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Environment-friendly synthetic method of 6(5H)-phenanthridine derivative

A technology of green synthesis and derivatives, applied in the field of synthesis of pharmaceutical and chemical intermediates, can solve the problems of unavailable starting materials, difficult derivation, and complicated experimental operations, and achieve high reaction chemical selectivity and regioselectivity, and great implementation value and social and economic benefits, and the effect of easy availability of raw materials

Inactive Publication Date: 2018-10-26
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The main disadvantages of this type of method: the use of noble metal catalysts, the price is relatively expensive, and the product of the reaction is an N-protected phenanthridinone derivative, which is difficult to further derivatize and requires an additional step to remove its protective group
There are many disadvantages in this type of method: the use of metal palladium and stoichiometric metal oxidant increases the cost, the use of toxic and harmful reagents is not friendly to the environment, the starting materials are not easy to obtain, and the experimental operation is complicated.

Method used

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  • Environment-friendly synthetic method of 6(5H)-phenanthridine derivative
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  • Environment-friendly synthetic method of 6(5H)-phenanthridine derivative

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Example 1: Preparation of phenanthridine-6(5H)-one (Ⅲa)

[0022] Will N -(1,1'-biphenyl)-2-pyridineamide (0.82g, 3mmol), diisopropyl azodicarboxylate (1.21g, 6mmol), cobalt acetate tetrahydrate (0.11g, 0.45mmol), A solution of sodium pivalate (0.85g, 6mmol) and oxygen (1 atm) in dioxane (8mL) was stirred at 80°C for 24 hours and separated by silica gel column chromatography to obtain a white solid phenanthridine-6(5H) - Ketone (Ⅲa) 0.36g, yield: 62%, melting point: 297.5~298.3°C. The structural formula of Ⅲa is:

[0023]

[0024] 1 H NMR (600 MHz, DMSO- d 6 , ppm) δ 11.70 (s, 1H), 8.50 (d, J = 8.4 Hz, H),8.38 (d, J = 7.8 Hz, 1H), 8.34 (d, J = 7.8 Hz, 1H), 7.86 – 7.83 (m,1H), 7.66– 7.63 (m, 1H), 7.50 – 7.47 (m, 1H) , 7.39 (d, J = 7.8 Hz, 1H), 7.27 – 7.24(m, 1H). 13 C NMR (150 MHz, DMSO- d 6 , ppm) δ 161.3, 137.0, 134.7, 133.2, 130.0,128.4, 127.9, 126.2, 123.7, 123.1, 122.7, 118.0, 116.6. 13 h 8 NO [M-H] - : 194.0611; Found: 194.0610.

Embodiment 2

[0025] Example 2: Preparation of phenanthridine-6(5H)-one (Ⅲa)

[0026] Will N -(1,1'-biphenyl)-2-pyridineamide (0.82g, 3mmol), diisopropyl azodicarboxylate (1.21g, 6mmol), cobalt acetate tetrahydrate (0.11g, 0.45mmol), A solution of sodium pivalate (0.85g, 6mmol) and oxygen (1 atm) in dioxane (8mL) was stirred at 150°C for 24 hours and separated by silica gel column chromatography to obtain a white solid phenanthridine-6(5H) - Ketone (Ⅲa) 0.47g, yield: 80%.

Embodiment 3

[0027] Embodiment 3: Preparation of phenanthridine-6(5H)-one (Ⅲa)

[0028] Will N-(1,1'-biphenyl)-2-pyridineamide (0.82g, 3mmol), diisopropyl azodicarboxylate (1.21g, 6mmol), cobalt chloride (0.06g, 0.45mmol), Tetra A solution of sodium valerate (0.85g, 6mmol) and oxygen (1 atm) in dioxane (8mL) was stirred and reacted at 120°C for 10 hours. After the reaction, it was separated by silica gel column chromatography to obtain a white solid phenanthridine-6 (5H)-ketone (Ⅲa) 0.44g, yield: 75%.

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Abstract

The invention discloses an environment-friendly synthetic method of a 6(5H)-phenanthridine derivative. The method specifically comprises the step of carrying out catalyzed oxidation by virtue of metalcobalt, so as to realize the high-selectivity and high-yield preparation of the 6(5H)-phenanthridine derivative, wherein N-([1,1'-biphenyl]-2-yl)pyridine amide is take as the raw material, azodiformate is taken as a carbonyl source for replacing poisonous and harmful carbon monoxide, and oxygen is taken as an oxidant. The environment-friendly synthetic method has the characteristics that the rawmaterial is easily available, the operation is simple and convenient, the chemical selectivity and the regional selectivity are high, and the like; and the environment-friendly synthetic method has relatively high implement values and social and economic values.

Description

technical field [0001] The invention belongs to the technical field of synthesis of pharmaceutical and chemical intermediates, and relates to a green synthesis method of 6(5H)-phenanthridinone derivatives, in particular to a method for preparing 6(5H)-phenanthridinone through a cobalt-catalyzed oxidation method. Background technique [0002] 6(5H)-Phenanthridinone is the core of a class of very important natural compounds, and has wide application prospects in the field of medicine and chemical industry. Phenanthridone and its derivatives have strong biological activity and can be modified to prepare a variety of drugs, for example: PJ34HCl inhibitor is the hydrochloride form of PJ34, which is a PARP (polyadenosine diphosphate-ribose polymerase) Inhibitor, IC 50 20 nM, equally potent on PARP1 / 2. It is a potent phenanthridone PARS (polyadenosine diphosphate-ribose synthetase) inhibitor, 10,000 times more active than the typical PARS inhibitor 3-aminobenzamide. PJ34 inhibit...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D221/12
CPCC07D221/12
Inventor 凌飞艾崇仁钟为慧
Owner ZHEJIANG UNIV OF TECH
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