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Multi-substituent isocoumarin derivative and preparation method thereof

An isocoumarin, multi-substitution technology, applied in the direction of organic chemistry, can solve the problems of low reaction selectivity, unfriendly environment, narrow substrate range, etc., to achieve strong reaction specificity, green post-processing, substrate wide range of effects

Active Publication Date: 2015-07-29
HUAQIAO UNIVERSITY
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  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

However, there are many problems in these methods: 1) 2-halogenated benzoic acid method has narrow substrate range; 2) C-H activation method needs to add oxidant, which is not environmentally friendly; 3) the reaction selectivity of these methods is not high

Method used

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  • Multi-substituent isocoumarin derivative and preparation method thereof
  • Multi-substituent isocoumarin derivative and preparation method thereof
  • Multi-substituent isocoumarin derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Preparation of 3,4-diphenyl-1H-isochromen-1-one

[0024]

[0025] 0.5 mmol of tert-butyl peroxybenzoate, 0.75 mmol of 1,2-tolueneacetylene, 0.005 mmol of dichloro(pentamethylcyclopentadienyl) rhodium (III), 0.15 mmol of cesium pivalate, and 0.15 mmol of pivalate Add 0.5 mmol of the acid to a nitrogen-filled Slinky tube, place it in an oil bath at 80°C, and react for 18 hours. Remove the reaction from the heat source and cool to room temperature. The reaction solution was concentrated and purified by column chromatography to obtain 141 mg of the target product with a yield of 95%. The NMR characterization of this compound is as follows: 1 H NMR (400MHz, CDCl 3 )δ8.41(dd,J=7.9,1.2Hz,1H),7.68–7.60(m,1H),7.55–7.49(m,1H),7.45–7.37(m,3H),7.36–7.30(m, 2H),7.29–7.25(m,2H),7.24–7.16(m,4H). 13 C NMR (101MHz, CDCl 3 ) δ 162.4, 151.1, 139.0, 134.8, 134.5, 133.1, 131.4, 129.7, 129.4, 129.2, 129.1, 128.3, 128.2, 128.0, 125.5, 120.6, 117.0.

Embodiment 2

[0027] Preparation of 3,4-bis(4-methoxyphenyl)-1H-isochromen-1-one

[0028]

[0029] 0.5mmol of tert-butyl peroxybenzoate, 0.75mmol of 1,2-bis(4-methoxyphenyl)acetylene, 0.005mmol of dichloro(pentamethylcyclopentadienyl)rhodium (III), and Add 0.15 mmol of cesium valerate and 0.5 mmol of pivalic acid to a nitrogen-filled Schlinker tube, place in an oil bath at 80° C., and react for 18 hours. Remove the heat source from the reaction and cool to room temperature. The reaction solution was concentrated and purified by column chromatography to obtain 122 mg of the target product with a yield of 68%. The NMR characterization of this compound is as follows: 1 H NMR (400MHz, CDCl 3 )δ8.38(d, J=7.8Hz, 1H), 7.62(t, J=7.7Hz, 1H), 7.48(t, J=7.5Hz, 1H), 7.30(d, J=8.7Hz, 2H) ,7.18(dd,J=12.0,8.3Hz,3H),6.97(d,J=8.4Hz,2H),6.73(d,J=8.7Hz,2H),3.86(s,3H),3.77(s, 3H); 13 C NMR (101MHz, CDCl 3 )δ 162.6, 160.0, 159.5, 151.0, 139.6, 134.6, 132.5, 130.8, 129.6, 127.8, 126.8, 125.6, 125.3, 120...

Embodiment 3

[0031] Preparation of 3,4-bis(4-methylphenyl)-1H-isochromen-1-one

[0032]

[0033] 0.5mmol of tert-butyl peroxybenzoate, 0.75mmol of 1,2-bis(4-methylphenyl)acetylene, 0.005mmol of dichloro(pentamethylcyclopentadienyl) rhodium (III), pentapentyl Add 0.15 mmol of cesium acid and 0.5 mmol of pivalic acid to a nitrogen-filled Schlinker tube, place in an oil bath at 80°C, and react for 18 hours. Remove the heat source from the reaction and cool to room temperature. The reaction solution was concentrated and purified by column chromatography to obtain 134 mg of the target product with a yield of 82%. 1 H NMR (400MHz, CDCl 3 )δ8.40(d, J=7.8Hz, 1H), 7.62(t, J=7.6Hz, 1H), 7.50(t, J=7.5Hz, 1H), 7.27–7.22(m, 4H), 7.20( d, J=8.1Hz, 1H), 7.14(d, J=7.9Hz, 2H), 7.01(d, J=8.1Hz, 2H), 2.42(s, 3H), 2.29(s, 3H); 13 C NMR (101MHz, CDCl 3 )δ 162.4, 151.0, 139.3, 139.0, 137.8, 134.5, 131.4, 131.1, 130.2, 129.8, 129.5, 129.1, 128.6, 127.8, 125.3, 120.4, 116.3,, 21.4, 21.3.

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Abstract

The invention discloses a multi-substituent isocoumarin derivative and a preparation method thereof. According to the preparation method, substituted tert-butyl peroxybenzoate represented by a formula II, 1,2-disubstituted acetylene represented by a formula III, a catalyst, alkali, acid and a solvent are uniformly mixed and are heated under the protection of nitrogen for a cyclization reaction, and a compound represented by a general structure formula I is obtained after the reaction. According to the method, the reaction conditions are mild, the reaction time is short, the substrate range is wide, the reaction specificity is high, the yield is high, the post-processing is simple and convenient, and the multi-substituent isocoumarin derivative which cannot be synthesized with other methods can be synthesized and has a wide application.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to multi-substituted isocoumarin derivatives and a preparation method thereof. Background technique [0002] Multi-substituted isocoumarin derivatives are a class of organic synthesis intermediates with a wide range of uses, and have important application values ​​in natural products, pharmaceutical production, and organic synthesis. Therefore, the research on new synthesis methods of multi-substituted isocoumarins has important application value and has attracted the attention of researchers in related fields. [0003] Traditional synthesis methods of isocoumarin derivatives include the cyclization reaction of 2-halobenzoic acid with 1,2-disubstituted alkyne, and the transition metal-catalyzed C-H activation reaction of benzoic acid with 1,2-disubstituted alkyne. However, there are many problems in these methods: 1) 2-halogenated benzoic acid method has narrow substrate ...

Claims

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Application Information

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IPC IPC(8): C07D311/76
CPCC07D311/76
Inventor 崔秀灵莫家珏
Owner HUAQIAO UNIVERSITY
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