CN108250174B - Naphthopyran compounds and preparation method thereof - Google Patents
Naphthopyran compounds and preparation method thereof Download PDFInfo
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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- C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
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Abstract
The invention discloses a naphthopyran compound and a preparation method thereof, wherein the compound has stable performance and breaks through the structural deficiency of the prior naphthopyran compound. The preparation method comprises the following steps: (1) dissolving diaryl divinyl compounds and naphthol compounds in a solvent to obtain a pre-reaction mixed solution; (2) and (2) reacting the pre-reaction mixed solution obtained in the step (1) at the temperature of 50-80 ℃ under the condition of a catalyst to obtain the naphthopyran compounds. The preparation method has the advantages of simple steps, mild conditions, easy realization, greenness, environmental protection and more suitability for industrial production.
Description
Technical Field
The invention relates to a compound and a preparation method thereof, in particular to a novel naphthopyran compound and a preparation method thereof.
Background
The pyran compound has better light responsiveness, faster fading speed and better light stability, so that the pyran compound becomes another photochromic dye with practical application value after the spirooxazine compound. In particular to the preparation of protective materials for photochromic resin glasses and vehicles. The pyran-based photochromic compounds are roughly classified into naphthopyrans and heteroaromatic benzopyran-based compounds.
Photochromic materials are receiving attention because of their increasing popularity in light energy conversion, optical lenses, automotive windshields, optical anti-counterfeiting, decorative materials, etc., and their great potential application prospects in the fields of optical information storage, optical recording, optical switches, etc. Many studies and preparations of organic photochromic materials have been reported. The naphthopyran compound is an important organic photochromic material, has better photoresponse, higher fading speed and better light stability, and has wide application in the fields of non-silver salt photosensitive materials, erasable optical discs, organic photochromic resin lenses, anti-counterfeiting and the like.
The photochromic phenomenon of photochromic materials is generated by the structural change of compounds, and is realized by heterolysis and recombination of bonds under illumination, as shown in the following illumination reaction:
the photoresponse performance and the fatigue resistance are two important indexes of the photochromic substance, and the required color can also be realized by blending different colors, so that the synthesis of various photochromic substances with good photoresponse, excellent fatigue resistance and different color-changing effects has important application value. Since the color-changing effect of the photochromic compound depends on the change of the absorption wavelengths of the closed ring body and the open ring body, and the conjugation degree of the molecular structure of the photochromic compound has the influence of blue shift or red shift on the absorption wavelength, the common structural change is to add a proper substituent group on a reaction substrate to change the conjugation degree of the product molecule so as to achieve the purpose of changing the color-changing effect of the photochromic substance.
In general, the currently used synthesis methods mainly include the following three methods: the first is Kabbe synthesis method, which is usually carried out by condensation reaction of o-hydroxyacetophenone or o-hydroxynaphthophenone compound and ketone, and reduction and dehydration of the obtained intermediate; the second method is that aryl Grignard reagent reacts with benzocoumarin, and then the product is obtained by dehydration; and thirdly, propargyl aryl ether is synthesized in situ by propargyl alcohol and naphthol or phenol, and then under the acidic condition, the propargyl aryl ether is subjected to claisen rearrangement reaction to obtain a product. However, each of these methods has disadvantages such as severe reaction conditions, difficult storage of intermediates, low yield, etc., which limits the industrial production process.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a naphthopyran compound and a preparation method thereof, wherein the compound has stable performance and fills the structural defect of the naphthopyran compound in the prior art; the preparation method solves the problems that the existing preparation method has harsh conditions, difficult storage of intermediates, low yield, unsuitability for industrial production and the like.
The technical scheme is as follows: the naphthopyran compound has a structural general formula shown as a formula (III):
in the structural general formula, R1、R2And R3Each independently selected from the group consisting of H, halogen, cyano, alkyl, alkoxy, formyl, carboxamido, benzoyl, and ethyl formate.
Wherein R is1Independently selected from the group consisting of H, cyano, halogen, alkoxy, formyl, carboxamido, benzoyl and ethyl formate.
The halogen is one or more of F, Cl and Br, preferably Br.
The alkoxy is one or more of C1-C4 alkoxy, preferably methoxy.
And, R2And R3Each independently selected from H, halogen, alkyl and alkoxy.
The halogen is one or more of F, Cl and Br.
The alkyl is one or more of C1-C4 alkyl, preferably methyl.
The alkoxy is one or more of C1-C4 alkoxy, preferably methoxy.
The preparation method of the naphthopyran compound comprises the following steps:
(1) dissolving diaryl allene compound of formula (I) and naphthol compound of formula (II) in solvent to obtain pre-reaction mixed solution.
(2) And (2) reacting the pre-reaction mixed solution obtained in the step (1) at the temperature of 50-80 ℃ under the condition of a catalyst to obtain the naphthopyran compounds.
The reaction route is as follows:
R1、R2and R3Each independently selected from the group consisting of H, halogen, cyano, alkyl, alkoxy, formyl, carboxamido, benzoyl, and ethyl formate.
Wherein R is1Independently selected from the group consisting of H, cyano, halogen, alkoxy, formyl, carboxamido, benzoyl and ethyl formate.
The halogen is one or more of F, Cl and Br, preferably Br.
The alkoxy is one or more of C1-C4 alkoxy, preferably methoxy and ethoxy, and further preferably methoxy.
And, R2And R3Each independently selected from H, halogen, alkyl and alkoxy.
The halogen is one or more of F, Cl and Br.
The alkyl is one or more of C1-C4 alkyl, preferably methyl and ethyl, and further preferably methyl.
The alkoxy is one or more of C1-C4 alkoxy, preferably methoxy and ethoxy, and further preferably methoxy.
In the step (1), the concentration of the diarylethene compound is 0.1 to 0.2mol/L, preferably 0.13 to 0.17mol/L, and more preferably 0.15 mol/L.
The molar ratio of the diarylethene compound to the naphthol compound is 1-2:1, preferably 1.3-1.7:1, and more preferably 1.5: 1.
The solvent is selected from organic solvent with better solubility, and is one or more of dichloromethane, dichloroethane, chloroform and toluene, preferably dichloroethane.
In the step (2), the reaction temperature is preferably 80 ℃.
The catalyst is a phosphonic acid catalyst. The phosphonic acid catalyst is preferably diphenyl phosphate, and the using amount of the catalyst is 5 mol% of the amount of the naphthol compound.
In the reaction with poor substrate activity, a cocatalyst is also added in the step (2).
The cocatalyst is an acidic cocatalyst. The acidic cocatalyst is one or more of benzoic acid, trifluorobenzoic acid, p-toluenesulfonic acid and trifluorosulfonic acid, the dosage of the acidic cocatalyst is the dosage of the catalyst, and the specific dosage of the acidic cocatalyst is less than 5 mmol% of the amount of the naphthol compound. However, the reaction substrate having a high reactivity may be free of a cocatalyst.
The specific preparation method of the naphthopyran compound comprises the following steps:
(1) diaryl allene compounds of formula (I) and naphthol compounds of formula (II) are dissolved in dichloroethane to obtain a pre-reaction mixture solution.
(2) Adding a catalyst (relative to 5mmol of the naphthol compound) into the pre-reaction mixed solution obtained in the step (1), and reacting at normal temperature for 20-40min, preferably 30 min; heating to 50-80 deg.C, stirring for 7-9h, preferably 80 deg.C, stirring for 8h, cooling to room temperature, adding cocatalyst (5 mmol% relative to naphthol compound), stirring at 70-90 deg.C and 80 deg.C for 20-40min, preferably 80 deg.C for 30min, to obtain reaction mixture solution.
(3) After the reaction is completed, cooling the reaction mixed solution to normal temperature, and separating by using a silica gel column to obtain the product naphthopyran compound.
The naphthopyran compounds prepared by the method are nearly thirty or more, wherein the structural formula of partial products is as follows:
the compound name corresponding to the above structural formula is:
1. 3-diphenylmethylenenaphthopyran; 2. 6-methoxy-3-diphenylmethylenenaphthopyran; 3. 10-methoxy-3-diphenylmethylenenaphthopyran; 4. 7-bromo-3-diphenylmethylenenaphthopyran; 5. 6-bromo-3-diphenylmethylenenaphthopyran; 6. 10-bromo-3-diphenylmethylenenaphthopyran; 7. 7-cyano-3-diphenylmethylene naphthopyran; 8. 7-benzoyl-3-diphenylmethylenenaphthopyran; 9. 7-formate-3-diphenylmethylenenaphthopyran; 10. 3-diphenylmethyleneanthrapyrane; 11. 3-diphenylmethylenepyrene-benzopyran; 12. n-benzoyl-3-diphenylmethyleneindolopyran; 13. 3, 5-dimethoxy-3-diphenylmethylenebenzopyran; 14. 3-diphenylmethylenebenzopyran; 15. 3, 10-bis (diphenylmethyl) -naphthopyran; 16. 3, 11-bis (diphenylmethylene) -naphthopyran; 17. 2, 8-bis (diphenylmethyl) -naphthopyran; 18. 1, 2-bis (3-diphenylmethylene) naphtho-and-pyrane peroxosulfide; 19. 3-bis (4-fluorophenylmethylene) naphthopyran; 20. 3-bis (4-bromophenylmethylene) naphthopyran; 21. 3-bis (4-chlorophenylmethylene) naphthopyran; 22. (E) -3- (4-chlorophenyl) phenylmethylene-naphthopyran; 23. (E) -3- (4-methylphenyl) phenylmethylene-naphthopyran; 24. (E) -3- (naphthyl) phenylmethylene-naphthopyran; 25. (E) -3-phenylthiophenylmethylene-naphthopyran; 26. (Z) - [ (1, 3-diphenylmethylenenaphthopyranyl) phenylmethylene ] naphthopyran.
Has the advantages that: 1. the novel naphthopyran compound provided by the invention has stable performance and higher purity; 2. breaks through the structural deficiency of the prior naphthopyran compounds; 3. a brand new large pi bond delocalized electron body is beneficial to the development of the photochromic performance of the structure; 4. the preparation method has simple steps, and the naphthopyran compounds can be prepared by one-step reaction; 5. the condition is mild and easy to realize; 6. the preparation process does not generate new three wastes, is environment-friendly, and provides a green and environment-friendly synthetic method for adapting to the development of times; 7. the preparation method has the advantages of fewer raw materials, fewer reaction devices, fewer preparation steps and lower cost, and is more suitable for industrial production.
Drawings
FIG. 1 is a drawing of 3-diphenylmethylenenaphthopyran as prepared in example 1 of the present invention1H-NMR spectrum;
FIG. 2 is a drawing of 3-diphenylmethylenenaphthopyran as prepared in example 1 of the present invention13C-NMR spectrum.
Detailed Description
Example 1
Preparation of 1, 3-diphenylmethylene naphthopyrans comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 2-naphthol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 30 minutes. The temperature is increased to 80 ℃ and stirring is continued for 8 h. After the reaction is completed, the reaction product is cooled to normal temperature, and the product 1, 3-diphenyl methylene naphthopyran is obtained by silica gel column separation, with the yield of 93%.
Structural characterization data:1H-NMR(400MHz,CDCl3)δ7.90(d,J＝8.5Hz,1H),7.72(dd,J＝8.2,1.3Hz,1H),7.64(d,J＝8.9Hz,1H),7.47(ddd,J＝8.5,7.4,1.4Hz,3H),7.41–7.25(m,8H),7.23–7.14(m,1H),7.10–7.05(m,1H),7.02(d,J＝10.3Hz,1H),6.46(d,J＝10.3Hz,1H)。
13C-NMR(101MHz,CDCl3)δ151.74,146.86,140.31,139.39,131.30,130.03,129.87,129.66,128.84,128.58,128.57,127.71,126.98,126.87,126.03,124.32,121.80,121.14,120.41,116.75,116.27,114.30。
HRMS(ESI+):m/z Calcd.for C26H19O[M+H]+:347.1436.Found:347.1421；for C26H18NaO[M+Na]+:369.1255.Found:369.1283。
example 2
The preparation of 6-methoxy-3-diphenylmethylene naphthopyran, comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 7-methoxynaphthol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 8 h. The reaction intermediate was separated off, added again to dichloroethane DCE (5mL) and the catalyst phosphonic acid (5 mmol%) was added, the temperature was raised to 80 ℃ and stirring was carried out for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, the reaction product is cooled to normal temperature, and is separated by a silica gel column to obtain a product, namely 6-methoxy-3-diphenyl methylene naphthopyran, with the yield of 73%.
1H-NMR(400MHz,CDCl3)δ7.60(d,J＝8.9Hz,1H),7.55(d,J＝8.8Hz,1H),7.50–7.43(m,2H),7.40–7.33(m,2H),7.29(tdd,J＝7.9,5.2,2.4Hz,6H),7.23–7.15(m,2H),7.01(dd,J＝8.9,2.4Hz,1H),6.94(t,J＝8.9Hz,2H),6.44(d,J＝10.3Hz,1H),3.88(s,3H)。
13C-NMR(101MHz,CDCl3)δ158.74,152.37,146.84,140.37,139.41,131.32,130.23,130.12,129.84,129.66,128.53,127.69,126.82,125.98,125.24,121.19,120.51,116.33,116.12,114.25,113.43,100.43,77.32,77.00,76.68,55.22。
HRMS(ESI+):m/z Calcd.for C27H21O2[M+H]+:377.1542.Found:377.1526；C27H20NaO2[M+Na]+:399.1361.Found:399.1360。
Example 3
Preparation of 10-methoxy-3-diphenylmethylene naphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 3-methoxynaphthol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 8 h. The reaction intermediate was separated off, added again to dichloroethane DCE (5mL) and the catalyst phosphonic acid (5 mmol%) was added, the temperature was raised to 80 ℃ and stirring was carried out for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, the mixture is cooled to normal temperature, and is separated by a silica gel column to obtain a product, namely 10-methoxy-3-diphenyl methylene naphthopyran, with the yield of 60%.
1H-NMR(400MHz,CDCl3)δ7.90–7.81(m,1H),7.73–7.62(m,3H),7.44–7.38(m,2H),7.38–7.33(m,3H),7.33–7.28(m,4H),7.20–7.14(m,1H),7.08(s,1H),6.99(d,J＝10.3Hz,1H),6.40(d,J＝10.3Hz,1H),3.97(s,3H).
13C-NMR(101MHz,CDCl3)δ147.32,146.70,140.08,138.75,131.56,130.07,129.49,128.71,128.17,127.76,127.56,127.24,126.96,125.90,124.87,124.65,124.08,122.36,120.99,120.18,115.04,108.02,77.32,77.00,76.68,56.02.
HRMS(ESI+):m/z Calcd.for C27H21O2[M+H]+:377.1542.Found:377.1533；C27H20NaO2[M+Na]+:399.1361.Found:399.1354.
Example 4
Preparation of 7-bromo-3-diphenylmethylenenaphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 6-bromonaphthol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 30 minutes. The temperature is increased to 80 ℃ and stirring is continued for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, the reaction product is cooled to normal temperature, and the product 7-bromo-3-diphenyl methylene naphthopyran is obtained by silica gel column separation, with the yield of 79%.
1H-NMR(400MHz,CDCl3)δ7.82(d,J＝2.1Hz,1H),7.69(d,J＝9.0Hz,1H),7.52–7.40(m,4H),7.40–7.33(m,2H),7.33–7.23(m,5H),7.22–7.16(m,1H),7.03(d,J＝8.9Hz,1H),6.88(d,J＝10.3Hz,1H),6.44(d,J＝10.3Hz,1H).
13C-NMR(101MHz,CDCl3)δ151.82,146.49,140.08,139.17,131.20,130.94,130.44,130.10,129.65,128.91,128.58,127.72,127.26,126.97,126.18,122.94,122.35,119.80,118.06,117.80,116.90,114.56,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C26H17BrNaO[M+Na]+:447.0360.Found:447.0365.
Example 5
The preparation of 6-bromo-3-diphenylmethylene naphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 7-methoxynaphthol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 30 minutes. The temperature is increased to 80 ℃ and stirring is continued for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, the reaction product is cooled to normal temperature, and is separated by a silica gel column to obtain the product 6-bromo-3-diphenylmethylene naphthopyran with the yield of 69 percent.
1H-NMR(400MHz,CDCl3)δ8.04(d,J＝1.9Hz,1H),7.58(t,J＝8.5Hz,2H),7.49–7.42(m,2H),7.42–7.34(m,2H),7.34–7.25(m,5H),7.23–7.16(m,1H),7.07(d,J＝8.9Hz,1H),6.90(d,J＝10.3Hz,1H),6.48(d,J＝10.3Hz,1H).
13C-NMR(101MHz,CDCl3)δ152.38,146.50,140.08,139.22,131.21,130.15,130.02,129.86,129.69,128.60,128.25,127.74,127.66,127.01,126.21,123.76,116.98,122.28,121.61,119.81,117.19,113.74,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C26H17BrNaO[M+Na]+:447.0360.Found:447.0334.
Example 6
Preparation of 10-bromo-3-diphenylmethylenenaphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 3-bromonaphthol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 30 minutes. The temperature is increased to 80 ℃ and stirring is continued for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, the reaction product is cooled to normal temperature, and the product 10-bromo-3-diphenyl methylene naphthopyran is obtained by silica gel column separation, with the yield of 63%.
1H-NMR(400MHz,CDCl3)δ7.91(s,1H),7.86(d,J＝8.5Hz,1H),7.67–7.54(m,3H),7.53–7.44(m,1H),7.42–7.35(m,3H),7.35–7.26(m,6H),7.25–7.16(m,1H),6.95(d,J＝10.3Hz,1H),6.47(d,J＝10.3Hz,1H).
13C-NMR(101MHz,CDCl3)δ148.33,146.36,140.03,138.40,132.45,131.26,130.41,130.19,128.63,127.84,127.66,127.60,127.18,127.10,126.41,125.24,122.75,121.29,119.67,117.89,116.10,110.39,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C26H18BrO[M+H]+:425.0541.Found:425.0539；C26H17BrNaO[M+Na]+:447.0360.Found:447.0364.
Example 7
Preparation of 7-cyano-3-diphenylmethylene naphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 6-cyanonaphthol 2(0.5mmol) were added to dichloroethane DCE (5mL) and stirred until the dienol was dissolved and the insoluble naphthol was stirred until there were no solid particles. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 8 h. The reaction intermediate was separated off, added again to dichloroethane DCE (5mL) and the catalyst phosphonic acid (5 mmol%) was added, the temperature was raised to 80 ℃ and stirring was carried out for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, cooling to normal temperature, adding a little silica gel, spin-drying, and separating by using a silica gel column to obtain the product 7-cyano-3-diphenyl methylene naphthopyran with the yield of 72%.
1H-NMR(400MHz,CDCl3)δ8.05(d,J＝1.7Hz,1H),7.92(d,J＝8.8Hz,1H),7.65(d,J＝8.9Hz,1H),7.59–7.52(m,1H),7.48–7.40(m,2H),7.41–7.34(m,2H),7.32(t,J＝7.5Hz,3H),7.29–7.19(m,4H),7.12(d,J＝8.9Hz,1H),6.91(d,J＝10.4Hz,1H),6.50(d,J＝10.3Hz,1H).
13C-NMR(101MHz,CDCl3)δ153.90,146.03,139.72,138.86,134.50,131.05,130.37,130.23,129.67,128.68,128.61,127.77,127.47,127.18,126.48,122.91,122.45,119.25,119.08,118.58,117.95,114.80,107.61,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C27H18NO[M+H]+:372.1388.Found:372.1380；C27H17NNaO[M+Na]+:394.1208.Found:394.1202.
Example 8
Preparation of 7-benzoyl-3-diphenylmethylene naphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 6-benzoylnaphthol 2(0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 8 h. The reaction intermediate was separated off, added again to dichloroethane DCE (5mL) and the catalyst phosphonic acid (5 mmol%) was added, the temperature was raised to 80 ℃ and stirring was carried out for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, cooling to normal temperature, adding a little silica gel, spin-drying, and separating by using a silica gel column to obtain the product 7-benzoyl-3-diphenyl methylene naphthopyran with the yield of 84%.
1H-NMR(400MHz,CDCl3)δ8.15(d,J＝1.6Hz,1H),8.03–7.92(m,2H),7.87–7.80(m,2H),7.71(d,J＝8.8Hz,1H),7.64–7.57(m,1H),7.52–7.44(m,4H),7.42–7.35(m,2H),7.34–7.26(m,5H),7.24–7.17(m,1H),7.12(d,J＝8.9Hz,1H),7.02(d,J＝10.3Hz,1H),6.51(d,J＝10.3Hz,1H).
13C-NMR(101MHz,CDCl3)δ196.15,153.61,146.38,139.96,139.08,137.83,133.19,132.62,132.27,131.56,131.15,130.83,129.92,129.68,128.63,128.60,128.31,127.74,127.06,127.00,126.29,122.38,121.56,119.95,117.73,117.31,114.62,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C33H23O2[M+H]+:451.1698.Found:451.1690；C33H22NaO2[M+Na]+:473.1517.Found:473.1514.
Example 9
Preparation of 7-formate-3-diphenylmethylene naphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 6-cyanonaphthol 2(0.5mmol) were added to dichloroethane DCE (5mL) and stirred until the dienol was dissolved and the insoluble naphthol was stirred until there were no solid particles. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 8 h. The reaction intermediate was separated off, added again to dichloroethane DCE (5mL) and the catalyst phosphonic acid (5 mmol%) was added, the temperature was raised to 80 ℃ and stirring was carried out for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, cooling to normal temperature, adding a little silica gel, then spin-drying, and separating by using a silica gel column to obtain the product 7-formate-3-diphenylmethylene naphthopyran with the yield of 64%.
1H-NMR(400MHz,CDCl3)δ8.46(d,J＝1.7Hz,1H),8.04(dd,J＝8.9,1.7Hz,1H),7.91(dd,J＝8.8,2.4Hz,1H),7.77–7.68(m,1H),7.45(dd,J＝8.3,1.4Hz,2H),7.40–7.34(m,2H),7.34–7.25(m,5H),7.25–7.18(m,1H),7.14–7.09(m,1H),7.05–6.95(m,1H),6.48(d,J＝10.3Hz,1H),3.95(s,3H).
13C-NMR(101MHz,CDCl3)δ166.98,153.52,146.42,140.02,139.13,131.61,131.44,131.18,131.09,129.69,128.94,128.60,127.75,127.04,126.41,126.28,125.88,122.30,121.40,119.99,117.65,114.55,77.32,77.00,76.68,52.16.
HRMS(ESI+):m/z Calcd.for C28H21O3[M+H]+:405.1491.Found:405.1479；C28H20NaO3[M+Na]+:427.1310.Found:427.1258.
Example 10
Preparation of 3-diphenylmethylene naphthopyrans comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 9-anthracenol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 30 minutes. The temperature is increased to 80 ℃ and stirring is continued for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, the reaction product is cooled to normal temperature, and is separated by a silica gel column to obtain the product 3-diphenylmethylene anthrapyran, wherein the yield is 85%.
1H-NMR(400MHz,CDCl3)δ8.60–8.45(m,2H),8.17(dd,J＝8.2,1.4Hz,1H),7.94(dd,J＝8.2,1.5Hz,1H),7.66–7.45(m,6H),7.44–7.23(m,8H),7.04(d,J＝10.3Hz,1H),6.58(d,J＝10.3Hz,1H).
13C-NMR(101MHz,CDCl3)δ148.02,146.75,140.35,139.71,131.18,131.03,129.66,128.53,127.88,127.70,127.65,127.18,127.00,126.93,126.83,126.35,124.94,123.68,123.03,122.46,122.23,121.69,121.56,120.96,116.40,110.93,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C30H21O[M+H]+:397.1592.Found:397.1572；C30H20NaO[M+Na]+:419.1412.Found:419.1311.
Example 11
The preparation method of the 3-diphenyl methylenepyrene benzopyran comprises the following steps:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 4-pyrenephenol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 30 minutes. The temperature is increased to 80 ℃ and stirring is continued for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, the reaction product is cooled to normal temperature, and is separated by a silica gel column to obtain a product, namely 3-diphenyl methylene pyrene benzopyran, with the yield of 50%.
1H-NMR(400MHz,CDCl3)δ8.13(d,J＝9.2Hz,1H),8.06–7.95(m,2H),7.93–7.85(m,2H),7.82(d,J＝1.4Hz,2H),7.66(s,1H),7.64–7.59(m,2H),7.49–7.37(m,5H),7.37–7.30(m,4H),6.70(d,J＝10.0Hz,1H),6.57(d,J＝10.0Hz,1H).
13C-NMR(101MHz,CDCl3)δ147.11,146.69,140.12,139.53,131.67,131.49,131.19,129.90,128.54,127.87,127.32,127.05,126.83,126.62,126.46,126.28,125.88,125.72,125.67,124.85,124.78,124.51,122.41,121.76,120.40,118.90,118.61,117.87,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C30H21O[M+H]+:397.1592.Found:397.1572；C30H20NaO[M+Na]+:419.1412.Found:419.1311.
Example 12
The preparation of N-benzoyl-3-diphenylmethylene indolopyran comprises the following steps:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and N-benzoylindole-7-ol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved (insoluble naphthol was stirred until no solid particles, 3g,3 i). Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 8 h. The reaction intermediate was separated off, added again to dichloroethane DCE (5mL) and the catalyst phosphonic acid (5 mmol%) was added, the temperature was raised to 80 ℃ and stirring was carried out for 8 h. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, cooling to normal temperature, adding a little silica gel, spin-drying, and separating by using a silica gel column to obtain the product N-benzoyl-3-diphenylmethylene indolopyran with the yield of 55%.
1H-NMR(400MHz,CDCl3)δ8.21(d,J＝8.9Hz,1H),7.75–7.68(m,2H),7.64–7.57(m,1H),7.56–7.46(m,4H),7.43–7.34(m,2H),7.34–7.24(m,6H),7.23–7.15(m,1H),6.92(d,J＝8.9Hz,1H),6.66(d,J＝10.1Hz,1H),6.61(d,J＝3.8Hz,1H),6.44(d,J＝10.1Hz,1H).
13C-NMR(101MHz,CDCl3)δ168.45,150.06,146.93,140.36,139.35,134.25,131.96,131.67,131.36,129.73,129.13,128.81,128.60,128.53,127.69,127.01,126.86,126.09,122.24,121.21,117.15,117.02,112.98,112.93,105.47,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C31H22NO2[M+H]+:440.1651.Found:440.1638；C31H21NNaO2[M+Na]+:462.1470.Found:462.1477.
Example 13
The preparation of 3, 5-dimethoxy-3-diphenylmethylene benzopyran comprises the following steps:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 3, 5-dimethoxyphenol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 8 h. The reaction intermediate was isolated, added again to dichloroethane DCE (5mL), p-toluene sulfonic acid TsOH (20 mmol%) was added, and stirred at 80 ℃ for 8 h. After the reaction is completed, cooling to normal temperature, adding a little silica gel, spin-drying, and separating by using a silica gel column to obtain the product 3, 5-dimethoxy-3-diphenylmethylene benzopyran with the yield of 40%.
1H-NMR(400MHz,CDCl3)δ7.44–7.38(m,2H),7.36–7.30(m,2H),7.30–7.20(m,5H),6.64(d,J＝10.2Hz,1H),6.15(d,J＝10.2Hz,1H),6.05(q,J＝2.3Hz,2H),3.77(s,3H),3.76(s,3H).
13C-NMR(101MHz,CDCl3)δ161.55,155.59,154.93,146.90,140.56,139.71,131.34,129.72,128.42,127.65,126.64,125.77,119.62,117.29,115.64,104.79,92.94,92.81,77.32,77.00,76.68,55.59,55.52.
HRMS(ESI+):m/z Calcd.for C24H21O3[M+H]+:357.1491.Found:357.1483；C24H20NaO3[M+Na]+:379.1310.Found:379.1305.
Example 14
Preparation of 3, 10-bis (diphenylmethyl) -naphthopyran comprising the steps of:
2-benzyloxy-1, 1-diphenyl-2, 3-dienol (0.75mmol,1.5equiv.) and 2, 7-naphthalenediol (0.5mmol) were added to dichloroethane DCE (5mL) and stirred until both substrates were dissolved. Catalyst phosphonic acid (5 mmol%) was added and the reaction was carried out at room temperature for 30 minutes. The temperature is increased to 80 ℃, and the stirring is continued for 8 hours. After cooling to normal temperature, p-toluenesulfonic acid TsOH (5 mmol%) was added, and the mixture was stirred at 80 ℃ for 30 min. After the reaction is completed, cooling to normal temperature, adding a little silica gel, then spin-drying, separating by using a silica gel column to obtain a product containing impurities, and then volatilizing and crystallizing in a mixed solvent of DCM/MeOH to obtain a clean product of 3, 10-bis (diphenylmethyl) -naphthopyran, wherein the yield is 73%.
1H-NMR(400MHz,CDCl3)δ7.88–7.82(m,2H),7.48–7.33(m,12H),7.31–7.27(m,4H),7.02–6.92(m,2H),6.89–6.71(m,6H),6.46(d,J＝10.3Hz,2H).
13C-NMR(101MHz,CDCl3)δ146.28,140.80,140.68,138.05,131.59,129.54,128.67,127.33,127.00,126.36,125.49,124.87,123.72,121.69,119.24,118.60,116.80,77.32,77.00,76.68.
HRMS(ESI+):m/z Calcd.for C42H29O2[M+H]+:565.2168.Found:565.2155；C42H28NaO2[M+Na]+:587.1987.Found:587.1979.
The amounts of catalyst and cocatalyst in examples 1-14 above were in mole percent relative to the naphthol compound.
Claims (4)
1. A preparation method of a naphthopyran compound is characterized by comprising the following steps:
(1) dissolving a diaryl allene compound shown in a formula (I) and a naphthol compound shown in a formula (II) in a solvent to obtain a pre-reaction mixed solution;
(2) reacting the pre-reaction mixed solution obtained in the step (1) at the temperature of 50-80 ℃ under the condition of a catalyst to obtain the naphthopyran compound formula (III);
the reaction route is as follows:
wherein R is1、R2And R3Each independently selected from H, halogen, cyano, alkyl, alkoxy, formyl, carboxamido, benzoyl and ethyl formate;
in the step (1), dichloroethane is used as a solvent, and diphenyl phosphate is used as a catalyst in the step (2).
2. The process for producing a naphthopyran-based compound according to claim 1, characterized in that: in the step (1), the concentration of the diaryl allene compound is 0.1-0.2 mol/L.
3. The process for producing a naphthopyran-based compound according to claim 1, characterized in that: the molar ratio of the diaryl allene compound to the naphthol compound is 1-2: 1.
4. The process for producing a naphthopyran-based compound according to claim 1, characterized in that: a cocatalyst is also added in the step (2); the cocatalyst is toluenesulfonic acid.
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