Preparation of 4-iodophenylene ether_Kain Industrial Additives

Background and Overview

4-Iodophenylethyl ether is also known as p-ethoxyiodobenzene and 4-methoxyiodobenzene. Iodinated aromatics are important chemical intermediates and are widely used in organic synthesis. Under the catalysis of transition metals, Heck, Stille, Suzuki, and Ullmann coupling reactions can occur to form C-C and C-heteroatom bonds, and then synthesize many A variety of organic compounds.

Preparation^[1]

Method 1: CN201410511646.6 provides a method for preparing alkoxyiodobenzene, adding alkoxybenzene, I₂, catalyst nitrosium tetrafluoroborate and organic Solvent, seal the reaction vessel, magnetically stir the reaction at a reaction temperature of 20 to 60°C in the presence of air, cool to room temperature after the reaction, and purify the reaction mixture through column chromatography to obtain alkoxyiodobenzene.

Add 0.5mmol ethoxybenzene, 0.25mmol I2, and 1.5mL acetonitrile solution of nitrosium tetrafluoroborate (1.5mL solution contains 0.1mmol nitrosium tetrafluoroborate) into an approximately 45mL reaction tube, and seal it tightly In the reaction tube, control the temperature to 30°C, react under magnetic stirring for 5 hours, and then cool the reaction system to room temperature. The reaction mixture was purified by column chromatography to obtain p-ethoxyiodobenzene, with a GC internal standard yield of 81%. Use ¹H-NMR and ¹³C-NMR to determine the structure of the product, see Figure 3-4.

Method 2,

CN201310069208.4 provides a method for preparing iodoaromatic hydrocarbons, which is characterized in that: adding aromatic ring-containing compounds, I₂, and catalyst NO₂ into the reaction vessel and organic solvent, the material ratio of the aromatic ring compound, I₂ and catalyst NO₂ is 1:0.2~3:0.01~5, and then the reaction is sealed Container, there is air in the sealed reaction container, stir and react at 10 to 180°C for 5 minutes to 40 hours, cool to room temperature after the reaction, and purify the reaction mixture through column chromatography to obtain iodoaromatic hydrocarbons.

Add 0.5 mmol phenethyl ether, 0.3 mmol I₂ and 1.5 mL acetonitrile in sequence into the reaction vessel, and pass in 1.35 mL NO₂ (normal pressure, normal temperature) . Seal the reaction vessel. If there is air in the sealed reaction vessel, place the reaction vessel in an oil bath preheated to 120°C and stir magnetically at 120°C for 12 hours. After the reaction is completed, cool the reaction system to room temperature. The reaction mixture was purified by column chromatography. The 4-ethoxyiodobenzene product was obtained with a yield of 87%.

Main reference materials

[1] CN201410511646.6 A method for preparing alkoxyiodobenzene

[2] CN201310069208.4 A method for preparing iodoaromatic hydrocarbons