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Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt

A compound and metal salt technology, applied in the field of nitration, can solve problems such as low yield of nitration products, difficulties in product separation and purification, and difficulties in nitration methods

Inactive Publication Date: 2005-12-21
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Phenols and phenyl ether compounds are a class of compounds that are very easy to nitrate, but phenols and phenyl ether compounds themselves are easily oxidized, so there are certain difficulties in the selection of nitration methods
For example, in industrial production, nitrophenol is generally produced by indirect methods. This is mainly due to the fact that oxidation reactions easily occur when phenol is directly nitrated, and the yield of nitrated products is very low, and the generated oxidation products are oily, which makes the product Separation and purification become difficult

Method used

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  • Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt
  • Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt
  • Nitrofication method for catalysis of phenol and diphenyl ether compounds using metal salt

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Experimental program
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Effect test

Embodiment 1

[0049] 12mg Fe(NO 3 )3*9H 2 O (3mol%), 3mL THF and 94mg phenol (1.0mmol) were added to the reactor, 60% concentrated nitric acid (0.095mL, 1.2mmol) was added dropwise with stirring, and the reaction was stirred at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane, and the insoluble matter and residual moisture were heated under vacuum conditions to remove moisture, and the obtained solid was used as a catalyst for nitration reaction again; the extract was spin-dried on a rotary evaporator and passed through a column to obtain a yellow Solid 60mg, yield 43%, 2-nitrophenol; Pale yellow solid 68mg, yield 49%, 4-nitrophenol. 2-Nitrophenol: m.p.45-47℃, IR(KBr)ν1522, 1416cm -1 (NO 2 ), 3250, 1240cm -1 (OH); 1 H NMR (CDCl 3 , 300MHz, TMS) δ7.00 (1H, dt, J = 7.5Hz, 1.5Hz, Ar), 7.16 (1H, d, J = 7.4Hz, Ar), 7.59 (1H, dt, J = 7.5Hz, 1.5 Hz, Ar), 8.12 (1H, dd, J=7.5Hz, 1.5Hz, Ar), 10.60 (1H, s, ArOH); MS (EI) m / z 139 (M + ), 122 (M + -17, 6.46...

Embodiment 2

[0051] 10mg Cu(OAc) 2 *H 2 O (3mol%), 3mL THF and 94mg phenol (1.0mmol) were added to the reactor, 60% concentrated nitric acid (0.095mL, 1.2mmol) was added dropwise with stirring, and the reaction was stirred at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane, and the insoluble matter and residual moisture were heated under vacuum conditions to remove moisture, and the obtained solid was used as a catalyst for nitration reaction again; the extract was spin-dried on a rotary evaporator and passed through a column to obtain a yellow 60 mg of solid, 43% yield, 2-nitrophenol; 72 mg of light yellow solid, 52% yield, 4-nitrophenol.

Embodiment 3

[0053] 12mg CoCl 2 *6H 2 O (5mol%), 3mL THF and 94mg phenol (1.0mmol) were added to the reactor, 60% concentrated nitric acid (0.095mL, 1.2mmol) was added dropwise with stirring, and the reaction was stirred at room temperature for 12 hours. The reaction mixture was extracted with dichloromethane, and the insoluble matter and residual moisture were heated under vacuum conditions to remove moisture, and the obtained solid was used as a catalyst for nitration reaction again; the extract was spin-dried on a rotary evaporator and passed through a column to obtain a yellow 58 mg of solid, 42% yield, 2-nitrophenol; 70 mg of light yellow solid, 50% yield, 4-nitrophenol.

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Abstract

This invention involves the nitration method for phenols and phenylate compounds whose structural formula is RR1R2R3Z. Using the catalyst of metallic salt, in the organic solvent, nitrify the phenols and phenolic compounds with nitric acid. Thereinto, R1, R2 or R3 is H, alkyl that carbon atomicity is 1-5, halogen, phenolic hydroxyl, phenyl or alkoxy that carbon atomicity is 1-5; R is phenolic hydroxyl or alkoxy that carbon atomicity is 1-5; Z is phenyl, naphthyl, tetrahydronaphthyl, anthranyl or fluorenyl. This method is to use the nitric acid of lower concentration; it is comparatively economic and safe in production. Catalyst is cheap and easy to getting, meanwhile, metallic salt should be used repeatedly in nitrify reaction and reclaim easy.

Description

technical field [0001] The invention relates to a kind of nitration method, in particular to a gold salt-catalyzed nitration method of phenols and phenyl ether compounds. Background technique [0002] The nitration reaction of aromatic compounds is a very important chemical reaction, among which the nitration of phenols and phenyl ethers plays an important role in the fields of industrial production and drug synthesis. For example, nitrophenol is a kind of carbon steel corrosion inhibitor, and p-chloro-o-nitrophenol is an intermediate of the drug chlorzoxazone. P-aminophenol, the reduction product of p-nitrophenol, is an intermediate of drugs such as acetaminophen and clofibrate, and is also used in developing agents, antioxidants, and vinyl monomer polymerization inhibitors. [0003] Phenols and phenylene ether compounds are a class of compounds that are very easy to nitrate, but phenols and phenylene ether compounds themselves are easy to be oxidized, so it is difficult t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C205/21
Inventor 施敏尹万坡
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI