A kind of synthetic method of 3-substituted isocoumarin catalyzed by ruthenium

A technology of isocoumarin and synthesis method, which is applied in the direction of organic chemistry, can solve the problems of complex process, high cost, and many synthesis steps, and achieve the effect of simple operation and few reaction steps

Active Publication Date: 2022-03-15
LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
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Problems solved by technology

[0005] In view of this, the present invention discloses and provides a synthetic method of 3-substituted isocoumarin catalyzed by ruthenium, to at least solve the problem of many synthetic steps, complex process and high cost in the prior art when synthesizing isocoumarin, which lead to practical low level problem

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  • A kind of synthetic method of 3-substituted isocoumarin catalyzed by ruthenium
  • A kind of synthetic method of 3-substituted isocoumarin catalyzed by ruthenium
  • A kind of synthetic method of 3-substituted isocoumarin catalyzed by ruthenium

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Experimental program
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Effect test

Embodiment 1

[0053]

[0054]The reactor was placed under nitrogen, and 0.40mmol (78.4mg) α-carbonylsulfide ylide (1a), 0.02mmol (12.2mg) [Ru(p-cymene)Cl 2 ] 2 , 0.08mmol (27.5mg) AgSbF 6 , 0.40mmol (24.0mg) AcOH, 2mL TFE, stirred at 100°C for 12h. After the reaction was completed, the solvent was adjusted with a rotary evaporator, and the crude product was subjected to column chromatography with a mixed solvent of petroleum ether and ethyl acetate as the eluent to obtain 40.5 mg of 3-substituted isocoumarin 2a with an isolated yield of 91%.

[0055] join figure 1 , figure 2 , the characterization data of compound 2a are as follows:

[0056] 1 H NMR (400MHz, CDCl 3 )δ8.29(d, J=8.4Hz, 1H), 7.87(dd, J=8.0, 1.6Hz, 2H), 7.72-7.68(m, 1H), 7.50-7.40(m, 5H), 6.94(s ,1H). 13 C NMR (100MHz, CDCl 3 ) δ 162.3, 153.6, 137.5, 134.9, 132.0, 130.0, 129.6, 128.8, 128.2, 126.0, 125.2, 120.5, 101.8.

Embodiment 2

[0058]

[0059] The reactor was placed under nitrogen, and 0.40mmol (84.0mg) α-carbonylsulfide ylide (1b), 0.02mmol (12.2mg) [Ru(p-cymene)Cl 2 ] 2 , 0.08mmol (27.5mg) AgSbF 6 , 0.40mmol (24.0mg) AcOH, 2mL TFE, stirred at 100°C for 12h. After the reaction was completed, the solvent was adjusted with a rotary evaporator, and the crude product was subjected to column chromatography with a mixed solvent of petroleum ether and ethyl acetate as the eluent to obtain 45.0 mg of 3-substituted isocoumarin 2b with an isolation yield of 90%.

[0060] join image 3 , Figure 4 , the characterization data of compound 2b are as follows:

[0061] 1 H NMR (400MHz, CDCl3) δ8.17 (d, J = 8.0Hz, 1H), 7.76 (d, J = 8.4Hz, 2H), 7.29-7.24 (m, 4H), 6.83 (s, 1H), 2.47 (s,3H),2.40(s,3H). 13 C NMR (100MHz, CDCl3) δ 162.5, 153.9, 145.9, 140.2, 137.8, 129.6, 129.5, 129.4, 129.3, 125.8, 125.1, 118.0, 101.1, 22.0, 21.4.

Embodiment 3

[0063]

[0064] The reactor was placed under nitrogen, and 0.40mmol (92.0mg) α-carbonylsulfide ylide (1c), 0.02mmol (12.2mg) [Ru(p-cymene)Cl 2 ] 2 , 0.08mmol (27.5mg) AgSbF 6 , 0.40mmol (24.0mg) AcOH, 2mL TFE, stirred at 100°C for 12h. After the reaction was completed, the solvent was adjusted with a rotary evaporator, and the crude product was subjected to column chromatography with a mixed solvent of petroleum ether and ethyl acetate as the eluent to obtain 48.9 mg of 3-substituted isocoumarin 2c with an isolation yield of 84%.

[0065] see Figure 5 , Image 6 , the characterization data of compound 2c are as follows:

[0066] 1 H NMR (400MHz, CDCl3) δ8.23(d, J=8.4Hz, 1H), 7.81(d, J=8.4Hz, 2H), 7.49-7.44(m, 4H), 6.86(s, 1H). 13 C NMR (100MHz, CDCl3) δ 161.2, 153.8, 141.7, 138.7, 136.5, 131.4, 130.0, 129.2, 128.9, 126.6, 125.5, 118.8, 101.0.

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Abstract

The invention discloses a synthesis method of 3-substituted isocoumarin catalyzed by ruthenium. In the synthesis method, ruthenium is used as a catalyst to realize the activation of the ortho carbon-hydrogen bond of aromatic hydrocarbons and the intramolecular A variety of 3‑substituted isocoumarin compounds were efficiently synthesized in one step through a simple operation. The raw materials of the reactants are cheap and easy to obtain, the reaction steps are few, the operation is simple, and it has step economy and market economy.

Description

technical field [0001] The disclosure of the invention relates to the technical field of organic chemical synthesis, in particular to a ruthenium-catalyzed synthesis method of 3-substituted isocoumarins. Background technique [0002] Isocoumarins are fundamental building blocks in many natural products, pharmaceuticals, and bioactive compounds. A large number of isocoumarins have been isolated from natural products, especially the 3-substituted isocoumarins have remarkable special effects in medicine, such as anti-tumor, anti-inflammatory, antibacterial and anti-AIDS. In addition, isocoumarin is also a valuable synthetic intermediate, and its functional modification can synthesize meaningful molecules, such as anesin, isochromenes, alkaloids, etc. Given the wide applicability of isocoumarins, scientists have made great and persistent efforts to find efficient ways to synthesize isocoumarins. [0003] The traditional methods for synthesizing isocoumarins mainly rely on the ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D311/76
CPCC07D311/76
Inventor 李蕾王贺周明东彭振
Owner LIAONING UNIVERSITY OF PETROLEUM AND CHEMICAL TECHNOLOGY
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