Method for preparing benzothiapyran [4,3-b] quinoline and derivative of benzothiapyran [4,3-b] quinoline

A kind of technology of benzothiopyran and derivatives, applied in the field of preparation of benzothiopyran[4,3-b]quinoline and derivatives thereof

Inactive Publication Date: 2015-01-21
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The second method: in 1983, Swaminathan, K.S. et al. used thiochromene and aniline as the reaction raw materials to obtain the target product in two steps (Tetrahedron Letters, 1983, vol .24, p.3653–3656) (formula 1-2), although the method is simple to operate, the reaction conditions are relatively harsh, and the target product needs to be obtained under the condition of light and the total yield of the two steps is only 11%.
The reaction process of this method is cumbersome, the raw material is expensive, and the yield is low, which is inconsistent with the concept of "atom economy" pursued by people.

Method used

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  • Method for preparing benzothiapyran [4,3-b] quinoline and derivative of benzothiapyran [4,3-b] quinoline
  • Method for preparing benzothiapyran [4,3-b] quinoline and derivative of benzothiapyran [4,3-b] quinoline
  • Method for preparing benzothiapyran [4,3-b] quinoline and derivative of benzothiapyran [4,3-b] quinoline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1: Synthesis of 2-methyl-6H-benzothiopyran[4,3-b]quinoline (1a)

[0036]

[0037] 5-methyl-2-propargylthio-N-benzylidene aniline (53.2mg, 0.2mmol), cuprous oxide (0.3mg, 0.002mmol), 2,3,5,6-tetrachloro-p-benzoquinone (49.0mg, 0.2mmol), sodium chloride (5.8mg, 0.1mmol) were successively added into the Schlenk reaction flask, and after vacuum and nitrogen replacement three times, in a nitrogen atmosphere, 0.01mL of ethylene glycol dimethyl ether was added, 30 ℃ for 4 hours, after the reaction, the solvent was removed under reduced pressure, separated by column chromatography (eluent: petroleum ether: ethyl acetate = 20:1, V:V), and 42.0 mg of a light yellow solid product was obtained, with a yield of 81 %. Mp110-112°C; 1 H-NMR (400MHz, CDCl 3 )δ8.43(d, J=1.2Hz, 1H), 8.16(d, J=8.4Hz, 1H), 7.96(s, 1H), 7.79(d, J=8.0Hz, 1H), 7.71-7.67( m,1H),7.53-7.49(m,1H),7.31(d,J=8.0Hz,1H),7.16(dd,J=1.6,8.0Hz,1H),4.09(d,J=0.8Hz,2H ),2.46(s,3H).

Embodiment 2

[0038] Example 2: Synthesis of 2-methyl-9-chloro-6H-benzothiopyran[4,3-b]quinoline (1b)

[0039]

[0040] 5-Methyl-2-propargylthio-N-(4-chloro)-benzylidene aniline (60.0mg, 0.2mmol), cuprous iodide (1.9mg, 0.01mmol), 2,3,5, 6-Tetrachloro-p-benzoquinone (980.0mg, 4.0mmol) and potassium chloride (14.9mg, 0.2mmol) were successively added to the Schlenk reaction flask, and after vacuum and nitrogen replacement for 3 times, in a nitrogen atmosphere, 0.5mL of acetonitrile was added , reacted at 60°C for 6 hours, after the reaction was completed, the solvent was removed under reduced pressure, separated by column chromatography (eluent was petroleum ether:ethyl acetate=20:1, V:V), and 43.0 g of the main product was obtained as a light yellow solid, Yield 69%. Mp148-150℃; 1 H-NMR (400MHz, CDCl 3 )δ8.38(d, J=1.6Hz, 1H), 8.06(d, J=9.2Hz, 1H), 7.81(d, J=3.2Hz, 1H), 7.73(d, J=2.0Hz, 1H) ,7.60(dd, J=2.4,9.2Hz,1H),7.29(d,J=7.6Hz,1H),7.16(dd,J=2.0,8.0Hz,1H),4.05(s, 2H),2.45( s,3H); ...

Embodiment 3

[0041] Example 3: Synthesis of 2-methyl-9-iodo-6H-benzothiopyran[4,3-b]quinoline (1c)

[0042]

[0043] 5-methyl-2-propargylthio-N-(4-iodo)-benzylidene aniline (78.4mg, 0.2mmol), cuprous bromide (2.9mg, 0.02mmol), 2,3,5, 6-Tetrachloro-p-benzoquinone (148.0mg, 6.0mmol) and calcium chloride (44.4mg, 0.4mmol) were successively added to the Schlenk reaction flask, and after vacuum and nitrogen replacement for 3 times, 1.0mL of toluene was added in a nitrogen atmosphere , reacted at 90°C for 8 hours, after the reaction was completed, the solvent was removed under reduced pressure, separated by column chromatography (eluent was petroleum ether: ethyl acetate = 20:1, V:V), and 56.0 mg of the main product was obtained as a light yellow solid, Yield 72%. Mp181-183°C; 1 H-NMR (400MHz, CDCl 3 )δ8.39(d,J=2.0Hz,1H),8.15(d,J=2.0Hz,1H),7.91(dd,J=1.6,8.8Hz,1H),7.84,(d,J=8.8Hz ,1H),7.80(s,1H),7.30(d,J=8.0Hz,1H),7.18-7.15(m,1H); 13 C-NMR (125MHz, CDCl 3 )δ153.1, 146.8, 138.2, 136.7, 13...

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Abstract

The invention belongs to the technical field of medical and chemical midbodies and relevant chemical engineering, and relates to a method for preparing benzothiapyran [4,3-b] quinoline and derivatives of benzothiapyran [4,3-b] quinoline. Benzothiapyran [4,3-b] quinoline is an important component with bioactive molecules, has a very good against hepatitis B virus curative effect, has significant application in the organic synthesis and medical and chemical fields, and has wide market prospect. The benzothiapyran [4,3-b] quinoline is generated by performing Diels-Alder reaction by taking a schiff base derivative as a raw material in the presence of a metal copper catalyst. The preparation method has the advantages of short synthesis route, gentle condition, simplicity in operation, relatively high yield, and the like, and has relatively great use values and social and economical benefits.

Description

technical field [0001] The invention belongs to the field of pharmaceutical and chemical intermediates and related chemical technologies, and relates to a preparation method of benzothiopyran[4,3-b]quinoline and derivatives thereof. Background technique [0002] Benzothiopyran[4,3-b]quinoline compounds are a class of important biologically active molecules, which have good anti-hepatitis B virus curative effect, and have important applications in the fields of organic synthesis and medicinal chemistry. market expectation. About benzothiopyran [4,3-b] quinoline compounds, usually adopt the following three methods: the first method: in 1973, Jacquigno et al. used thiochromanone and isatin as initial raw materials, after two One-step synthesis target product benzothiopyran [4,3-b] quinoline (Journal of the Chemical Society, 1951,1909-1913) (formula 1-1), but this reaction operation is loaded down with trivial details, and raw material price is expensive, and final yield Only ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D495/04
CPCC07D495/04
Inventor 于晓强王娇冯秀娟包明
Owner DALIAN UNIV OF TECH
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