Use of bismuth nitrate and iron nitrate as nitrification agent in aromatic compound nitrification

Abstract

Use of bismuth nitrate and ferric nitrate in aromatic substance nitrating reaction as nitrating agent and its method are disclosed.

Description

technical field

[0001] The invention relates to the application of bismuth nitrate and / or iron nitrate as a nitrating agent in the nitration reaction of aromatic compounds. Background technique

[0002] The nitration reaction of aromatic compounds is an important class of organic synthesis reactions. The classic industrial nitration reaction method is the mixed acid method, that is, under the catalysis of concentrated sulfuric acid, the nitration reaction is carried out with concentrated nitric acid as the nitrating reagent. This traditional synthesis method has many side reactions, low selectivity, high requirements for reaction equipment, and serious environmental pollution. Therefore, exploring novel green nitration reactions of aromatic compounds is still a research hotspot.

[0003] In recent years, people have developed some new nitrification methods.

[0004] For example, A.V.Joshi et al. reported that using 4-substituted phenol as a substrate and 6-15wt% dilute ni...

Examples

Embodiment 1

[0036] Weigh phenol 107mg, Bi(NO 3 ) 3 ·5H 2 Add 485mg of O and 1ml of acetone into a 10ml ground-mouthed round bottom flask, stir the reaction at 25°C, the reaction is exothermic and completes quickly, filter with a sand core funnel, and use CH 2 Cl 2 Wash the solids, combine the filtrates, concentrate to about 1ml, and separate with thin layer chromatography. The developer is selected from the mixed solvent of cyclohexane: ether=1:1 to obtain 72 mg of o-nitrophenol and 74 mg of p-nitrophenol. The yields are respectively 46% and 47%, and the total yield is 93%.

Embodiment 2

[0038] Weigh p-cresol 108mg, Bi(NO 3 ) 3 ·5H 2 Add 245mg of O and 2ml of dichloromethane into a 10ml ground-mouth round bottom flask, stir and react in a water bath at 10°C, and filter with a sand core funnel for 12 hours, and use CH 2 Cl 2 Wash the solids, combine the filtrates, evaporate most of the solvent, concentrate to about 1ml, separate by thin-layer chromatography, and develop with a mixed solvent of cyclohexane and ether to obtain 110mg of 2-nitro-4methylphenol with a yield of 72%. .

Embodiment 3

[0040] Weigh o-cresol 108mg, Fe(NO 3 ) 3 9H 2 Add 135mg of O and 0.5ml of diethyl ether into a 10ml ground-mouth round bottom flask, stir and react at 0°C for 15 hours, filter through a sand core funnel, and use CH 2 Cl 2 Wash the solids, combine the filtrates, evaporate most of the solvent, concentrate to about 1ml, separate by thin layer chromatography, and develop with a mixed solvent of cyclohexane and ether to obtain 65 mg of 2-methyl-6 nitrophenol, 2-methyl -4-Nitrophenol 78 mg, yields were 42% and 51%, total yield 93%.

technical field

[0001] The invention relates to the application of bismuth nitrate and / or iron nitrate as a nitrating agent in the nitration reaction of aromatic compounds. Background technique

[0002] The nitration reaction of aromatic compounds is an important class of organic synthesis reactions. The classic industrial nitration reaction method is the mixed acid method, that is, under the catalysis of concentrated sulfuric acid, the nitration reaction is carried out with concentrated nitric acid as the nitrating reagent. This traditional synthesis method has many side reactions, low selectivity, high requirements for reaction equipment, and serious environmental pollution. Therefore, exploring novel green nitration reactions of aromatic compounds is still a research hotspot.

[0003] In recent years, people have developed some new nitrification methods.

[0004] For example, A.V.Joshi et al. reported that using 4-substituted phenol as a substrate and 6-15wt% dilute ni...

Examples

Embodiment 1

[0036] Weigh phenol 107mg, Bi(NO 3 ) 3 ·5H 2 Add 485mg of O and 1ml of acetone into a 10ml ground-mouthed round bottom flask, stir the reaction at 25°C, the reaction is exothermic and completes quickly, filter with a sand core funnel, and use CH 2 Cl 2 Wash the solids, combine the filtrates, concentrate to about 1ml, and separate with thin layer chromatography. The developer is selected from the mixed solvent of cyclohexane: ether=1:1 to obtain 72 mg of o-nitrophenol and 74 mg of p-nitrophenol. The yields are respectively 46% and 47%, and the total yield is 93%.

Embodiment 2

[0038] Weigh p-cresol 108mg, Bi(NO 3 ) 3 ·5H 2 Add 245mg of O and 2ml of dichloromethane into a 10ml ground-mouth round bottom flask, stir and react in a water bath at 10°C, and filter with a sand core funnel for 12 hours, and use CH 2 Cl 2 Wash the solids, combine the filtrates, evaporate most of the solvent, concentrate to about 1ml, separate by thin-layer chromatography, and develop with a mixed solvent of cyclohexane and ether to obtain 110mg of 2-nitro-4methylphenol with a yield of 72%. .

Embodiment 3

[0040] Weigh o-cresol 108mg, Fe(NO 3 ) 3 9H 2 Add 135mg of O and 0.5ml of diethyl ether into a 10ml ground-mouth round bottom flask, stir and react at 0°C for 15 hours, filter through a sand core funnel, and use CH 2 Cl 2 Wash the solids, combine the filtrates, evaporate most of the solvent, concentrate to about 1ml, separate by thin layer chromatography, and develop with a mixed solvent of cyclohexane and ether to obtain 65 mg of 2-methyl-6 nitrophenol, 2-methyl -4-Nitrophenol 78 mg, yields were 42% and 51%, total yield 93%.