Isocoumarin compound, derivatives and synthesis method thereof

A technology of isocoumarin and synthesis method, applied in the field of isocoumarin, can solve the problems of harsh reaction conditions, increased cost and the like, and achieves the effects of low cost, simple operation and high yield

Inactive Publication Date: 2013-07-31
SHANGHAI JIAO TONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Existing synthetic method mainly contains following several kinds: the first kind is to utilize expensive metal catalyst such as: metal rhodium, metal palladium etc., relevant research such as Shimizu, M.; Hirano, K.; Satoh, T.; Miura, M.J. Org. Chem. 2009, 74, 3478; Ueura, T.; Satoh, T.; Miura, M. Org. Lett. 2007, 9, 1407; Ueura, K.; Satoh, T.; .2007, 72, 5362; Zhao, P.; Chen, D.; Song, G.; Han, K.; Li, X.J.Org.Chem.2012, 77, 1579; X.J.Org.Chem.1999,64,8770; Larock, R.C.; Yum, E.K.; Doty, M.J.; Multi-step reaction and harsh reaction conditions, related research such as Majumdar, K.C.; Ansary, I.; Narayan De, R.; Roy, B.Synthesis2011, 2951; Larock, R.C.; ; Chin, L.-Y.; Lee, C.-Y.; Lo, Y.-H.; Wu, M.-J.J. R.; Kradanrat, P.; Hohn, E.; Young, L.; Ruchirawat, S. J. Org. Chem. 2007, 72, 9379; .Synthesis2007, 400
[0004] However, in the synthetic method of isocoumarin compounds and derivatives thereof, the method for synthesizing isocoumarin compounds and derivatives thereof by one-pot method has not been reported yet, using cheap metal copper as a catalyst, starting from simple and easy-to-obtain raw materials

Method used

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  • Isocoumarin compound, derivatives and synthesis method thereof
  • Isocoumarin compound, derivatives and synthesis method thereof
  • Isocoumarin compound, derivatives and synthesis method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] 3,4-dimethoxycarbonyl isocoumarin, its structural formula is:

[0026]

[0027] The synthetic method of this compound is as follows:

[0028] In a reaction tube, add 4.0mg cupric chloride, 74.4mg 2-iodobenzoic acid, 85.2mg dimethyl butyndioate, 82.9mg potassium carbonate, and 2.0mL toluene under nitrogen protection, and slowly heat up from room temperature to 130°C, react for 12 hours. Conventional treatment yielded 64.5 mg of pure product with a yield of 82%.

[0029] The melting point of the product is 132-133°C; the result of NMR characterization is: 1 H NMR (400MHz, CDCl 3 )δ8.36(d, J=8.6Hz, 1H), 7.84(d, J=8.6Hz, 1H), 7.70(d, J=8.6Hz, 1H), 7.54(d, J=8.6Hz, 1H) , 4.01(s, 3H), 3.96(s, 3H); 13 C NMR (CDCl 3 )δ 53.5 (2C), 119.1, 122.0, 125.6, 130.4, 131.4, 132.8, 135.7, 140.9, 159.3, 160.2, 165.1. The above results indicated that the desired product was synthesized.

Embodiment 2

[0031] 5-methyl-3,4-dimethoxycarbonyl isocoumarin, its structural formula is:

[0032]

[0033] The synthetic method of this compound is as follows:

[0034] In a reaction tube, add 4.0mg cupric chloride, 78.6mg 3-methyl-2-iodobenzoic acid, 85.2mg dimethyl butyndioate, 82.9mg potassium carbonate, and 2.0mL toluene under nitrogen protection, from room temperature Start to slowly heat up to 130°C, and react for 12 hours. Conventional treatment yielded 54.7 mg of pure product with a yield of 66%.

[0035]The melting point of the product is 144-145°C; the result of NMR characterization is: 1 H NMR (400MHz, CDCl 3 )δ8.31(d, J=8.0Hz, 1H), 7.55-7.63(m, 2H), 4.01(s, 3H), 3.96(s, 3H), 2.51(s, 3H); 13 C NMR (CDCl 3 )δ20.1, 53.4 (2C), 118.9, 123.2, 129.1, 130.9, 131.1, 136.2, 139.1, 140.4, 159.9, 160.5, 167.0; high-resolution mass spectrometry HRMS (ESI) calculated as: C 14 h 13 o 6 , 277.0712(M+H) + , found: 277.0706. The above results indicated that the desired product was...

Embodiment 3

[0037] 7-methyl-3,4-dimethoxycarbonyl isocoumarin, its structural formula is:

[0038]

[0039] The synthetic method of this compound is as follows:

[0040] In a reaction tube, under nitrogen protection, add 4.0mg copper chloride, 78.6mg 5-methyl-2-iodobenzoic acid, 85.2mg dimethyl butynedioate, 82.9mg potassium carbonate, and 2.0mL toluene, from room temperature Start to slowly heat up to 130°C, and react for 12 hours. Conventional treatment yielded 57.9 mg of pure product with a yield of 70%.

[0041] The melting point of the product is 164-165°C; the result of NMR characterization is: 1 H NMR (400MHz, CDCl 3 )δ8.18(s, 1H), 7.65(d, J=8.0Hz, 1H), 7.42(d, J=8.0Hz, 1H), 4.02(s, 3H), 3.96(s, 3H), 2.52( s, 3H); 13 CNMR (CDCl 3 )δ21.7, 53.4, 53.5, 119.3, 121.9, 125.5, 130.3 (2C), 136.8, 140.1, 142.4, 159.5, 160.3, 165.3; high resolution mass spectrometry HRMS (ESI) calculated as: C 14 h 13 o 6 (M+H) + , 277.0712, found: 277.0699. The above results indicated that the...

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Abstract

The present invention discloses a class of isocoumarin derivatives, which have the following general formula, wherein R is selected from hydrogen atom, C1-C10 alkyl, halogen, carbonyl, hydroxyl, nitrile, ester, alkoxy or trifluoromethoxyl, and E1 or E2 is selected from C1-C6 alkyl formate, phenyl or nitrile. The present invention further discloses a synthesis method of the isocoumarin derivatives. According to the present invention, divalent copper is adopted as a catalyst, a simple and easily-available o-halogenated benzoic acid and an alkyne compound are adopted as starting raw materials to synthesize an isocoumarin compound and derivatives thereof, and advantages of low cost, high yield, simple operation, easily-available raw materials, simple reaction equipment, easy industrial production, and the like are provided.

Description

technical field [0001] The invention relates to isocoumarin, in particular to an isocoumarin compound and derivatives thereof, and also relates to a synthesis method of these compounds and derivatives. Background technique [0002] Isocoumarin (scientific name: 1 hydrogen-2-benzopyran-1-one) is the basic structure of some natural products, widely distributed in nature, and there are many kinds. People have used various methods to synthesize such compounds , especially recently found that its derivatives have physiological and biological activities such as antibacterial, anti-inflammatory, anti-cancer, protease inhibition and herbicide, and have obvious anti-cancer activity, and the research on such compounds is more active. [0003] At present, a large number of literatures have reported the synthesis methods of isocoumarin compounds and their derivatives. Existing synthetic method mainly contains following several kinds: the first kind is to utilize expensive metal catalys...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D311/76
Inventor 郭勋祥
Owner SHANGHAI JIAO TONG UNIV
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