle, adding KOH (1.624 g, 0.029 mol) under magnetic stirring, heating to 90 ℃ to completely dissolve, then slowly adding M3 (7.000 g, 0.026 mol), after the addition is finished, continuing stirring at 90 ℃, carrying out reflux reaction for 6 hours (TCL monitoring), after the reaction is finished, dropwise adding 20ml of 10% diluted hydrochloric acid into the reaction solution, fully and uniformly stirring, after a product is separated out, adjusting the pH value to 5-6, carrying out suction filtration, washing with water for three times, and carrying out vacuum drying to obtain M4 with the yield of 92%;
the fourth step: synthesis of M5, reaction formula:
3d9c661b87563c604552f77aa15832e |
adding M4 (5.200 g, 0.025 mol) into a 100ml four-mouth bottle, adding a 5% sodium hydroxide aqueous solution, magnetically stirring, completely dissolving, cooling to 0 ℃, then adding NaNO2 (2.070 g, 0.030 mol), slowly dripping 30% dilute sulfuric acid solution under vigorous stirring for about 1h, continuously stirring at 0 ℃ for reaction for 4h (TCL monitoring) after the addition is finished, naturally heating to room temperature after the reaction is finished, directly filtering the reaction solution, washing with water to neutrality, and vacuum drying to obtain M5 with the yield of 75%;
the fifth step: the synthesis of I, reaction formula is as follows:
a87ba8c6e7c49af9bbd9f4fbf2b1f42 |
adding M5 (5.123 g, 0.021 mol) into a 100ml four-neck bottle, adding 50ml ethanol solvent, magnetically stirring, heating to 90 ℃, completely dissolving, keeping a reflux state, slowly dropwise adding indoline (4.227 g, 0.021 mol) under the protection of nitrogen, finishing dropwise adding for 1.5h, continuing reflux reaction at 90 ℃ for 5.5h (TCL monitoring) after finishing adding, spin-drying ethanol of the reaction solution after finishing the reaction, then performing petroleum ether/dichloromethane column chromatography, and spin-drying to obtain a target product I with the yield of 66%.
The results of the obtained product I after the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum are as follows:
the nuclear magnetic resonance hydrogen spectrum characterization data of I are as follows: 1H NMR (400 MHz, CDCl 3): δ (ppm)7.8 (d, J =7.6Hz, 1H), 7.7 (s, 1H), 7.6 (s, 1H), 7.4 (s, 1H), 7.3 (s, 1H), 6.9 (d, J =7.4Hz, 1H), 6.79 (s, 1H), 6.19 (d, J =7.6Hz, 1H), 2.85(d, J =7.6Hz, 1H, 3H), 2.41-2.59 (d, 6H), 1.72(s, 2H), 1.65(s, 1H), 1.39(s, 6H), 0.96(s, 3H);
the nuclear magnetic resonance carbon spectrum characterization data of I are as follows: 13C NMR (400 MHz, CDCl 3): 151.6, 141.9, 138.1, 136.5, 136.5, 136.1, 135.1, 129.4, 128.9, 128.6, 127.9, 127.9, 127.5, 127.1, 126.7, 126.5, 113.5, 113.3, 103.8, 82.94, 44.2, 33.4, 31.4, 31.4, 29.2, 18.4, 18.4, 14.7, 14.4,8.4.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A spirooxazine photochromic compound is characterized in that the molecular structure is as follows:
wherein R is1，R2Is hydrogen, C1-C6Alkyl radical (C)mH2m+1M ═ 1,2,3,4,5,6), benzyl; r3，R4Is hydrogen, halogen, C1-C6Alkyl radical (C)mH2m+1，m＝1,2,3,4,5,6)。
2. The method for preparing the spirooxazine photochromic compound according to claim 1, which is characterized by comprising the following main steps:
s1: the raw material fluorene M1 and N-bromosuccinimide (NBS) are subjected to electrophilic substitution to generate a bromofluorene M2 compound, and the reaction formula is as follows:
s2: the compound M2 is subjected to substitution reaction with halogenated hydrocarbon under the action of alkali to prepare M3, wherein the reaction formula is as follows:
s3: compound M3 was hydrolyzed under basic conditions to prepare compound M4, of the formula:
s4: compound M5 is prepared by the substitution reaction of compound M4 under acidic condition, and the reaction formula is as follows:
s5: compound M5 and indoline in a solvent to prepare target compound I, the reaction formula is as follows:
3. the process for preparing a spirooxazine-based photochromic compound according to claim 2, wherein: the bromination reagent used in the S1 is NBS, the usage amount is 1.0 to 1.2 equivalents, the solvent is glacial acetic acid, the usage amount is 10 to 20 times of the mass of the compound M1, the reaction temperature is 25 to 60 ℃, and the reaction time is 3 to 10 hours.
4. The process for preparing a spirooxazine-based photochromic compound according to claim 2, wherein: the hydrogen removing reagent used in the S2 is sodium hydride, calcium hydride or potassium tert-butoxide, the dosage of the hydrogen removing reagent is 1.0 to 2.5 equivalents, the reaction solvent is one or more of N, N-dimethylformamide, 1, 4-dioxane, toluene or tetrahydrofuran, and the used halohydrocarbon is C1-C6One or more of alkyl chloride, bromide and iodide, the reaction temperature is 0-80 ℃, and the reaction time is 2-12 h.
5. The process for preparing a spirooxazine-based photochromic compound according to claim 2, wherein: the alkali used for hydrolyzing the compound M3 in the S3 is one of sodium hydroxide or potassium hydroxide, the using amount is 1.1 to 1.5 equivalents, the solvent can be one of water, a mixed solvent of water and ethanol or a mixed solvent of water and methanol, the reaction temperature is 80 to 120 ℃, and the reaction time is 5 to 16 hours.
6. The process for preparing a spirooxazine-based photochromic compound according to claim 2, wherein: the acidic catalyst used in S4 is dilute sulfuric acid with the concentration of 20-50%, the nitrosation reagent is sodium nitrite, and the molar ratio of the use amount of the nitrosation reagent to the compound M4 is (1.0-1.3): 1, the reaction temperature is-10-0 ℃, and the reaction time is 1-8 h.
7. The process for preparing a spirooxazine-based photochromic compound according to claim 2, wherein: the mol ratio of the compound M5 to indoline in the S5 is 1: (1.0-1.5), the used solvent is one of methanol, ethanol or isopropanol, the reacted protective gas is one of nitrogen or argon, the reaction temperature is 60-110 ℃, and the reaction time is 2-24 h.
8. The use of the spirooxazine photochromic compound according to claims 1-7 in the field of preparing photochromic glasses, architectural window films and automobile and train window films.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111440193A (en) * | 2020-05-20 | 2020-07-24 | 南开大学 | Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof |
| CN111440193B (en) * | 2020-05-20 | 2023-01-24 | 南开大学 | Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof |
| CN111675723A (en) * | 2020-06-11 | 2020-09-18 | 畅的新材料科技（上海）有限公司 | High-temperature-resistant spirooxazine photochromic compound and preparation method and application thereof |
| CN111808120A (en) * | 2020-06-11 | 2020-10-23 | 畅的新材料科技（上海）有限公司 | Photochromic compound of colorless-to-blue spirooxazine and preparation method and application thereof |
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