Iodine → 4-Hexyloxyphenylboronic Acid

Participants

Reaction Steps

In an apparatus which had been baked out and blanketed with argon, magnesium turnings (1.89 g; 78 mmol) were treated with a crystal of iodine and covered with dried THF. A few drops of 4-hexyloxybromobenzene were then added to the solution without stirring. The Grignard reaction began very quickly and, while stirring, the 4-hexyloxybromobenzene (total amount: 20 g; 78 mmol) was then added dropwise at such a rate that the mixture boiled gently. During this addition, the mixture was diluted with a little THF (total amount: about 100 ml). The mixture was refluxed for 3 hours (only a few flakes of magnesium remaining in the solution) and subsequently allowed to cool. The Grignard solution was transferred to a 250 ml dropping funnel in a countercurrent of protective gas and added dropwise to a solution of trimethyl borate (8.9 g; 9.6 ml; 86 mmol) in 50 ml of dry THF while stirring at −70° C., resulting in formation of a precipitate. The reaction mixture was allowed to warm to RT overnight and was then introduced while stirring into a mixture of 100 g of ice and 3 ml of concentrated sulfuric acid. The organic phase was separated off, the aqueous phase was extracted 3 times with 100 ml each time of chloroform and the combined organic phases were evaporated. The crude product was subsequently recrystallized from hexane. Product: colorless, wax-like solid (11.28 g; 66%); melting point: 84-87° C.

Provenance & Evidence