CN117126131A - Efficient synthesis method of gamma-thiopyranone derivative - Google Patents

Efficient synthesis method of gamma-thiopyranone derivative Download PDF

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CN117126131A
CN117126131A CN202310940053.0A CN202310940053A CN117126131A CN 117126131 A CN117126131 A CN 117126131A CN 202310940053 A CN202310940053 A CN 202310940053A CN 117126131 A CN117126131 A CN 117126131A
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thiopyranone
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黄良斌
黄斌
冯梦霞
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of organic light emission, and discloses a high-efficiency synthesis method of a gamma-thiopyranone derivative. The method comprises the following steps: the preparation method comprises the steps of taking a polar organic solvent as a reaction medium, and reacting a thiadiazole compound with a 4-hydroxy pyrone compound under the action of an alkaline compound to obtain the gamma-thiopyranone derivative. The structure of the gamma-thiopyranone derivative is shown as a formula III. The method has mild reaction conditions, does not need a transition metal catalyst, has low energy consumption, is favorable for environmental protection and is favorable for industrialized mass production; the method has high chemical selectivity, high product yield, wide range of reaction substrates and strong functional group compatibility. The fluorescent organic compound prepared from the gamma-thiopyranone derivative has the characteristics of wide absorption range, large Stokes shift, longer emission wavelength and the like as a fluorescent probe.

Description

Efficient synthesis method of gamma-thiopyranone derivative
Technical Field
The invention belongs to the technical field of organic light emission, and particularly relates to a high-efficiency synthesis method of a gamma-thiopyranone derivative.
Background
The derivatives using gamma-pyrone or gamma-thiopyranone as core skeleton have wide application in fluorescent probe field, such as protein detection (Design and Synthesis of Intramolecular Charge Transfer-Based Fluorescent Reagents for the Highly-Sensitive Detection of protein. J.am. Chem. Soc.2005,127, 17799-17802), amino acid detection (A red-emitting fluorescent probe with large Stokes shift for real-time tracking of cysteine over glutathione and homocysteine in living cells. Spectrochimica Acta Part A: molecular and Biomolecular spectroscope. 2019,214, 469-475), mercapto detection (Photophysical Properties and Ultrafast Excited-State Dynamics of a New Two-Photon Absorbing Thiopyranyl probe. J.Phys.chem.C 2013,117,11941-11952), etc. Of course, such compounds also have an Aggregation-induced emission (AIE) effect (Aggregation-Induced Emission of 4-dicyanometric-2, 6-distyryl-4H-pyran. J. Chin. Chem. Soc.2006,53, 243-246), targeted localized mitochondrial effects (Novel mitochondria-targeted, nitrogen mustard-based DNA alkylation agents with near infrared fluorescence emision. Talanta,2016,161 888-893), second order nonlinear optical properties (Synthesis and second-order optical nonlinearities of chiral nonracemic "Y-shaped" chromates. Synthetic Metals,2004,142,259-262), and other optical properties.
At present, the main synthesis mode of gamma-thiopyranone is that propyne is used as a starting material, and reacts with methyl formate to generate dialkynol under the action of n-butyllithium, and manganese dioxide or barium manganate is oxidized into the dialkynone, and then cyclizes with thiourea to construct a gamma-thiopyranone skeleton. The reaction strategy requires the use of more severe conditions such as strong alkali, strong oxidant, nitrogen protection, etc. The synthesis mode is single and complex, the steps are long, the conditions are harsh, and the wide and large-scale synthesis is difficult. The synthesis of the compounds is limited, and the application of the compounds in the fields of biological medicine, photoelectric materials and the like is limited. Thus, exploring synthetic strategies that are inexpensive and readily available in raw materials, mild in reaction conditions, high in selectivity, and environmentally friendly remains an attractive piece of research.
The invention aims to provide a high-efficiency synthesis method of gamma-thiopyranone derivatives, which aims to solve a plurality of defects of the existing thiopyranone synthesis, and provides a method for synthesizing gamma-thiopyranone and various derivatives thereof with low-cost and easily available raw materials and high specificity.
The invention is realized by the following technical scheme:
a method for the efficient synthesis of gamma-thiopyranone derivatives, comprising the steps of: taking a polar organic solvent as a reaction medium, and reacting a thiadiazole compound with a 4-hydroxy pyrone compound under the action of an alkaline compound to obtain a gamma-thiopyranone derivative;
the structural formula of the thiadiazole compound is shown as formula I
R 1 H, COOR ', X, OR', CF3, CN, SR 'R' is alkyl (preferably C 1～5 Alkyl), X is halogen; het is thienyl, furyl, pyridyl, naphthyl, het represents a cyclic group which can be a benzene ring or thienyl, furyl, pyridyl or naphthyl; or in a structureIs->
The structural formula of the 4-hydroxy pyrone compound is formula II
R 2 Is an aromatic ring, a heterocycle, an alkyl group, an alkenyl group, an alkynyl group;
the aryl is phenyl or naphthyl, the alkenyl comprises styryl, and the alkyl is C 1～6 An alkyl group.
The alkaline compound is one or more of cesium carbonate, sodium carbonate, potassium phosphate, potassium carbonate, potassium bicarbonate and sodium bicarbonate; preferably, the catalyst is one or more of sodium carbonate, potassium phosphate and potassium carbonate.
The reaction temperature is 60-100 ℃, and the reaction time is 1-2 days.
The mol ratio of the thiadiazole compound to the 4-hydroxy pyrone compound is 1:1.1-1:1.5.
The polar organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone, preferably one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
The concentration of the thiadiazole compound in the polar organic solvent is 0.5-2 mol/L.
The molar ratio of the weakly basic salt to the thiadiazole compound is 1: (1.8-2.5).
After the reaction, water extraction is carried out, and the crude product is separated by column chromatography.
The structure of the gamma-thiopyranone derivative is shown in a formula III:
R 1 、R 2 het is as defined above.
The gamma-thiopyranone derivatives are useful for the preparation of fluorescent organic compounds.
The fluorescent organic compound has the structure that
R 3 H, OR ', N (R') 2 SR ', R' is alkyl (preferably C 1～4 Alkyl groups such as: methyl, ethyl, isopropyl, butyl), ar (aryl, preferably phenyl, thiophene, furan), OH;
the preparation method of the fluorescent organic compound comprises the following steps:
reacting a gamma-thiopyranone derivative with malononitrile to obtain a thiopyran compound containing a nitrile group; reacting thiopyran compounds containing nitrile groups with benzaldehyde compounds to obtain fluorescent compounds;
the gamma-thiopyranone derivative is as defined above and R is at this point 2 Is methyl.
Structure of thiopyrans containing nitrile groups:
the structure of the benzaldehyde compound is that
R 3 As defined above.
In the reaction of gamma-thiopyranone derivative and malononitrile, acetic anhydride is used as reaction medium;
in the reaction of thiopyran compound containing nitrile group and benzaldehyde compound, ethanol is used as reaction medium and piperidine is used as catalyst.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The reaction condition is mild, a transition metal catalyst is not needed, the reaction is carried out at a lower temperature, the energy consumption is low, and the method is favorable for environmental protection and industrial mass production.
(2) The reaction has high chemoselectivity and high product yield.
(3) The reaction substrate has wide range and strong functional group compatibility.
(4) The fluorescent organic compound prepared from the gamma-thiopyranone derivative has the characteristics of wide absorption range, large Stokes shift, longer emission wavelength and the like as a fluorescent probe.
Drawings
FIG. 1 is a graph of the hydrogen spectrum of Compound 3a (1H NMR:400MHz,CDCl3);
FIG. 2 is a graph of the carbon spectrum of Compound 3a (13C NMR:101MHz,CDCl3);
FIG. 3 is a graph of the hydrogen spectrum of Compound 3b (1H NMR:400MHz,CDCl3);
FIG. 4 is a graph of the carbon spectrum of Compound 3b (13C NMR:101MHz,CDCl3);
FIG. 5 is a graph of the hydrogen spectrum of Compound 3c (1H NMR:400MHz,CDCl3);
FIG. 6 is a graph of the carbon spectrum of Compound 3c (13C NMR:101MHz,CDCl3);
FIG. 7 is a graph of the hydrogen spectrum of Compound 5a (1H NMR:500MHz,CDCl3);
FIG. 8 is a graph of the carbon spectrum of Compound 5a (13C NMR:126MHz,CDCl3);
FIG. 9 is a graph of the hydrogen spectrum of Compound 7a (1H NMR:500MHz,CDCl3);
FIG. 10 is a graph of the carbon spectrum of Compound 7a (13C NMR:126MHz,CDCl3);
FIG. 11 is an absorption and emission spectrum of Compound 7 a;
FIG. 12 is an absorption and emission spectrum of Compound 7 b;
FIG. 13 is a diagram showing the structure of the X-ray crystal of Compound 3b.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to examples, but embodiments of the present invention are not limited thereto.
Example 1
(1) Synthesis of 2-benzyl-6-methyl-4H-thiopyrazin-4-one 3a
4-phenyl-1, 2, 3-thiadiazole 1a (R) 1 =h) (0.01 mol,1.62 g) and 4-hydroxy-6-methyl-2-pyrone 2a (0.015 mol,1.89 g) were used as starting materials, potassium phosphate (0.02 mol,4.25 g) was added, 15ml of n, n-dimethylacetamide was finally added, and the reaction was stirred with heating in an oil bath (80 ℃ for 1 day) until the reaction of compound 1a was completed. The crude product was isolated by extraction with water and column chromatography (petroleum ether: ethyl acetate=5:1-2:1) to give compound 3a. The product prepared in this example was produced in 90% yield with 100% selectivity.
Product 3a has the structural formula:
product 3a nuclear magnetic resonance spectroscopy data: 1 H NMR(400MHz,Chloroform-d)δ7.36-7.27(m,3H),7.21(d,J＝8.0Hz,2H),6.78(s,1H),6.71(s,1H),3.88(s,2H),2.31(s,3H). 13 C NMR(101MHz,Chloroform-d)δ182.3,154.6,151.0,136.3,128.9,128.9,128.1,128.0,127.5,42.6,22.5.HRMS-ESI(m/z):[M+H] + Calcd.for C 13 H 12 OS+H + 217.0681；found:217.0680.
the hydrogen spectrum (1H NMR:400MHz,CDCl3) of compound 3a is shown in FIG. 1, and the carbon spectrum (13 CNMR:101MHz, CDCl 3) is shown in FIG. 2.
Example 2
Synthesis of methyl 4- (6-methyl-4-oxo-4H-thiopyran-2-yl) methyl) benzoate 3b
4- (1, 2, 3-thiadiazol-4-yl) benzoic acid methyl ester 1b (R) 1 ＝CO 2 Me) (0.01 mol,1.62 g) and 4-hydroxy-6-methyl-2-pyrone 2a (0.015 mol,1.89 g) were used as starting materials, potassium phosphate (0.02 mol,4.25 g) was added, 15ml of N, N-dimethylformamide was finally added, and the mixture was heated and stirred in an oil bath (80 ℃ C., 1 day) until the reaction of the compound 1b was completed. The crude product was isolated by extraction with water and column chromatography (petroleum ether: ethyl acetate=5:1-2:1) to give compound 3b. The product prepared in this example was 77% yield and 100% selectivity.
Product 3b Structure
Product 3b nuclear magnetic resonance spectroscopy data: 1 H NMR(400MHz,Chloroform-d)δ8.00(d,J＝8.0Hz,2H),7.30(d,J＝8.0Hz,2H),6.78(s,1H),6.72(s,1H),3.93(s,2H),3.90(s,3H),2.32(s,3H). 13 C NMR(101MHz,Chloroform-d)δ182.0,166.5,153.3,150.8,141.4,130.1,129.4,128.9,128.4,128.2,52.1,42.4,22.5.HRMS-ESI(m/z):[M+H] + Calcd.for C 15 H 14 O 3 S+H + 275.0736；found:275.0733.
the hydrogen spectrum (1H NMR:400MHz,CDCl3) of compound 3b is shown in FIG. 3, and the carbon spectrum (13 CNMR:101MHz, CDCl 3) is shown in FIG. 4.
Example 3
Synthesis of 2-benzyl-6-styryl-4H-thiopyran-4-one 3c
4-phenyl-1, 2, 3-thiadiazole 1a (R) 1 =h) (0.01 mol,1.62 g) and 4-hydroxy-6-styryl-2H-pyran-2-one 2b (0.015 mol,3.21 g) were used as starting materials, potassium phosphate (0.02 mol,4.25 g) was added, 15ml of n, n-dimethylformamide was finally added, and the reaction was heated and stirred in an oil bath (80 ℃ for 1 day) until the reaction of compound 1a was completed. The crude product was isolated by extraction with water and column chromatography (petroleum ether: ethyl acetate=5:1-2:1) to give compound 3c. The product prepared in this example was 40% yield and 100% selectivity.
Product 3c has the structural formula:
product 3c nuclear magnetic resonance spectroscopy data: 1 H NMR(400MHz,Chloroform-d)δ7.48(d,J＝4.0Hz,2H),7.41-7.33(m,5H),7.31(d,J＝8.0Hz,1H),7.27(d,J＝8.0Hz,2H),7.13(d,J＝16.0Hz,1H),6.91(d,J＝16.0Hz,1H),6.87(s,1H),6.81(s,1H),3.95(s,2H). 13 C NMR(101MHz,Chloroform-d)δ182.6,153.5,149.5,136.2,135.1,135.0,129.5,129.0,129.0,128.9,128.5,127.6,127.4,127.3,125.1,43.0.HRMS-ESI(m/z):[M+H] + Calcd.for C 20 H 16 OS+H + 305.0995；found:305.0992.
the hydrogen spectrum (1H NMR:400MHz,CDCl3) of compound 3c is shown in FIG. 5, and the carbon spectrum (13 CNMR:101MHz, CDCl 3) is shown in FIG. 6.
Example 4
Synthesis of 2- (4-methoxybenzyl) -6-methylthiopyrazin-4-one 3d
The procedure used in example 1 was repeated except for replacing 4-phenyl-1, 2, 3-thiadiazole 1a in example 1 with 4- (4-methoxyphenyl) -1,2, 3-thiadiazole 1c to give 3d as a product in 82% yield.
Product 3d nmr spectrum data: 1 H NMR(400MHz,CDCl 3 )δ7.12(d,J＝10.0Hz,2H),6.84(d,J＝10.0Hz,2H),6.75(s,1H),6.69(s,1H),3.82(s,2H),3.77(s,3H),2.30(s,3H). 13 C NMR(101MHz,CDCl 3 )δ182.3,158.9,155.2,150.9,130.0,128.2,128.0,127.7,114.2,55.2,41.8,22.5.HRMS-ESI(m/z):[M+H] + Calcd.for C 14 H 14 O 2 S+H + 247.0787；found:247.0786.
example 5
Synthesis of 2-methyl-6- (4-methylsulfanyl) benzyl-4H-thiopyran-4-one 3e
The procedure used in example 1 was repeated except for replacing 4-phenyl-1, 2, 3-thiadiazole 1a with 4- (4-methylsulfanyl) phenyl-1, 2, 3-thiadiazole 1d to give a product 3e in 77% yield.
Product 3e nuclear magnetic resonance spectroscopy data: 1 H NMR(500MHz,CDCl 3 )δ7.21(d,J＝5.0Hz,2H),7.13(d,J＝10.0Hz,2H),6.77(s,1H),6.72(s,1H),3.84(s,2H),2.46(s,3H),2.32(s,3H). 13 C NMR(126MHz,CDCl 3 )δ182.3,154.6,151.0,137.9,132.9,129.4,128.1,128.0,126.9,42.1,22.6,15.7.HRMS-ESI(m/z):[M+H] + Calcd.for C 14 H 14 OS 2 +H + 263.0559；found:263.0558.
example 6
Synthesis of 2- (benzo [ d ] [1,3] dioxol-5-ylmethyl) -6-methyl-4H-thiopyradin-4-one 3f
The procedure used in example 1 was repeated except for replacing 4-phenyl-1, 2, 3-thiadiazole 1a of example 1 with 4- (benzo [ d ] [1,3] dioxol-5-yl) -1,2, 3-thiadiazole 1e to give a product 3f in 78% yield.
Product 3f nuclear magnetic resonance spectroscopy data: 1 H NMR(500MHz,CDCl 3 )δ6.76-6.72(m,2H),6.69(s,1H),6.68-6.63(m,2H),5.93(s,2H),3.78(s,2H),2.31(s,3H). 13 C NMR(126MHz,CDCl 3 )δ182.2,154.8,150.9,148.0,146.9,129.8,128.1,127.8,122.2,109.2,108.4,101.1,42.2,22.5.HRMS-ESI(m/z):[M+H] + Calcd.for C 14 H 12 O 3 S+H + 261.0580；found:261.0577.
example 7
Synthesis of 2-benzyl-6-naphthyl-4H-thiopyrazin-4-one 3g
The remainder of example 3 was the same as that of example 3 except that 4-hydroxy-6-styryl-2H-pyran-2-one 2b was replaced with 4-hydroxy-6-naphthalen-2-ylpyran-2-one 2c to obtain 3g of a product with a yield of 70%.
Product 3g nmr spectrum data: 1 H NMR(500MHz,CDCl 3 )δ8.00-7.95(m,1H),7.88-7.76(m,3H),7.55(dd,J＝10.0,1.9Hz,1H),7.52-7.46(m,2H),7.31(t,J＝10.0Hz,2H),7.27-7.22(m,3H),7.20-7.16(m,1H),6.89-6.85(m,1H),3.95(s,2H). 13 C NMR(126MHz,CDCl 3 )δ182.3,154.9,153.2,136.2,134.0,133.1,132.9,129.2,129.0,128.6,128.4,127.7,127.6,127.1,127.0,126.7,123.6,42.9.HRMS-ESI(m/z):[M+H] + Calcd.for C 22 H 16 OS+H + 329.0994；found:329.0992.
comparative example 1
Cesium carbonate was used instead of potassium phosphate in example 1, with the other conditions being the same as in example 1. The selectivity to 3a was 45%.
Comparative example 2
N-methylpyrrolidone was used instead of N, N-dimethylacetamide in example 1, and the other conditions were the same as in example 1. The selectivity to 3a was 40%.
Application example 1
(E) Synthesis of-2- (2-benzyl-6- (4- (dimethylamino) styryl) -4H-thiopyran-4-ylidene) malononitrile 7a
2-benzyl-6-methyl-4H-thiopyr-4-one 3a and malononitrile (the specific amounts of both compounds were 0.01mol, 1:1) were refluxed in acetic anhydride (20 ml) for 3H (the reaction temperature was 139 ℃ C.), acetic anhydride was removed by extraction with ethyl acetate, and then passed through a column of the appropriate polarity (petroleum ether: ethyl acetate=10:1) to give 2- (2-benzyl-6-methyl-4H-thiopyran-4-ylidene) malononitrile 5a. Then 5a was refluxed in ethanol for 2 days with piperidine as a catalyst and p-dimethylaminobenzaldehyde (5 a was used in an amount of 0.01mmol, piperidine was used in an amount of 20. Mu.l, and p-dimethylaminobenzaldehyde was used in an amount of 0.011 mmol), and the compound 7a was obtained by recrystallization or beating after spin-drying. The yield of the product was 77%.
Product 5a has the structural formula:
product 5a nuclear magnetic resonance spectroscopy data: 1 H NMR(500MHz,Chloroform-d)δ7.39-7.30(m,3H),7.29(s,1H),7.23(d,J＝7.0Hz,2H),7.17(s,1H),3.98(s,2H),2.40(s,3H). 13 C NMR(126MHz,Chloroform-d)δ156.81,154.48,150.63,135.70,129.12,128.86,127.90,121.36,121.28,115.13,64.48,43.06,22.99.
product 7a has the structural formula:
product 7a nuclear magnetic resonance spectroscopy data: 1 H NMR(500MHz,Chloroform-d)δ7.44-7.31(m,5H),7.29-7.22(m,2H),7.19(s,1H),7.14(s,1H),7.05(d,J＝16.0Hz,1H),6.73(d,J＝16.0Hz,2H),6.69-6.61(m,1H),3.96(s,2H),3.03(s,6H). 13 C NMR(126MHz,Chloroform-d)δ156.67,152.34,151.81,150.63,137.66,136.17,134.52,129.96,129.53,129.26,129.01,127.97,122.46,121.13,119.35,119.20,115.91,112.07,63.61,43.52,40.22.
the hydrogen spectrum (1H NMR:500MHz,CDCl3) of the compound 5a is shown in FIG. 7, and the carbon spectrum (13 CNMR:126MHz, CDCl 3) is shown in FIG. 8.
The hydrogen spectrum (1H NMR:500MHz,CDCl3) of the compound 7a is shown in FIG. 9, and the carbon spectrum (13 CNMR:126MHz, CDCl 3) is shown in FIG. 10.
Application example 2
The p-dimethylaminobenzaldehyde in application example 1 was changed to p-hydroxybenzaldehyde, and the compound 7b was obtained under the same conditions as in application example 1.
Compound 7b has the structural formula:
the UV-visible absorption (UV 2600 Shimadzu, japan) and fluorescence and excitation spectra (LS 55, perkinelmer, USA) of compounds 7a,7b were measured qualitatively.
The test results of (E) -2- (2-benzyl-6- (4- (dimethylamino) styryl) -4H-thiopyran-4-ylidene) malononitrile 7a with the above-mentioned instrument are shown in FIG. 11, wherein the compound 7a has a wide absorption from 400nm to 580nm, and the compound 7a has emission peaks at both 510nm and 710nm at an excitation wavelength of 400 nm.
(E) -2- (2-benzyl-6- (4-hydroxystyryl) -4H-thiopyran-4-ylidene) malononitrile 7b was tested in a similar manner, and as a result, as shown in FIG. 12, compound 7b had a broad absorption from 350nm to 500nm, and at an excitation wavelength of 400nm, compound 7b had an emission peak at 730 nm. Therefore, the fluorescent probe has the characteristics of wide absorption range, large Stokes shift, long emission wavelength and the like.
FIG. 11 is an absorption and emission spectrum of Compound 7 a; FIG. 12 is an absorption and emission spectrum of Compound 7b.
FIG. 13 is a diagram showing the structure of the X-ray crystal of Compound 3b.

Claims (10)

1. A high-efficiency synthesis method of gamma-thiopyranone derivatives is characterized in that: the method comprises the following steps: taking a polar organic solvent as a reaction medium, and reacting a thiadiazole compound with a 4-hydroxy pyrone compound under the action of an alkaline compound to obtain a gamma-thiopyranone derivative;
the structural formula of the thiadiazole compound is shown in formula I:
R 1 h, COOR ', X, OR', CF 3 CN, SR ', R' is alkyl, X is halogen; het represents a cyclic group selected from phenyl, thienyl, furyl, pyridyl, naphthyl; or in a structureIs->The structural formula of the 4-hydroxy pyrone compound is shown in formula II:
R 2 aryl, heterocycle, alkyl, alkenyl, alkynyl; the aryl is phenyl and naphthyl, and the alkenyl comprises styryl;
the structure of the gamma-thiopyranone derivative is shown in a formula III:
2. the efficient synthesis method of the gamma-thiopyranone derivative according to claim 1, which is characterized in that: r' is C 1～5 An alkyl group; r is R 2 Wherein the alkyl is C 1～6 Alkyl group；
The alkaline compound is one or more of cesium carbonate, sodium carbonate, potassium phosphate, potassium carbonate, potassium bicarbonate and sodium bicarbonate;
the polar organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone.
3. The efficient synthesis method of the gamma-thiopyranone derivative according to claim 2, characterized in that: the alkaline compound is one or more of sodium carbonate, potassium phosphate and potassium carbonate;
the polar organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide.
4. The efficient synthesis method of the gamma-thiopyranone derivative according to claim 1, which is characterized in that: the reaction temperature is 60-100 ℃, and the reaction time is 1-2 days;
the mol ratio of the thiadiazole compound to the 4-hydroxy pyrone compound is 1:1.1-1:1.5.
5. The efficient synthesis method of the gamma-thiopyranone derivative according to claim 1, which is characterized in that: the concentration of the thiadiazole compound in the polar organic solvent is 0.5-2 mol/L;
the molar ratio of the weakly basic salt to the thiadiazole compound is 1: (1.8-2.5);
after the reaction, water extraction is carried out, and the crude product is separated by column chromatography.
6. Use of a gamma-thiopyranone derivative obtained by the synthesis process according to any one of claims 1 to 5, characterized in that: the gamma-thiopyranone derivatives are useful for the preparation of fluorescent organic compounds.
7. The use according to claim 6, characterized in that:
the fluorescent organic compound has the structure that
R 3 Is H, OH, OR ', N (R') 2 SR ', R' is alkyl, ar aryl;
R 1 h, COOR ', X, OR', CF 3 CN, SR ', R' is alkyl, X is halogen; het represents a cyclic group selected from phenyl, thienyl, furyl, pyridyl, naphthyl; or in a structureIs->
8. The use according to claim 7, characterized in that: r is R 3 Wherein the alkyl is C 1～4 Alkyl and aryl are phenyl, thiophene and furan.
9. The use according to claim 7, characterized in that: the preparation method of the fluorescent organic compound comprises the following steps:
reacting a gamma-thiopyranone derivative with malononitrile to obtain a thiopyran compound containing a nitrile group; reacting thiopyran compounds containing nitrile groups with benzaldehyde compounds to obtain fluorescent compounds;
the structure of the gamma-thiopyranone derivative is shown in a formula III:
R 1 h, COOR ', X, OR', CF 3 CN, SR ', R' is alkyl, X is halogen; het represents a cyclic group selected from phenyl, thienyl, furyl, pyridyl, naphthyl; or in a structureIs->R 2 Is methyl;
the structure of the thiopyran compound containing nitrile group:
the structure of the benzaldehyde compound is that
R 3 Is H, OH, OR ', N (R') 2 SR ', R' is alkyl, ar aryl.
10. The use according to claim 9, characterized in that: in the reaction of gamma-thiopyranone derivative and malononitrile, acetic anhydride is used as reaction medium;
in the reaction of thiopyran compound containing nitrile group and benzaldehyde compound, ethanol is used as reaction medium and piperidine is used as catalyst.
CN202310940053.0A 2023-07-28 2023-07-28 Efficient synthesis method of gamma-thiopyranone derivative Pending CN117126131A (en)

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