Organic Syntheses, Coll. Vol. 4, p.351 (1963); Vol. 31, p.43 (1951).
Sixty-five grams (0.50 mole) of hydrazine sulfate (Note 1)
is dissolved in 400 ml. of 10% sodium hydroxide
in a 1-l. round-bottomed flask
, fitted with a separatory funnel
, a thermometer
, and a stirrer. The flask is immersed in an ice bath
and cooled. When the temperature of the mixture reaches 15° (Note 2)
, 50 g. (0.50 mole) of acetylacetone (Note 3)
is added dropwise with stirring while the temperature is maintained at about 15°. The addition requires about 30 minutes to complete, and the mixture is stirred for 1 hour at 15° (Note 4)
. The contents of the flask are diluted with 200 ml. of water to dissolve precipitated inorganic salts, transferred to a 1-l. separatory funnel
, and shaken with 125 ml. of ether
. The layers are separated, and the aqueous layer is extracted with four 40-ml. portions of ether
. The ether
extracts are combined, washed once with saturated sodium chloride
solution, and dried over anhydrous potassium carbonate
. The ether
is removed by distillation, and the slightly yellow residue of crystalline 3,5-dimethylpyrazole
obtained by drying at reduced pressure (approximately 20 mm.) weighs 37–39 g.
), m.p. 107–108°.
This product, which is of good quality, can be recrystallized from about 250 ml. of 90–100° petroleum ether
without significant change in appearance or melting point. The yield after drying in a vacuum desiccator
containing paraffin chips is 35–37 g.
) (Note 5)
Hydrazine sulfate supplied by the Eastman Kodak Company
is satisfactory, or it may be prepared by a previously described procedure.2
Union Carbide and Carbon Corporation technical 2,4-pentanedione
was used without purification.
Recrystallization from methanol
gives practically colorless material of the same melting point, but it is more difficult to obtain good recovery owing to the high solubility of the pyrazole
in these solvents.
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