CN115109021B - Synthesis of N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide, gel prepared by same and application thereof - Google Patents

Synthesis of N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide, gel prepared by same and application thereof Download PDF

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CN115109021B
CN115109021B CN202210795657.6A CN202210795657A CN115109021B CN 115109021 B CN115109021 B CN 115109021B CN 202210795657 A CN202210795657 A CN 202210795657A CN 115109021 B CN115109021 B CN 115109021B
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methoxycoumarin
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carboxamide
alkoxyphenyl
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CN115109021A (en
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曲红梅
许松林
张家财
李晓龙
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Tianjin University
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Abstract

The invention discloses a method for synthesizing N- (4-alkoxyl phenyl) -7-methoxyl coumarin-3-formamide, which utilizes an amide bond to directly introduce long-chain alkylbenzene gel-forming groups containing six carbons, eight carbons and ten carbons onto a 7-methoxyl coumarin-3-carboxylic acid skeleton, so as to synthesize 3N- (4-alkoxyl phenyl) -7-methoxyl coumarin-3-formamide gel factors; gel properties and AIE characteristics of 3 gel factors were studied; the ethyl acetate gel formed by 3 gel factors is used for adsorbing the methyl orange dye, and the result shows that the gel has better dye adsorption performance. According to the invention, long-chain alkylbenzene gel forming groups are directly introduced into coumarin derivative skeletons through amide bonds, and the aggregation fluorescence quenching effect of coumarin derivatives is converted into AIE effect by utilizing a specific gel forming aggregation mode of gel factors and intra-molecular movement limitation caused by gel forming, so that potential reference value is provided for the coumarin derivatives in the application aspect of optical materials.

Description

Synthesis of N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide, gel prepared by same and application thereof
Technical Field
The invention relates to the field of coumarin derivative gel materials, in particular to a synthetic method of N- (4-alkoxyl phenyl) -7-methoxyl coumarin-3-formamide gel factor, and gel prepared by the same and application thereof.
Background
Supermolecular gel is a 3D network cross-linked system saturated with a dispersion medium, the particles forming such a spatial network structure are called gelators or gelators, and the dispersion medium may be water, an organic solvent or air. The supermolecular gel is formed by self-assembling a low molecular weight gel factor serving as a driving force to form a three-dimensional network structure through a plurality of intermolecular non-covalent interactions such as hydrogen bonds, pi-pi stacking, van der Waals forces, electrostatic attraction, hydrophobic interactions, halogen bonds, coordination interactions and the like, and combining and fixing solvent molecules. The supermolecular gel is used as an important soft nano-structure material, can endow the supermolecular gel with multifunction through specific structural design, and has great application value in many research fields such as ion detection, drug delivery, biological sensing, environmental repair and the like. Among them, the application of supermolecular gel in the field of photoelectric materials has been one of the research hotspots. In particular, the AIE effect suggests that the luminescent characteristics of AIE compounds in the aggregated state are well compatible with the coacervate nature of the gel, which provides the possibility to manufacture advanced stimuli-responsive optical materials. The gel factor with AIE characteristics can promote the deep development of gel materials in the optical field through reasonable structural design.
Coumarin derivatives are important organic heterocyclic compounds, have the advantages of high fluorescence quantum yield, strong fluorescence, easiness in functional modification and the like, and are very widely applied. However, coumarin derivatives are prone to ACQ effects in the aggregated state, limiting their use. The AIE effect provides a method for solving the problem of ACQ of the traditional fluorophores, and the conversion of coumarin derivatives from ACQ to AIE can be realized through reasonable structural design. The coacervate characteristic of the gel provides a path for the aggregation behavior of AIE, and the introduction of coumarin derivatives into the gel field can provide a method for the application of coumarin derivatives in the aggregation state, and provides a potential reference value for the application of coumarin derivatives in optical materials.
Disclosure of Invention
Aiming at the prior art, the invention provides a synthesis method of an N- (4-alkoxyl phenyl) -7-methoxyl coumarin-3-formamide gel factor with AIE characteristics, and gel prepared by the synthesis method and application thereof. Specifically, different long-chain alkylbenzene gel forming groups are introduced to a 7-methoxy coumarin-3-carboxylic acid skeleton through an amide bond, 3 novel N- (4-alkoxyphenyl) -7-methoxy coumarin-3-carboxamide gel factors are synthesized, the performance and application of the prepared gel are researched, the ACQ effect of coumarin derivatives is converted into AIE effect by utilizing a specific gel forming aggregation mode of the gel factors and limited intramolecular movement caused by gel forming, and potential reference value is provided for the coumarin derivatives in the application aspect of optical materials.
In order to solve the technical problems and achieve the purposes of the invention, in a first aspect, the synthesis method of N- (4-alkoxyl phenyl) -7-methoxyl coumarin-3-formamide provided by the invention has a process route shown in figure 1, and comprises the following specific steps:
1) Adding 2-hydroxy-4-methoxybenzaldehyde, mirabilic acid and ammonium acetate into distilled water, and vigorously stirring at room temperature for 4h; then hydrochloric acid is used for regulating the pH value to 2-3, filtering is carried out, the precipitate is washed by distilled water and dried, and finally, the light black solid 7-methoxy coumarin-3-carboxylic acid is obtained, and the product can be directly used for the next reaction without purification;
2) Adding 4- (Boc-amino) phenol and potassium carbonate into acetonitrile, raising the temperature to 75 ℃, then slowly adding 1-bromoalkane, and reacting for 10 hours at 75 ℃; cooling, adding dichloromethane to dissolve out solid, washing with distilled water, and separating; drying the organic phase, and removing the solvent by rotary evaporation to obtain a crude product, and purifying the crude product by column chromatography to obtain white solid (4-alkoxyl phenyl) tert-butyl carbamate;
3) Adding tert-butyl (4-alkoxyphenyl) carbamate into a mixed solution of dichloromethane and trifluoroacetic acid in a volume ratio of 6:1, and reacting for 2 hours at room temperature; quenching the reaction with 5% naoh solution; regulating the pH value of the reaction solution to about 10 by using a 5% NaOH solution, separating the solution, extracting the water phase by using dichloromethane, drying the combined organic phases, and removing the solvent by rotary evaporation to obtain brown solid 4-alkoxy aniline, wherein the product can be put into the next reaction without purification;
4) Dissolving 7-methoxycoumarin-3-carboxylic acid, 4-alkoxyaniline, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole monohydrate and N, N-diisopropylethylamine in anhydrous N, N-dimethylformamide, and reacting for 5 hours at room temperature; then the mixed solution is fully diluted by a large amount of distilled water, extracted by methylene dichloride, and the combined organic phases are dried and then are distilled off by rotation to remove the solvent so as to obtain crude products; the crude product is purified by column chromatography to obtain light yellow solid N- (4-alkoxyl phenyl) -7-methoxyl coumarin-3-formamide.
Further, the synthesis method of the invention comprises the following steps:
in step 1), 2-hydroxy-4-methoxybenzaldehyde: mi's acid: the molar ratio of ammonium acetate is 1: (1.1-1.2): 0.2.
in step 2), 4- (Boc-amino) phenol: 1-bromoalkane: the molar ratio of potassium carbonate is 1:1.1:2; the 1-bromoalkane is any one of 1-bromo-n-hexane, 1-bromo-n-octane and 1-bromo-n-decane; in the step 2), the eluent in the crude product column chromatography purification process adopts a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 30:1.
The product obtained in the step 3) is any one of 4-hexyalkoxy aniline, 4-octyloxyaniline and 4-decyloxyaniline.
In the step 4), in the process of purifying the crude product by column chromatography, the eluent adopts a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 8:1. 7-methoxycoumarin-3-carboxylic acid: 4-alkoxyaniline: 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride: 1-hydroxybenzotriazole monohydrate: the molar ratio of N, N-diisopropylethylamine is 1:1.1:1.3:1.3:3, a step of; wherein the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is used as a condensing agent, the 1-hydroxybenzotriazole monohydrate is used as an acylation catalyst, and the N, N-diisopropylethylamine provides an alkaline environment. The obtained product N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide comprises one of N- (4-hexyloxyphenyl) -7-methoxycoumarin-3-carboxamide and N- (4-octyloxyphenyl) -7-methoxycoumarin-3-carboxamide, and N- (4-decoxyphenyl) -7-methoxycoumarin-3-carboxamide; the N- (4-hexoxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C6bC, the N- (4-octoxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C8bC, and the N- (4-decoxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C10bC. The structural formula is as follows:
in the second aspect, the gel performance of the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gel factor is researched, the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide obtained by the synthesis method is used as the gel factor to prepare gel, and 25 organic solvents selected in the gel performance test are methanol, ethanol, isopropanol, N-butanol, tert-amyl alcohol, N-pentane, N-hexane, cyclohexane, petroleum ether, benzene, toluene, chlorobenzene, o-dichlorobenzene, aniline, dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, tetrahydrofuran (THF), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, ethyl acetate and acetone respectively; wherein, the gel forming property test concentration is 20.00mg/mL. Finally screening the organic compound with solvent selected from the following according to the gel forming property test result: ethanol, isopropanol, n-butanol, t-amyl alcohol, 1, 2-dichloroethane, dimethyl sulfoxide, acetonitrile, ethyl acetate and acetone; the gel has aggregation-induced fluorescence characteristic, and the scanning wavelength range of fluorescence spectrum is 400-650nm.
In the third aspect, AIE characteristics of N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gel factors are studied, isopropyl alcohol gel is prepared by taking N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide obtained by the synthesis method of the invention as a gel factor, isopropyl alcohol is selected as a solvent in the gelling process, and the prepared gel system and concentration thereof are cou-C6bC isopropyl alcohol gel (12.50 mg/mL), cou-C8bC isopropyl alcohol gel (12.50 mg/mL) and cou-C10bC isopropyl alcohol gel (10.00 mg/mL) respectively. In addition, the fluorescence spectrum of the system scans the wavelength range of 400-650nm.
In the fourth aspect, the invention provides a gel prepared by using ethyl acetate gel prepared by taking N- (4-alkoxyl phenyl) -7-methoxyl coumarin-3-formamide as a gel factor for adsorption application research of methyl orange dye, namely, in the gel forming process, selecting ethyl acetate as a solventThe system and the concentration thereof are cou-C6bC ethyl acetate gel (30.00 mg/mL), cou-C8bC ethyl acetate gel (16.67 mg/mL) and cou-C10bC ethyl acetate gel (16.67 mg/mL) respectively; the prepared Methyl Orange (MO) dye is 10 -4 M in water. In addition, the scanning wavelength range of the ultraviolet spectrum is 300-600nm; the samples used for the measurements were aqueous solutions adsorbed for 2h and 10h, respectively.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the synthesis step of the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gel factor, the intermediate products 7-methoxycoumarin-3-carboxylic acid and 4-alkoxyaniline can be directly used for the next reaction without purification, so that the product purity is high, and the industrial production is facilitated.
(2) According to the invention, different long-chain alkylbenzene gel forming groups are introduced onto a 7-methoxy coumarin-3-carboxylic acid skeleton through an amide bond, 3 novel N- (4-alkoxyl phenyl) -7-methoxy coumarin-3-formamide gel factors are synthesized, and the ACQ effect of coumarin derivatives is successfully converted into AIE effect by utilizing a specific gel forming aggregation mode of the gel factors and limited intramolecular movement caused by gel forming.
(3) Gel property researches on gel factors in the invention show that 3 gel factors mainly form gel in various alcohol solvents (including ethanol, isopropanol, n-butanol, tertiary butanol and tertiary amyl alcohol), 1, 2-dichloroethane, DMSO, acetonitrile, ethyl acetate and acetone, and in addition, cou-C6bC can be formed into gel in carbon tetrachloride, and cou-C8bC and cou-C10bC can be formed into gel in DMF.
(4) Critical gel concentration CGC and gel-sol phase transition temperature T of the integrated gel factor gel As a result, the optimal gelling solvent for the 3 gel factors was isopropanol.
(5) The AIE characteristic study of the gel factor in the invention shows that the system shows weaker fluorescence intensity in a hot-melt state, and the gel system gradually changes from the sol state to the gel state along with the gradual reduction of the temperature, and the AIE effect is obvious along with the increase of the fluorescence intensity and the red shift of the maximum emission wavelength. Furthermore, the gel system exhibits very pronounced fluorescence reversibility during multiple heat-cool treatments.
(6) The adsorption application research of the ethyl acetate gel formed by the gel factors in the invention for methyl orange dye shows that the adsorption rates of the cou-C6bC ethyl acetate gel, the cou-C8bC ethyl acetate gel and the cou-C10bC ethyl acetate gel on methyl orange at 10h are respectively 84.2%, 85.0% and 87.3%, which shows that the ethyl acetate gel formed by the 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gel factors synthesized by the invention has better adsorption effect on methyl orange dye.
Drawings
FIG. 1 is a process route of the synthetic method of the present invention.
FIG. 2 is a fluorescence spectrum of AIE characteristic test in gel state of 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gel factors in example 5.
FIG. 3 is a UV spectrum of ethyl acetate gel formed by 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gelators of example 6 for use in adsorption application testing of methyl orange dye.
FIGS. 4 to 9 show 3 gel factors of N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide 1 H NMR spectra 13 C NMR spectrum.
Detailed Description
The design idea of the synthesis method of the invention is as follows: 1) 3 novel N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gel factors are synthesized by directly introducing long-chain alkylbenzene gel-forming groups containing six carbons, eight carbons and ten carbons onto a 7-methoxycoumarin-3-carboxylic acid skeleton by using an amide bond (in the invention, N- (4-hexalkoxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C6bC, N- (4-octyloxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C8bC, and N- (4-decyloxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C10 bC); 2) Gel properties and AIE characteristics of 3 gel factors, cou-C6bC, cou-C8bC and cou-C10bC, were studied; 3) The ethyl acetate gel formed by the 3 gel factors, namely the cou-C6bC ethyl acetate gel, the cou-C8bC ethyl acetate gel and the cou-C10bC ethyl acetate gel, are used for adsorbing the methyl orange dye, and the result shows that the gel has better dye adsorption performance. According to the invention, long-chain alkylbenzene gel forming groups are directly introduced into coumarin derivative skeletons through amide bonds, and the aggregation fluorescence quenching (ACQ) effect of coumarin derivatives is converted into AIE effect by utilizing a specific gel forming aggregation mode of gel factors and limited intramolecular movement caused by gel forming, so that potential reference value is provided for the coumarin derivatives in the application aspect of optical materials.
The invention will now be further described with reference to the accompanying drawings and specific examples, which are in no way limiting. Unless otherwise indicated, the technical means used in the examples are conventional means well known to those skilled in the art, and all raw materials used are commercially available reagents.
Example 1 synthesis of N- (4-hexoxyphenyl) -7-methoxycoumarin-3-carboxamide (cou-C6 bC) following the process scheme shown in FIG. 1, the specific steps are as follows:
(1) 2-hydroxy-4-methoxybenzaldehyde (7.17 g,47.1 mmol), mielic acid (7.75 g,53.8 mmol) and ammonium acetate (0.75 g,9.73 mmol) were added to 120mL of distilled water and vigorously stirred at room temperature for 4h; then hydrochloric acid is used for adjusting the pH value to 2-3, filtering is carried out, the sediment is washed by distilled water and dried, and finally the light black solid 7-methoxy coumarin-3-carboxylic acid is obtained.
(2) 4- (Boc-amino) phenol (3.14 g,15.0 mmol) and K 2 CO 3 (4.15 g,30.0 mmol) was added to acetonitrile (75 mL), the temperature was raised to 75deg.C, then 1-bromohexane (2.72 g,16.5 mmol) was added slowly, and the reaction was continued at 75deg.C for 10h; after cooling, dichloromethane (75 mL) was added to dissolve the precipitated solid, which was then washed with distilled water (2×25 mL) and separated; drying the organic phase, and removing the solvent by rotary evaporation to obtain a crude product; the crude product was purified by column chromatography (eluent: petroleum ether/ethyl acetate, 30:1, v/v) to give tert-butyl (4-hexyloxyphenyl) carbamate as a white solid.
(3) Tert-butyl (4-hexoxyphenyl) carbamate (1.47 g,5.00 mmol) was added to DCM: tfa=6:1 in mixture (42 mL), 2h at room temperature; the reaction was quenched with 5% naoh solution (40 mL); the reaction mixture was adjusted to about 10 with 5% NaOH solution, separated, the aqueous phase extracted with methylene chloride (2X 20 mL), and the combined organic phases dried and distilled off to remove the solvent to give 4-hexyalkoxyaniline as a brown solid.
(4) 7-Methoxycoumarin-3-carboxylic acid (0.66 g,3.00 mmol), 4-hexoxyaniline (0.64 g,3.30 mmol), EDCI. HCl (0.75 g,3.90 mmol), HOBt. H 2 O (0.60 g,3.90 mmol) and DIEA (1.16 g,9.00 mmol) were dissolved in anhydrous DMF (30 mL) and reacted at room temperature for 5h; then the mixed solution is fully diluted by a large amount of distilled water (70 mL), then extracted by methylene dichloride (3X 50 mL), and the combined organic phases are dried and then distilled to remove the solvent to obtain crude products; the crude product was purified by column chromatography (eluent: petroleum ether/ethyl acetate, 8:1, v/v) to finally give a yellow solid, cou-C6bC. The specific synthetic route is shown in figure 1.
Characterization analysis of cou-C6bC using liquid Nuclear magnetic resonance Spectrometry 1 H NMR spectra 13 The C NMR spectrum test results were: 1 H NMR(400MHz,DMSO-d 6 )δ10.52(s,1H),8.91(s,1H),7.95(d,J＝8.7Hz,1H),7.66–7.59(m,2H),7.19–7.05(m,2H),6.97–6.91(m,2H),3.95(t,J＝6.5Hz,2H),3.92(s,3H),1.76–1.65(m,2H),1.42(t,J＝7.6Hz,2H),1.30–1.21(m,4H),0.89–0.84(m,3H). 13 C NMR(101MHz,THF-d 8 ) Delta 163.20,159.88,156.95,154.98,154.00,129.96,129.15,118.98,113.55,112.41,111.80,110.81,98.11,65.88,53.63,29.76,27.45,23.87,20.68,11.53. As shown in fig. 4 and 5.
EXAMPLE 2 Synthesis of N- (4-octyloxyphenyl) -7-methoxycoumarin-3-carboxamide (cou-C8 bC)
The synthesis of steps (1) to (3) is similar to example 1, except that 1-bromo-n-hexane is replaced with 1-bromo-n-octane, see in particular example 1. (4) 7-Methoxycoumarin-3-carboxylic acid (0.66 g,3.00 mmol), 4-octaalkoxyaniline (0.73 g,3.30 mmol), EDCI. HCl (0.75 g,3.90 mmol), HOBt. H 2 O (0.60 g,3.90 mmol) and DIEA (1.16 g,9.00 mmol) were dissolved in anhydrous DMF (30 mL) and reacted at room temperature for 5h; the mixture was then diluted thoroughly with copious amounts of distilled water (70 mL), extracted with dichloromethane (3X 50 mL) and combined organicsPhase drying and rotary steaming to remove solvent to obtain crude product; the crude product was purified by column chromatography (eluent: petroleum ether/ethyl acetate, 8:1, v/v) to finally give a yellow solid, cou-C8bC. The specific synthetic route is shown in figure 1.
Characterization analysis of cou-C8bC using liquid Nuclear magnetic resonance Spectrometry 1 H NMR spectra 13 The C NMR spectrum test results were: 1 H NMR(400MHz,DMSO-d 6 )δ10.52(s,1H),8.91(s,1H),7.95(d,J＝8.8Hz,1H),7.66–7.60(m,2H),7.20–7.05(m,2H),6.97–6.91(m,2H),3.95(t,J＝6.5Hz,2H),3.92(s,3H),1.69(dt,J＝15.2,7.6Hz,2H),1.41(d,J＝6.0Hz,2H),1.31–1.27(m,8H),0.85(dt,J＝5.2,2.6Hz,3H). 13 C NMR(101MHz,THF-d 8 ) δ 163.20,159.88,156.95,154.99,154.00,129.96,129.15,118.98,113.56,112.41,111.80,110.81,98.12,65.88,53.63,29.96,27.78,27.51 (d, j=2.8 Hz), 27.40,20.70,11.57. As shown in fig. 6 and 7.
EXAMPLE 3 Synthesis of N- (4-decyloxyphenyl) -7-methoxycoumarin-3-carboxamide (cou-C10 bC)
The synthesis of steps (1) to (3) is similar to that of example 1, except that 1-bromo-n-hexane is replaced by 1-bromo-n-decane, see in particular example 1. (4) 7-Methoxycoumarin-3-carboxylic acid (0.66 g,3.00 mmol), 4-decyloxyaniline (0.82 g,3.30 mmol), EDCI. HCl (0.75 g,3.90 mmol), HOBt. H 2 O (0.60 g,3.90 mmol) and DIEA (1.16 g,9.00 mmol) were dissolved in anhydrous DMF (30 mL) and reacted at room temperature for 5h; then the mixed solution is fully diluted by a large amount of distilled water (70 mL), then extracted by methylene dichloride (3X 50 mL), and the combined organic phases are dried and then distilled to remove the solvent to obtain crude products; the crude product was purified by column chromatography (eluent: petroleum ether/ethyl acetate, 8:1, v/v) to finally give a yellow solid, cou-C10bC. The specific synthetic route is shown in figure 1.
Characterization analysis of cou-C10bC using liquid Nuclear magnetic resonance Spectrometry 1 H NMR spectra 13 The C NMR spectrum test results were: 1 H NMR(400MHz,DMSO-d 6 )δ10.52(s,1H),8.91(s,1H),7.96(d,J＝8.9Hz,1H),7.63(d,J＝8.6Hz,2H),7.22–7.06(m,2H),6.94(d,J＝8.6Hz,2H),3.96(d,J＝6.4Hz,2H),3.92(s,3H),1.70(dd,J＝14.4,7.0Hz,2H),1.34(s,2H),1.26(s,16H),0.88(s,2H). 13 C NMR(101MHz,THF-d 8 ) Delta 165.06,161.74,158.81,156.85,155.86,131.82,131.01,120.84,115.42,114.27,113.66,112.67,99.98,67.74,55.49,31.87,29.72-29.34 (m), 29.30,26.05,22.56,13.44, as shown in figures 8 and 9.
Example 4 gel Performance test of gel factors cou-C6bC, cou-C8bC and cou-C10bC
Gel property studies include gel property test, CGC test and T gel And (5) measuring. Gel formation property test is studied by a test tube inversion method, 10.00mg of gel factor and 0.50mL of solvent are added into a sealed test tube, fully heated to a solid completely dissolved or liquid boiling state, and then cooled to room temperature; the test tube was turned over and the flow conditions of the system were observed, which were designated gel (G), partial Gel (PG), insoluble (I), soluble (S) and precipitate (P), respectively, according to the flow conditions of the system. The determination of CGC is performed on the basis of the gel formation property test, and is still observed by a test tube inversion method; for a system forming gel, a solvent adding method is utilized until the system can not form gel, and the concentration of the system before the last solvent adding is marked as a CGC value; for a system forming partial gel, a small amount of gel factor is added to form gel, and then a solvent adding method is used until the system cannot form gel, and the concentration of the system before the last solvent adding is marked as a CGC value. T (T) gel The measurement of the value is carried out by adopting a falling ball method, namely, a gel system with known concentration is prepared firstly, and then glass pellets with the mass of about 0.15g are respectively placed on the surface of the obtained gel system; the gel system is fixedly placed in a constant-temperature water bath, then the water bath temperature is increased at a speed of 1 ℃/min, the sinking condition of the glass pellets in the gel system is observed, when the glass pellets are completely sunk below the liquid level of the gel system, the water bath temperature at the moment is recorded to be T of the system gel Values. Gel Performance test results, CGC test data and T gel The test data are shown in tables 1 to 3, wherein Table 1 shows the gel forming property test results of the 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gel factors in example 4 of the present invention, table 2 shows the critical gel concentration of the 3 gel factor CGC test in example 4 of the present invention, and Table 3 shows the critical gel concentration of the 3 gel factor CGC test in example 4 of the present inventionSeed gel factor T gel The phase transition temperature was determined.
TABLE 1 results of gel Performance test of co5u-C6bC, cou-C8bC and cou-C10bC
TABLE 2 critical gel concentrations of cou-C6bC, cou-C8bC and cou-C10bC
TABLE 3 phase transition temperatures of cou-C6bC, cou-C8bC and cou-C10bC
EXAMPLE 5 AIE characterization of gel factors cou-C6bC, cou-C8bC and cou-C10bC
The fluorescence spectrum changes of the cou-C6bC isopropyl alcohol gel (12.50 mg/mL), the cou-C8bC isopropyl alcohol gel (12.50 mg/mL) and the cou-C10bC isopropyl alcohol gel (10.00 mg/mL) in the transition process from sol state to gel state are studied; firstly heating the system to a sol state, and then testing the change condition of a fluorescence spectrum of the system along with time; in order to verify the fluorescence reversibility of the system, the gel system is also subjected to multiple heating-cooling circulation treatment to test the fluorescence intensity in the multiple circulation treatment process at a certain moment; the result shows that the system is converted from sol state to gel state and shows obvious AIE effect along with the increase of fluorescence intensity and the red shift of maximum emission wavelength; the fluorescence spectrum is shown in FIG. 2.
EXAMPLE 6 adsorption application test of gel factors cou-C6bC, cou-C8bC and cou-C10bC formed ethyl acetate gel for methyl orange dye
First, a certain concentration of cou-C6bC ethyl acetate gel (30.00 mg/mL), cou-C8bC ethyl acetate gel (16.67 mg/mL) and cou-C10bC ethyl acetate gel (16.67 mg/mL) was prepared, and the concentration of the aqueous solution of methyl orange dye was formulated to be 10 -4 M; adding the same volume of dye water solution into the gel, heating at 60deg.C until the gel is dissolved, standing, cooling, timing, respectively taking small amounts of water solution of 2 hr and 10 hr, and diluting to 10 hr -5 M concentration is measured to measure ultraviolet visible spectrum, so as to monitor the adsorption rate of the gel to dye; the results showed that the adsorption rates of the cou-C6bC ethyl acetate gel, the cou-C8bC ethyl acetate gel and the cou-C10bC ethyl acetate gel on methyl orange at 10h were 84.2%, 85.0% and 87.3%, respectively; in addition, the adsorption rate of pure ethyl acetate to methyl orange in the blank experiment is 13.1%; the ultraviolet visible spectrum test results are shown in figure 3.
Although the invention has been described above with reference to the accompanying drawings, the invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many modifications may be made by those of ordinary skill in the art without departing from the spirit of the invention, which fall within the protection of the invention.

Claims (9)

1. The synthesis method of the N- (4-alkoxyphenyl) -7-methoxyl coumarin-3-carboxamide is characterized by comprising the following steps of:
1) Adding 2-hydroxy-4-methoxybenzaldehyde, mirabilic acid and ammonium acetate into distilled water, and vigorously stirring at room temperature for 4h; then hydrochloric acid is used for adjusting the pH value to 2-3, filtering is carried out, and the sediment is washed by distilled water and dried to obtain light black solid 7-methoxy coumarin-3-carboxylic acid;
2) Adding 4- (Boc-amino) phenol and potassium carbonate into acetonitrile, raising the temperature to 75 ℃, then slowly adding 1-bromoalkane, and reacting for 10 hours at 75 ℃; cooling, adding dichloromethane to dissolve out solid, washing with distilled water, and separating; drying the organic phase, and removing the solvent by rotary evaporation to obtain a crude product, and purifying the crude product by column chromatography to obtain white solid (4-alkoxyl phenyl) tert-butyl carbamate;
3) Adding the tert-butyl (4-alkoxyphenyl) carbamate obtained in the step 2) into a mixed solution of dichloromethane and trifluoroacetic acid with the volume ratio of 6:1, and reacting for 2 hours at room temperature; quenching the reaction with 5% naoh solution; regulating the pH value of the reaction solution to about 10 by using 5% NaOH solution, separating the solution, extracting the water phase by using dichloromethane, drying the combined organic phases, and removing the solvent by rotary evaporation to obtain brown solid 4-alkoxy aniline;
4) Dissolving 7-methoxycoumarin-3-carboxylic acid, 4-alkoxyaniline, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, 1-hydroxybenzotriazole monohydrate and N, N-diisopropylethylamine in anhydrous N, N-dimethylformamide, and reacting for 5 hours at room temperature; then the mixed solution is fully diluted by a large amount of distilled water, extracted by methylene dichloride, and the combined organic phases are dried and then are distilled off by rotation to remove the solvent so as to obtain crude products; purifying the crude product by column chromatography to obtain light yellow solid N- (4-alkoxyphenyl) -7-methoxycoumarin-3-formamide;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide comprises one of N- (4-hexyloxyphenyl) -7-methoxycoumarin-3-carboxamide and N- (4-octyloxyphenyl) -7-methoxycoumarin-3-carboxamide, and N- (4-decoxyphenyl) -7-methoxycoumarin-3-carboxamide; the N- (4-hexoxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C6bC, the N- (4-octoxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C8bC, and the N- (4-decoxyphenyl) -7-methoxycoumarin-3-carboxamide is abbreviated as cou-C10bC;
the structural formula is as follows:
2. the synthetic method of claim 1 wherein in step 2), 4- (Boc-amino) phenol: 1-bromoalkane: the molar ratio of potassium carbonate is 1:1.1:2; the 1-bromoalkane is any one of 1-bromo-n-hexane, 1-bromo-n-octane and 1-bromo-n-decane; the product obtained in the step 3) is any one of 4-hexyalkoxy aniline, 4-octyloxyaniline and 4-decyloxyaniline.
3. The synthetic method according to claim 2, wherein in step 4), 7-methoxycoumarin-3-carboxylic acid: 4-alkoxyaniline: 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride: 1-hydroxybenzotriazole monohydrate: the molar ratio of N, N-diisopropylethylamine is 1:1.1:1.3:1.3:3, a step of; wherein the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride is used as a condensing agent, the 1-hydroxybenzotriazole monohydrate is used as an acylation catalyst, and the N, N-diisopropylethylamine provides an alkaline environment.
4. The method of claim 1, wherein in step 1), 2-hydroxy-4-methoxybenzaldehyde: mi's acid: the molar ratio of ammonium acetate is 1: (1.1-1.2): 0.2.
5. the method according to claim 1, wherein in the step 2), the eluent in the crude product column chromatography purification process adopts a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 30:1; in the step 4), in the process of purifying the crude product by column chromatography, the eluent adopts a mixed solution of petroleum ether and ethyl acetate with the volume ratio of 8:1.
6. A gel prepared by using N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide obtained by the synthesis method according to any one of claims 1 to 5 as a gelator, characterized in that,
in the gel forming process, the mass volume ratio of the gel factor to the solvent is 20.00mg/mL, and the solvent is one of the following organic compounds: ethanol, isopropanol, n-butanol, t-amyl alcohol, 1, 2-dichloroethane, dimethyl sulfoxide, acetonitrile, ethyl acetate and acetone; the gel has aggregation-induced fluorescence characteristic, and the scanning wavelength range of fluorescence spectrum is 400-650nm.
7. The gel of claim 6, wherein the solvent during the gelling process is isopropyl alcohol and the gel is formed as follows, depending on the specific structure of the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide:
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is the cou-C6bC, the mass volume ratio of the gel factor to the solvent is 12.50mg/mL, and the formed gel is the cou-C6bC isopropanol gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is the cou-C8bC, the mass volume ratio of the gel factor to the solvent is 12.50mg/mL, and the formed gel is the cou-C8bC isopropyl alcohol gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is the cou-C10bC, the mass volume ratio of the gel factor to the solvent is 10.00mg/mL, and the formed gel is the cou-C10bC isopropanol gel;
the fluorescence spectrum scanning wavelength range of the gel is 400-650nm.
8. The gel of claim 6, wherein the solvent used in the gelling process is ethyl acetate and the gel is formed according to the specific structure of N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide as follows:
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is the cou-C6bC, the mass volume ratio of the gel factor to the solvent is 30.00mg/mL, and the formed gel is cou-C6bC ethyl acetate gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is the cou-C8bC, the mass volume ratio of the gel factor to the solvent is 16.67mg/mL, and the formed gel is cou-C8bC ethyl acetate gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is the cou-C10bC, the mass volume ratio of the gel factor to the solvent is 16.67mg/mL, and the formed gel is cou-C10bC ethyl acetate gel;
the fluorescence spectrum scanning wavelength range of the gel is 400-650nm.
9. The gel according to claim 8 for use in the adsorption of methyl orange dye, wherein the concentration is formulated to be 10 -4 M, wherein the volume ratio of the gel to the dye aqueous solution is 1:1, heating at the water temperature of 60 ℃ until the gel is dissolved, standing and cooling, and starting timing; measuring the dye adsorption result by using an ultraviolet-visible spectrometer, wherein the scanning wavelength range of the ultraviolet-visible spectrum is 300-600nm; the samples used for measurement are aqueous phase solutions for adsorption for 2h and 10h respectively; in 2 hours, the absorption rate of methyl orange is 59.6 to 85.0 percent; at 10h, the absorption rate of the methyl orange is 84.2-87.3%.
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CN109970751A (en) * 2019-04-04 2019-07-05 济南大学 A kind of double site, highly sensitive pH fluorescence probe and its synthesis and application
JP2020007383A (en) * 2018-07-02 2020-01-16 山本化成株式会社 Resin composition and molding

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JP2020007383A (en) * 2018-07-02 2020-01-16 山本化成株式会社 Resin composition and molding
CN109970751A (en) * 2019-04-04 2019-07-05 济南大学 A kind of double site, highly sensitive pH fluorescence probe and its synthesis and application

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