CN117567436A - Novel fluorescent dialdehyde compound, preparation method, chitosan Schiff base copper functional material and application thereof - Google Patents

Novel fluorescent dialdehyde compound, preparation method, chitosan Schiff base copper functional material and application thereof Download PDF

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CN117567436A
CN117567436A CN202311416877.4A CN202311416877A CN117567436A CN 117567436 A CN117567436 A CN 117567436A CN 202311416877 A CN202311416877 A CN 202311416877A CN 117567436 A CN117567436 A CN 117567436A
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chitosan
functional material
compound
schiff base
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朱磊
李博解
李维双
张泽浪
夏甜
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Hubei Engineering University
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Abstract

The invention discloses a novel fluorescent dialdehyde compound, a preparation method and a chitosan Schiff base copper functional material and application thereof, wherein the preparation method of the novel fluorescent dialdehyde compound comprises the following steps: a. adding indole-6-formaldehyde into N, N-dimethylformamide for dissolution, stirring in an ice water bath, then adding sodium hydride in batches, stirring in an ice water bath, adding 2-chloropyrimidine, heating for reaction, and then adding water for quenching to obtain an intermediate A; b. dissolving silver hexafluoroantimonate in dichloroethane, sequentially adding an intermediate A, p-ethynyl benzaldehyde, pentamethyl cyclopentadienyl carbonyl diiodocobalt and trimethylacetic acid, and heating and refluxing; c. and after the reaction is finished, filtering, and separating and purifying filtrate to obtain the novel fluorescent dialdehyde compound B. According to the invention, the novel fluorescent dialdehyde compound is used for modifying the chitosan Schiff base copper functional material, and the synthesis of the beta-silanized amide compound can be realized by using low-cost and easily available active metal and lower functional material dosage.

Description

Novel fluorescent dialdehyde compound, preparation method, chitosan Schiff base copper functional material and application thereof
Technical Field
The invention relates to the field of organic synthesis, in particular to a novel fluorescent dialdehyde compound, a preparation method, a chitosan Schiff base copper functional material and application thereof.
Background
In recent years, organosilicon compounds containing C-Si bonds have been widely used in pharmaceutical chemistry and material science and have unique biological activities. The organosilicon compound is used as an important organic synthesis intermediate, and the contained C-Si bond can be converted into various chemical bonds such as C-O bond, C-C bond and C-X bond. Alpha-acrylamide compounds are an important class of drug molecules and active intermediates that react rapidly with nucleophiles to form various acrylamide derivatives and that can be silanized to improve pharmacological properties. The formation of β -silylated amides has been very limited in the silicon addition reaction of α -acrylamides with carbonyl conjugated double bond compounds. Recently, literature (chem. Commun.,2020,56,11058-11061) utilized cupric (CuSO 4 1mol% relative to the mass percentage of the template reaction substrate) of the beta-silylated polypeptide to catalyze the conversion of the polypeptide containing the alpha-acrylamide structure to the beta-silylated polypeptide, the work uses 10 equivalents of the pinacol dimethyl phenyl silicon reagent, 10mol% of 4-methylpyridine is added as a base, and the beta-silylated polypeptide with higher yield is obtained by the reaction at room temperature under the condition of illumination and the mixed solution of trifluoroethanol and water is taken as a solvent. However, the reaction mode disclosed in the document has low utilization rate and high cost on the dimethyl phenyl silicon reagent of the pinacol, the use of a strong base ligand and the trifluoroethanol as an organic solvent causes environmental pollution, the catalyst cannot be recycled, the substrate range is narrow, and the application of the method in actual production is greatly limited only by the addition of polypeptide silicon. Therefore, the development of a novel environment-friendly method which is simple and easy to operate, mild in condition and low in cost and can directly convert the alpha-acrylamide compound into the beta-silanized amide compound with higher yield is urgent.
The chitosan is obtained by deacetylation of chitin which is the second most abundant resource in nature, has no pollution to the environment, and can be recycled. As the only alkaline polysaccharide in the nature, the novel antibacterial polysaccharide has the characteristics of antibacterial property, biocompatibility, degradability and the like, and has the defects of poor solubility in neutral and alkaline environments, easiness in swelling, poor mechanical strength and the like. The chitosan Schiff base material obtained by modifying chitosan with aldehyde not only can retain the characteristics of antibacterial property, biocompatibility, degradability and the like of chitosan, but also can improve the physicochemical property of chitosan and the stability and solubility of chitosan. In the prior art, chinese patent application CN111087490A discloses a novel demulsifier which is prepared by utilizing salicylaldehyde to modify chitosan to obtain a chitosan Schiff base material and adsorbing iron, manganese and copper metals. The chitosan Schiff base material contains a large amount of hydroxyl and amino groups, and is easy to coordinate with transition metal, so that the chitosan Schiff base material has wide application in the fields of industrial adsorption, corrosion inhibitors, catalysis and the like. For example, it has been reported that (chemistry select.) 2017,2,6865, chitosan is modified with 8-hydroxyquinoline-2-carbaldehyde to give chitosan Schiff base material, and Cu is adsorbed 2+ Catalyzing the oxidative coupling reaction of terminal alkyne. However, there are few reports about such functional materials in constructing c—si bonds.
Because the substrate range for synthesizing the beta-silanized amide compound is narrow, the silicon reagent is large in use amount and expensive, and cannot be industrialized; and alkali is required to be added during the reaction, so that the catalyst cannot be recycled. Therefore, a novel fluorescent dialdehyde compound, a preparation method and a chitosan Schiff base copper functional material thereof are required to be developed, an alpha-acrylamide compound is converted to prepare a beta-silanized amide compound, a catalytic reaction can be realized under mild conditions, and the catalyst can be recycled.
Disclosure of Invention
The invention aims to solve the defects of the background technology, and provides a novel fluorescent dialdehyde compound, a preparation method and a chitosan Schiff base copper functional material thereof, wherein an alpha-acrylamide compound is converted to prepare a beta-silanized amide compound, a catalytic reaction can be realized under mild conditions, and a catalyst can be recycled.
The technical scheme of the invention is as follows: a method for preparing a novel fluorescent dialdehyde compound, comprising the steps of:
a. adding indole-6-formaldehyde into N, N-dimethylformamide DMF, stirring and dissolving in an ice-water bath, then adding sodium hydride in batches, continuing stirring in an ice-water bath for 30-60 min, adding 2-chloropyrimidine, reacting at 120-140 ℃ for 20-30 h, finally adding water for quenching, and performing post-treatment to obtain an intermediate A, wherein the reaction formula is shown in the formula i);
b. adding silver hexafluoroantimonate into dichloroethane DCE for dissolution, then sequentially adding an intermediate A, p-ethynyl benzaldehyde, pentamethyl cyclopentadienyl carbonyl diiodocobaltous and trimethyl acetic acid, heating and refluxing at 70-90 ℃ for 5-20 min, filtering after the reaction is finished, separating and purifying filtrate to obtain a fluorescent dialdehyde compound B, wherein the reaction formula is shown in the following formula ii),
preferably, in step a, indole-6-carbaldehyde: 2-chloropyrimidine: molar ratio of sodium hydride=1 (1-1.5): 1-1.5. More preferably, indole-6-carbaldehyde: 2-chloropyrimidine: molar ratio of sodium hydride = 1:1.2:1.2.
Preferably, in step a, reaction is carried out at 130℃for 24h.
Preferably, in step b, the molar ratio of intermediate a, p-ethynylbenzaldehyde, pentamethyl cyclopentadienyl carbonyl diiodocobalt, silver hexafluoroantimonate, and trimethylacetic acid=1, (0.5-1.5): (0.01-0.10): (0.08-0.15): (0.08-0.15). More preferably, the molar ratio of intermediate a, p-ethynylbenzaldehyde, pentamethyl cyclopentadienyl cobalt carbonyl diiodoxide, silver hexafluoroantimonate, and trimethylacetic acid = 1:1:0.05:0.1:0.1.
Preferably, in step b, reflux is carried out at 80℃for 10min.
Preferably, in step a, the post-treatment comprises: extraction with ethyl acetate, filtration and column chromatography gave intermediate a.
The invention also provides a novel fluorescent dialdehyde compound, which is prepared by the preparation method of any novel fluorescent dialdehyde compound.
The invention also provides a preparation method of the chitosan Schiff base copper functional material, which comprises the following steps:
1) Dissolving chitosan in 1-2 wt% acetic acid aqueous solution to obtain chitosan acetic acid solution, dissolving the fluorescent dialdehyde compound B in THF, slowly dripping the THF solution of the fluorescent dialdehyde compound B into the chitosan acetic acid solution, heating and stirring at 60-70 ℃ for 20-40 min to form hydrogel;
2) After the reaction is finished, taking out the hydrogel, standing at room temperature to volatilize the solvent, and soaking and washing the hydrogel by THF until the washing liquid is colorless and has no fluorescence;
3) Putting the hydrogel into water, adding a saturated copper sulfate solution, soaking the hydrogel for loading metal copper ions for 20-30 h, taking out and drying to obtain Schiff-CS@Cu.
Preferably, in step 1), the aldehyde-CHO contained in the fluorescent dialdehyde compound B and the amino-NH contained in the chitosan 2 The molar ratio is 3-4:1.
Further, in step 1), the dosage ratio of chitosan to acetic acid aqueous solution is 60mg: 5-10 mL, the dosage ratio of fluorescent dialdehyde compound B to THF is 0.62mmol: 3-5 mL.
Preferably, in the step 3), the usage ratio of the hydrogel to the water and the saturated copper sulfate solution is 60 mg:120-150 mL:1.8-2.0 mL.
The invention also provides a chitosan Schiff base copper functional material, which is prepared by the preparation method of any one of the chitosan Schiff base copper functional materials.
The invention also provides an application of the chitosan Schiff base copper functional material in preparing the beta-silanized amide compound, which comprises the following steps:
adding an alpha-acrylamide compound I, (dimethylbilyl) boric acid pinacol ester and the chitosan Schiff base copper functional material Schiff-CS@Cu described in claim 9 into a mixed solvent of methanol and water, stirring at room temperature under the illumination condition for reacting for 8-16 h, wherein the molar ratio of copper contained in the alpha-acrylamide compound, (dimethylbilyl) boric acid pinacol ester and Schiff-CS@Cu is 1:2:0.01-0.05, the reaction formula is shown in the following formula iii),
wherein R is hydrogen, methyl, methoxy or fluoro.
After the reaction is finished, filtering, and treating the precipitate to obtain a recovered chitosan Schiff base copper functional material Schiff-CS@Cu for recycling, and separating and purifying the filtrate to obtain the beta-silanized amide compound II.
Preferably, the ratio of the copper content of the Schiff-CS@Cu to the amount of the mixed solvent is 0.002-0.005 mmol/2 ml. The volume ratio of methanol to water was 4:1.
Preferably, the reaction is stirred at room temperature for 12h.
Preferably, the obtained filtrate is separated and purified to obtain the beta-silanized amide compound II, which specifically comprises the following steps: extracting the filtrate with ethyl acetate to obtain organic phase containing the product, and passing through anhydrous Na 2 SO 4 Drying, filtering, rotary evaporating to remove excessive organic solvent, and purifying the obtained residual organic phase by column chromatography of a mixed solvent of ethyl acetate and petroleum ether to obtain the beta-silanized amide compound.
The technical principle of the invention is that the unique space structure and biocompatibility of the chitosan Schiff base immobilized copper material are utilized, and the strong coordination capability of the material on copper promotes the catalytic activity of the material to be higher; the chitosan Schiff base also contains a large amount of imine bonds, an alkaline environment is provided for the reaction, the catalytic reaction can be realized in pure water without adding any alkali, the catalyst can be recycled, the environment-friendly chemical concept is met, and the method has a very high industrial application prospect. Specifically, the method is realized by the following technology.
The invention prepares the beta-silanization amide compound by using the chitosan Schiff base copper functional material. The reaction can be realized only by illumination. The catalyst provides an alkaline environment for the whole reaction system by utilizing a large amount of imine groups contained in the chitosan Schiff base material, and no alkali is required to be added; the special space structure and biocompatibility of the chitosan Schiff base copper functional material are added, so that the catalyst has higher catalytic activity and stronger complexation; can be recycled and has wide industrial application prospect.
The beneficial effects of the invention are as follows:
1. the fluorescent dialdehyde compound and the chitosan Schiff base copper functional material are synthesized for the first time. The fluorescent dialdehyde compound modified chitosan Schiff base copper functional material can be realized by using the fluorescent effect and only needing illumination.
3. The method can realize the synthesis of the beta-silanized amide compound by using cheap and easily available active metals and lower consumption of functional materials.
4. The method does not need to add alkali, and can be used for reaction at room temperature, the reaction condition is mild, the operation is simple and easy, and the reaction process can be observed through observation fluorescence.
5. The method has good substrate universality, and can realize the silicon addition reaction of different types of alpha-acrylamide compounds to prepare corresponding beta-silanized amide compounds.
6. The chitosan Schiff base has good adsorption effect on metal copper, excellent biocompatibility, low cost and environment friendliness. After the reaction is finished, the chitosan Schiff base copper functional material can be separated from other components in a reaction system by a solid-liquid phase separation method, can be reused after simple regeneration, reduces the production cost and is environment-friendly.
7. Chitosan Schiff base materialMaterial pair Cu 2+ The adsorption of (2) is mainly based on imine group coordination, and the main reaction comprises:
schiff reaction: r' -NH 2 +RCHO→R'-N＝CHR (1)
After the aldehyde compound modifies the biomass-based functional material chitosan, the coordination capacity of the chitosan to metal is changed, and the catalytic activity is improved. Aldehyde group (rhc=o) of aldehyde compound and amino group (R' -NH) on chitosan 2 ) Amination reaction is carried out to generate an imine group (-C=N-), N atoms in the imine group formed by the amination reaction are structurally adjacent to O atoms in OH and adjacent hetero atoms of aldehyde compounds in chitosan, and are easy to be connected with Cu 2+ Multidentate coordination occurs, a stable conjugate plane is formed, and the complexing effect on copper ions is stronger.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the target product of example 1;
FIG. 2 is a nuclear magnetic resonance spectrum of the target product of example 1;
FIG. 3 is a fluorescence spectrum of Schiff-CS@Cu prepared in example 2.
Detailed Description
The invention is illustrated in further detail by the following specific examples. The drugs used in the examples are commercially available products unless otherwise specified, and the methods used are conventional in the art.
Example 1
The present example provides a method for synthesizing a novel fluorescent dialdehyde compound (Z) -2- (4-formyl) -1- (pyrimidin-2-yl) -1H-indole-6-carbaldehyde 8, which comprises the following steps:
indole-6-carbaldehyde (10 mmol) was added to N, N-dimethylformamide (DMF, 20 mL) and dissolved, stirred in ice-water bath, then sodium hydride (12 mmol) was added in portions and stirred in ice-water bath for 30min, then 2-chloropyrimidine (12 mmol) was added, the mixture was reacted at 130℃for 24h, finally water was added for quenching, extraction with ethyl acetate, filtration and column chromatography to give intermediate A. The chemical reaction equation of indole-6-carbaldehyde, 2-chloropyrimidine and sodium hydride is as follows:
silver hexafluoroantimonate (0.3 mmol) was added to dichloroethane (DCE, 2 mL) for dissolution, followed by intermediate a (3 mmol), p-ethynylbenzaldehyde (3 mmol), pentamethylcyclopentadienyl cobalt carbonyl diiodoxide (0.15 mmol) and trimethylacetic acid (30.6 μl,0.3 mmol) in sequence, and heated to reflux at 80 ℃ for 10min. After the reaction is finished, filtering is carried out, and the obtained filtrate is purified by a multi-step complex separation mode to obtain a fluorescent dialdehyde compound B, wherein the name of the fluorescent dialdehyde compound B is (Z) -2- (4-formyl) -1- (pyrimidine-2-yl) -1H-indole-6-formaldehyde, and the chemical reaction equation is as follows:
the nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product (fluorescent dialdehyde compound B) are shown below, and the spectra are shown in fig. 1 and 2.
1H NMR(400MHz,Chloroform-d)δ＝10.08(s,1H),10.01(s,1H),8.94(d,J＝4.8Hz,2H),8.84(s,1H),7.97–7.84(m,3H),7.83–7.62(m,4H),7.32(dd,J＝10.3,5.4Hz,2H),7.15(s,1H).
13 C NMR(100MHz,Chloroform-d)δ＝192.6,191.7,158.8,157.6,143.03,142.1,137.1,135.7,134.3,132.6,130.4,130.1,127.3,123.4,123.3,121.0,118.2,117.9,106.1.
Example 2
The embodiment provides a method for preparing Schiff-CS@Cu by modifying chitosan with fluorescent dialdehyde compound B, which comprises the following specific preparation processes:
1) 60mg of chitosan (1.0 g of chitosan containing about 6.2 mmol-NH) 2 ) Dissolving in 5mL of 1wt% acetic acid solution, weighing fluorescent dialdehyde compound B (219.10 mg,0.62 mmol) and dissolving in 3mL of THF (tetrahydrofuran) solution, slowly dripping into chitosan acetic acid solution, and heating and refluxing at 65 ℃ for 30min to form hydrogel.
2) After the reaction is finished, the hydrogel is placed at room temperature for three days to volatilize the solvent, and the hydrogel is soaked and washed in THF for many times until the solution becomes colorless and non-fluorescent.
3) 60mg of hydrogel is put into 120mL of water, 1.8mL of saturated copper sulfate solution is added, the solution is soaked for 24 hours for loading metal copper ions, and the solution is taken out and dried overnight at 50 ℃ to obtain Schiff-CS@Cu.
The relative copper content in Schiff-CS@Cu was determined to be 0.9mmol/g by ICP.
FIG. 3 shows the fluorescence spectrum of Schiff-CS@Cu (a excitation spectrum, b emission spectrum), and the emission wavelength of sample fluorescence is about 582nm as can be seen from FIG. 3.
Example 3
The embodiment provides a method for preparing a beta-silanized amide compound by catalyzing a chitosan Schiff base copper functional material Schiff-CS@Cu, which comprises the following specific steps:
1) Alpha-acrylamide compound I, pinacol ester of (dimethylbilyl) boric acid and Schiff-CS@Cu (prepared in example 2) are added into a mixed solvent (2 ml) with a volume ratio of methanol to water of 4:1, wherein the alpha-acrylamide compound I is 0.20mmol, the pinacol ester of (dimethylbilyl) boric acid is 0.40mmol, the copper content in Schiff-CS@Cu is 0.002mmol, the reaction is carried out under illumination and stirring at room temperature for 12 hours, and the alpha-acrylamide compound I in this example is 2-phenyl-N-phenylacrylamide (R is hydrogen group) and has the following reaction formula;
2) After the reaction is finished, filtering, washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper functional material Schiff-CS@Cu, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent=1:35 to give β -silylated amide compound II. The product yield was 89% (64.0 mg).
The nuclear magnetic hydrogen and carbon spectra of the target product II are shown below.
1 H NMR(400MHz,Chloroform-d)；δ＝7.47-7.44(m,2H),7.36-7.33(m,5H),7.32-7.22(m,7H),7.06-7.02(t,1H),6.91(s,1H)，3.50-3.45(q,1H),1.87-1.81(q,1H),1.45-1.38(q,1H),0.16(s,3H),0.10(s,3H).
13 C NMR(100MHz，Chloroform-d)；δ＝172.5,141.2,138.5,138.0,133.8,129.2,129.1,129.0,128.0,127.9,127.7,124.3,120.0,50.3,20.3,-2.4,-2.8.
Under the catalysis condition of the Schiff-CS@Cu material provided in example 2, the conversion rate of the 2-phenyl-N-phenyl acrylamide is very high, and the yield of a silicon addition product reaches 89%.
Example 4
The embodiment provides a method for preparing a beta-silanized amide compound by catalyzing a chitosan Schiff base copper functional material Schiff-CS@Cu, which comprises the following specific steps:
1) Alpha-acrylamide compound I, pinacol ester of (dimethylbilyl) boric acid and Schiff-CS@Cu (prepared in example 2) are added into a mixed solvent (2 ml) with a volume ratio of methanol to water of 4:1, wherein the alpha-acrylamide compound I is 0.20mmol, the pinacol ester of (dimethylbilyl) boric acid is 0.40mmol, the copper content in Schiff-CS@Cu is 0.002mmol, the reaction is carried out under illumination and stirring at room temperature for 12 hours, and the alpha-acrylamide compound I in this example is 2-phenyl-N- (p-tolyl) acrylamide (R is methyl) with the following reaction formula;
2) After the reaction is finished, filtering, washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper functional material Schiff-CS@Cu, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent=1:35 to give β -silylated amide compound II. The product yield was 82% (61.3 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H NMR(400MHz，Chloroform-d)；δ＝7.47-7.42(m,2H),7.40-7.32(m,3H),7.32-7.20(m,7H),7.10-7.01(t,2H),6.89(s,1H),3.50-3.44(q,1H),2.27(s,3H),1.87-1.81(q,1H),1.44–1.38(q,1H),0.16(s,3H),0.10(s,3H).
13 CNMR(100MHz，Chloroform-d)；δ＝172.4,141.4,138.5,135.4,133.8,133.7,129.4,129.1,129.0,128.0,127.9,127.6,119.9,50.1,20.9,20.3,-2.5,-2.8.
example 5 shows that under the catalytic condition of the Schiff-CS@Cu material provided by the example of the invention, the conversion rate of the 2-phenyl-N- (p-tolyl) acrylamide is also very high, and the yield of the silicon addition product reaches 82%.
Example 5
The embodiment provides a method for preparing a beta-silanized amide compound by catalyzing a chitosan Schiff base copper functional material Schiff-CS@Cu, which comprises the following specific steps:
1) Alpha-acrylamide compound I, pinacol ester of (dimethylbilyl) boric acid and Schiff-CS@Cu (prepared in example 2) are added into a mixed solvent (2 ml) with a volume ratio of methanol to water of 4:1, wherein the alpha-acrylamide compound I is 0.20mmol, the pinacol ester of (dimethylbilyl) boric acid is 0.40mmol, the copper content in Schiff-CS@Cu is 0.002mmol, the reaction is carried out under illumination and stirring at room temperature for 12h, and the alpha-acrylamide compound I in this example is 2-phenyl-N- (4-methoxyphenyl) acrylamide (R is methoxy) and has the following reaction formula;
2) After the reaction is finished, filtering, washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper functional material Schiff-CS@Cu, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was purified by column chromatography using ethyl acetate/petroleum ether mixed solvent=1:35 to give β -silylated amide compound II. The yield of the product was 80% (62).3mg)。
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H NMR(400MHz，Chloroform-d)；δ＝7.38-7.35(m,2H),7.27-7.14(m,10H),6.79(s,1H),6.70-6.68(q,2H),3.66(s,3H),3.40-3.36(q,1H),1.78-1.72(q,1H),1.36-1.29(q,1H),0.07(s,3H),0.01(s,3H).
13 CNMR(100MHz，Chloroform-d)；δ＝172.3,156.4,141.4,138.6,133.8,131.1,129.1,128.1,128.0,127.9,127.6,121.6,114.1,55.6,50.0,20.4,-2.4,-2.7.
example 5 shows that under the catalytic condition of the Schiff-CS@Cu material provided by the example of the invention, the conversion rate of the 2-phenyl-N- (4-methoxyphenyl) acrylamide is also very high, and the yield of the silicon addition product reaches 80%.
Example 6
The embodiment provides a method for preparing a beta-silanized amide compound by catalyzing a chitosan Schiff base copper functional material Schiff-CS@Cu, which comprises the following specific steps:
1) Alpha-acrylamide compound I, pinacol ester of (dimethylbilyl) boric acid and Schiff-CS@Cu (prepared in example 2) are added into a mixed solvent (2 ml) with a volume ratio of methanol to water of 4:1, wherein the alpha-acrylamide compound I is 0.20mmol, the pinacol ester of (dimethylbilyl) boric acid is 0.40mmol, the copper content in Schiff-CS@Cu is 0.002mmol, the reaction is carried out under illumination and stirring at room temperature for 12h, and the alpha-acrylamide compound I in this example is 2-phenyl-N- (p-fluorophenyl) acrylamide (R is fluoro group) and has the following reaction formula;
2) After the reaction is finished, filtering, washing and drying a precipitate by using water and ethanol, recycling a chitosan Schiff base copper functional material Schiff-CS@Cu, extracting filtrate by using ethyl acetate (3X 10 mL) to obtain an organic phase containing a product, and performing anhydrous Na treatment 2 SO 4 Drying, filtering and rotary steaming to remove redundant organic solvent. The remaining organic phase obtained was mixed with ethyl acetate/petroleum ether solvent=1Purifying by 35 column chromatography to obtain the beta-silanized amide compound II. The product yield was 87% (65.7 mg).
The nuclear magnetic hydrogen spectrum and the carbon spectrum of the target product are shown as follows:
1 H NMR(400MHz，Chloroform-d)；δ＝7.46-7.43(m,2H),7.36-7.24(m,10H),6.96-6.91(q,2H),6.86(s,1H),3.48-3.44(q,1H),1.86-1.80(q,1H),1.44-1.38(q,1H),0.16(s,3H),0.10(s,3H).
13 CNMR(100MHz，Chloroform-d)；δ＝172.6,160.6,158.1,141.2,138.4,133.9,129.2,129.1,128.0,121.7,121.6,115.7,115.4,50.1,20.4,-2.4,-2.8.
example 6 shows that under the catalytic condition of the Schiff-CS@Cu material provided by the example of the invention, the conversion rate of the 2-phenyl-N- (p-fluorophenyl) acrylamide is also very high, and the yield of the silicon addition product reaches 87%.

Claims (10)

1. A method for preparing a novel fluorescent dialdehyde compound, comprising the steps of:
a. adding indole-6-formaldehyde into N, N-dimethylformamide DMF, stirring and dissolving in an ice-water bath, then adding sodium hydride in batches, continuing stirring in an ice-water bath for 30-60 min, adding 2-chloropyrimidine, reacting at 120-140 ℃ for 20-30 h, finally adding water for quenching, and performing post-treatment to obtain an intermediate A, wherein the reaction formula is shown in the formula i);
b. adding silver hexafluoroantimonate into dichloroethane DCE for dissolution, then sequentially adding an intermediate A, p-ethynyl benzaldehyde, pentamethyl cyclopentadienyl carbonyl diiodocobaltous and trimethyl acetic acid, heating and refluxing at 70-90 ℃ for 5-20 min, filtering after the reaction is finished, separating and purifying filtrate to obtain a fluorescent dialdehyde compound B, wherein the reaction formula is shown in the following formula ii),
2. the method of preparing a novel fluorescent dialdehyde as set forth in claim 1, wherein in step a, indole-6-carbaldehyde: 2-chloropyrimidine: molar ratio of sodium hydride=1 (1-1.5): 1-1.5.
3. The method for preparing a novel fluorescent dialdehyde compound as set forth in claim 1, wherein in step b, the molar ratio of intermediate a, p-ethynylbenzaldehyde, pentamethyl cyclopentadienyl cobalt carbonyl diiodoxide, silver hexafluoroantimonate, and trimethylacetic acid=1, (0.5-1.5): (0.01-0.10): (0.08-0.15): (0.08-0.15).
4. The method for preparing a novel fluorescent dialdehyde compound as set forth in claim 1, wherein in step a, the post-treatment comprises: extraction with ethyl acetate, filtration and column chromatography gave intermediate a.
5. A novel fluorescent dialdehyde compound prepared by the process for preparing a novel fluorescent dialdehyde compound as claimed in any one of claims 1 to 4.
6. The preparation method of the chitosan Schiff base copper functional material is characterized by comprising the following steps of:
1) Dissolving chitosan in 1-2 wt% acetic acid aqueous solution to obtain chitosan acetic acid solution, dissolving the fluorescent dialdehyde compound B in THF, slowly dripping the THF solution of the fluorescent dialdehyde compound B into the chitosan acetic acid solution, heating and stirring at 60-70 ℃ for 20-40 min to form hydrogel;
2) After the reaction is finished, taking out the hydrogel, standing at room temperature to volatilize the solvent, and soaking and washing the hydrogel by THF until the washing liquid is colorless and has no fluorescence;
3) Putting the hydrogel into water, adding a saturated copper sulfate solution, soaking the hydrogel for loading metal copper ions for 20-30 h, taking out and drying to obtain Schiff-CS@Cu.
7. The copper-based functional material according to claim 6, wherein in step 1), aldehyde group-CHO contained in the fluorescent dialdehyde compound B and amino-NH contained in the chitosan 2 The molar ratio is 3-4:1.
8. The chitosan schiff base copper functional material according to claim 6, wherein in the step 3), the usage ratio of hydrogel to water and saturated copper sulfate solution is 60 mg:120-150 mL:1.8-2.0 mL.
9. The chitosan Schiff base copper functional material is characterized by being prepared by a preparation method of the chitosan Schiff base copper functional material according to any one of claims 6-8.
10. The application of the chitosan Schiff base copper functional material in the preparation of the beta-silanized amide compound is characterized by comprising the following steps:
adding an alpha-acrylamide compound I, (dimethylbilyl) boric acid pinacol ester and the chitosan Schiff base copper functional material Schiff-CS@Cu described in claim 9 into a mixed solvent of methanol and water, stirring at room temperature under the illumination condition for reacting for 8-16 h, wherein the molar ratio of copper contained in the alpha-acrylamide compound, (dimethylbilyl) boric acid pinacol ester and Schiff-CS@Cu is 1:2:0.01-0.05, the reaction formula is shown in the following formula iii),
wherein R is hydrogen, methyl, methoxy or fluoro;
after the reaction is finished, filtering, and treating the precipitate to obtain a recovered chitosan Schiff base copper functional material Schiff-CS@Cu for recycling, and separating and purifying the filtrate to obtain the beta-silanized amide compound II.
CN202311416877.4A 2023-10-30 2023-10-30 Novel fluorescent dialdehyde compound, preparation method, chitosan Schiff base copper functional material and application thereof Pending CN117567436A (en)

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