CN110437096B - Preparation method of 2, 6-di (aminophenoxy) -N- (2-aminofluorene) benzamide monomer - Google Patents
Preparation method of 2, 6-di (aminophenoxy) -N- (2-aminofluorene) benzamide monomer Download PDFInfo
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Abstract
The invention discloses a preparation method of a symmetrical 2, 6-di (aminophenoxy) -N- (2-aminofluorene) benzamide high molecular monomer with fluorescence activity, belonging to the field of functional high molecular materials. The monomer is prepared by one-step reaction of p-aminophenol or m-aminophenol and 2-fluorenyl-2, 6-difluorobenzamide. The monomer synthesized by the method contains not only aniline segments capable of further polymerizing but also fluorenyl segments with fluorescence activity, and is used for further synthesizing high polymer materials with fluorescence function.
Description
Technical Field
The invention relates to a preparation method of a symmetrical 2, 6-bis (aminophenoxy) -N- (2-aminofluorene) benzamide high molecular monomer with fluorescence activity, belonging to the field of functional high molecular materials.
Technical Field
The ideal electroluminescent material can simultaneously have good carrier transmission performance and good luminescence performance, under general conditions, the hole transmission performance of the material can be improved by a strong electron-donating group, and the electron transmission performance of the material can be improved by a strong electron-withdrawing group and conjugation, so that organic molecules with an electron-donating group-electron-withdrawing group/conjugation system can often become potential substances for preparing the electroluminescent material. If the material is made into an organic electroluminescent device, the cost can be saved, and the commercial value of the device can be improved.
Fluorene is mainly separated from coal tar, and derivatives thereof are also important raw materials for synthesizing fine chemicals, and can be widely applied to the fields of plastics, dyes, medicines, pesticides, functional materials and the like. The C-H bonds of 2,7 and 9-positions of the fluorene compounds are relatively active and easy to generate chemical reaction, so that the fluorene derivatives are obtained. Based on the characteristics of the fluorene derivative, chemists often introduce various functional groups into a fluorene ring to improve the fluorescence quantum yield of the fluorene derivative, so that the fluorene derivative becomes an organic photoelectric material with high fluorescence quantum yield, and especially an organic blue light material is prepared.
However, in terms of the macromolecular electroluminescent materials, there are few reports on the symmetric organic fluorene macromolecular monomers having an "electron donating group-electron withdrawing group/conjugated" system.
Disclosure of Invention
The invention discloses a preparation method of a symmetrical 2, 6-bis (aminophenoxy) -N- (2-aminofluorene) benzamide high molecular monomer with fluorescence activity. The preparation method comprises the steps of carrying out amidation reaction on 2-aminofluorene and 2, 6-difluorobenzoyl chloride to obtain 2-fluorenyl-2, 6-difluorobenzamide, and then carrying out reaction on the 2-fluorenyl-2, 6-difluorobenzamide and aminophenol through nucleophilic substitution reaction of fluoro aromatic hydrocarbon to synthesize the high molecular monomer compound simultaneously containing aniline segments capable of being further polymerized and fluorenyl segments with fluorescence activity. The organic fluorene star-shaped molecule with the electron donating group-electron withdrawing group/conjugate system has higher fluorescence emission efficiency, is a symmetrical molecule, has the potential of becoming a macromolecular electroluminescent material, and accords with the development trend of multifunctional application of high molecular materials.
The invention relates to a symmetrical 2, 6-di (4-aminophenoxy) -N- (2-aminofluorene) benzamide high molecular monomer compound with fluorescence activity, which has the following structural formula:
the structural monomer has a small Stokes displacement value, excited molecules have low energy loss and high luminous efficiency, and is an excellent blue light material.
The preparation method of the 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide high molecular monomer compound comprises the following steps:
the first step is as follows: synthesis of 2-fluorenyl-2, 6-difluorobenzamide: controlling the temperature to be 0 ℃, adding 2-aminofluorene and triethylamine into dichloromethane, then starting to dropwise add 2, 6-difluorobenzoyl chloride, and then keeping the temperature to be 0 ℃ for reaction; after the reaction is finished, pouring the mixed solution into ice water, and performing sedimentation and filtration to obtain 2-fluorenyl-2, 6-difluorobenzamide;
the second step is that: synthesis of 2, 6-bis (aminophenoxy) -N- (2-aminofluorene) benzamide high-molecular monomer: adding aminophenol and potassium carbonate or cesium carbonate into a DMF/toluene mixed solvent, reacting for 2h at 140 ℃, then adding 2-fluorenyl-2, 6-difluorobenzamide, and heating to 160-180 ℃ for reacting for 15-20 h; after the reaction is finished, pouring the mixture into ice water, and carrying out sedimentation and filtration to obtain a 2, 6-bis (aminophenoxy) -N- (2-aminofluorene) benzamide polymer monomer; wherein the aminophenol is selected from p-aminophenol or m-aminophenol.
Further, in the above technical scheme, in the first step, the concentration of 2-aminofluorene dissolved in the dichloromethane solvent is 0.2-0.5 mol/L.
Further, in the technical scheme, in the first step, the molar ratio of 2-aminofluorene, triethylamine and 2, 6-difluorobenzoyl chloride is 1:1.5-2.0: 1.2-1.5.
Further, in the above technical scheme, in the first step, after the sedimentation filtration, the obtained filter cake is washed with water and petroleum ether in sequence, after the washing is completed, the filter cake is collected and dried in a vacuum oven at about 60 ℃ for 6 hours to obtain the 2-fluorenyl-2, 6-difluorobenzamide.
Further, in the technical scheme, in the second step, the volume ratio of the DMF and the toluene mixed solvent is 5-15: 1; the total reaction concentration is 0.1-0.15 mol/L.
Further, in the above technical solution, in the second step, when the aminophenol is p-aminophenol, potassium carbonate or cesium carbonate is used as an alkali; when the aminophenol is m-aminophenol, cesium carbonate is used as alkali; wherein the molar ratio of the aminophenol, the potassium carbonate or the cesium carbonate to the 2-fluorenyl-2, 6-difluorobenzamide is 2-4:2-4.4: 1.
Further, in the above technical scheme, in the second step, after settling and filtering, the obtained crude product is purified by column chromatography to obtain a pure monomer product, and the eluent is a mixed solvent of dichloromethane and methanol, and the volume ratio of dichloromethane to methanol is 150:1 to 50: 1.
Drawings
FIG. 1 is a NMR spectrum of 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide 2 synthesized in example 1;
FIG. 2 is an IR spectrum of 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide 2 synthesized in example 1;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1a synthesized in example 1;
FIG. 4 is a NMR carbon spectrum of 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1a synthesized in example 1;
FIG. 5 is an infrared-visible absorption spectrum of 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1a synthesized in example 1;
FIG. 6 is an ultraviolet-visible light absorption spectrum of 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1a synthesized in example 1;
FIG. 7 is a fluorescence spectrum of 2, 6-bis (p-aminophenoxy) -N- [2- (fluorenylamino) ] benzamide 1a synthesized in example 1.
Shown in figure 1 as 2, 6-difluoro-N- [2- (fluorenylamino)]Benzamide 2 nuclear magnetic resonance hydrogen spectrum. The analysis of the hydrogen nuclear magnetic resonance spectrum is as follows:1H NMR(400MHz,CDCl3)： 10.91(br,1H),8.05(s,1H),7.84-7.89(m,2H),7.56-7.67(m,3H),7.37(t, J＝7.2Hz,1H),7.243-7.305(m,3H),3.944(s,2H)。
FIG. 2 shows 2, 6-difluoro-N- [2- (fluorenylamino)]Infrared spectrum of benzamide 2. In the infrared spectrum, the wave number is 1640cm-1A vibration absorption peak of C ═ O belonging to an amide structure; wave number of 3394cm-1A shock absorption peak at-NH-; 3040cm-1Is the C-H stretching vibration peak on the benzene ring. At 1600cm-1The vicinity is the stretching vibration absorption peak of C ═ C skeleton on the benzene ring. At 2850cm-1Here, we can conclude that there is the presence of methylene. At 1400cm-1The position shows that the crystal has an extremely strong peak, which proves that the carbon-fluorine bond exists.
As shown in fig. 3 and 4, the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1a are shown as follows: the nuclear magnetic resonance analysis of hydrogen and carbon spectra is as follows:1H NMR(400MHz,CDCl3)δ10.62(br,1H),8.09(s,1H),7.82(dd,J＝2.0, 7.6Hz,2H),7.70(dd,J＝1.6,7.6Hz,1H),7.35(d,J＝7.6Hz,4H),7.35 (t,J＝7.2Hz,1H),7.26(t,J＝7.2Hz,1H),7.17(t,J＝8.4Hz,1H),6.85 (d,J＝8.8Hz,4H),6.60(d,J＝8.8Hz,4H),6.34(d,J＝8.4Hz,2H), 5.007(br,4H),3.906(s,2H)；13C NMR(100MHz,CDCl3)δ163.2,157.4, 146.3,145.8,144.3,143.3,141.5,139.1,136.9,125.5,121.8,120.6, 119.9,119.8,118.4,116.3,115.2,109.3,37.0。
as shown in fig. 5, the infrared visible absorption spectrum of 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1a is as follows: at 1647cm-1The presence of carbonyl groups can be seen as a strong absorption peak. At below 1700cm-1The position of (A) is only an amide group. At 3300cm-1On the left, we can see two blunt absorption peaks like the saddle shape, demonstrating the presence of primary amines. At 3040cm-1Has a certain height, and the absorption peak is the absorption peak of the aromatic ring. At 1600cm-1Nearby we can see the bending vibration of the double bond on the benzene ring. At 2850cm-1Here, we can conclude that there is the presence of methylene.
The ultraviolet and visible absorption spectrum of 2, 6-bis (p-aminophenoxy) -N- [2- (fluorenylamino) ] benzamide 1a is shown in FIG. 6. the ultraviolet and visible absorption spectrum is characterized by a T6-Xinyue-visible spectrophotometer, and as can be seen from FIG. 6, a very strong absorption peak is present around 300nm, which is presumed to be an absorption peak generated by the transition of a pi-pi conjugated system of a benzene ring, so that it can be concluded that the maximum excitation wavelength of the compound is around 300 nm.
FIG. 7 shows the fluorescence emission spectrum of 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1 a: when 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide is excited by light with the wavelength of 340nm, as can be seen from figure 7, 2, 6-bis (4-aminophenoxy) -N- (2-aminofluorene) benzamide has a fluorescence emission peak, and generates fluorescence with the maximum emission wavelength of 340nm after excitation, and when the ultraviolet spectrogram is contrasted, the Stokes shift of the fluorescence is about 40 nm. The surface has smaller Stokes displacement value, lower energy loss of excited molecules and higher luminous efficiency, and is a more excellent blue light material.
Detailed Description
Example 1
Synthesis of 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide:
9.06g (50mmol) of 2-aminofluorene, 150mL of methylene chloride and 10.6 mL (75mmol) of triethylamine were added to a thick-walled eggplant-shaped flask (250mL) equipped with magnetons in this order under a nitrogen atmosphere in an ice-water bath, and the mixture was sufficiently stirred and mixed well, and then 6.9mL (65mmol) of 2, 6-difluorobenzoyl chloride was slowly dropped into the reaction mixture. The mixture is continuously stirred for 8 hours under the condition, after the 2-aminofluorene is completely reacted, 100mL of saturated ammonium chloride aqueous solution is used for quenching the reaction, at this time, a large amount of white solid is separated out from the mixed system, the mixture is placed still for half an hour and then is filtered, filter cakes are sequentially washed by water and petroleum ether to obtain the target product 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide 2, and the yield is 90%.
Synthesis of 2, 6-bis (p-aminophenoxy) -N- [2- (fluorenylamino) ] benzamide:
4.58g (40.0mmol) of p-aminophenol and 6.08g (44.0mmol) of potassium carbonate are dissolved in a mixed solvent of 50mL of DMF and 5mL of toluene, stirred uniformly, and heated to 140 ℃ under a nitrogen atmosphere for reaction for 2 h. Then, 3.21g (10.0mmol) of 2, 6-difluoro-N- [2- (fluorenylamino) was added to the reaction mixture]Benzamide 2, and continuously reacting for 20h at 170 ℃ in a nitrogen atmosphere, after the raw materials completely react, cooling the reaction mixture to room temperature, pouring into a large amount of ice water, standing for 2h, and filtering to obtain 2, 6-di (p-aminophenoxy) -N- [2- (fluorenylamino)]Benzoyl radicalAnd (4) crude amine. The crude product is subjected to column Chromatography (CH)2Cl2MeOH 150/1-60/1) gave pure 2- (4-aminophenoxy) -N- (2-aminofluorene) benzamide 1a in 80% yield.
Example 2
Synthesis of 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide:
9.06g (50mmol) of 2-aminofluorene, 150mL of methylene chloride and 10.6 mL (75mmol) of triethylamine were added to a thick-walled eggplant-shaped flask (250mL) equipped with magnetons in this order under a nitrogen atmosphere in an ice-water bath, and the mixture was sufficiently stirred and mixed well, and then 6.9mL (65mmol) of 2, 6-difluorobenzoyl chloride was slowly dropped into the reaction mixture. The mixture is continuously stirred for 8 hours under the condition, after the 2-aminofluorene is completely reacted, 100mL of saturated ammonium chloride aqueous solution is used for quenching the reaction, at the moment, a large amount of white solid is separated out from a mixed system, the mixture is placed still for half an hour and then is filtered, a filter cake is sequentially washed by water and petroleum ether to obtain the target product 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide 2, and the yield is 90%.
Synthesis of 2, 6-bis (p-aminophenoxy) -N- [2- (fluorenylamino) ] benzamide:
4.81g (42.0mmol) of p-aminophenol and 14.4g (44.0mmol) of cesium carbonate were dissolved in a mixed solvent of 50mL of DMF and 5mL of toluene, stirred uniformly, and heated to 140 ℃ under a nitrogen atmosphere for reaction for 2 hours. Then, 6.42g (20.0mmol) of 2, 6-difluoro-N- [2- (fluorenylamino) was added to the reaction mixture]Benzamide 2, and continuously reacting for 10h at 170 ℃ in a nitrogen atmosphere, after the raw materials completely react, cooling the reaction mixture to room temperature, pouring into a large amount of ice water, standing for 2h, and filtering to obtain 2, 6-di (p-aminophenoxy) -N- [2- (fluorenylamino)]And (4) crude benzamide. The crude product is subjected to column Chromatography (CH)2Cl2MeOH 150/1-60/1) to give 2, 6-bis (4-aminophenoxy) -N- [2- (fluorenylamino)]Benzamide 1a was pure in 86% yield.
Example 3
Synthesis of 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide:
9.06g (50mmol) of 2-aminofluorene, 150mL of methylene chloride and 10.6 mL (75mmol) of triethylamine were added to a thick-walled eggplant-shaped flask (250mL) equipped with magnetons in this order under a nitrogen atmosphere in an ice-water bath, and the mixture was sufficiently stirred and mixed well, and then 6.9mL (65mmol) of 2, 6-difluorobenzoyl chloride was slowly dropped into the reaction mixture. The mixture is continuously stirred for 8 hours under the condition, after the 2-aminofluorene is completely reacted, 100mL of saturated ammonium chloride aqueous solution is used for quenching the reaction, at this time, a large amount of white solid is separated out from the mixed system, the mixture is placed still for half an hour and then is filtered, filter cakes are sequentially washed by water and petroleum ether to obtain the target product 2, 6-difluoro-N- [2- (fluorenylamino) ] benzamide 2, and the yield is 90%.
Synthesis of 2, 6-bis (m-aminophenoxy) -N- [2- (fluorenylamino) ] benzamide:
4.81g (42.0mmol) of m-aminophenol and 14.4g (44.0mmol) of cesium carbonate are dissolved in a mixed solvent of 50mL of DMF and 5mL of toluene, stirred uniformly, and heated to 140 ℃ under a nitrogen atmosphere for reaction for 2 h. Then, 3.21g (10.0mmol) of 2, 6-difluoro-N- [2- (fluorenylamino) was added to the reaction mixture]Benzamide 2, and continuously reacting for 14h at 170 ℃ in a nitrogen atmosphere, after the raw materials completely react, cooling the reaction mixture to room temperature, pouring into a large amount of ice water, standing for 2h, and filtering to obtain 2, 6-bis (m-aminophenoxy) -N- [2- (fluorenylamino)]And (4) crude benzamide. The crude product is subjected to column Chromatography (CH)2Cl2/MeOH 150/1-60/1) to give 2, 6-bis (m-aminophenoxy) -N- [2- (fluorenylamino)]Benzamide 1b was pure in 84% yield.
The foregoing embodiments have described the general principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, and that various changes and modifications may be made without departing from the scope of the principles of the present invention, and the invention is intended to be covered by the appended claims.
Claims (8)
1.2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide high molecular monomer with fluorescence activity has the following structural formula:
2. the method for preparing the 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymer monomer according to claim 1, comprising the steps of:
the first step is as follows: synthesis of 2-fluorenyl-2, 6-difluorobenzamide: controlling the temperature to be 0 ℃, adding 2-aminofluorene and triethylamine into dichloromethane, then starting to dropwise add 2, 6-difluorobenzoyl chloride, and then keeping the temperature to be 0 ℃ for reaction; after the reaction is finished, pouring the mixed solution into ice water, and performing sedimentation and filtration to obtain 2-fluorenyl-2, 6-difluorobenzamide;
the second step is that: synthesis of 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide high molecular monomer: adding aminophenol and potassium carbonate or cesium carbonate into a DMF/toluene mixed solvent, reacting for 2h at 140 ℃, then adding 2-fluorenyl-2, 6-difluorobenzamide, and heating to 160-180 ℃ for reacting for 15-20 h; after the reaction is finished, pouring the mixture into ice water, and carrying out sedimentation and filtration to obtain a 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymer monomer; wherein the aminophenol is selected from p-aminophenol or m-aminophenol.
3. The method for preparing 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymeric monomer according to claim 2, characterized in that: in the first step, 2-aminofluorene is dissolved in a dichloromethane solvent at a concentration of 0.2 to 0.5 mol/L.
4. The method for preparing 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymeric monomer according to claim 2, characterized in that: in the first step, the molar ratio of 2-aminofluorene, triethylamine and 2, 6-difluorobenzoyl chloride is 1:1.5-2.0: 1.2-1.5.
5. The method for preparing 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymeric monomer according to claim 2, characterized in that: in the first step, after sedimentation and filtration, the obtained filter cake is washed by water and petroleum ether in sequence, and after washing, the filter cake is collected and dried in a vacuum oven at about 60 ℃ for 6 hours to obtain the 2-fluorenyl-2, 6-difluorobenzamide.
6. The method for preparing 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymeric monomer according to claim 2, characterized in that: in the second step, when the aminophenol is p-aminophenol, potassium carbonate or cesium carbonate is used as alkali; when the aminophenol is m-aminophenol, cesium carbonate is used as alkali; wherein the molar ratio of the aminophenol, the potassium carbonate or the cesium carbonate to the 2-fluorenyl-2, 6-difluorobenzamide is 2-4:2-4.4: 1.
7. The method for preparing 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymeric monomer according to claim 2, characterized in that: and in the second step, after settling and filtering, the obtained crude product is purified by column chromatography to obtain a pure monomer product, and the eluent is a mixed solvent of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is 150: 1-50: 1.
8. The use of the 2, 6-bis (aminophenoxy) -N- (2-fluorenyl) benzamide polymeric monomer of claim 1 in blue-light emitting materials.
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| A Multifunctional Poly(aryl ether) with Oligoaniline and Fluorene Pendants: Synthesis, Electrochromic Performance, and Tunable Fluorescent Properties;Danming Chao等;《JOURNAL OF POLYMER SCIENCE PART A: POLYMER CHEMISTRY》;20120311;第50卷;第2330-2336页 * |
| Distribution of dendritic, terminal and linear units and relationship between degree of branching and molecular weight of AB2-type hyperbranched polymer: A 13C-NMR study;Shanmugam, T.等;《Journal of Macromolecular Science, Part A: Pure and Applied Chemistry》;20061231;第43卷(第9期);第1387-1397页 * |
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