Org. Synth. 1941, 21, 79
Submitted by R. B. Moffett and R. L. Shriner.
Checked by W. E. Bachmann and W. S. Struve.
A solution of phenylmagnesium bromide
is prepared in a 2-l. three-necked flask
, fitted with a separatory funnel
, reflux condenser
, and a mercury-sealed stirrer
, from 8.8 g. (0.36 gram atom) of magnesium
, 56.5 g. (38 ml., 0.36 mole) of bromobenzene
, and a total of 350 ml. of dry ether
by the procedure described in Org. Syntheses Coll. Vol. 1, 226 (1941)
To the solution of the Grignard reagent, cooled by an ice-salt bath
, a mixture of 21.3 g. (0.3 mole) of methoxyacetonitrile [Org. Syntheses Coll. Vol. 2, 387 (1943)]
and 50 ml. of dry ether
is slowly added with stirring. The colorless addition product separates at once. After standing at room temperature for 2 hours, the mixture is again cooled and then decomposed by adding, with stirring, 500 ml. of water and cracked ice, and then 100 ml. of cold dilute sulfuric acid (Note 1)
. When the decomposition is complete (Note 2)
, the ether
layer is separated and the aqueous layer is extracted with a little ether
. This ether
extract is combined with the ether
layer, and the whole is washed with 5% aqueous sodium carbonate
solution and then with water. The solution is dried with anhydrous sodium sulfate
The ether is removed by distillation from a steam bath, and the residue is distilled under diminished pressure. ω-Methoxyacetophenone is a colorless liquid which boils at 118–120° /15 mm. or 228–230° /760 mm. (Note 3). The yield is 32–35 g. (71–78% based on the methoxyacetonitrile).
One volume of concentrated sulfuric acid
is added to 2 volumes of water, and the mixture is cooled in an ice-salt bath.
The two layers should be light yellow in color with only a small amount of solid or tarry material present.
The checkers observed a boiling point of 110–112° /9 mm.
The method described is essentially that of Pratt and Robinson.1 ω-Methoxyacetophenone
has also been prepared by chromic acid
oxidation of α-phenyl-β-methoxyethanol
, which in turn was prepared from styrene oxide
Chemical Abstracts Nomenclature (Collective Index Number);
sulfuric acid (7664-93-9)
sodium carbonate (497-19-8)
sodium sulfate (7757-82-6)
chromic acid (7738-94-5)
Phenylmagnesium bromide (100-58-3)
Styrene oxide (96-09-3)
Acetophenone, ω-methoxy- (4079-52-1)
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