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Palladium-catalyzed ortho-orientation nitrification method of aza calixarene compounds

A technology for azaaromatics and compounds, which is applied in the field of ortho-directed nitration of azaaromatics, can solve problems such as inconvenient operation, and achieve good adaptability

Inactive Publication Date: 2012-03-14
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The above methods can partially solve the problems caused by the traditional nitration process, but they have a common deficiency that pre-functionalized aromatic compounds must be used as substrates, and the organometallic reagents and ligands involved must be kept anhydrous during operation. Anaerobic conditions, inconvenient to operate

Method used

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  • Palladium-catalyzed ortho-orientation nitrification method of aza calixarene compounds
  • Palladium-catalyzed ortho-orientation nitrification method of aza calixarene compounds
  • Palladium-catalyzed ortho-orientation nitrification method of aza calixarene compounds

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Experimental program
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Effect test

Embodiment 1

[0043]

[0044] Combine 103 mg (0.5 mmol) of 2-phenylquinoxaline, 11 mg (0.05 mmol) of palladium diacetate, 154 mg (1.0 mmol) of silver nitrite, 270 mg (1.0 mmol) of potassium persulfate and 1,2-bis Chloroethane (5 ml) was sequentially added to a 10 ml sealed pressure vessel. The mixture was heated and reacted in an oil bath at 130°C for 48 hours. After the reaction is detected by TLC, the reaction solution is diluted with dichloromethane and filtered to obtain a clear liquid, which is separated by column chromatography (eluent ratio: petroleum ether to ethyl acetate volume ratio 4:1) to obtain a yellow solid 2-( 2-Nitrophenyl)quinoxaline 107 mg (86% yield).

[0045] Characterization data: mp 114-115 ℃; IR (KBr): n = 1531 (NO 2 ) cm -1 ; 1 H NMR (CDCl 3 , 500 MHz): δ 8.97 (s, 1H), 8.18-8.10 (m, 3H), 7.83-7.68 (m, 5H); 13 C NMR (CDCl 3 , 125 MHz): δ 151.1, 148.8, 144.3, 141.8, 141.6, 133.3, 133.0, 131.9, 130.6, 130.4, 130.3, 129.6, 129.3, 125.0; MS (EI, 70eV): m / z (%) = 251 (83)...

Embodiment 2

[0047]

[0048] Combine 103 mg (0.5 mmol) of 2-phenylquinoxaline, 11 mg (0.05 mmol) of palladium diacetate, 154 mg (1.0 mmol) of silver nitrite, 270 mg (1.0 mmol) of potassium persulfate and dichloromethane (5 ml) in order to add 10 ml sealed pressure vessel. The mixture was heated and reacted in an oil bath at 130°C for 48 hours. After the reaction is detected by TLC, the reaction solution is diluted with dichloromethane and filtered to obtain a clear liquid, which is separated by column chromatography (eluent ratio: petroleum ether to ethyl acetate volume ratio 4:1) to obtain a yellow solid 2-( 2-Nitrophenyl)quinoxaline 102 mg (81% yield).

Embodiment 3

[0050]

[0051] Combine 103 mg (0.5 mmol) of 2-phenylquinoxaline, 35 mg (0.05 mmol) of bis(triphenylphosphine) palladium dichloride, 154 mg (1.0 mmol) of silver nitrite, and 270 mg (1.0 mmol) of potassium persulfate. mmol) and 1,2-dichloroethane (5 ml) were sequentially added to a 10 ml sealed pressure vessel. The mixture was heated and reacted in an oil bath at 130°C for 48 hours. After the reaction is detected by TLC, the reaction solution is diluted with dichloromethane and filtered to obtain a clear liquid, which is separated by column chromatography (eluent ratio: petroleum ether to ethyl acetate volume ratio 4:1) to obtain a yellow solid 2-( 2-Nitrophenyl)quinoxaline 91 mg (72% yield).

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Abstract

The invention discloses a palladium-catalyzed ortho-orientation nitrification method of aza calixarene compounds, relating to a nitrification method, comprising the following steps: successively adding the aza calixarene compounds, palladium catalyst, nitrated reagent, oxidizing agent and reaction solvent in a sealed pressure container, controlling the pressure between 1 mbar and 100 bar, heatingthe mixture for 6-72 hour in an oil bath with the reaction temperature of 30-200 DEG C to obtain a product of the ortho-orientation nitrification. According to the invention, the method is carried out under neutral conditions, and has no generation of exhaust gas and waste water; directional mononitration is only carried out on the ortho-position of the nitrogen containing substituents without being influenced from other substituents on aromatic nucleus, and the chemo-selectivity and region-selectivity are good; the functional groups and the substrate have good adaptability, and the directional ortho-position nitration of a plurality of aromatic nucleus containing various substituents and a plurality of aromatic nucleus containing various nitrogen containing oriented groups can all be realized; and pre-functionalized aromatic compounds are not needed.

Description

technical field [0001] The invention relates to a nitration method, in particular to a method for ortho-directed nitration of nitrogen heteroaromatic compounds using metal as a catalyst. Background technique [0002] Nitrification is the introduction of nitro groups (-NO 2 ) of the reaction process. The most widely used in industry is the nitration of aromatic compounds. Aromatic nitro compounds are important intermediates for the synthesis of drugs, spices, dyes and explosives, and are widely used in pesticides, pharmaceuticals, fine chemicals and other organic synthesis industries. The traditional nitration method of aromatic compounds (mixed acid nitration method) can be expressed by the following general formula: Ar─H + HNO 3 → Ar─NO 2 + H 2 O. The traditional nitration method has difficult-to-control chemical and regioselectivity problems. The nitration process often occurs with excessive nitration or uncertain nitro position, making the product a mixture and di...

Claims

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Application Information

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IPC IPC(8): C07B43/02B01J31/04B01J31/24C07D241/42C07D409/04C07D213/26C07D231/12C07C251/40C07C249/12
Inventor 刘运奎娄绍杰许丹倩徐振元
Owner ZHEJIANG UNIV OF TECH
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