CN115109021A - Synthesis of N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide, gel prepared from N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide and application of gel - Google Patents

Synthesis of N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide, gel prepared from N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide and application of gel Download PDF

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CN115109021A
CN115109021A CN202210795657.6A CN202210795657A CN115109021A CN 115109021 A CN115109021 A CN 115109021A CN 202210795657 A CN202210795657 A CN 202210795657A CN 115109021 A CN115109021 A CN 115109021A
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methoxycoumarin
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曲红梅
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-alkoxy phenyl) -7-methoxy coumarin-3-formamide, which directly introduces a colloid forming group of long-chain alkyl benzene containing six carbons, eight carbons and ten carbons onto a 7-methoxy coumarin-3-carboxylic acid skeleton by utilizing an amido bond to synthesize 3N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide gel factors; the gel properties and AIE characteristics of 3 gel factors were studied; the ethyl acetate gel formed by the 3 gel factors is used for the adsorption application of methyl orange dye, and the result shows that the gel has better dye adsorption performance. According to the invention, a long-chain alkylbenzene gelatinizing group is directly introduced into a coumarin derivative framework through an amido bond, and the aggregation fluorescence quenching effect of the coumarin derivative is converted into the AIE effect by utilizing a specific gelatinizing aggregation mode of a gelator and intramolecular movement limitation caused by gelatinizing, so that a potential reference value is provided for the application of the coumarin derivative in optical materials.

Description

Synthesis of N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide, gel prepared from N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide and application of gel
Technical Field
The invention relates to the field of coumarin derivative gel materials, in particular to a synthetic method of an N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide gel factor, a gel prepared by the same and application of the gel factor.
Background
Supramolecular gels are crosslinked systems of 3D networks saturated with a dispersion medium, the particles forming such a spatial network structure being called gelators or gelling agents, while the dispersion medium can be water, organic solvents or air. The supermolecule gel is formed by self-assembling a three-dimensional network structure which is formed by taking various intermolecular non-covalent interactions such as hydrogen bond, pi-pi accumulation, van der waals force, electrostatic attraction, hydrophobic interaction, halogen bond, coordination and the like as driving force by a low-molecular-weight gel factor, and combining and fixing solvent molecules. The supermolecule gel is used as an important soft nano-structure material, can be endowed with multiple functions through specific structure design, and has great application value in many research fields such as ion detection, drug delivery, biosensing, environmental remediation and the like. Among them, the application of supramolecular gel in the field of photoelectric materials has been one of the research hotspots. In particular, the AIE effect has been proposed, and the characteristics of AIE compounds that emit light in an aggregated state are well compatible with the condensed state properties of gels, which offers the possibility of fabricating advanced stimuli-responsive optical materials. The gel factor with AIE characteristics obtained through reasonable structural design can promote the deep development of gel materials in the optical field.
The coumarin derivative is an important organic heterocyclic compound, has the advantages of high fluorescence quantum yield, strong fluorescence, easiness in functional modification and the like, and is a compound with wide application. However, in the aggregated state, coumarin derivatives are prone to ACQ effects, thereby limiting their use. The proposal of AIE effect provides a solution to the ACQ problem of conventional fluorophores, and the conversion of coumarin derivatives from ACQ to AIE can be achieved by rational structural design. The condensed state characteristic of the gel provides a path for the aggregation behavior of the AIE, and the coumarin derivative is introduced into the field of the gel, so that a method for applying the coumarin derivative in an aggregation state is provided, and a potential reference value is provided for the coumarin derivative in the application aspect of optical materials.
Disclosure of Invention
Aiming at the prior art, the invention provides a synthesis method of an N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide gelator with AIE characteristics, and a prepared gel and application thereof. Specifically, different long-chain alkylbenzene gelling groups are introduced to a 7-methoxycoumarin-3-carboxylic acid skeleton through amido bonds to synthesize 3 novel N- (4-alkoxy phenyl) -7-methoxycoumarin-3-formamide gel factors, the performance and the application of the gel prepared from the gel factors are researched, the ACQ effect of the coumarin derivative is converted into the AIE effect by utilizing the specific gelling aggregation mode of the gel factors and the intramolecular movement limitation caused by gelling, and the potential reference value is provided for the coumarin derivative in the aspect of optical material application.
In order to solve the technical problems and achieve the purpose of the invention, in a first aspect, a process route of the synthetic method of the N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide provided by the invention is shown in figure 1, and the specific steps are as follows:
1) adding 2-hydroxy-4-methoxybenzaldehyde, Meldrum's acid and ammonium acetate into distilled water, and vigorously stirring at room temperature for 4 h; then regulating the pH value to 2-3 by using hydrochloric acid, filtering, washing the precipitate by using distilled water and drying to finally obtain light black solid 7-methoxycoumarin-3-carboxylic acid, wherein 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 ℃; after cooling, adding dichloromethane to dissolve precipitated solid, then washing with distilled water and separating liquid; drying the organic phase, and then performing rotary evaporation to remove the solvent to obtain a crude product, and purifying the crude product by column chromatography to obtain a white solid (4-alkoxy phenyl) tert-butyl carbamate;
3) adding tert-butyl (4-alkoxy phenyl) carbamate 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 by using a 5% NaOH solution; adjusting the pH 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 phase, and then removing the solvent by rotary evaporation to obtain brown solid 4-alkoxyaniline, 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) carbonyl diimine hydrochloride, 1-hydroxybenzotriazole monohydrate and N, N-diisopropylethylamine in anhydrous N, N-dimethylformamide, and reacting at room temperature for 5 hours; then fully diluting the mixed solution with a large amount of distilled water, extracting with dichloromethane, drying the combined organic phase, and removing the solvent by rotary evaporation to obtain a crude product; and purifying the crude product by column chromatography to obtain a light yellow solid N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide.
Further, the synthesis method of the present invention comprises:
in step 1), 2-hydroxy-4-methoxybenzaldehyde: meldrum'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-bromon-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 in a volume ratio of 30: 1.
The product obtained in the step 3) is any one of 4-hexyloxyaniline, 4-octyloxyaniline and 4-decyloxyalniline.
In the step 4), in the crude product column chromatography purification process, the eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 8: 1. 7-methoxycoumarin-3-carboxylic acid: 4-alkoxyaniline: 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride: 1-hydroxybenzotriazole monohydrate: the molar ratio of N, N-diisopropylethylamine is 1: 1.1: 1.3: 1.3: 3; 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 a basic environment. The obtained product N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide comprises one of N- (4-hexane oxyphenyl) -7-methoxy coumarin-3-formamide, N- (4-octane oxyphenyl) -7-methoxy coumarin-3-formamide and N- (4-decane oxyphenyl) -7-methoxy coumarin-3-formamide; the N- (4-hexyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C6bC, the N- (4-octyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C8bC, and the N- (4-decyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C10 bC. The structural formula is as follows:
Figure BDA0003735727440000031
in the second aspect, the invention researches the gel property of the N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide gel factor, the N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide obtained by the synthesis method is used as a gelator to prepare gel, and in a gelling property test, the 25 organic solvents selected are respectively methanol, ethanol, isopropanol, N-butanol, tert-amyl alcohol, N-pentane, N-hexane, cyclohexane, petroleum ether, benzene, toluene, chlorobenzene, o-dichlorobenzene, aniline, dichloromethane, trichloromethane, carbon tetrachloride, 1, 2-dichloroethane, Tetrahydrofuran (THF), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, ethyl acetate and acetone; wherein the test concentration of the gelling property is 20.00 mg/mL. Finally screening out organic compounds with solvents selected from the following according to the gelling performance 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 characteristics, and the scanning wavelength range of the fluorescence spectrum is 400-650 nm.
In the third aspect, the invention researches the AIE characteristics of the N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide gelators, N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide obtained by the synthesis method is used as the gelators to prepare isopropanol gel, isopropanol is selected as a solvent in the gelling process, and the prepared gel system and the concentration thereof are respectively cou-C6bC isopropanol gel (12.50mg/mL), cou-C8bC isopropanol gel (12.50mg/mL) and cou-C10bC isopropanol gel (10.00 mg/mL). In addition, the fluorescence spectrum scanning wavelength range of the system is 400-650 nm.
In the fourth aspect of the invention, the ethyl acetate gel prepared by taking N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide as a gelator is used for the adsorption application research of methyl orange dye, in the process of gel formation, ethyl acetate is selected as a solvent, and the prepared gel system and the concentration thereof are respectively cou-C6bC ethyl acetate gel (30.00mg/mL), cou-C8bC ethyl acetate gel (16.67mg/mL) and cou-C10bC ethyl acetate gel (16.67 mg/mL); the prepared Methyl Orange (MO) dye is 10 -4 An aqueous solution of M. In addition, the ultraviolet spectrum scanning wavelength range is 300-600 nm; the samples used for the measurement 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-alkoxy phenyl) -7-methoxy coumarin-3-formamide gel factor, the intermediate products 7-methoxy coumarin-3-carboxylic acid and 4-alkoxy aniline can be directly used for the next reaction without purification, the product purity is high, and the industrial production is facilitated.
(2) The invention introduces different long-chain alkylbenzene gelling groups onto a 7-methoxycoumarin-3-carboxylic acid skeleton through amido bonds to synthesize 3 novel N- (4-alkoxy phenyl) -7-methoxycoumarin-3-formamide gel factors, and successfully converts the ACQ effect of the coumarin derivative into the AIE effect by utilizing a specific gelling aggregation mode of the gel factors and intramolecular movement limitation caused by gelling.
(3) The gel property research of the gel factor in the invention shows that 3 gel factors mainly form gel in various alcohol solvents (including ethanol, isopropanol, n-butanol, tert-butanol and tert-amyl alcohol) and 1, 2-dichloroethane, DMSO, acetonitrile, ethyl acetate and acetone, besides, the cou-C6bC can also form gel in carbon tetrachloride, and the cou-C8bC and the cou-C10bC can also form gel in DMF.
(4) Critical gel concentration CGC and gel-sol phase transition temperature T of integrated gel factor gel As a result, it was found that the most preferable gelling solvents for the 3 gelling agents were isopropyl alcohol.
(5) The AIE characteristic study of the gelator in the invention shows that the system shows weaker fluorescence intensity under the hot sol state, the gel system gradually changes from the sol state to the gel state along with the gradual reduction of the temperature and shows obvious AIE effect along with the increase of the fluorescence intensity and the red shift of the maximum emission wavelength. Moreover, the gel system exhibits very significant fluorescence reversibility during multiple heat-cool treatments.
(6) The application research of the ethyl acetate gel formed by the gelator in the invention for adsorbing the 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 to the methyl orange at 10h are 84.2%, 85.0% and 87.3% respectively, which shows that the ethyl acetate gel formed by the 3N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide gelators synthesized by the invention has better adsorption effect on the methyl orange dye.
Drawings
FIG. 1 is a process scheme of the synthetic method of the present invention.
FIG. 2 is a fluorescence spectrum of AIE characteristic test of 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gelators in example 5 in a gel state.
FIG. 3 is a UV spectrum of ethyl acetate gel formed by 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide gelators in example 6 for adsorption application test of methyl orange dye.
FIG. 4-FIG. 9 show 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3Of-carboxamides gelators 1 H NMR spectrum and 13 c NMR spectrum.
Detailed Description
The design idea of the synthetic method is as follows: 1) the amide bond is utilized to directly lead the catalyst to contain six carbons, long-chain alkylbenzene gelling groups with eight carbon atoms and ten carbon atoms are introduced to a 7-methoxycoumarin-3-carboxylic acid skeleton to synthesize 3 novel N- (4-alkoxyphenyl) -7-methoxycoumarin-3-formamide gelators (in the invention, N- (4-hexyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C6bC, N- (4-octyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C8bC, and N- (4-decyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C10 bC); 2) the gel properties and AIE characteristics of 3 gel factors, cou-C6bC, cou-C8bC and cou-C10bC, were investigated; 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 the adsorption application of the methyl orange dye, and the result shows that the gel has better dye adsorption performance. According to the invention, a long-chain alkylbenzene gelatinizing group is directly introduced into a coumarin derivative framework through an amido bond, and the aggregation fluorescence quenching (ACQ) effect of the coumarin derivative is converted into the AIE effect by utilizing a specific gelatinizing aggregation mode of a gelator and intramolecular movement limitation caused by gelatinizing, so that a potential reference value is provided for the application of the coumarin derivative in optical materials.
The invention will be further described with reference to the following drawings and specific examples, which are not intended to limit the invention in any way. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the starting materials used are all commercially available reagents.
Example 1 synthesis of N- (4-hexyloxyphenyl) -7-methoxycoumarin-3-carboxamide (cou-C6bC) according to the scheme of fig. 1, the specific steps are as follows:
adding 2-hydroxy-4-methoxybenzaldehyde (7.17g, 47.1mmol), Meldrum's acid (7.75g, 53.8mmol) and ammonium acetate (0.75g, 9.73mmol) to 120mL of distilled water, and vigorously stirring at room temperature for 4 h; then adjusting pH to 2-3 with hydrochloric acid, filtering, washing precipitate with distilled water and drying to obtain light black solid 7-methoxy coumarin-3-carboxylic acid.
② 4- (Boc-amino) phenol (3.14g, 15.0mmol) and K 2 CO 3 (4.15g, 30.0mmol) was added to acetonitrile (75mL), the temperature was raised to 75 deg.C, then 1-bromohexane (2.72g, 16.5mmol) was slowly added and reacted at 75 deg.C for 10 h; after cooling, dichloromethane (75mL) was added to dissolve the precipitated solid, which was then washed with distilled water (2X 25mL) and separated; drying the organic phase, and then 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.
(4-Hexanyloxyphenyl) carbamic acid tert-butyl ester (1.47g, 5.00mmol) was added to DCM: in a mixed solution (42mL) of TFA 6:1, the reaction was carried out at room temperature for 2 h; the reaction was quenched with 5% NaOH solution (40 mL); the reaction was again adjusted to pH 10 with 5% NaOH solution and the layers were separated, the aqueous layer was extracted with dichloromethane (2X 20mL), the combined organic layers were dried and the solvent removed by rotary evaporation to give 4-hexoxyaniline as a brown solid.
Fourthly, 7-methoxycoumarin-3-carboxylic acid (0.66g, 3.00mmol), 4-hexane oxygen aniline (0.64g, 3.30mmol), EDCI & HCl (0.75g, 3.90mmol), HOBt & H 2 O (0.60g, 3.90mmol) and DIEA (1.16g, 9.00mmol) were dissolved in anhydrous DMF (30mL) and reacted at room temperature for 5 h; then fully diluting the mixed solution with a large amount of distilled water (70mL), extracting with dichloromethane (3X 50mL), drying the combined organic phases, 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, 8:1, v/v) to yield cou-C6bC as a yellow solid. The specific synthetic route is shown in figure 1.
Characteristic analysis of cou-C6bC by liquid NMR spectrometer 1 H NMR spectrum of 13 The results of the C NMR spectrum test are as follows: 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 ) δ 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-C8bC)
The synthesis process of the steps from (i) to (iii) is similar to that of example 1, and only 1-bromon-hexane is replaced by 1-bromon-octane, which is shown in example 1. Fourthly, 7-methoxycoumarin-3-carboxylic acid (0.66g, 3.00mmol), 4-octyloxyaniline (0.73g, 3.30mmol), EDCI & HCl (0.75g, 3.90mmol), HOBt & H 2 O (0.60g, 3.90mmol) and DIEA (1.16g, 9.00mmol) were dissolved in anhydrous DMF (30mL) and reacted at room temperature for 5 h; then fully diluting the mixed solution with a large amount of distilled water (70mL), extracting with dichloromethane (3X 50mL), drying the combined organic phases, 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, 8:1, v/v) to yield cou-C8bC as a yellow solid. The specific synthetic route is shown in figure 1.
Characteristic analysis of cou-C8bC was carried out using a liquid NMR spectrometer, which 1 H NMR spectrum and 13 the results of the C NMR spectrum test are as follows: 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 ═ 2.8Hz),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-C10bC)
The synthesis process of the steps I to III is similar to that of the example 1, and only 1-bromon-hexane is replaced by 1-bromon-decane, which is shown in the example 1. Fourthly, the 7-methoxy coumarin-3-carboxylic acid (0.66g, 3.00mmol) and the 4-decaneOxyaniline (0.82g, 3.30mmol), EDCI. HCl (0.75g, 3.90mmol), HOBt. H 2 O (0.60g, 3.90mmol) and DIEA (1.16g, 9.00mmol) were dissolved in anhydrous DMF (30mL) and reacted at room temperature for 5 h; then fully diluting the mixed solution with a large amount of distilled water (70mL), extracting with dichloromethane (3X 50mL), drying the combined organic phases, 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, 8:1, v/v) to yield cou-C10bC as a yellow solid. The specific synthetic route is shown in figure 1.
Characteristic analysis of cou-C10bC by liquid NMR spectrometer 1 H NMR spectrum and 13 the results of the C NMR spectrum test are as follows: 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 ) δ 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 fig. 8 and 9.
EXAMPLE 4 gel Performance testing of the gel factors cou-C6bC, cou-C8bC and cou-C10bC
The gel property research comprises a gel property test, a CGC test and a T test gel And (4) measuring. The gelling performance test is researched by a test tube inversion method, 10.00mg of gelator and 0.50mL of solvent are added into a sealed test tube, the sealed test tube is fully heated until the solid is completely dissolved or the liquid is boiled, and then the sealed test tube is cooled to room temperature; the tube was inverted and the flow of the system was observed and then labeled as gel (G), Partial Gel (PG), insoluble (I), soluble (S) and precipitate (P) depending on the flow of the system. The determination of CGC is carried out on the basis of a gelling 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 system concentration before the last solvent adding is marked as a CGC value; for a system forming part of the gel, a small amount of gelator is added until the gel is formed, and then a solvent adding method is used until the system does not form the gelUntil the gel can be formed, the system concentration before the last solvent addition is marked as a CGC value. T is gel The value is measured by adopting a falling ball method, namely, a gel system with known concentration is prepared, and then glass beads with the mass of about 0.15g are respectively placed on the surface of the obtained gel system; fixing the gel system in a constant temperature water bath, then increasing the water bath temperature at the speed of 1 ℃/min, observing the immersion condition of the glass beads in the gel system, and recording the water bath temperature at the moment as the T of the system when the glass beads are completely immersed below the liquid level of the gel system gel The value is obtained. Gelling Performance test results, CGC test data and T gel The test data are shown in tables 1-3, table 1 shows the results of gel forming performance test of 3N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamides gelators in example 4 of the present invention, table 2 shows the critical gel concentrations of 3 CGC gelators in example 4 of the present invention, and table 3 shows 3T gelators in example 4 of the present invention gel The measured phase transition temperature.
TABLE 1 test results of gelling Properties of co5u-C6bC, cou-C8bC and cou-C10bC
Figure BDA0003735727440000071
Figure BDA0003735727440000081
TABLE 2 Critical gel concentrations of cou-C6bC, cou-C8bC, and cou-C10bC
Figure BDA0003735727440000082
Figure BDA0003735727440000091
TABLE 3 phase transition temperatures of cou-C6bC, cou-C8bC, and cou-C10bC
Figure BDA0003735727440000092
EXAMPLE 5 AIE characterization of the gelators cou-C6bC, cou-C8bC and cou-C10bC
The changes of fluorescence spectra of the conversion process from the sol state to the gel state of the cou-C6bC isopropanol gel (12.50mg/mL), the cou-C8bC isopropanol gel (12.50mg/mL) and the cou-C10bC isopropanol gel (10.00mg/mL) were studied; heating the system to a sol state, and then testing the change condition of the fluorescence spectrum of the system along with time; in order to verify the fluorescence reversibility of the system, the gel system is subjected to multiple heating-cooling cyclic treatment to test the fluorescence intensity of a certain moment in the multiple cyclic treatment process; the results show that the system is transformed 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 Ethyl acetate gels formed by the gelators cou-C6bC, cou-C8bC and cou-C10bC for adsorption application testing of methyl orange dye
First, a concentration of a cou-C6bC ethyl acetate gel (30.00mg/mL), a cou-C8bC ethyl acetate gel (16.67mg/mL), and a cou-C10bC ethyl acetate gel (16.67mg/mL) was prepared, and the concentration of the methyl orange dye aqueous solution was formulated to be 10 -4 M; adding equal volume of dye aqueous solution into the gel, heating at 60 deg.C until the gel is dissolved, standing, cooling, timing, respectively taking small amount of 2h and 10h aqueous solution, and diluting to 10% -5 Measuring the concentration of M in the ultraviolet-visible spectrum, so as to monitor the adsorption rate of the gel on the dye; the results show 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 84.2%, 85.0% and 87.3%, respectively; in addition, the adsorption rate of pure ethyl acetate to methyl orange in the blank control experiment is 13.1%; the results of the UV-Vis test are shown in FIG. 3.
While the present invention has been described with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are illustrative only and not restrictive, and various modifications which do not depart from the spirit of the present invention and which are intended to be covered by the claims of the present invention may be made by those skilled in the art.

Claims (10)

1. A synthetic method of N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide is characterized by comprising the following steps:
1) adding 2-hydroxy-4-methoxybenzaldehyde, Meldrum's acid and ammonium acetate into distilled water, and vigorously stirring at room temperature for 4 h; then regulating the pH value to 2-3 by using hydrochloric acid, filtering, washing the precipitate by using distilled water and drying to obtain light black solid 7-methoxycoumarin-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 ℃; after cooling, adding dichloromethane to dissolve precipitated solid, then washing with distilled water and separating liquid; drying the organic phase, and then performing rotary evaporation to remove the solvent to obtain a crude product, and purifying the crude product by column chromatography to obtain a white solid (4-alkoxy phenyl) tert-butyl carbamate;
3) adding the tert-butyl (4-alkoxy phenyl) 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 by using a 5% NaOH solution; adjusting the pH 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 phase, and removing the solvent by rotary evaporation to obtain brown solid 4-alkoxyaniline;
4) dissolving 7-methoxycoumarin-3-carboxylic acid, 4-alkoxyaniline, 1-ethyl- (3-dimethylaminopropyl) carbonyl diimine hydrochloride, 1-hydroxybenzotriazole monohydrate and N, N-diisopropylethylamine in anhydrous N, N-dimethylformamide, and reacting at room temperature for 5 hours; then fully diluting the mixed solution with a large amount of distilled water, extracting with dichloromethane, drying the combined organic phase, and removing the solvent by rotary evaporation to obtain a crude product; and purifying the crude product by column chromatography to obtain a light yellow solid N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide.
2. The method of claim 1, wherein in step 2), the ratio of 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-bromon-hexane, 1-bromo-n-octane and 1-bromo-n-decane; the product obtained in the step 3) is any one of 4-hexyloxyaniline, 4-octyloxyaniline and 4-decyloxyalniline.
3. The method of claim 2, wherein in step 4), the ratio of 7-methoxycoumarin-3-carboxylic acid: 4-alkoxyaniline: 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride: 1-hydroxybenzotriazole monohydrate: the molar ratio of N, N-diisopropylethylamine is 1: 1.1: 1.3: 1.3: 3; 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 a basic environment.
4. The synthesis method according to claim 2, wherein the product N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide obtained in step 4) comprises one of N- (4-hexyloxyphenyl) -7-methoxycoumarin-3-carboxamide, N- (4-octyloxyphenyl) -7-methoxycoumarin-3-carboxamide, and N- (4-decyloxyphenyl) -7-methoxycoumarin-3-carboxamide; the N- (4-hexyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C6bC, the N- (4-octyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C8bC, and the N- (4-decyloxyphenyl) -7-methoxycoumarin-3-formamide is abbreviated as cou-C10 bC;
the structural formula is as follows:
Figure FDA0003735727430000021
5. the method of claim 1, wherein in step 1), the ratio of 2-hydroxy-4-methoxybenzaldehyde: meldrum's acid: the molar ratio of ammonium acetate is 1: (1.1-1.2): 0.2.
6. the synthetic method according to claim 1, characterized in that in the step 2), the eluent in the crude column chromatography purification process adopts a mixed solution of petroleum ether and ethyl acetate with a volume ratio of 30: 1; in the step 4), in the crude product column chromatography purification process, the eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 8: 1.
7. A gel prepared by taking N- (4-alkoxy phenyl) -7-methoxy coumarin-3-formamide obtained by the synthesis method according to any one of claims 1 to 6 as a gelator, wherein in the gelling process, the mass-to-volume ratio of the gelator to a 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 characteristics, and the scanning wavelength range of the fluorescence spectrum is 400-650 nm.
8. The gel of claim 7, wherein the solvent used in the gelling process is isopropanol and, depending on the specific structure of N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide, the gel is formed as follows:
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is cou-C6bC as defined in claim 4, the mass to volume ratio of gelator to solvent is 12.50mg/mL, and the gel formed is a cou-C6bC isopropanol gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is cou-C8bC as defined in claim 4, the mass to volume ratio of gelator to solvent is 12.50mg/mL, and the gel formed is a cou-C8bC isopropanol gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is cou-C10bC according to claim 4, the mass-to-volume ratio of gelator to solvent is 10.00mg/mL, and the gel formed is a cou-C10bC isopropanol gel.
The fluorescence spectrum scanning wavelength range of the gel is 400-650 nm.
9. The gel of claim 7, wherein the solvent used in the gel formation 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 cou-C6bC as defined in claim 4, the mass-to-volume ratio of gelator to solvent is 30.00mg/mL, and the gel formed is a cou-C6bC ethyl acetate gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is cou-C8bC as defined in claim 4, the mass-to-volume ratio of gelator to solvent is 16.67mg/mL, and the gel formed is a cou-C8bC ethyl acetate gel;
the N- (4-alkoxyphenyl) -7-methoxycoumarin-3-carboxamide is cou-C10bC as defined in claim 4, the mass-to-volume ratio of gelator to solvent is 16.67mg/mL, and the gel formed is a cou-C10bC ethyl acetate gel;
the fluorescence spectrum scanning wavelength range of the gel is 400-650 nm.
10. Use of the gel according to claim 9 for the adsorption of methyl orange dye, characterized in that the formulation concentration is 10 - 4 M, wherein the volume ratio of the gel to the dye aqueous solution is 1: 1, heating at the temperature of 60 ℃ until the gel is dissolved, then standing and cooling, and starting timing; the scanning wavelength range of the ultraviolet-visible spectrum for determining the dye adsorption result by using an ultraviolet-visible spectrometer is 300-600 nm; the samples used for measurement were aqueous phase solutions that were adsorbed for 2h and 10h, respectively; when the reaction time is 2 hours, the adsorption rate of methyl orange is 59.6-85.0%; the adsorption rate of methyl orange is 84.2-87.3% when the reaction time is 10 hours.
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