CN111440193B - Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof - Google Patents
Indene-thick naphtho-spirooxazine photochromic compound and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic photochromic materials, and particularly discloses an indene-condensed naphthospirooxazine photochromic compound which has a structure shown as a formula I, wherein R is 1 Is hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen or nitro; r 2 And R 3 Is straight chain or branched chain alkyl with 1-6 carbon atoms, and provides a synthesis method of the compound. The indene-thick naphthospirooxazine photochromic compound has the characteristics of quick photoresponse, quick fading, no ground color, good fatigue resistance and the like.
Description
Technical Field
The invention relates to the field of organic photochromic materials, in particular to an indene-condensed naphthospirooxazine photochromic compound and a preparation method thereof.
Background
Photochromic refers to that under the irradiation of light with a certain wavelength, the molecular structure of some compounds changes, which results in the obvious change of the absorption spectrum and the accompanying color change. And the original state is recovered under the irradiation of light with another wavelength or under the action of heat. The phenomenon of photochromism is a reversible chemical change process. In recent years, photochromic materials have been widely used in the fields of optical information storage, optical switches, optical modulation, optical devices, photochromic glasses, photochromic clothes, and the like.
The organic photochromic compound mainly comprises various types such as diarylethene, azobenzene, benzene/naphthopyran, spirooxazine and the like. Wherein, the color change mechanism of the diaryl ethylene photochromic compound is a pericyclic reaction and is a P-type photochromic compound. The color-changing compound has the characteristics of bistable structure (open ring body and closed ring body), high photoresponse rate (open ring and closed ring reaction is in picosecond range), excellent fatigue resistance and the like, and is widely applied to the fields of information storage, anti-counterfeiting printing and the like. The main drawback of diarylethene photochromic materials is represented by the low efficiency of the photoreaction conversion, generally not more than 50%. In addition, the synthesis conditions of the compounds are harsh, the cost is high, and the main factors limiting the application of the compounds are high.
Azobenzene is a widely researched photochromic material, and the color change mechanism of azobenzene is cis-trans isomerization reaction based on azo double bonds, and the azobenzene is a T-type photochromic material. The azobenzene photochromic material has the main characteristics of simple structure and easy synthesis. The disadvantages are low conversion and slow conversion rates of the cis-trans isomerisation reaction, especially at room temperature. In addition, the color and the insignificant contrast of cis-trans isomers also limit the practical application range.
The benzene/naphthopyran compounds also belong to T-type color-changing materials, and the color-changing mechanism is that C-O bond heterolysis under ultraviolet irradiation causes a ring-opening reaction, and the ring-closing reaction is stopped to return to an initial state after the ultraviolet irradiation. The compound has the outstanding advantages that the closed ring body is colorless, the color of the open ring body is presented, the color can be regulated and controlled through structural modification, the fatigue resistance is better, and the compound has use value in the aspects of sunlight protective glasses, color-changing curtains and the like. The benzene/naphthopyran photochromic compounds have the disadvantages that the color change bodies contain TT-type isomers, the color fading speed is slow, and the complete color fading is generally required to be more than 8 minutes or even several hours.
The spirooxazine photochromic compound also belongs to a T-type photochromic material, a spiro C-O bond in a molecule is heterolytic under the excitation of ultraviolet light, so that a ring-opening reaction is caused to generate a color-changing body, and the color-changing body is subjected to a ring-closing reaction under the action of visible light or heat to return to an initial colorless state. Compared with naphthopyran photochromic compounds, spirooxazine photochromic compounds have outstanding photosensitivity and fatigue resistance, and have higher color ratio, so that the spirooxazine photochromic compounds have wider practical application range.
The development of photochromic compounds with fast photoresponse, fast fading and good fatigue resistance has become one of the research hotspots in the field of organic functional materials in recent years. Recently, we have disclosed a process for preparing photochromic compounds of indene fused-ring naphthopyrans (CN 110295037A, CN110343084A). The introduction of indene fused rings improves the rate of color and the rate of color fading of naphthopyran compounds, but the rate of color fading still needs to be further improved due to the presence of the color-changing TT-type isomer.
Therefore, the same intermediate for synthesizing the indene fused ring naphthopyran compound is adopted to prepare the novel indene fused ring naphthospirooxazine photochromic compound through two-step reaction, and the compound has the advantages of outstanding photoresponse, rapid fading, good fatigue resistance and the like, and has practical application value in the fields of solar protective glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like.
Disclosure of Invention
The invention aims to provide an indene thick naphtho spirooxazine photochromic compound which has the advantages of quick photoresponse, quick fading, no bottom color and good fatigue resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an indene thick naphtho spirooxazine photochromic compound has a structure shown in a formula I:
in formula I: r 1 Hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen, nitro and the like; r 2 And R 3 Each independently is a linear or branched hydrocarbon group having 1 to 6 carbon atoms.
Preferably, R 1 Is hydrogen, straight chain or branched chain alkyl, straight chain or branched chain alkoxy, halogen; r 2 And R 3 Each independently is a straight-chain or branched-chain hydrocarbon group having 1 to 6 carbon atoms.
Further preferably, R 1 Hydrogen, straight chain alkyl, straight chain alkoxy, halogen; r 2 And R 3 Is a straight chain hydrocarbon group with 1-6 carbon atoms.
Most preferably, R 1 Hydrogen, methyl, methoxy, chlorine; r 2 And R 3 Is methyl.
In another aspect, the present invention provides a method for preparing the compound as described above, comprising the steps of:
(1) Synthesis of 7,7-dimethyl-5-nitroso-7H-benzo [ c ] fluoren-6-ol
Mixing 7,7-dimethyl-7H-benzo [ c ]]Adding fluorene-6-alcohol, a proper amount of organic solvent and water with the same volume into a round-bottom flask, and cooling in an ice bath. Adding NaOH dilute solution, continuously stirring for 30 minutes, and slowly adding a small amount of NaNO 2 The reaction was carried out in an ice bath for 1 hour. And (3) dropwise adding a dilute sulfuric acid solution into the reaction system, reacting for 1 hour at low temperature after dropwise adding is finished, and concentrating the reaction solution under reduced pressure to remove the solvent after the reaction is finished. The residue was subjected to silica gel column chromatography to obtain an orange solid product.
(2) Synthesis of Compounds of formula I
The 7,7-dimethyl-5-nitroso-7H-benzo [ c ] obtained in the previous step]Adding the fluorene-6-alcohol into a reaction bottle, and adding ethanol for dissolving. N is a radical of 2 Protecting, stirring and heating to 90 ℃. Slowly dripping the ethanol solution of the 2-methylene indoline derivative, and carrying out reflux reaction for 12-24 hours. The reaction mixture was cooled to room temperature, and the solvent was removed by concentrating the reaction mixture under reduced pressure. Separating the residue with silica gel column chromatography to obtain brown solidI。
In the preparation method as described above, preferably, the organic solvent in the first step reaction is a water-miscible solvent, and may be acetone, acetonitrile, tetrahydrofuran, dioxane; in the reaction, the mole number of the sodium nitrite is 7,7-dialkyl-7H-benzo [ c ] fluorene-6-alcohol which is 1 to 1.2 times that of the sodium nitrite; an eluent for silica gel column chromatography adopts a mixed solution with the volume ratio of petroleum ether to ethyl acetate = 20.
Preferably, the mole number of the 2-methyleneindoline derivative in the second step reaction is 7,7-dimethyl-5-nitroso-7H-benzo [ c ] fluorene-6-alcohol is 1.1-1.5 times, and the eluent for silica gel column chromatography adopts a mixed solution with the volume ratio of petroleum ether to ethyl acetate = 200.
The invention provides application of a compound shown as a formula I as a photochromic material in the fields of sun protection glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like.
The compound solution of the formula I can change from colorless to blue or green under the irradiation of ultraviolet rays. The light can fade from a colored state to colorless after stopping illumination, and the fading rate is high, and the light can fade to the colorless state within 3 seconds. The compound has the advantages of quick photoresponse, quick fading, no ground color, good fatigue resistance and the like, and has practical application prospects in the fields of sun protection glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like.
Drawings
FIG. 1 shows the discoloration phenomena of the compound Ia of example 1 before and after light irradiation in a toluene solution, from left to right, before light irradiation, after light irradiation was stopped, respectively.
FIG. 2 shows the discoloration phenomena before and after irradiation with light of the compound Ib of example 2 in a toluene solution, wherein the discoloration phenomena are, from left to right, before irradiation with light, after the irradiation with light is stopped.
FIG. 3 is a graph showing the change of absorbance with the number of cycles in a toluene solution of Compound Id of example 4
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, the drugs and reagents used are commercially available or known in the art.
Example 1 preparation of photochromic Compound Ia
The first step is as follows: synthesis of 7,7-dimethyl-5-nitroso-7H-benzo [ c ] fluoren-6-ol
7,7-dihydrocarbyl-7H-benzo [ c ] fluoren-6-ol (0.41g, 1.6 mmol), 20mL acetonitrile, 20mL water and 3mL sodium hydroxide (2%) solution were added to a round bottom flask, iced, and stirred. A small amount of sodium nitrite (0.11g, 1.65mmol) as a solid was added thereto, and the mixture was stirred at 0 to 5 ℃ for 1 hour. To the reaction mixture was added 0.38mL of a dilute sulfuric acid solution (5.6M), and the reaction was continued for 1 hour. Filtering, washing the filter cake with small amount of water for 2 times, and drying. The crude product was purified by silica gel column chromatography using a mixed solution of petroleum ether and ethyl acetate =30 as an eluent in a volume ratio of 0.36g to obtain a product as an orange solid in a yield of 78%.
7,7-dihydrocarbyl-7H-benzo [ c]The nuclear magnetic resonance hydrogen spectrum characterization data of the fluorene-6-alcohol is as follows: 1 H NMR(400MHz,CDCl 3 )δ8.36(d,J＝7.7Hz,1H),8.26(d,J＝7.8Hz,1H),8.20(d,J＝7.2Hz,1H),7.74(t,J＝7.2Hz,1H),7.59–7.52(m,3H),7.52–7.47(m,1H),1.56(s,6H).
7,7-dihydrocarbyl-7H-benzo [ c]The nuclear magnetic resonance carbon spectrum characterization data of the fluorene-6-alcohol are as follows: 13 C NMR(101MHz,CDCl 3 )δ:181.33,177.15,158.62,149.44,146.97,136.91,135.06,133.46,131.84,130.85,130.54,130.20,127.75,126.38,125.35,122.81,48.59,24.54.
the second step is that: preparation of photochromic Compound Ia, the reaction scheme is as follows:
7,7-dimethyl-5-nitroso-7H-benzo [ c]Adding 0.35g (1.20 mmol) of fluorene-6-alcohol and 30mL of ethanol into a reaction bottle, stirring for dissolving, and heatingTo 90 ℃. N is a radical of 2 Protection, slowly adding dropwise 5mL ethanol solution containing 1,3,3,5-tetramethyl-2-methylene indoline 0.27g (1.50 mmol), refluxing and reacting for 24 hours. The reaction mixture was cooled to room temperature, and the solvent was removed by concentrating the reaction mixture under reduced pressure. The crude product was purified by silica gel column chromatography using a mixed solution of petroleum ether and ethyl acetate =200 as an eluent in a volume ratio of the residue to yield 90mg of a brown oily product in a yield of 17%.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ia are: 1 H NMR(400MHz,CDCl 3 )δ8.73(d,J＝8.0Hz,1H),8.70(d,J＝8.0Hz,1H),8.32(d,J＝8.0Hz,1H),7.83(s,1H),7.63–7.60(m,1H),7.56–7.53(m,1H),7.42–7.40(m,2H),7.36–7.32(m,1H),7.00(d,J＝8.0Hz),6.94(s,1H),6.43(d,J＝8.0Hz,1H),2.63(s,3H),2.36(s,3H),1.46(s,3H),1.44(s,6H),1.34(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ia are as follows: 13 C NMR(101MHz,CDCl 3 )δ:155.82,148.77,145.24,141.78,139.76,139.55,136.44,136.27,131.34,129.21,128.13,127.14,126.89,126.15,125.39,124.69,123.78,123.38,123.06,122.72,122.18,122.12,106.87,98.00,51.27,47.49,29.81,25.90,24.72,24.21,21.11,20.75.
example 2 preparation of photochromic Compound Ib, the reaction scheme is as follows:
7,7-dimethyl-5-nitroso-7H-benzo [ c]0.29g (1.00 mmol) of fluorene-6-ol and 30mL of ethanol were added to a reaction flask, dissolved by stirring, and heated to 90 ℃. N is a radical of hydrogen 2 Protection, slowly adding dropwise 5mL ethanol solution containing 0.25g (1.20 mmol) of 5-chloro-1,3,3-trimethyl-2-methylene indoline, and refluxing for 24 hours. The reaction mixture was cooled to room temperature, and the solvent was removed by concentrating the reaction mixture under reduced pressure. The crude product was purified by silica gel column chromatography using a mixture of petroleum ether/ethyl acetate =200 as an eluent in a volume ratio of 80mg to 17% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ib are as follows: 1 H NMR(400MHz,CDCl 3 )δ8.71(d,J＝8.0Hz,2H),8.32(d,J＝8.0Hz,1H),7.82(s,1H),7.64–7.60(m,1H),7.57–7.53(m,1H),7.42–7.38(m,2H),7.37–7.33(m,1H),7.16(d,J＝8.0Hz),7.09(s,1H),6.44(d,J＝8.0Hz,1H),2.64(s,3H),1.44(s,3H),1.42(s,6H),1.33(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ib are as follows: 13 C NMR(101MHz,CDCl 3 )δ:155.74,147.81,146.06,141.45,139.54,139.43,138.11,136.76,131.30,127.76,127.19,127.04,126.27,125.49,124.85,124.66,123.80,123.42,122.98,122.72,122.23,121.86,108.02,97.75,51.27,47.47,29.78,25.69,24.76,24.24,20.47
example 3 preparation of photochromic Compound Ic the reaction scheme is as follows:
the 7,7-dimethyl-5-nitroso-7H-benzo [ c ] obtained in the previous step]0.15g (0.52 mmol) of fluorene-6-ol and 20mL of ethanol were added to a reaction flask, dissolved by stirring, and heated to 90 ℃. N is a radical of hydrogen 2 Protection, slowly adding 5mL ethanol solution containing 1,3,3-trimethyl-2-methylene indoline 111mg (0.62 mmol), refluxing reaction for 24 hours. The reaction mixture was cooled to room temperature, and the solvent was removed by concentrating the reaction mixture under reduced pressure. The crude product was purified by silica gel column chromatography using a mixed solution of petroleum ether and ethyl acetate =200 as an eluent in a volume ratio of the residue to give 70mg of a brown oily product in a yield of 30%.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ic are: 1 H NMR(400MHz,CDCl 3 )δ8.74(d,J＝8.0Hz,1H),8.70(d,J＝8.0Hz,1H),8.31(d,J＝8.0Hz,1H),7.84(s,1H),7.63–7.59(m,1H),7.56–7.52(m,1H),7.43–7.39(m,2H),7.35–7.31(m,1H),7.22–7.19(m,1H),7.13(d,J＝8.0Hz,1H),6.92(t,J＝8.0Hz,1H),6.53(d,J＝8.0Hz,1H),2.67(s,3H),1.45(s,3H),1.44(s,3H),1.43(s,3H),1.32(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Ic are: 13 C NMR(101MHz,CDCl 3 )δ:155.81,148.64,147.41,141.71,139.72,139.54,136.55,136.17,131.35,128.00,127.18,126.95,126.21,125.44,124.76,123.81,123.41,123.01,122.75,122.22,121.25,120.01,107.13,97.83,51.27,47.48,29.72,25.81,24.68,24.18,20.71.
example 4 preparation of photochromic compound Id, the reaction scheme is as follows:
7,7-dimethyl-5-nitroso-7H-benzo [ c]0.30g (1.04 mmol) of fluorene-6-ol and 30mL of ethanol are added into a reaction flask, stirred to be dissolved, and heated to 90 ℃. N is a radical of 2 Protection, slowly adding 5mL ethanol solution containing 0.25g (1.25 mmol) of 5-methoxy-1,3,3-trimethyl-2-methylene indoline dropwise, and refluxing for 24 hours. The reaction mixture was cooled to room temperature, and the solvent was removed by concentrating the reaction mixture under reduced pressure. The crude product was purified by silica gel column chromatography using a mixed solution of petroleum ether and ethyl acetate =200 as an eluent in a volume ratio of 100mg to 20% yield.
The NMR hydrogen spectrum characterization data of Id is: 1 H NMR(400MHz,CDCl 3 )δ8.71(d,J＝8.4Hz,1H),8.68(d,J＝8.4Hz,1H),8.30(d,J＝8.4Hz,1H),7.82(s,1H),7.62–7.58(m,1H),7.55–7.52(m,1H),7.41–7.39(m,2H),7.35–7.31(m,1H),6.76–6.71(m,2H),6.42(d,J＝8.4Hz,1H),3.83(s,3H),2.61(s,3H),1.44(s,3H),1.43(s,3H),1.42(s,3H),1.32(s,3H).
the nuclear magnetic resonance carbon spectrum characterization data of Id are as follows: 13 C NMR(101MHz,CDCl 3 )δ:155.80,154.28,148.51,141.77,141.58,139.73,139.52,137.81,136.46,131.32,127.13,126.90,126.16,125.38,124.68,123.77,123.37,122.69,126.19,111.51,109.15,107.31,98.19,55.92,51.38,47.48,30.04,25.75,24.70,24.19,20.55.
example 5 photochromic Properties testing of Compound Ia
Weighing compound Ia to prepare 8X 10 -5 A toluene solution of mol/L. Before illumination, the solution is colorless, and the toluene solution is rapidly changed from colorless to blue-green by illumination with a xenon lamp light source (electric power of 180W; optical power of 50W; ultraviolet power of 2.6W; visible light power of 19.6W).
FIG. 1 shows the discoloration of a toluene solution of compound Ia after 30 seconds of light exposure. The compound is colorless before color change and is blue-green after illumination according to the color change phenomenon. The light was stopped and the solution changed from blue-green to colorless and transparent within 3 seconds.
EXAMPLE 6 testing of photochromic Properties of Compound Ib
Weighing compound Ib, and preparing into 8 × 10 -5 A toluene solution of mol/L. Before illumination, the solution is colorless, and the toluene solution is rapidly changed from colorless to blue by irradiation of a xenon lamp light source (electric power is 180W; optical power is 50W; ultraviolet power is 2.6W; visible light power is 19.6W).
FIG. 2 shows the discoloration of a toluene solution of compound Ib after 30 seconds of light irradiation. The compound is colorless before color change and blue after illumination according to the color change phenomenon. The light was stopped and the solution changed from blue to colorless and transparent within 3 seconds.
As can be seen from the color-changing property test, the indene thick naphthospirooxazine photochromic compound has the outstanding advantages of colorless solution before illumination, quick illumination color change, high decoloring speed (complete decoloring time is 3 seconds) and no bottom color. The decolorization rate is obviously better than that of the currently commercialized indene-thick naphthopyran compounds (the complete decolorization time is 8 minutes, dyespigments 2019,169, 118-124.).
In practical tests, after the illumination is stopped, the solution is instantly changed from blue or blue-green to colorless and transparent, even is lower than the lowest detection limit of an instrument and can only be observed by naked eyes.
Fatigue resistance test of Compound Id of example 7
Weighing compound Id, configuring by 8 × 10 -5 And (3) testing a photochromic/fading cycle curve by using an ultraviolet spectrophotometer in a toluene solution of mol/L. In the experiment, the solution was irradiated under Xe-150 xenon for 30 seconds to saturate the absorbance. The solution was then left in the dark for 30min, and the maximum absorption wavelength (. Lamda.) was measured at the time of photochromic saturation and at the time of fading to the colorless state, respectively max =560 nm). The cycle was repeated 10 times and the collected data was plotted as a cycle graph as shown in fig. 3.
Although the preferred embodiments of the present invention have been described in detail, the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (6)
1. An indene thick naphtho spirooxazine photochromic compound has a structural formula shown as the following formula I:
in the formula: r 1 Hydrogen, methyl, methoxy, chlorine; r 2 And R 3 Each independently is a linear or branched hydrocarbon group having 1 to 6 carbon atoms.
2. The indene-fused naphthospirooxazine photochromic compound of claim 1, wherein: r 1 Is hydrogen, methyl, methoxy, chlorine, R 2 And R 3 Is methyl.
3. The process for preparing indene-thick naphthospirooxazine photochromic compounds according to any of claims 1 to 2, characterized in that the process comprises the following steps:
(1) Synthesis of 7,7-dimethyl-5-nitroso-7H-benzo [ c ] fluoren-6-ol
Mixing 7,7-dimethyl-7H-benzo [ c ]]Adding fluorene-6-alcohol, a proper amount of organic solvent and water with the same volume into a round-bottom flask, and cooling in an ice bath; adding NaOH dilute solution, continuously stirring for 30 minutes, and slowly adding a small amount of NaNO 2 Reacting for 1 hour in ice bath; dropwise adding a dilute sulfuric acid solution into the reaction system, and reacting for 1 hour at low temperature after dropwise adding; after the reaction is finished, concentrating the reaction solution under reduced pressure to remove the solvent; separating the residue by a silica gel column chromatography to obtain an orange solid product;
(2) Synthesis of Compounds of formula I
The 7,7-dimethyl-5-nitroso-7H-benzo [ c ] obtained in the previous step]Adding fluorene-6-ol and ethanol into a reaction flask, N 2 Protecting, stirring and heating to 90 ℃; slowly dripping ethanol solution of 2-methylene indoline derivative, and carrying out reflux reaction for 12-24 hours; cooling to room temperature, and concentrating the reaction solution under reduced pressure to remove the solvent; the residue was separated by silica gel column chromatography to give brown solid I.
4. The method for preparing the indene-fused naphthospirooxazine photochromic compound according to claim 3, wherein the photochromic compound comprises: the organic solvent in the first step of reaction is a water-miscible solvent selected from acetone, acetonitrile, tetrahydrofuran and dioxane; the mole number of the sodium nitrite in the reaction is 7,7-dialkyl-7H-benzo [ c ] fluorene-6-alcohol which is 1 to 1.2 times; the eluent for silica gel column chromatography adopts a mixed solution with the volume ratio of petroleum ether to ethyl acetate = 20.
5. The method for preparing the indene-fused naphthospirooxazine photochromic compound according to claim 3, wherein the photochromic compound comprises: the mole number of the 2-methylene indoline derivative in the second step reaction is 7,7-dimethyl-5-nitroso-7H-benzo [ c ] fluorene-6-alcohol is 1.1-1.5 times, and the eluent for silica gel column chromatography adopts a mixed solution with the volume ratio of petroleum ether to ethyl acetate = 200.
6. Use of a compound according to any one of claims 1 to 2 in the field of sun protection glasses, glazings, decorative articles, clothing, paint inks, security materials.
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