Organic Syntheses, Coll. Vol. 5, p.412 (1973); Vol. 49, p.50 (1969).
3,3'-Dimethoxybiphenyl2 (8 g., 0.037 mole)
is dissolved in 120 ml. of methylene chloride
in a 250-ml. conical flask
, and the flask is placed in an acetone-dry ice bath
at −80°. The flask is fitted with an air condenser
. A solution of 15.9 g. (6.0 ml., 0.063 mole) of boron tribromide (Note 1)
, (Note 2)
in 40 ml. of methylene chloride (Note 3)
, (Note 4)
is added carefully to the stirred solution through the condenser. When the addition is complete, a calcium chloride tube
is fitted to the top of the air condenser in order to protect the reaction mixture from moisture. As the solution of boron tribromide
is added, a white precipitate is formed. The reaction mixture is allowed to attain room temperature overnight with stirring, when a clear, brownish yellow solution is obtained. The reaction mixture is then hydrolyzed by careful shaking with 130 ml. of water, thus precipitating a white solid which is dissolved by the addition of 500 ml. of ether
. The organic layer is separated and extracted with 240 ml. of 2N sodium hydroxide
; the alkaline extract is neutralized with dilute hydrochloric acid
, extracted with 300 ml. of ether
, and the ether
extract is dried over anhydrous magnesium sulfate
. On removal of the ether
under reduced pressure, a brownish yellow oil remains which soon crystallizes to give an off-white solid; this is recrystallized twice from hot benzene
, the first time with the addition of charcoal, and gives 3,3'-dihydroxybiphenyl
as white needles with a pinkish tint, m.p. 126–127° (Note 5)
. The yield is 5.4–6.0 g.
Boron tribromide of 99.9% purity, from Koch-Light Laboratories Ltd., Colnbrook, Bucks, England
, was used.
is a heavy, colorless liquid (d
= 2.6) when pure but begins to decompose on exposure to light, liberating free bromine
. It fumes vigorously in air, being rapidly hydrolyzed to boric acid
, with the evolution of considerable heat.
When making up the solution of boron tribromide
in methylene chloride
, it has been found best to stand the vessel containing the solvent in an acetone-dry ice bath at −80° and to add the required amount (it is difficult to measure accurately) to the methylene chloride
as rapidly as possible.
In order to obtain a perfectly white product, recrystallization from water is necessary;3,4
prismatic needles several centimeters long are obtained. The compound is moderately soluble in boiling water and slightly soluble in cold water.
Almost all the methods previously employed7
for the demethylation of aromatic methyl ethers have involved fairly high temperatures, e.g.
, hydrogen halides in water or acetic acid
at reflux temperature, whereas the present method is effective at, or well below, room temperature although in a few cases it has been found necessary to boil the solution (b.p. of methylene chloride
). Boron tribromide
does not effect cleavage of methylenedioxy groups nor of diphenyl ethers. It can be used for the demethylation of aryl methyl ethers in the presence of many functional groups without affecting these.5
It is especially valuable for the demethylation of iodinated ethers5
and of methoxy biphenylenes8
where the usual reagents are either ineffective or else cause decomposition. Boron tribromide
was the reagent of choice for the final (demethylation) step in the synthesis of the naturally occurring macrolide, Zearalenone.9
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