CN110483328B - 2, 6-di (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide monomer and preparation method thereof - Google Patents
2, 6-di (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide monomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide high molecular monomer and a preparation method based on the photochromic property of azobenzene and the mechanical property of polyamide, belonging to the field of functional high molecular materials. The monomer is prepared by one-step reaction of p-aminophenol or m-aminophenol and 4- (phenylazo) phenyl-2, 6-difluorobenzamide. The monomer synthesized by the method contains not only aniline segments which can be polymerized but also azo-based segments with photochromic performance, and can be used for synthesizing high polymer materials with functions of liquid crystal display, dye laser and the like.
Description
Technical Field
The invention relates to a symmetrical 2, 6-di (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide high molecular monomer with photochromic performance and a preparation method thereof, belonging to the field of functional high molecular materials.
Technical Field
Photochromic materials exhibit changes in macroscopic properties, such as color, shape, refractive index, etc., as a function of molecular structure or morphology upon light stimulation. The illumination effect has the advantages of environmental protection, wavelength adjustability, instantaneity, remote controllability and the like, so that the photochromic material receives more and more attention.
Polyamide (PA) is a high molecular compound of a translucent or milky crystalline resin, and has an amide group (-NHCO-) in its main chain. The high-temperature-resistant and corrosion-resistant rubber has high mechanical strength and excellent mechanical property due to large molecular weight, high softening point and low friction coefficient, and is high-temperature-resistant and corrosion-resistant. As a result, aromatic polyamides can be obtained by introducing benzene rings into the main molecular chain of polyamides, and the rigidity and heat resistance of Polyamides (PA) can be further improved.
However, the aromatic polyamide has a symmetrical structure and contains dense benzene rings and amide groups in the main chain, so that the aromatic polyamide has high melting point, poor solubility and complex processing, and the application of the aromatic polyamide in the industry is limited. The azobenzene compound not only has excellent processing performance and mechanical performance of a high molecular compound, but also has cis (cis) -trans (trans) tautomer, has good optical performance, and has wide application in the aspects of optical information storage, luminescent materials, biological application, nano materials and the like. The structure of the macromolecule has a great influence on the discoloration of the compound containing the azobenzene group on the side chain.
However, how to introduce the azobenzene compound into the aromatic polyamide to solve the solubility problem and make it not only generate cis-trans isomeric conversion, but also generate dipole moment and size changes of polyamide molecules under illumination of a certain wavelength, and still has a problem to be further researched.
Disclosure of Invention
The invention discloses a preparation method of a symmetrical 2, 6-di (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide high molecular monomer with photochromic performance. Carrying out amidation reaction on 4-aminoazobenzene and 2, 6-difluorobenzoyl chloride to obtain 4- (phenylazo) phenyl-2, 6-difluorobenzamide, and then carrying out reaction on the 4-aminoazobenzene and the 2, 6-difluorobenzoyl chloride and an aminophenol compound through nucleophilic substitution reaction of fluoro aromatic hydrocarbon to synthesize a high molecular monomer compound simultaneously containing a polymerizable aniline segment and a segment with photochromic performance.
In the invention, the macromolecular monomer compound with the aniline segment and the azo segment with photochromic performance has the potential of becoming macromolecular photochromic material, and accords with the development trend of multi-functionalization of macromolecular material. The macromolecular monomer compound with the azobenzene segment synthesized by the method has potential application value and huge development prospect in the aspects of synthesizing photochromic materials, liquid crystal materials and the like.
The invention relates to a symmetrical 2, 6-di (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide high molecular monomer compound with a photo-induced modification property, which has the following structural formula:
in the process of ultraviolet lamp irradiation, the trans isomer absorbs energy and is converted into cis isomer, and when the monomer is placed in a dark place, the cis isomer and the trans isomer can return to the cis isomer ratio when the ultraviolet light is not irradiated.
The preparation method of the symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide high molecular monomer comprises the following steps:
the first step is as follows: synthesis of 4- (phenylazo) phenyl-2, 6-difluorobenzamide: adding p-aminoazobenzene and triethylamine into dichloromethane, stirring uniformly at 0 ℃, then beginning to dropwise add 2, 6-difluorobenzoyl chloride, and keeping the temperature at 0 ℃ for reaction after dropwise adding; pouring the mixture into ice water after the reaction is completed, precipitating and filtering to obtain 4- (phenylazo) phenyl-2, 6-difluorobenzamide;
the second step is that: synthesis of 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer: adding aminophenol and potassium carbonate or cesium carbonate into a DMF/toluene mixed solvent, reacting for 2h at 140 ℃, then adding 4- (phenylazo) phenyl-2, 6-difluorobenzamide, and heating to 160-180 ℃ for reacting for 8-20 h; after the reaction is finished, pouring the mixture into ice water, settling and filtering to obtain the 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer.
Further, in the above technical solution, the aminophenol is selected from p-aminophenol or m-aminophenol.
Furthermore, in the technical scheme, in the first step, the concentration of the 4-aminoazobenzene in a dichloromethane solvent is 0.2-0.5 mol/L.
Further, in the technical scheme, in the first step, the molar ratio of the aminoazobenzene, the triethylamine and the 2, 6-difluorobenzoyl chloride is 1:1.5-2.0: 1.2-1.5.
Further, in the above technical solution, in the first step, after the settling 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 at room temperature for 6 hours, and then 4- (phenylazo) phenyl-2, 6-difluorobenzamide is obtained.
Further, in the technical scheme, in the second step, the volume ratio of DMF to toluene 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 p-aminophenol, potassium carbonate or cesium carbonate to 4- (phenylazo) phenyl-2, 6-difluorobenzamide is 2-5:2-4.4: 1; the molar ratio of m-aminophenol, cesium carbonate and 4- (phenylazo) phenyl-2, 6-difluorobenzamide is 2-2.2:2-2.5: 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 120:1 to 30: 1.
Drawings
FIG. 1 is a NMR spectrum of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 synthesized in example 1;
FIG. 2 is an IR spectrum of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 synthesized in example 1;
FIG. 3 is an ultraviolet spectrum of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 synthesized in example 1;
FIG. 4 is a NMR spectrum of 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1a synthesized in example 1;
FIG. 5 is a NMR carbon spectrum of 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1a synthesized in example 1;
FIG. 6 is an infrared-visible absorption spectrum of 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1a synthesized in example 1;
FIG. 7 shows an ultraviolet spectrum of 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1a synthesized in example 1.
The NMR spectrum of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 is shown in FIG. 1. The analysis of the hydrogen nuclear magnetic resonance spectrum is as follows:1H NMR(400MHz,DMSOd-6) δ11.17(br,1H),7.88-7.98(m,6H),7.53-7.66(m,4H),7.285(t,J＝8.0 Hz,2H)。
FIG. 2 shows an IR spectrum of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2. In the infrared spectrum, the wave number is 2925cm-1And 2964cm-1The peak is a characteristic stretching vibration peak of saturated C-H, and the peak of the benzene ring skeleton is 3086cm-1The peak of stretching vibration of C ═ O of secondary amide was 1669cm-1It is basically similar to the displacement law of carbonyl group, but the double bond property of amino-linked carbonyl group is lowered due to resonance effect, and the absorption frequency is shifted to a low wave number. The N-H stretching vibration peak of the amide is 3288cm-1. At 1400cm-1In the vicinity, there is a very strong peak, and a shock absorption peak due to a fluorocarbon bond is estimated.
FIG. 3 is a UV spectrum of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 synthesized in the present invention. The uv-vis spectrum of compound 2 is shown in fig. 3, where curve 2 corresponds to the absorption curve of the material without the violet light having a wavelength of 365nm (t ═ 0s), and the last curve 10 corresponds to the absorption curve of the violet light having the longest irradiation time (t ═ 391s) until the material reaches a steady state. As can be seen, the maximum absorption peak of this compound is at 352nm, at which time azobenzene undergoes a π - π transition due to the absorption peak due to the trans isomer of azobenzene. The peak value of the absorption peak of the ultraviolet lamp gradually decreases along with the superposition of the irradiation time of the ultraviolet lamp. Meanwhile, an absorption peak of cis isomer of azobenzene appears at 442nm, at which azobenzene undergoes transition of n-pi of azobenzene, and the absorption peak at this point gradually rises with the increase of the ultraviolet lamp irradiation time. Under 365nm ultraviolet lamp irradiation, the trans isomer of the substance is less and less, and the cis isomer is more and more, which indicates that the azobenzene is converted from the trans isomer to the cis isomer.
As shown in figures 4 and 5, is 2, 6-di (p-aminophenoxy) -N- [4- (phenylazo) phenyl]Nuclear magnetic resonance hydrogen spectrum and carbon spectrum of benzamide 1 a: the nuclear magnetic resonance hydrogen and carbon spectrum analysis is as follows:1H NMR(400MHz,DMSO d-6)δ10.94(br,1H),7.92(m,6H), 7.58(m,3H),7.19(s,1H),6.86(m,4H),6.61(m,4H),6.35(m,2H), 5.02(br,4H)；13C NMR(100MHz,DMSOd-6)δ163.7,157.5,152.5, 148.1,146.4,145.7,143.0,131.5,130.7,129.9,124.2,122.8,121.8, 119.2,109.2.
as shown in figure 6, is 2, 6-di (p-aminophenoxy) -N- [4- (phenylazo) phenyl]Infrared visible absorption spectrum of benzamide 1 a: the absorption peak of the stretching vibration of the N-H bond of the unsubstituted secondary amine in the amide is 3322cm-1At a wave number of 2931cm-1And 2896cm-1The absorption peak is the absorption peak of the stretching vibration of saturated C-H bond, and the stretching vibration peak of C ═ O bond in secondary amide is 1686cm-1. At 3262cm-1And 3399cm-1There is a relatively broad peak pattern, presumably the absorption peak of the amino group.
Fig. 7 shows the ultraviolet spectrum of 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1a, fig. 7 shows the spectrum of the ultraviolet light and the visible light observed by using UV-vis after azo para-disubstituted compound is dissolved in DMF, in which curve 1 shows the absorption curve of the substance without being irradiated by an ultraviolet lamp (t ═ 0s), and the last curve 10 shows the maximum irradiation time with an ultraviolet lamp (t ═ 392s) until the curve does not change any more. The two absorption peaks in the figure are at 357nm and 441nm, respectively, corresponding to the transitions of the azobenzenes pi-pi and n-pi, respectively. With the increase of the time of the purple light, no new peak appears, and only the intensity of absorption peaks at 357nm and 441nm changes, which shows that the substance only has cis-trans isomeric change and no new substance appears during the ultraviolet lamp irradiation. Compared with the graph shown in FIG. 3, the difference between the maximum absorption wavelengths of the two substances is not great, which indicates that azobenzene is mainly cis-isomer under normal conditions, and after the azobenzene is irradiated by 365nm ultraviolet and visible light, the trans-isomer absorbs energy and is converted into cis-isomer. It can be concluded that: the trans-isomer has low energy, and is more sterically hindered when converted to the cis-isomer, and is more stable than the cis-isomer, so that when the substance is placed in the dark for a while, it returns to the state in which the ultraviolet light is not irradiated.
Detailed Description
Example 1
Synthesis of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2
9.362g (50mmol) of p-aminoazobenzene, 150mL of methylene chloride and 10.6mL (75mmol) of triethylamine were sequentially added to a Magnetitum-equipped thick-walled eggplant-shaped flask (250mL) 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 6 hours under the condition, after the p-aminoazobenzene 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 stood for half an hour and is filtered, a filter cake is sequentially washed by water and petroleum ether to obtain 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2, and the yield is 84%.
Synthesis of 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1a
4.58g (40.0mmol) of p-aminophenol and 6.08g (44.0mmol) of anhydrous 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 3.37g (10 mmol) of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 was added to the reaction mixture and the reaction was continued at 170 ℃ under nitrogen for 10h, after the starting materials had completely reacted, the reaction mixture was cooled to room temperature and poured into a large amount of water, left to stand overnight, and filtered to give 2, 6-bis (p-aminophenoxy) -N- [4- (benzene)Phenylazo) phenyl]Crude benzamide 1 a. The crude product is subjected to column Chromatography (CH)2Cl2MeOH 150/1-60/1) to give 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl]Benzamide 1a was pure in 73% yield.
Example 2
Synthesis of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2
9.362g (50mmol) of p-aminoazobenzene, 150mL of methylene chloride and 10.6mL (75mmol) of triethylamine were sequentially added to a Magnetitum-equipped thick-walled eggplant-shaped flask (250mL) 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 6 hours under the condition, after the p-aminoazobenzene 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 stood for half an hour and is filtered, a filter cake is sequentially washed by water and petroleum ether to obtain 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2, and the yield is 84%.
Synthesis of 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1a
4.58g (40.0mmol) of p-aminophenol and 13.03g (44.0mmol) of cesium carbonate are dissolved in a mixed solvent of 70mL of DMF and 7mL of toluene, stirred uniformly, and heated to 140 ℃ under a nitrogen atmosphere for reaction for 2 hours. 6.74g (20mmol) of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 are then added to the reaction mixture and the reaction is continued for 8h at 160 ℃ under nitrogen, after complete reaction of the starting materials, the reaction mixture is cooled to room temperature and poured into a large amount of water, left overnight and filtered to give 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 2]Crude benzamide 1. The crude product is subjected to column Chromatography (CH)2Cl2MeOH 150/1-60/1) to give 2, 6-bis (p-aminophenoxy) -N- [4- (phenylazo) phenyl]Benzamide 1b pure product, yield 92%.
Example 3
Synthesis of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2
9.362g (50mmol) of p-aminoazobenzene, 150mL of methylene chloride and 10.6mL (75mmol) of triethylamine were sequentially added to a Magnetitum-equipped thick-walled eggplant-shaped flask (250mL) 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 6 hours under the condition, after the p-aminoazobenzene 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 stood for half an hour and is filtered, a filter cake is sequentially washed by water and petroleum ether to obtain 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2, and the yield is 84%.
Synthesis of 2, 6-bis (m-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 1b
4.58g (40.0mmol) of m-aminophenol and 13.03g (44.0mmol) of cesium carbonate are dissolved in a mixed solvent of 70mL of DMF and 7mL of toluene, stirred uniformly, and heated to 140 ℃ under a nitrogen atmosphere for reaction for 2 hours. 6.74g (20mmol) of 4- (phenylazo) phenyl-2, 6-difluorobenzamide 2 are then added to the reaction mixture and the reaction is continued for 8h at 170 ℃ under nitrogen, after complete reaction of the starting materials, the reaction mixture is cooled to room temperature and poured into a large amount of water, left overnight and filtered to give 2, 6-bis (m-aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide 2]Crude benzamide 1. The crude product is subjected to column Chromatography (CH)2Cl2MeOH 150/1-60/1) to give 2, 6-bis (m-aminophenoxy) -N- [4- (phenylazo) phenyl]Benzamide 1b was pure in 86% 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 given by way of illustration 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 such changes and modifications are within the scope of the present invention.
Claims (8)
1. The symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide high molecular monomer has the following structural formula:
2. the method for preparing the symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer according to claim 1, comprising the steps of:
the first step is as follows: synthesis of 4- (phenylazo) phenyl-2, 6-difluorobenzamide: adding p-aminoazobenzene and triethylamine into dichloromethane, stirring uniformly at 0 ℃, then beginning to dropwise add 2, 6-difluorobenzoyl chloride, and keeping the temperature at 0 ℃ for reaction after dropwise adding; pouring into ice water after the reaction is completed, precipitating and filtering to obtain 4- (phenylazo) phenyl-2, 6-difluorobenzamide;
the second step is that: synthesis of 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer: adding aminophenol and cesium carbonate into a DMF/toluene mixed solvent, reacting for 2h at 140 ℃, then adding 4- (phenylazo) phenyl-2, 6-difluorobenzamide, and heating to 160-180 ℃ for reacting for 8-20 h; after the reaction is finished, pouring the mixture into ice water, and settling and filtering to obtain a 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer; wherein the aminophenol is selected from p-aminophenol or m-aminophenol; the molar ratio of the aminophenol, the cesium carbonate and the 4- (phenylazo) phenyl-2, 6-difluorobenzamide is 2-5:2-4.4: 1.
3. The method for preparing the symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer according to claim 2, wherein: in the first step, the concentration of 4-aminoazobenzene in dichloromethane solvent is 0.2-0.5 mol/L.
4. The method for preparing the symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer according to claim 2, wherein: in the first step, the molar ratio of the aminoazobenzene, the triethylamine and the 2, 6-difluorobenzoyl chloride is 1:1.5-2.0: 1.2-1.5.
5. The method for preparing 2- (3-aminophenoxy) -6- (4-aminophenoxy) -N- (2-aminofluorene) benzamide polymer monomer according to claim 2, which comprises: 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 for 6 hours at room temperature, so that 4- (phenylazo) phenyl-2, 6-difluorobenzamide is obtained.
6. The method for preparing the symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymer monomer according to claim 2, wherein: 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 dichloromethane to methanol is 120: 1-30: 1.
7. The use of the symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymeric monomer according to claim 1, wherein: in the ultraviolet lamp irradiation process of the monomer, the trans isomer absorbs energy and is converted into cis isomer, and when the monomer is placed in a dark place, the cis isomer and the trans isomer can return to the cis isomer ratio when the ultraviolet light is not irradiated.
8. The use of the symmetrical 2, 6-bis (aminophenoxy) -N- [4- (phenylazo) phenyl ] benzamide polymeric monomer according to claim 7, wherein: the ultraviolet lamp is 365nm ultraviolet visible light.
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