CN110343084B - Double-condensed ring naphthopyran photochromic compound and preparation method thereof - Google Patents
Double-condensed ring naphthopyran photochromic compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of organic functional materials, and provides a double-condensed-ring naphthopyran photochromic compound shown in formula I and a preparation method thereof, wherein the preparation method comprises the following steps: 4-methoxy naphthalene-1-yl boric acid pinacol ester reacts with 2-bromoisophthalic acid dimethyl ester under the condition of palladium catalyst to obtain 2- (4-methoxy naphthalene-1-yl) isophthalic acid dimethyl ester M1, and the addition, acidification, cyclization and demethylation of M1 and methyl magnesium bromide are carried out to obtain 1,1,5,5-tetramethyl-1,5-dihydrobenzo [ mno ] M]And reacting the compound M4 with 1,1- (diaryl) -2-propyn-1-ol to generate the target compound I under the catalysis of acid. The compound I can be changed from colorless to purple or blue under the irradiation of ultraviolet light, has the characteristics of reversible process, rapid photoresponse, excellent fatigue resistance, high color ratio and the like.
In the formula I, R 1 And R 2 Identical or different, each represents: hydrogen, straight or branched alkyl of 1 to 6 carbon atoms, straight or branched alkoxy of 1 to 6 carbon atoms, aryl, halogen, NH 2 、‑NRR。
Description
Technical Field
The invention relates to the field of organic photochromic materials, in particular to a double-condensed-ring naphthopyran photochromic compound and a preparation method thereof.
Background
The photochromic property of the natural pyran compound is firstly discovered by Becker in the 60 th century of 20 th century, but as a photochromic material, the stability and the cycle performance are poor, and the use value is low. In the 90 s of the 20 th century, 2,2-diphenyl naphthopyran compounds with better performance are developed and used for commercial color-changing resin lenses. Thus, a large number of photochromic compounds such as naphthopyrans, heteroaromatic pyrans, and indene-condensed ring naphthopyrans have been synthesized. The indene condensed ring naphthopyran compound has better photoresponse, higher fading speed and better fatigue resistance, is a photochromic material with practical application value, and particularly has wide application value in the fields of optical information storage materials, anti-counterfeiting identification, color-changing paint ink, color-changing clothes, color-changing glasses and the like. However, the materials have some disadvantages, such as low color rendering index of color bodies and insufficient quick light response, which limits the application range of the materials.
The development of indene fused ring naphthopyran compounds with good photochromic properties has become one of the hot researches on photochromic materials in recent years. Recently, we have invented a preparation method of polysubstituted indene fused ring 3H-naphtho [1,2-b ] pyran photochromic compounds (CN 108623554A). The material has good fatigue resistance, good photoresponse speed and high color ratio, and researches show that indene condensed rings in the molecular skeleton of the compound are beneficial to improving the performances of the photochromic material. The design and synthesis of the novel naphthopyran photochromic compound further improves the performance of the photochromic compound, expands the actual application range of the photochromic compound, and is a key problem expected to be solved in the field of photochromic materials at present.
Disclosure of Invention
The invention aims to design and synthesize a novel double-condensed-ring naphthopyran photochromic compound and develop a photochromic material with high color ratio, excellent fatigue resistance and quick photoresponse.
In order to achieve the purpose, the invention provides the following technical scheme:
a compound of formula I:
in the formula I, R 1 And R 2 Identical or different, each represents: hydrogen, straight or branched alkyl of 1 to 6 carbon atoms, straight or branched alkoxy of 1 to 6 carbon atoms, aryl, halogen, NH 2 -NRR, R representing a linear or branched alkyl or heterocyclic group containing from 1 to 6 carbon atoms.
Further, it is possible to provideIn particular, the invention protects R in formula I 1 And R 2 Identical or different, each independently represent: hydrogen, straight or branched alkyl of 1 to 3 carbon atoms, straight or branched alkoxy of 1 to 3 carbon atoms, phenyl or substituted phenyl, halogen, NH 2 -NRR, R represents a compound structure of a linear or branched alkyl or heterocyclic group containing 1 to 3 carbon atoms.
In another aspect, the present invention provides a method for preparing the compound as described above, comprising the steps of:
the first step is as follows: 4-methoxy naphthalene-1-yl boronic acid pinacol ester and 2-bromoisophthalic acid dimethyl ester react under the conditions of alkalinity and palladium catalyst to obtain an intermediate compound M1, and the reaction formula is as follows:
the second step is that: the intermediate M1 reacts with a methyl Grignard reagent to obtain a compound M2, and the reaction formula is as follows:
the third step: the compound M3 is obtained by the cyclization of M2 under acidic conditions, and the reaction formula is as follows:
the fourth step: m3 reacts with boron tribromide to obtain a compound M4, wherein the reaction formula is as follows:
the fifth step: m4 and 1,1- (diphenyl) -2-propyne-1-ol generate a target compound I under the catalysis of dodecylbenzene sulfonic acid, wherein the reaction formula is as follows:
in the preparation method as described above, preferably, the base used in the first-step reaction is cesium carbonate, potassium carbonate, sodium carbonate, or the like; the catalyst used in the reaction is palladium tetrakis (triphenyl) phosphine, palladium acetate, palladium dichloride and the like; the reaction solvent is ether solvent tetrahydrofuran and 1,4-dioxane; the reaction temperature is 80-100 ℃. Wherein the mole number of the 4-methoxy naphthalene-1-yl boronic acid pinacol ester is 1.0 to 1.5 times that of the 2-bromoisophthalic acid dimethyl ester.
Preferably, the Grignard reagent used in the second step reaction is methyl magnesium chloride or methyl magnesium bromide, and the mole number of the methyl Grignard reagent is 4 to 6 times that of M2. The reaction temperature is 40-60 ℃. The ether solvent used in the reaction is tetrahydrofuran.
Preferably, the acid used in the third step is polyphosphoric acid, and the reaction temperature is 90-120 ℃.
Preferably, the molar ratio of M3 to boron tribromide in the fourth reaction step is 1: 1-3, and the reaction temperature is-5 ℃ to 0 ℃.
Preferably, the acid used in the fifth step reaction is dodecylbenzene sulfonic acid; the molar ratio of M4 to 1,1- (diaryl) -2-propyn-1-ol is 1: 1.2-1.4; the solvent is toluene, xylene, etc.; the reaction temperature is 40-50 ℃, and the reaction time is 4-6h.
The drugs and reagents used in the above reaction are well known in the art and are commercially available.
The compound solution of the formula I can be changed from colorless to purple under the irradiation of ultraviolet rays, and can be changed from purple to colorless after the irradiation of the ultraviolet rays is stopped, so that the process is reversible. The compound has rapid response to ultraviolet light, can reach a saturated state by maximum absorption of 12.6 seconds of ultraviolet light, has high color ratio and excellent fatigue resistance, and has wide application prospect.
The compound shown in the formula I provided by the invention can be widely applied to the fields of solar protective glasses, glass windows, decorative articles, clothes, paint ink, anti-counterfeiting materials and the like as a photochromic material.
Drawings
FIG. 1 discoloration of Compound Ia before and after light irradiation in Ethyl acetate solution
FIG. 2 the time relationship between the discoloration of compound Ia in ethyl acetate solution and the UV irradiation
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1 preparation of photochromic Compound Ia
The first step is as follows: preparation of compound M1, reaction formula:
a100 mL three-necked flask was charged with 2.4g (8.45 mmol) of 4-methoxynaphthalen-1-ylboronic acid pinacol ester, 1.75g (6.4 mmol) of dimethyl 2-bromoisophthalate, 890mg (0.768 mmol) of palladium tetratriphenylphosphine, and 3.9g (36.86 mmol) of anhydrous sodium carbonate, and the apparatus was evacuated and charged with nitrogen. Injecting 1,4-dioxane/water (V) by syringe Dioxane (dioxane) /V Water (I) = 5:2) mixed solvent 56mL, reaction 12h at 80 ℃, reaction was stopped after tlc monitored disappearance of starting material point. Cooled to room temperature, filtered through celite, the organic phase is washed three times with water and extracted with ethyl acetate. The organic layers were combined and anhydrous MgSO 4 And (5) drying. Distillation under reduced pressure gave a crude product which was isolated by column chromatography (petroleum ether/ethyl acetate = 20) to give M1.8 g as a white solid in 67% yield.
The nuclear magnetic resonance hydrogen spectrum characterization data of M1 is as follows: 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.29(d,J＝8.0Hz,1H),8.00(d,J＝8.0Hz,2H),7.55(t,J＝8.0Hz,1H),7.45–7.41(m,1H),7.39–7.31(m,2H),7.13(d,J＝8.0Hz,1H),6.81(d,J＝8.0Hz,1H),4.03(s,3H),3.83(s,6H).
the second step: preparation of compound M2, reaction formula is as follows:
a100 mL three-necked flask was charged with 1.00g (2.86 mmol) of Compound M1, evacuated, and charged with nitrogen. 20mL of redistilled toluene was injected by a syringe and dissolved by stirring with electric power. 5.71mL (17.14mmol, 3M, 2-methyltetrahydrofuran) of methylmagnesium bromide was injected by syringe, the reaction was refluxed overnight at 100 ℃ and stopped after TLC monitoring the disappearance of the starting material spot. Cooling to room temperature, quenching with saturated sodium chloride solution, washing the organic phase with water three times, and extracting with ethyl acetate. The organic layers were combined and anhydrous MgSO 4 And (5) drying. Distillation under reduced pressure followed by column chromatography (petroleum ether/ethyl acetate/dichloromethane =10 = 1) gave a white solid M2 250mg, yield 25%.
The nuclear magnetic resonance hydrogen spectrum characterization data of M2 is as follows: δ (ppm) 8.29 (d, J =8.0hz, 1h), 7.68 (d, J =8.0hz, 2h), 7.44-7.34 (m, 4H), 7.30 (d, J =8.0hz, 1h), 6.87 (d, J =8.0hz, 1h), 4.06 (s, 3H), 1.64 (s, 2H), 1.30 (s, 6H), 1.19 (s, 6H).
The third step: preparation of compound M3, reaction formula:
a50 mL Schlenk tube was charged with 220mg (0.63 mmol) of Compound M2, 10mL of polyphosphoric acid, evacuated, and purged with nitrogen. Stirring at 100 deg.C until the polyphosphoric acid is dissolved, and reacting for 3h. Pouring the hot reaction solution into an ice-water bath, filtering and drying. Column chromatography separation (petroleum ether/dichloromethane = 20).
The nuclear magnetic resonance hydrogen spectrum characterization data of M3 is as follows: 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.01(d,J＝8.0Hz,1H),7.58(d,J＝8.0Hz,1H),7.51(t,J＝8.0Hz,1H),7.36(d,J＝8.0Hz,1H),7.25-7.22(m,2H),6.92(s,1H),4.06(s,3H),1.74(s,6H),1.59(s,6H).
the fourth step: preparation of photochromic compound M4, the reaction formula is as follows:
adding into 50mL Schlenk tube50mg (0.16 mmol) of compound M3 are evacuated and flushed with nitrogen. 5mL of anhydrous dichloromethane was added, 0.03mL (0.32 mmol) of boron tribromide was injected via syringe, the mixture was allowed to react at 0 ℃ for 1 hour, then the mixture was allowed to cool to room temperature for another 3 hours, and the reaction was stopped by TLC after the disappearance of the starting material. Quenching by adding water, washing the organic phase with water for three times, and extracting with ethyl acetate. The organic layers were combined and anhydrous MgSO 4 And (5) drying. And carrying out reduced pressure distillation to obtain a crude product M4.
The fifth step: preparation of photochromic Compound Ia, the reaction scheme is as follows:
a25 mL single-neck flask was charged with compound M4 mg (0.09 mmol), 1,1, 23mg (0.11 mmol) of diphenyl-2-propyn-1-ol and 10mL of toluene, and the mixture was dissolved by stirring with electric motor. 1-2 drops of dodecylbenzenesulfonic acid were added dropwise and the solution was observed to turn dark purple. The reaction was stopped at 40 ℃ for 3h, after which TLC monitored the disappearance of the starting material. Cooled to room temperature, distilled under reduced pressure and then separated by column chromatography (petroleum ether/ethyl acetate = 50) to obtain Ia 3mg as a white solid with a yield of 6.8%.
The nuclear magnetic resonance hydrogen spectrum characterization data of Ia are: 1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.08(dd,J＝6.4,2.8Hz,1H),7.56-7.48(m,6H),7.34-7.29(m,6H),7.24-7.21(m,2H),7.15(t,J＝9.0Hz,1H),6.24(d,J＝9.0Hz,1H),1.70(s,6H),1.66(s,6H).
example 2 testing of photochromic Properties of Compound Ia
Taking the compound Ia, preparing 8X 10 -5 mol/L ethyl acetate solution. The solution is colorless before illumination, and the solution is rapidly changed from colorless to purple respectively after ultraviolet light illumination.
FIG. 1 shows the discoloration of a toluene solution of compound Ia after 10 seconds of UV irradiation.
FIG. 2 shows the ethyl acetate solution of Compound Ia (8X 10) -5 mol/L) ultraviolet-visible absorption spectrum under light irradiation. From FIG. 2, it was calculated by fitting the formula that the time was 3.6s when the absorbance reached half of the saturation value and 12.6s when the absorbance reached full saturation, indicating that the compound was changedThe color is fast. At a dilute concentration of 8X 10 -5 At mol/L, the saturation absorbance still reaches 0.7, which indicates that the compound Ia has high color ratio.
Irradiation of an Ethyl acetate solution (8X 10) of Compound Ia with UV light -5 mol/L) for 30s, leading the absorbance to reach saturation, measuring the maximum absorbance through ultraviolet visible absorption spectrum, then placing the solution in the dark to be colorless, illuminating for 30s again, and measuring the maximum absorbance of the solution. When the above cycle is repeated for ten times, the maximum absorbance value can still keep 99% of the original value, which indicates that the compound Ia has good fatigue resistance.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any modifications and equivalents made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A dual fused ring naphthopyran photochromic compound having the structure shown in formula I below:
in the formula I, R 1 And R 2 Are all H.
2. A method of preparing a dual fused ring naphthopyran photochromic compound according to claim 1 comprising the steps of:
the first step is as follows: 4-methoxy naphthalene-1-yl boronic acid pinacol ester and 2-bromoisophthalic acid dimethyl ester react under the condition of alkali and palladium catalyst to obtain an intermediate compound M1, wherein the reaction formula is as follows:
the second step is that: the intermediate M1 reacts with a methyl Grignard reagent to obtain a compound M2, and the reaction formula is as follows:
the third step: the compound M3 is obtained by the cyclization of M2 under acidic conditions, and the reaction formula is as follows:
wherein PPA is polyphosphoric acid,
the fourth step: m3 reacts with boron tribromide to obtain a compound M4, wherein the reaction formula is as follows:
the fifth step: m4 and 1,1- (diaryl) -2-propyne-1-alcohol generate a target compound I under the catalysis of dodecylbenzene sulfonic acid, wherein the reaction formula is as follows:
3. the method for preparing a dual fused ring naphthopyran photochromic compound according to claim 2 wherein: in the first step of reaction, the reaction temperature is 80-100 ℃; wherein the mole number of the 4-methoxy naphthalene-1-yl boronic acid pinacol ester is 1.0 to 1.5 times that of the 2-bromoisophthalic acid dimethyl ester.
4. The method for preparing a dual fused ring naphthopyran photochromic compound according to claim 2 wherein: in the second step of reaction, the mole number of the methyl Grignard reagent is 4-6 times of that of M2, and the reaction temperature is 40-60 ℃.
5. The method for preparing a dual fused ring naphthopyran photochromic compound according to claim 2 wherein: the reaction temperature of the third step is 90-120 ℃.
6. The method for preparing a dual fused ring naphthopyran photochromic compound according to claim 2 wherein: in the fourth step of reaction, the molar ratio of M3 to boron tribromide is 1: 1-3, and the reaction temperature is-5 ℃ to 0 ℃.
7. The method for preparing a dual fused ring naphthopyran photochromic compound according to claim 2 wherein: in the fifth step, the acid used in the reaction is dodecyl benzene sulfonic acid, and the molar ratio of M4 to 1,1- (diaryl) -2-propyne-1-alcohol is 1: 1.2-1.4; the reaction temperature is 40-50 ℃, and the reaction time is 4-6h.
8. Use of the dual fused ring naphthopyran photochromic compound of claim 1 in the fields of solar protective eyewear, glazing, decorative articles, apparel, paint inks, and security materials.
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| CN114057682B (en) * | 2021-09-10 | 2023-06-20 | 江苏视科新材料股份有限公司 | Preparation method of dibenzochromene compound |
| CN114031596B (en) * | 2021-09-10 | 2023-07-28 | 江苏视科新材料股份有限公司 | Dibenzo chromene photochromic compound and application thereof |
| CN114031598B (en) * | 2021-09-10 | 2023-07-28 | 江苏视科新材料股份有限公司 | Preparation method of polysubstituted dibenzochromene compound |
| CN115073412B (en) * | 2022-07-08 | 2024-05-07 | 天津孚信阳光科技有限公司 | Fluorescent group modified indene fused ring naphthopyran photochromic compound and preparation method and application thereof |
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| JP2000327676A (en) * | 1999-05-24 | 2000-11-28 | Tokuyama Corp | Chromene compound |
| CN108623554A (en) * | 2018-05-08 | 2018-10-09 | 天津孚信阳光科技有限公司 | Polysubstituted indenes condensed ring photochromic compound of naphtho-pyrans and preparation method thereof |
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| JP2000327676A (en) * | 1999-05-24 | 2000-11-28 | Tokuyama Corp | Chromene compound |
| CN108623554A (en) * | 2018-05-08 | 2018-10-09 | 天津孚信阳光科技有限公司 | Polysubstituted indenes condensed ring photochromic compound of naphtho-pyrans and preparation method thereof |
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