Organic Syntheses, Coll. Vol. 3, p.140 (1955); Vol. 25, p.9 (1945).
A mixture of 28 g. (0.2 mole) of o-nitrophenol (Note 1)
, 30 g. (0.22 mole) of n-butyl bromide
, 28 g. (0.2 mole) of anhydrous potassium carbonate
, and 200 ml. of dry acetone
in a 1-l. round-bottomed flask
is refluxed on a steam bath
for 48 hours (Note 2)
. At the end of this time the acetone
is distilled from the mixture, 200 ml. of water is added to the residue, and the product is extracted with two 100-ml. portions of benzene
. The combined benzene
extracts are washed with three 100-ml. portions of 10% sodium hydroxide
, the benzene
is removed by distillation at ordinary pressure, and the residual oil is distilled under reduced pressure. The yield of product boiling at 118–121°/1 mm. (Note 3)
is 29–31 g.
) (Note 4)
and (Note 5)
A technical grade of o-nitrophenol
was used; the yield is no better with the pure material. In place of n-butyl bromide, a corresponding amount (36.8 g.) of the iodide
can be used with no change in yield.
The checkers shook the flask occasionally during the first 1.5 hours in order to prevent caking of the contents.
The boiling point is 126–129°/2 mm.
and 171–172°/19 mm.
Other nitrophenyl ethers can be prepared in a similar manner and in essentially the same yields. When the size of the run was increased to 2 moles, the yields were increased to 85–90%
. The hexyl derivatives require 72 hours for reaction.
The present procedure, which avoids the preparation of the salts of the phenols, is of general utility. It was first used by Claisen1
for allyl ethers. o-n-Butoxynitrobenzene
has been prepared in a similar manner previously.2
s have been obtained by alkylation of the phenol salts.3,4,5
The corresponding amines have been prepared previously by reduction of the nitro compounds by means of iron
and by stannous chloride
and hydrochloric acid
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