CN113149848B - Diphenylamine derivative organic room-temperature phosphorescent compound and preparation method and application thereof - Google Patents
Diphenylamine derivative organic room-temperature phosphorescent compound and preparation method and application thereof Download PDFInfo
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- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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Abstract
The invention provides a diphenylamine derivative organic room-temperature phosphorescent compound which is characterized in that the structural formula of the diphenylamine derivative organic room-temperature phosphorescent compound is shown as a formula 1,
wherein R is1、R2、R3、R4Each independently selected from hydrogen and C1-C6 alkyl. The diphenylamine derivative organic room-temperature phosphorescent compound has a long afterglow phenomenon, all solid crystals of the diphenylamine derivative can generate room-temperature phosphorescence, and the phosphorescence service life can reach 660ms at most under the room-temperature condition. The invention also provides a preparation method of the diphenylamine derivative organic room-temperature phosphorescent compound, which has the advantages of simple synthesis steps, mild preparation conditions, high yield and low cost and is suitable for large-scale production. The diphenylamine derivative organic room-temperature phosphorescent compound can be applied to preparation of anti-counterfeiting marks, anti-counterfeiting films and the like.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a diphenylamine derivative organic room-temperature phosphorescent compound and a preparation method and application thereof.
Background
The pure organic room temperature phosphorescent material with ultra-long luminescence life can be applied to the fields of Organic Light Emitting Diodes (OLED), biological images, chemical sensors, optical and anti-counterfeiting technologies and the like due to the property of afterglow after an excitation light source is removed. In recent years, the compound has attracted much attention because of its wide application prospect.
However, in the prior art, such materials have been scarce so far, and the main reason is that the knowledge of the light-emitting mechanism is not deep enough, so that the theoretical guidance of molecular design is lacked.
Therefore, there is a need to develop a long-life pure organic room temperature phosphorescent material.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art to a certain extent, and in a first aspect of the present invention, the present invention provides a diphenylamine derivative organic room-temperature phosphorescent compound, which has a structural formula shown in formula 1,
wherein R is1、R2、R3、R4Each independently selected from hydrogen and C1-C6 alkyl; preferably, R1One selected from hydrogen, methyl, isopropyl and tert-butyl; r2Is hydrogen or methyl; r3Is hydrogen or methyl; r4Is hydrogen or methyl.
In a second aspect of the present invention, the present invention provides a method for preparing a diphenylamine derivative organic room-temperature-phosphorescent compound as described in the first aspect of the present invention, which is prepared from a compound represented by formula 2 and a compound represented by formula 3, and has the following reaction formula:
wherein R is1、R2、R3、R4Each independently selected from hydrogen and C1-C6 alkyl; preferably, R1One selected from methyl, isopropyl and tert-butyl; r2Is hydrogen or methyl; r3Is hydrogen or methyl; r4Is hydrogen or methyl.
In one or more embodiments of the present invention, a method for preparing a diphenylamine derivative organic room-temperature-phosphorescent compound, includes the steps of:
step 1): under the inert gas atmosphere, reacting a compound shown in a formula 2, a compound shown in a formula 3 and alkali under the action of a catalyst;
step 2): cooling the reaction liquid obtained in the step 1) to 15-35 ℃, and purifying to obtain the diphenylamine derivative organic room-temperature phosphorescent compound.
In one or more embodiments of the present invention, in the step 1), the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium.
In one or more embodiments of the invention, in step 1), the base is sodium tert-butoxide; preferably, the solvent used for the reaction is toluene.
In one or more embodiments of the present invention, in the step 1), the amount ratio of the compound represented by formula 2 to the substance represented by formula 3, the base, and the catalyst is 1.0:1.1:2.0: 0.03.
In one or more embodiments of the invention, in the step 1), the reaction is heated to reflux reaction for 10-24 hours; preferably, the reaction is a heat to reflux reaction for 16 hours.
In one or more embodiments of the present invention, in the step 2), the purifying includes: extracting the reaction solution with dichloromethane, collecting the organic phase, and adding anhydrous Na2SO4Drying and spin-drying to obtain a crude product; separating the crude product by silica gel column chromatography with petroleum ether as eluent.
In a third aspect of the invention, the invention provides a diphenylamine derivative organic room-temperature phosphorescent compound in the first aspect of the invention and/or a preparation method of a diphenylamine derivative organic room-temperature phosphorescent compound in the second aspect of the invention, which is applied to preparation of an anti-counterfeiting mark.
In a fourth aspect of the present invention, there is provided an anti-counterfeiting film comprising the diphenylamine derivative organic room-temperature phosphorescent compound as described in the first aspect of the present invention.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a diphenylamine derivative organic room-temperature phosphorescent compound, which has a long afterglow phenomenon, wherein solid crystals of the diphenylamine derivative organic room-temperature phosphorescent compound can generate the room-temperature phosphorescence, and the phosphorescence service life is up to 660ms at room temperature.
2. The invention provides a preparation method of the diphenylamine derivative organic room-temperature phosphorescent compound, which has the advantages of simple synthesis steps, mild preparation conditions, high yield and low cost, and is suitable for large-scale production.
3. The diphenylamine derivative organic room-temperature phosphorescent compound provided by the invention can be applied to preparation of anti-counterfeiting marks, anti-counterfeiting films and the like.
4. The invention provides an anti-counterfeiting film which comprises the diphenylamine derivative organic room-temperature phosphorescent compound provided by the invention.
Drawings
FIG. 1 is a scheme for the synthesis of diphenylamine derivative organic room-temperature phosphorescent compounds;
FIG. 2 is a diagram showing the room temperature phosphorescent afterglow phenomenon of diphenylamine DPA and the organic room temperature phosphorescent compounds S1-DPA-Me, S4-DPA-iPr and S4-DPA-tBu prepared in examples 2, 3 and 4 of the present invention;
FIG. 3 is a graph of the room temperature fluorescence spectrum and phosphorescence lifetime of diphenylamine DPA and diphenylamine derivative organic room temperature phosphorescent compounds S1-DPA-Me, S4-DPA-iPr and S4-DPA-tBu prepared in examples 2, 3 and 4 of the present invention; wherein, FIG. 3a is a fluorescence spectrum and a phosphorescence spectrum, and FIG. 3b is a phosphorescence lifetime chart;
FIG. 4 shows a security device composed of DPA, S4-DPA-iPr and S4-DPA-tBu.
Detailed Description
The invention provides a diphenylamine derivative organic room-temperature phosphorescent compound, a preparation method of the diphenylamine derivative organic room-temperature phosphorescent compound, application of the diphenylamine derivative organic room-temperature phosphorescent compound and an anti-counterfeiting film.
Diphenylamine derivative organic room-temperature phosphorescent compound
In a first aspect of the invention, the invention provides a diphenylamine derivative organic room-temperature phosphorescent compound, the structural formula of which is shown in formula 1,
wherein R is1、R2、R3、R4Are respectively independentIs one selected from hydrogen and C1-C6 alkyl; preferably, R1One selected from hydrogen, methyl, isopropyl and tert-butyl; r2Is hydrogen or methyl; r3Is hydrogen or methyl; r4Is hydrogen or methyl.
Preparation method of diphenylamine derivative organic room-temperature phosphorescent compound
In a second aspect of the present invention, the present invention provides a method for preparing a diphenylamine derivative organic room-temperature-phosphorescent compound as described in the first aspect of the present invention, which is prepared from a compound represented by formula 2 and a compound represented by formula 3, and has the following reaction formula:
wherein R is1、R2、R3、R4Each independently selected from hydrogen and C1-C6 alkyl; preferably, R1One selected from methyl, isopropyl and tert-butyl; r2Is hydrogen or methyl; r3Is hydrogen or methyl; r4Is hydrogen or methyl.
In one or more embodiments of the present invention, a method for preparing a diphenylamine derivative organic room-temperature-phosphorescent compound, includes the steps of:
step 1): under the inert gas atmosphere, reacting a compound shown in a formula 2, a compound shown in a formula 3 and alkali under the action of a catalyst;
step 2): cooling the reaction liquid obtained in the step 1) to 15-35 ℃, and purifying to obtain the diphenylamine derivative organic room-temperature phosphorescent compound.
In one or more embodiments of the present invention, in the step 1), the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium.
In one or more embodiments of the invention, in step 1), the base is sodium tert-butoxide; preferably, the solvent used for the reaction is toluene.
In one or more embodiments of the present invention, in the step 1), the amount ratio of the compound represented by formula 2 to the substance represented by formula 3, the base, and the catalyst is 1.0:1.1:2.0: 0.03.
In one or more embodiments of the invention, in the step 1), the reaction is heated to reflux reaction for 10-24 hours; preferably, the reaction is a heat to reflux reaction for 16 hours.
In one or more embodiments of the present invention, in the step 2), the purifying includes: extracting the reaction solution with dichloromethane, collecting the organic phase, and adding anhydrous Na2SO4Drying and spin-drying to obtain a crude product; separating the crude product by silica gel column chromatography with petroleum ether as eluent.
Diphenylamine derivative organic room-temperature phosphorescent compound and/or application of preparation method thereof
In a third aspect of the invention, the invention provides a diphenylamine derivative organic room-temperature phosphorescent compound in the first aspect of the invention and/or a preparation method of a diphenylamine derivative organic room-temperature phosphorescent compound in the second aspect of the invention, which is applied to preparation of an anti-counterfeiting mark.
Anti-counterfeiting film
In a fourth aspect of the present invention, there is provided an anti-counterfeiting film comprising the diphenylamine derivative organic room-temperature phosphorescent compound as described in the first aspect of the present invention.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
Example 1: DPA
The structural formula of compound DPA is as follows:
the compound DPA is commercially available. Using petroleum ether as eluent, subjecting compound DPA to silica gel chromatography, separating and purifying, vacuum drying to obtain white solid compound DPA, and subjecting to hydrogen spectrum and carbon spectrum of nuclear magnetic resonance1H NMR,13C NMR) the structure was characterized, confirming that the white solid was compound DPA. The detection results are as follows:
DPA：1H NMR(400MHz,CDCl3)δ7.28(s,1H),7.27(d,J＝1.1Hz,2H),7.25(d,J＝2.0Hz,1H),7.09(d,J＝1.1Hz,3H),7.06(d,J＝1.0Hz,2H),6.95–6.90(m,2H),5.70(s,1H).13C NMR(100MHz,CDCl3)δ143.11,129.34,120.99,117.80.
example 2: synthesis of S1-DPA-Me
The structural formula of the target compound S1-DPA-Me is as follows:
the synthesis of S1-DPA-Me comprises the following steps:
under the protection of nitrogen, in a reaction bottle, 2-methylaniline (1.62mL, 15mmol, 1eq.), 2-bromobenzene (1.73mL, 16.5mmol, 1.1eq.), NaOtBu (2.88g, 30mmol, 2eq.) and Pd (dppf) Cl2·CH2Cl2([1,1' -bis (diphenylphosphino) ferrocene)]Palladium dichloride) (0.37g, 0.45mmol, 0.03eq.) was dissolved in sufficient toluene solvent. And the mixture was heated to 110 ℃ with stirring and the reaction was continued for 16 hours. After the reaction mixture was cooled to room temperature (15 to 35 ℃), the reaction was quenched with 1M dilute hydrochloric acid, extracted with dichloromethane, and the resulting organic layer was washed with a saturated aqueous sodium chloride solution (200mL), dried over anhydrous sodium sulfate, and the solvent was removed to obtain a crude product. Petroleum ether is used as eluent to remove crude productSubjecting the product to silica gel chromatography, separating and purifying, and vacuum drying to obtain white solid compound S1-DPA-Me (1.59g, 58%) and hydrogen spectrum and carbon spectrum by NMR (C:)1H NMR,13C NMR) the structure was characterized and confirmed to be the compound S1-DPA-Me as a white solid. The detection results are as follows:
S1-DPA-Me:1H NMR(400MHz,CDCl3)δ7.28(s,2H),7.24(s,1H),7.21(d,J＝7.4Hz,1H),7.15(t,J＝7.6Hz,1H),6.94(dt,J＝20.3,7.4Hz,4H),5.40(s,1H),2.27(s,3H).13C NMR(100MHz,CDCl3)δ143.98,141.22,130.95,129.32,128.29,126.77,121.99,120.48,118.78,117.46,77.36,77.04,76.72,17.92.
example 3: synthesis of S4-DPA-iPr
The structural formula of the target compound S4-DPA-iPr is as follows:
the synthesis of S4-DPA-iPr comprises the following steps:
under the protection of nitrogen, 2-isopropyl-6-methylaniline (2.38mL, 15mmol, 1eq.) 2-bromo-1, 3-xylene (2.27mL, 16.5mmol, 1.1eq.), NaO were placed in a reaction flasktBu (2.88g, 30mmol, 2eq.) and Pd (dppf) Cl2·CH2Cl2([1,1' -bis (diphenylphosphino) ferrocene)]Palladium dichloride) (0.37g, 0.45mmol, 0.03eq.) was dissolved in sufficient toluene solvent. And the mixture was heated to 110 ℃ with stirring and the reaction was continued for 16 hours. After the reaction mixture was cooled to room temperature (15 to 35 ℃), the reaction was quenched with 1M dilute hydrochloric acid, extracted with dichloromethane, and the resulting organic layer was washed with a saturated aqueous sodium chloride solution (200mL), dried over anhydrous sodium sulfate, and the solvent was removed to obtain a crude product. Separating and purifying the crude product by silica gel chromatography with petroleum ether as eluent, and vacuum drying to obtain white solid compound S4-DPA-iPr (2.42g, 62%), and hydrogen spectrum and carbon spectrum by NMR (C:)1H NMR,13C NMR) the structure was characterized and confirmed to be the compound S4-DPA-iPr. The detection results are as follows:
S4-DPA-iPr：1H NMR(400MHz,CDCl3)δ7.13(dd,J＝7.4,2.0Hz,1H),7.01–6.92(m,4H),6.78(t,J＝7.4Hz,1H),4.88(s,1H),3.23(p,J＝6.9Hz,1H),1.99(s,6H),1.90(s,3H),1.18(d,J＝6.9Hz,6H).13C NMR(100MHz,CDCl3)δ141.46,140.20,131.84,129.04,128.29,127.65,123.59,123.14,120.67,27.89,23.28,19.44,19.23.
example 4: synthesis of S4-DPA-tBu
The structural formula of the target compound S4-DPA-tBu is as follows:
the synthesis of S4-DPA-tBu comprises the following steps:
under the protection of nitrogen, 2-tert-butyl-6-methylaniline (2.25mL, 15mmol, 1eq.) 2-bromo-1, 3-xylene (2.27mL, 16.5mmol, 1.1eq.) and NaO were placed in a reaction flasktBu (2.88g, 30mmol, 2eq.) and Pd (dppf) Cl2·CH2Cl2([1,1' -bis (diphenylphosphino) ferrocene)]Palladium dichloride) (0.37g, 0.45mmol, 0.03eq.) was dissolved in sufficient toluene solvent. And the mixture was heated to 110 ℃ with stirring and reacted under reflux for 16 hours. After the reaction mixture was cooled to room temperature (15 to 35 ℃), the reaction was quenched with 1M dilute hydrochloric acid, extracted with dichloromethane, and the resulting organic layer was washed with a saturated aqueous sodium chloride solution (200mL), dried over anhydrous sodium sulfate, and the solvent was removed to obtain a crude product. Performing silica gel chromatography with petroleum ether as eluent, separating and purifying, and vacuum drying to obtain white solid compound S4-DPA-tBu (1.68g, 42%), and performing hydrogen and carbon nuclear magnetic resonance spectroscopy (NMR)1H NMR,13C NMR) and confirmed the white solid as the target compound S4-DPA-tBu. The detection results are as follows:
S4-DPA-tBu：1H NMR(400MHz,CDCl3)δ7.27(d,J＝2.2Hz,1H),7.02–6.93(m,4H),6.74(t,J＝7.4Hz,1H),5.32(s,1H),1.98(s,6H),1.75(s,3H),1.49(s,9H).13C NMR(100MHz,CDCl3)δ141.40,141.31,141.27,133.46,129.22,129.07,126.01,124.38,122.86,119.77,35.28,30.93,19.67,19.34.
example 5: performance testing
FIG. 2 is a diagram showing the room temperature phosphorescent afterglow phenomenon of diphenylamine DPA and the organic room temperature phosphorescent compounds S1-DPA-Me, S4-DPA-iPr and S4-DPA-tBu of the diphenylamine derivatives prepared in examples 2, 3 and 4 of the present invention; as can be seen from the figure, DPA has weaker room temperature phosphorescence property, and S1-DPA-Me, S4-DPA-iPr and S4-DPA-tBu have better room temperature phosphorescence property.
FIG. 3 is a graph of the room temperature fluorescence spectrum and phosphorescence lifetime of diphenylamine DPA and the organic room temperature phosphorescent compounds S1-DPA-Me, S4-DPA-iPr and S4-DPA-tBu obtained by preparation in examples 2, 3 and 4 of the present invention; wherein, FIG. 3a is a fluorescence spectrum and a phosphorescence spectrum, and FIG. 3b is a phosphorescence lifetime chart; as can be seen, the fluorescence emission of the compounds DPA, S1-DPA-Me, S4-DPA-iPr and S4-DPA-tBu is 351nm, 347nm, 355nm, 338 nm and 373nm respectively; phosphorescence emission is respectively at 525nm, 517nm, 525nm, 519 nm; the room temperature phosphorescence lifetimes are 182.87ms, 395.20ms, 267.12ms, 385.34ms, respectively.
FIG. 4 shows a security device composed of DPA, S4-DPA-iPr and S4-DPA-tBu. As shown in FIG. 4, the compounds S4-DPA-tBu (written in "Wu" word), S4-DPA-iPr (written in "Large" word) having strong room temperature phosphorescence properties and diphenylamine DPA (written in "Han" word) having weak room temperature phosphorescence properties were used. Under dark conditions, under the irradiation of an ultraviolet lamp (excitation wavelength of 365nm), the purple calligraphy of Wuhan university can be presented. When the ultraviolet lamp irradiation is stopped, the Wuhan university is switched to the character of Wuhan university and can last for 2 s.
Therefore, the compound has feasible application in information encryption and decryption, and can be used for preparing anti-counterfeiting marks, anti-counterfeiting films and the like. Although embodiments of the present invention have been shown and described, it should be understood that the above embodiments are illustrative and not restrictive, and that various changes, modifications, substitutions, combinations, and simplifications may be made without departing from the spirit and principles of the invention and are intended to be included within the scope of the invention.
Claims (10)
1. A diphenylamine derivative organic room-temperature phosphorescent compound is characterized in that the structural formula of the diphenylamine derivative organic room-temperature phosphorescent compound is shown as a formula 1,
wherein R is1One selected from isopropyl and tert-butyl; r2Is methyl; r3Is methyl; r4Is methyl.
2. A preparation method of a diphenylamine derivative organic room-temperature phosphorescent compound is characterized in that the diphenylamine derivative organic room-temperature phosphorescent compound is prepared from a compound shown in a formula 2 and a compound shown in a formula 3, and the reaction formula is as follows:
the diphenylamine derivative organic room-temperature phosphorescent compound is shown as a formula 1, wherein R1One selected from methyl, isopropyl and tert-butyl; r2Is hydrogen or methyl; r3Is hydrogen or methyl; r4Is hydrogen or methyl;
the preparation method of the diphenylamine derivative organic room-temperature phosphorescent compound comprises the following steps of:
step 1): under the inert gas atmosphere, reacting a compound shown in a formula 2, a compound shown in a formula 3 and alkali under the action of a catalyst;
step 2): cooling the reaction liquid obtained in the step 1) to 15-35 ℃, and purifying to obtain the diphenylamine derivative organic room-temperature phosphorescent compound;
in the step 1), the catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride.
3. The method for preparing a diphenylamine derivative organic room-temperature-phosphorescent compound as claimed in claim 2, wherein, in the step 1), the base is sodium tert-butoxide.
4. The method for preparing diphenylamine derivative organic room-temperature-phosphorescent compound as claimed in claim 3, wherein the solvent used in the reaction is toluene.
5. The method for preparing a diphenylamine derivative organic room-temperature-phosphorescent compound as claimed in claim 2, wherein, in the step 1), the amount ratio of the compound represented by formula 2 to the compound represented by formula 3, the base, and the catalyst is 1.0:1.1:2.0: 0.03.
6. The method for preparing diphenylamine derivative organic room-temperature phosphorescent compounds as claimed in claim 2, wherein in the step 1), the reaction is performed by heating to reflux for 10-24 hours.
7. The method for preparing diphenylamine derivative organic room-temperature-phosphorescent compounds as claimed in claim 6, wherein the reaction is a heating-to-reflux reaction for 16 hours.
8. The method for preparing a diphenylamine derivative organic room-temperature phosphorescent compound as claimed in claim 2, wherein, in the step 2), the purification comprises: extracting the reaction solution with dichloromethane, collecting the organic phase, and adding anhydrous Na2SO4Drying and spin-drying to obtain a crude product; separating the crude product by silica gel column chromatography with petroleum ether as eluent.
9. The application of the diphenylamine derivative organic room-temperature phosphorescent compound shown in the formula 1 and/or the compound obtained by the preparation method of the diphenylamine derivative organic room-temperature phosphorescent compound disclosed by any one of claims 2-8 in preparation of anti-counterfeiting marks;
wherein R is1One selected from methyl, isopropyl and tert-butyl; r2Is hydrogen or methyl; r3Is hydrogen or methyl; r4Is hydrogen or methyl.
10. An anti-counterfeiting film is characterized by comprising a diphenylamine derivative organic room-temperature phosphorescent compound shown in a formula 1;
wherein R is1One selected from methyl, isopropyl and tert-butyl; r2Is hydrogen or methyl; r3Is hydrogen or methyl; r4Is hydrogen or methyl.
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