CN110343083B - Method for preparing coumarin fluorescent agent by copper acetate catalysis - Google Patents
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Abstract
The invention discloses a method for preparing coumarin fluorescent agent by copper acetate catalysis, wherein a substrate 3,4, 5-thirty-hexaalkoxyl toluene shown in a formula (I) and a coumarin compound shown in a formula (II) react in a reaction medium with 1, 4-dioxane as a solvent, copper acetate is used as a catalyst, and 1, 8-diazabicyclo undec-7-ene (DBU) is used for preparing a target product, and the target product is subjected to post-treatment to prepare the coumarin fluorescent agent;
x in the formula (II) and the formula (III) is selected from one of the following: oxygen, nitrogen and hydrogen. The invention has the advantages of simple and easy acquisition of raw materials and mild synthesis conditions; the chemical selectivity is high and controllable; the reaction is carried out at normal pressure and a milder temperature; the catalyst is copper acetate, is cheap and low in toxicity, saves cost and has lower requirements on equipment; the solvent 1, 4-dioxane and water are mutually soluble, and the post-treatment is convenient; the catalyst system has wide adaptability, and the obtained product has wide application in the field of fluorescent agent preparation.
Description
Technical Field
The invention belongs to the technical field of fluorescent material preparation, and particularly relates to a method for preparing coumarin fluorescent agent by copper acetate catalysis.
Background
Coumarin derivatives are compounds and important dyes with many biological activities such as antiviral and the like. In recent years, coumarin compounds have been paid attention to their use in photoelectricity. Typical fluorescent agents are generally formed by connecting a fluorophore with a receptor through a connecting group, and the fluorophores reported in the literature relate to compounds such as luciferin, rhodamine, cyanine dye, naphthalimide and coumarin, wherein the fluorescent agents based on coumarin are gradually becoming an emerging research hotspot. The coumarin fluorescent agent has a benzopyrone structure, has the advantages of high fluorescence quantum yield, large Stocks displacement, adjustable photophysical and photochemical properties, good photostability and the like, and is an excellent candidate fluorophore in fluorescent probe molecular design. The known method for preparing coumarin fluorescent agent compounds is mainly obtained through multi-step coupling and series connection by transition metal catalysis, and has the defects of multiple reaction steps, low reaction efficiency, low application range of the method and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing coumarin fluorescent agent by copper acetate catalysis, which realizes the efficient preparation of coumarin fluorescent agent by adopting copper acetate with low price and low toxicity as a catalyst, has wide application range, excellent yield and low cost, and has important application prospect in the related fluorescent material preparation industrial field.
The invention is realized by the following technical scheme:
the method for preparing the coumarin fluorescent agent shown in the formula (III) by copper acetate catalysis is characterized by comprising the following steps of: a substrate 3,4, 5-thirty-hexaalkoxyl toluene shown in a formula (I) and a coumarin compound shown in a formula (II) react in a reaction medium with 1, 4-dioxane as a solvent under the action of a copper acetate serving as a catalyst and 1, 8-diazabicyclo undec-7-ene (DBU) to prepare a target product, and the target product is subjected to post-treatment to prepare the coumarin fluorescent agent; the catalyst is 0.1 molar equivalent of copper acetate, the DBU is 2 molar equivalents, and the reaction conditions are that the reaction is carried out under air;
x in the formula (II) and the formula (III) is selected from one of the following: oxygen, nitrogen and hydrogen.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized in that the ratio of 3,4, 5-thirty-hexaalkoxyl toluene to 1, 4-dioxane solvent is 3mmol/10mL.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized in that the ratio of 3,4, 5-thirty-hexaalkoxyl toluene to DBU is 3mmol/6mmol.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized in that the ratio of 3,4, 5-thirty-hexaalkoxyl toluene to copper acetate is 3mmol/0.3mmol.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized in that the equivalent ratio of the 3,4, 5-thirty-hexaalkoxyl toluene to the coumarin compound is 1:1-1.5.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized in that the reaction temperature is 100 ℃ and the reaction time is 20 hours.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized by comprising the following steps of:
1) Extraction: after the reactant is cooled to room temperature, 10mL of saturated sodium chloride aqueous solution is added into the reactant, then ethyl acetate is used for extraction for 3 times, 10mL of each time is used for extraction, and the extracts are combined;
2) Concentrating: drying the extract with anhydrous sodium sulfate, and spin-drying with a rotary evaporator to obtain concentrate;
3) Adsorbing the concentrate with column chromatography silica gel, adding into 200-300 mesh chromatography silica gel column, and adding n-hexane: and (3) carrying out quick column chromatography on ethyl acetate according to a certain proportion, merging eluents, spin-drying by a rotary evaporator, and pumping by an oil pump to obtain the coumarin fluorescent agent compound.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized in that the drying time in the step 2) is 1 hour.
The method for preparing the coumarin fluorescent agent by copper acetate catalysis is characterized in that the ratio of n-hexane to ethyl acetate in the step 3) is 3:1-5:1.
The invention has the advantages of simple and easy acquisition of raw materials and mild synthesis conditions; the chemical selectivity is high and controllable; the reaction is carried out at normal pressure and a milder temperature; the catalyst is copper acetate, is cheap and low in toxicity, saves cost and has lower requirements on equipment; the solvent 1, 4-dioxane and water are mutually soluble, and the post-treatment is convenient; the catalyst system has wide adaptability, and the obtained product has wide application in the field of fluorescent agent preparation, and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows the product 3a of the present invention 1 H NMR spectroscopy;
FIG. 2 shows the product 3a of the present invention 13 C NMR spectrum;
FIG. 3 is a FTIR spectrum of product 3a of the present invention;
FIG. 4 shows the product 3b of the present invention 1 H NMR spectroscopy;
FIG. 5 shows the product 3b of the present invention 13 C NMR spectrum;
FIG. 6 is a FTIR spectrum of product 3b of the present invention;
FIG. 7 shows product 3c of the present invention 1 H NMR spectroscopy;
FIG. 8 shows product 3c of the present invention 13 C NMR spectrum;
FIG. 9 is a FTIR spectrum of product 3c in the present invention;
FIG. 10 shows the product 3d of the present invention 1 H NMR spectroscopy;
FIG. 11 shows the product 3d of the present invention 13 C NMR spectrum;
FIG. 12 is a FTIR spectrum of product 3d of the present invention;
FIG. 13 shows product 3e of the present invention 1 H NMR spectroscopy;
FIG. 14 shows product 3e of the present invention 13 C NMR spectrum;
FIG. 15 is a FTIR spectrum of product 3e in the present invention;
FIG. 16 shows product 3f of the present invention 1 H NMR spectroscopy;
FIG. 17 shows the product 3f of the present invention 13 C NMR spectrum;
FIG. 18 is a FTIR spectrum of product 3f in the present invention.
Detailed Description
The invention is described in further detail below with reference to the drawings in the specification and the detailed description is given.
The synthesis step of the invention is that 3mmol of 3,4, 5-thirty-hexaalkoxyl toluene and 3.6mmol of coumarin compound are respectively added into a 25mL round bottom flask, then 10mL of 1, 4-dioxane, 0.3mmol of copper acetate and 6mmol of DBU are sequentially added, and the reaction is carried out at 100 o Stirring at C for 20 hours. After cooling, 10mL of saturated aqueous NaCl solution was added to the system, the mixture was extracted 3 times with ethyl acetate, 10mL each, and the organic phases were combined and dried over anhydrous Na 2 SO 4 After drying, evaporating the solvent, and performing 200-300 mesh silica gel column chromatography to obtain a pure product, wherein the yield is 90-95%, the reaction formula and the data are as follows, and all product structures are determined through nuclear magnetic resonance and mass spectrum result comparison.
Example 1: preparation of the 3a product
2440mg (3 mmol) of 3,4, 5-thirty-hexalkoxytoluene and 583mg (3.6 mmol) of coumarin compound 2a,54mg (0.1 equiv) of copper acetate, 912mg (2 equiv) of DBU in 10mL of 1, 4-dioxane are added to a 25mL round bottom flask at room temperature o C for 20 hours, adding 10mL saturated NaCl aqueous solution into the system after the reaction is cooled, extracting 3 times with ethyl acetate, 10mL each time, combining organic phases, and using anhydrous Na 2 SO 4 After drying, the solvent was distilled off, and 200-300 mesh silica gel column chromatography was performed to obtain 2720 mg of the compound 3a, with a yield of 93%. The nuclear magnetic resonance hydrogen spectrum of the compound 3a is shown in figure 1, the nuclear magnetic resonance carbon spectrum of the compound 3a is shown in figure 2, and the FTIR spectrum of the compound 3a is shown in figure 3.
Yellow powdery solid; mp 69 ℃.
1 H NMR (500 MHz, CDCl 3 )：δ 7.63 (d, J = 9.5 Hz, 1 H, a), 7.37 (d, J = 8.6 Hz, 1 H, b), 6.91 (d, J = 8.6 Hz, 1 H, c), 6.89 (s, 1 H, d), 6.61 (s, 2 H, e), 6.24 (d, J = 9.9 Hz, 1 H, f), 5.00 (s, 2 H, g), 4.03-3.89 (m, 6 H, -OCH 2 -), 1.83-1.72(m, 6 H, -OCH 2 CH 2 -), 1.46 (m, 6 H, -CH 2 CH 3 ), 1.26 (s, 72 H), 0.88 (t, J = 6.6 Hz, 11 H, -CH 2 CH 3 )。
13 C NMR(126 MHz, CDCl 3 )：δ 161.92 (s), 161.11 (s), 155.84 (s), 153.45 (s), 143.34 (s), 138.26 (s), 130.63 (s), 128.76 (s), 113.23 (s), 112.72 (s), 106.11 (s), 101.87 (s), 73.45 (s), 70.92 (s), 69.17 (s), 31.96 (s), 30.38 (s), 29.88-29.60 (m), 29.46 (s), 29.43 (s), 29.40 (s), 26.16 (s), 26.13 (s), 22.71 (s), 14.13 (s)。
FTIR (KBr) ν (cm -1 )：2918, 2850 (ν CH, alkyl), 1721 (ν C=O, ester), 1616, 1507 (ν C=C , benzene), 1467, 1438, 1383 (δ CH, alkyl), 1353，1339, 1283，1229，1201 (ν C-O-C , ehter), 1125, 995, 837 (δ CH , benzene or long chain alkyl)，721(ν CH ，methylene)。
Example 2: preparation of the 3b product
2440mg (3 mmol) of 3,4, 5-thirty-hexalkoxytoluene and 583mg (3.6 mmol) of coumarin compound 2b,54mg (0.1 equiv) of copper acetate, 912mg (2 equiv) of DBU in 10mL of 1, 4-dioxane are added to a 25mL round bottom flask at room temperature o C for 20 hours, adding 10mL saturated NaCl aqueous solution into the system after the reaction is cooled, extracting 3 times with ethyl acetate, 10mL each time, combining organic phases, and using anhydrous Na 2 SO 4 After drying, the solvent was distilled off, and 200-300 mesh silica gel column chromatography was performed to obtain 2603mg of the compound 3b, with a yield of 89%. The nuclear magnetic resonance hydrogen spectrum of the compound 3b is shown in fig. 4, the nuclear magnetic resonance carbon spectrum of the compound 3b is shown in fig. 5, and the FTIR spectrum of the compound 3b is shown in fig. 6.4- (3, 4, 5-Tris-hexadecycloxy-benzoyloxy) -chromen-2-one (3 b) as a yellow powdery solid; mp 77 ℃.
1 H NMR (500 MHz, CDCl 3 )：δ 7.74 (d, J = 7.6 Hz, 1 H, a), 7.44 (t, J = 7.4 Hz, 1 H, b), 7.22 (d, J = 8.4 Hz, 1 H, c), 7.16 (t, J = 8.2 Hz, 1 H,d), 6.50 (s, 2 H,e), 5.66 (s, 1 H, f), 4.96 (s, 2 H, g), 3.87 (t, J = 5.4 Hz, 6 H, -OCH 2 -), 1.73-1.60 (m, 6 H, -OCH 2 CH 2 -), 1.35 (m, 6 H, -CH 2 CH 3 ), 1.14 (s, 72 H, -CH 2 -), 0.76 (t, J = 6.8 Hz, 9 H, -CH 2 CH 3 )。
13 C NMR (126 MHz, CDCl 3 )：δ 165.40 (s), 162.85 (s), 153.50 (s), 138.69 (s), 132.43 (s), 129.20 (s), 123.90 (s), 123.18 (s), 116.80 (s), 115.76 (s), 106.56 (s), 105.30 (s), 91.15 (s), 73.51 (s), 71.65 (s), 69.27 (s), 31.96 (s), 30.37 (s), 29.72 (m), 29.46 (s), 29.40 (s), 26.16 (s), 26.13 (s), 22.72 (s), 14.14 (s)。
FTIR (KBr) ν (cm -1 ): 2918，2850 (ν CH, alkyl), 1718 (ν C=O, ester), 1623, 1506 (ν C=C , benzene), 1466, 1440, 1373 (δ CH, alkyl), 1340, 1272, 1249, 1190 (ν C-O-C , ehter), 1116, 993, 926, 886, 847 (δ CH , benzene or long chain alkyl)，767, 751, 721 (ν CH, methylene)。
Example 3: preparation of the 3c product
2440mg (3 mmol) of 3,4, 5-thirty-hexalkoxytoluene and 634mg (3.6 mmol) of coumarin compound 2c,54mg (0.1 equiv) of copper acetate, 912mg (2 equiv) of DBU in 10mL of 1, 4-dioxane are added to a 25mL round bottom flask at room temperature o C for 20 hours, adding 10mL saturated NaCl aqueous solution into the system after the reaction is cooled, extracting 3 times with ethyl acetate, 10mL each time, combining organic phases, and using anhydrous Na 2 SO 4 After drying, the solvent was distilled off, and 200-300 mesh silica gel column chromatography was performed to obtain 2668mg of the compound 3c, with a yield of 90%. Nuclear magnetism Co-production of Compound 3cThe hydrogen vibration spectrum is shown in FIG. 7, the nuclear magnetic resonance carbon spectrum of the compound 3c is shown in FIG. 8, and the FTIR spectrum of the compound 3c is shown in FIG. 9.4-Methyl-7- (3, 4, 5-tris-hexadecycloxy-benzoyloxy) -chromen-2-one (3 c) as a yellow powdery solid; mp 84 ℃.
1 H NMR (500 MHz, CDCl 3 )：δ 8.34 (s, 1 H, a), 7.72 (s, 1 H, b), 7.64-7.56 (m, 2 H, c), 7.19 (s, 1 H, d), 6.23 (s, 1 H, e), 4.03 (m, 6 H, -OCH 2 -), 2.44 (d, J = 1.1 Hz, 3 H,f), 1.88-1.70 (m, 6 H, -OCH 2 CH 2 -), 1.47 (m, 6 H, -CH 2 CH 3 ), 1.42-1.18 (m, 72 H, -CH 2 -), 0.91-0.84 (m, 9 H, -CH 2 CH 3 )。
13 C NMR (126 MHz, CDCl 3 )：δ 164.40 (s), 160.95 (s), 154.32 (s), 152.36 (s), 152.09 (s), 149.85 (s), 145.47 (s), 140.99 (s), 128.98 (s), 125.32 (s), 117.25 (s), 116.53 (s), 115.85 (s), 113.68 (s), 109.81 (s), 107.54 (s), 74.38 (s), 74.08 (s), 69.14 (s), 31.94 (s), 30.29 (s), 30.21 (s), 29.85-29.57 (m), 29.53 (s), 29.48 (s), 29.38 (s), 29.19 (s), 26.07 (s), 26.05 (s), 26.01 (s), 22.70 (s), 18.60 (s), 14.12 (s)。
FTIR (KBr) ν (cm -1 )：3440, 3325 (ν O-H ), 2917, 2850 (ν CH, alkyl), 1709 (ν C=O, ester), 1663(ν O-C ), 1622, 1583， 1531 (ν C=C , benzene), 1468, 1418, 1392, 1372, 1342 (δ CH ,alkyl), 1268, 1226, 1198, 1172 (ν C-O-C , ehter), 1115, 1070, 1018, 990, 845 (δ CH , benzene or long chain alkyl), 722(ν CH, methylene)。
Example 4: preparation of 3d product
2440mg (3 mmol) of 3,4, 5-thirty-hexalkoxytoluene and 580mg (3.6 mmol) of coumarin compound 2d,54mg (0.1 equiv) of copper acetate, 912mg (2 equiv) of DBU in 10mL of 1, 4-dioxane are added to a 25mL round bottom flask at room temperature o C, reacting for 20 hours, cooling the reaction, adding 10mL saturated NaCl aqueous solution into the system, using ethylEthyl acetate extraction 3 times with 10mL each, combining the organic phases with anhydrous Na 2 SO 4 After drying, the solvent was distilled off, and 200-300 mesh silica gel column chromatography was performed to obtain 3d 2508mg of the compound, with a yield of 86%. The nuclear magnetic resonance hydrogen spectrum of the compound 3d is shown in fig. 10, the nuclear magnetic resonance carbon spectrum of the compound 3d is shown in fig. 11, and the FTIR spectrum of the compound 3d is shown in fig. 12.7- (3, 4, 5-Tris-hexadecycloxy-benzoylamino) -chromen-2-one (3 d) as a yellow powdery solid; mp 65 ℃.
1 H NMR (500 MHz, CDCl 3 )：δ 7.63 (d, J = 9.5 Hz, 1 H, a), 7.37 (d, J = 8.6 Hz, 1 H, b), 6.91 (d, J = 8.6 Hz, 1 H, c), 6.89 (s, 1 H, d), 6.61 (s, 2 H, e), 6.24 (d, J = 9.9 Hz, 2 H, f), 5.00 (s, 2 H, g), 4.03-3.89 (m, 6 H, -OCH 2 -), 1.83-1.72(m, 6 H, -OCH 2 CH 2 -), 1.46 (m, 6 H, -CH 2 CH 3 ), 1.26 (s, 72 H), 0.88 (t, J = 6.6 Hz, 11 H, -CH 2 CH 3 )。
13 C NMR(126 MHz, CDCl 3 )：δ 161.92 (s), 161.11 (s), 155.84 (s), 153.45 (s), 143.34 (s), 138.26 (s), 130.63 (s), 128.76 (s), 113.23 (s), 112.72 (s), 106.11 (s), 101.87 (s), 73.45 (s), 70.92 (s), 69.17 (s), 31.96 (s), 30.38 (s), 29.88-29.60 (m), 29.46 (s), 29.43 (s), 29.40 (s), 26.16 (s), 26.13 (s), 22.71 (s), 14.13 (s)。
FTIR (KBr) ν (cm -1 )：2918, 2850 (ν NH , amino), 1721 (ν C=O ), 1616, 1507 (ν C=C , benzene), 1467, 1438, 1383 (δ CH, alkyl), 1353，1339, 1283，1229，1201 (ν C-N-C ), 1125, 995, 837，721(ν CH ，methylene)。
Example 5: preparation of the 3e product
2440mg (3 mmol) of 3,4, 5-thirty-hexalkoxytoluene and 580mg (3.6 mmol) of coumarin compound 2e,54mg (0.1 equiv) of copper acetate, 912mg (2 equiv) of DBU in 10mL of 1, 4-dioxane are added to a 25mL round bottom flask at room temperature o Reacting for 20 hours under the condition C, and cooling the reaction to a system after the reaction is completedAdding 10mL saturated NaCl aqueous solution, extracting with ethyl acetate 3 times, 10mL each time, mixing organic phases, and using anhydrous Na 2 SO 4 After drying, the solvent was distilled off, and 200-300 mesh silica gel column chromatography was performed to obtain 3e 2479mg of the compound in 85% yield. The nuclear magnetic resonance hydrogen spectrum of the compound 3e is shown in fig. 13, the nuclear magnetic resonance carbon spectrum of the compound 3e is shown in fig. 14, and the FTIR spectrum of the compound 3e is shown in fig. 15.4- (3, 4, 5-Tris-hexadecycloxy-benzoylamino) -chromen-2-one (3 e) as a yellow powdered solid; mp:78 ℃.
1 H NMR (500 MHz, CDCl 3 )：δ 7.74 (d, J = 7.6 Hz, 1 H, a), 7.44 (t, J = 7.4 Hz, 1 H, b), 7.22 (d, J = 8.4 Hz, 1 H, c), 7.16 (t, J = 8.2 Hz, 1 H,d), 6.50 (s, 2 H,e), 5.66 (s, 2 H, f), 4.96 (s, 2 H, g), 3.87 (t, J = 5.4 Hz, 6 H, -OCH 2 -), 1.73-1.60 (m, 6 H, -OCH 2 CH 2 -), 1.35 (m, 6 H, -CH 2 CH 3 ), 1.14 (s, 72 H, -CH 2 -), 0.76 (t, J = 6.8 Hz, 9 H, -CH 2 CH 3 )。
13 C NMR (126 MHz, CDCl 3 )：δ 165.40 (s), 162.85 (s), 153.50 (s), 138.69 (s), 132.43 (s), 129.20 (s), 123.90 (s), 123.18 (s), 116.80 (s), 115.76 (s), 106.56 (s), 105.30 (s), 91.15 (s), 73.51 (s), 71.65 (s), 69.27 (s), 31.96 (s), 30.37 (s), 29.72 (m), 29.46 (s), 29.40 (s), 26.16 (s), 26.13 (s), 22.72 (s), 14.14 (s)。
FTIR (KBr) ν (cm -1 ): 2918，2850 (ν CH, amino), 1718 (ν C=O ), 1623, 1506 (ν C=C , benzene), 1466, 1440, 1373 (δ NH ), 1340, 1272, 1249, 1190 (ν C-N-C ), 1116, 993, 926, 886, 847 (δ CH )，767, 751, 721 (ν CH, methylene)。
Example 6: preparation of the 3f product
2440mg (3 mmol) of 3,4, 5-thirty-hexalkoxytoluene and 630mg (3.6 mmol) of coumarin compound 2f,54mg (0.1 equiv) of copper acetate, 912mg (2 equiv) of DBU, at 1,100 in 10mL of 4-dioxane o C for 20 hours, adding 10mL saturated NaCl aqueous solution into the system after the reaction is cooled, extracting 3 times with ethyl acetate, 10mL each time, combining organic phases, and using anhydrous Na 2 SO 4 After drying, the solvent was distilled off, and 200-300 mesh silica gel column chromatography was performed to obtain the compound 3f 2695mg, with a yield of 91%. The nuclear magnetic resonance hydrogen spectrum of the compound 3f is shown in fig. 16, the nuclear magnetic resonance carbon spectrum of the compound 3f is shown in fig. 17, and the FTIR spectrum of the compound 3f is shown in fig. 18.4-Methyl-7- (3, 4, 5-tris-hexadecycloxy-benzoylamino) -chromen-2-one (3 f) as a yellow powdered solid; m14 ℃.
1 H NMR (500 MHz, CDCl 3 )：δ 8.34 (s, 1 H,a), 7.72 (s, 1 H,b), 7.64-7.56 (m, 2 H,c), 7.19 (s, 1 H,d), 6.23 (s, 2 H,e), 4.03 (m, 6 H, -OCH 2 -), 2.44 (d, J = 1.1 Hz, 3 H,f), 1.88-1.70 (m, 6 H, -OCH 2 CH 2 -), 1.47 (m, 6 H, -CH 2 CH 3 ), 1.42-1.18 (m, 72 H, -CH 2 -), 0.91-0.84 (m, 9 H, -CH 2 CH 3 )。
13 C NMR (126 MHz, CDCl 3 )：δ 164.40 (s), 160.95 (s), 154.32 (s), 152.36 (s), 152.09 (s), 149.85 (s), 145.47 (s), 140.99 (s), 128.98 (s), 125.32 (s), 117.25 (s), 116.53 (s), 115.85 (s), 113.68 (s), 109.81 (s), 107.54 (s), 74.38 (s), 74.08 (s), 69.14 (s), 31.94 (s), 30.29 (s), 30.21 (s), 29.85-29.57 (m), 29.53 (s), 29.48 (s), 29.38 (s), 29.19 (s), 26.07 (s), 26.05 (s), 26.01 (s), 22.70 (s), 18.60 (s), 14.12 (s)。
FTIR (KBr) ν (cm -1 )：3440, 3325 (ν N-H , amino), 2917, 2850 (ν CH, alkyl), 1709 (ν C=O, ester), 1663 （ν O-C ， amide）1622, 1583， 1531 (ν C=C , benzene), 1468, 1418, 1392, 1372, 1342 (δ CH ,alkyl), 1268, 1226, 1198, 1172 (ν C-O-C , ehter), 1115, 1070, 1018, 990, 845 (δ CH ), 722(ν CH, methylene)。
Claims (5)
1. A method for preparing coumarin fluorescent agent shown in formula (III) by copper acetate catalysis is characterized in that the preparation method comprises the following steps: a substrate 3,4, 5-thirty-hexaalkoxyl toluene shown in a formula (I) and a coumarin compound shown in a formula (II) react in a reaction medium with 1, 4-dioxane as a solvent under the action of a copper acetate serving as a catalyst and 1, 8-diazabicyclo undec-7-ene (DBU) to prepare a target product, and the target product is subjected to post-treatment to prepare the coumarin fluorescent agent; the catalyst is 0.1 molar equivalent of copper acetate, the DBU is 2 molar equivalents, and the reaction conditions are that the reaction is carried out under air;
x in the formula (II) and the formula (III) is selected from one of the following: oxygen, nitrogen and hydrogen;
the ratio of the 3,4, 5-thirty-hexalkoxytoluene to the 1, 4-dioxane solvent is 3mmol/10mL;3,4, 5-thirty-hexalkoxytoluene to DBU ratio of 3mmol/6mmol;3,4, 5-thirty-hexaalkoxytoluene to copper acetate at a ratio of 3mmol/0.3mmol; the equivalent ratio of the 3,4, 5-thirty-hexaalkoxyl toluene to the coumarin compound is 1:1-1.5.
2. The method for preparing coumarin fluorescent agent by copper acetate catalysis according to claim 1, wherein the reaction temperature is 100 ℃ and the reaction time is 20 hours.
3. The method for preparing coumarin fluorescent agent by copper acetate catalysis as claimed in claim 1, wherein the specific method for post-treatment comprises the following steps:
1) Extraction: after the reactant is cooled to room temperature, 10mL of saturated sodium chloride aqueous solution is added into the reactant, then ethyl acetate is used for extraction for 3 times, 10mL of each time is used for extraction, and the extracts are combined;
2) Concentrating: drying the extract with anhydrous sodium sulfate, and spin-drying with a rotary evaporator to obtain concentrate;
3) Adsorbing the concentrate with column chromatography silica gel, adding into 200-300 mesh chromatography silica gel column, and adding n-hexane: and (3) carrying out quick column chromatography on ethyl acetate according to a certain proportion, merging eluents, spin-drying by a rotary evaporator, and pumping by an oil pump to obtain the coumarin fluorescent agent compound.
4. A method for preparing coumarin fluorescent agents under catalysis of copper acetate according to claim 3, wherein the drying time in step 2) is 1 hour.
5. The method for preparing the coumarin fluorescent agent by copper acetate catalysis according to claim 3, wherein the ratio of n-hexane to ethyl acetate in the step 3) is 3:1-5:1.
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| "Copper(II)-Catalyzed Oxidative Esterification of Substituted p-Cresols under Ligand- and Additive-Free Conditions";Zhong-Nan Zhang et al.;《Syn lett》;20151231;第26卷;第2145-2150页 * |
| "Pd/Pivalic Acid Mediated Direct Arylation of 2-Pyrones and Related Heterocycles";Leticia M. Pardo et al.;《Eur. J. Org. Chem.》;20151231(第16期);第3540-3550页 * |
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