A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1948, 28, 44
DOI: 10.15227/orgsyn.028.0044
[4,6-Nonanedione, 2,8-dimethyl-]
Submitted by C. R. Hauser, J. T. Adams, and R. Levine.
Checked by Arthur C. Cope and Frank S. Fawcett.
1. Procedure
Approximately 300 ml. of commercial anhydrous liquid ammonia is added to a 500-ml. three-necked round-bottomed flask equipped with a mercury-sealed stirrer and a reflux condenser connected to a soda-lime drying tube (Note 1). The drying tube is attached to a gas-absorption trap, or the apparatus is assembled in a well-ventilated hood. The third neck of the flask is closed with a stopper. Freshly cut sodium (13.8 g., 0.6 gram atom) is weighed under xylene or kerosene, and a small amount is added to the liquid ammonia, with stirring, until a permanent blue color is produced. A few small crystals of ferric nitrate are added to catalyze the conversion of sodium to sodium amide (Note 2), and when the blue color has disappeared the remainder of the sodium is added in small pieces. When the sodium is converted completely to sodium amide, as indicated by change of the blue solution to a gray suspension, the ammonia is evaporated by warming the flask on a steam bath. During this operation sufficient dry ether is added through a dropping funnel (attached to the third neck of the flask) so that the volume of the liquid remains approximately 300 ml. After practically all the ammonia has been evaporated, as indicated by refluxing of the ether, the sodium amide suspension is stirred and heated under reflux for a few minutes and then cooled to room temperature. The procedure to this point requires approximately 1 hour.
A solution of 30 g. (0.3 mole) of redistilled methyl isobutyl ketone in 50 ml. of absolute ether is added to the stirred suspension of sodium amide during 5–10 minutes. After an additional 5 minutes, a solution of 78 g. (0.6 mole) of redistilled ethyl isovalerate in 50 ml. of dry ether is added during about 15 minutes. Stirring is continued for 2 hours while the mixture is heated under reflux on the steam bath. The gelatinous suspension of the sodium salt of diisovalerylmethane is poured into 300 ml. of water, made neutral to litmus by dilute hydrochloric acid, and extracted with three 100-ml. portions of ether. The solvent is removed by distillation under reduced pressure, and the residue is dissolved in an equal volume of methanol. A solution prepared from 44 g. of cupric acetate monohydrate and 350 ml. of water is heated nearly to the boiling point, filtered, and added to the methanol solution. The resulting mixture is allowed to stand until it has cooled to room temperature. The blue copper salt of diisovalerylmethane is collected on a Büchner funnel, pressed as dry as possible, washed on the funnel with 100 ml. of petroleum ether (b.p. 30–60°), and again sucked dry. The yield of the copper salt after air drying is 44–51 g. (69–79%); it melts in the range 150–155° (Note 3).
The diisovalerylmethane is regenerated by shaking the copper salt vigorously with 500 ml. of 10% sulfuric acid and 200 ml. of ether until all the salt has dissolved. The aqueous acid layer is extracted with two 100-ml. portions of ether, and the combined ether solutions are dried over anhydrous sodium sulfate. The solvent is removed, and the residue is distilled under reduced pressure. The yield of diisovalerylmethane is 32–42 g. (58–76%, based on methyl isobutyl ketone), b.p. 115–116°/20 mm., nD25 1.4565 (Note 4) and (Note 5).
2. Notes
1. Apparatus fitted with standard-taper ground-glass joints is convenient for this preparation.
2. It may be helpful to provide additional catalysis of the conversion to sodium amide of the small amount of sodium added initially by bubbling dry air through the solution.1
3. After recrystallization from methanol or 95% ethanol the fluffy light blue copper salt melts at 157–158°.
4. The submitters state that the reaction may be conducted with equal success by using 0.6 mole each of sodium amide and methyl isobutyl ketone, and 0.3 mole of ethyl isovalerate (yield 75% based on the ester).2,3
5. Acetone may be acylated with ethyl laurate by either procedure (with excess ester or excess ketone). Lauroylacetone (m.p. 31.5–32°) is obtained in 75% yield3 by either procedure.
3. Discussion
Diisovalerylmethane has been prepared by the method described2,3 and by the use of sodium hydride4 as the condensing agent.

References and Notes
  1. Leffler, Org. Reactions, 1, 99, John Wiley & Sons, New York, 1942; Vaughn, Vogt, and Nieuwland, J. Am. Chem. Soc., 56, 2120 (1934).
  2. Adams and Hauser, J. Am. Chem. Soc., 66, 1220 (1944).
  3. Levine, Conroy, Adams, and Hauser, J. Am. Chem. Soc., 67, 1510 (1945).
  4. Swamer and Hauser, J. Am. Chem. Soc., 72, 1352 (1950).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

petroleum ether


sodium salt of diisovalerylmethane

copper salt of diisovalerylmethane

ethanol (64-17-5)

sulfuric acid (7664-93-9)

hydrochloric acid (7647-01-0)

ammonia (7664-41-7)

methanol (67-56-1)

ether (60-29-7)

sodium sulfate (7757-82-6)

acetone (67-64-1)

sodium (13966-32-0)

xylene (106-42-3)

Methyl isobutyl ketone (108-10-1)

ethyl laurate (106-33-2)

sodium amide (7782-92-5)

ferric nitrate

4,6-Nonanedione, 2,8-dimethyl- (7307-08-6)

ethyl isovalerate (108-64-5)

cupric acetate monohydrate (6046-93-1)


sodium hydride (7646-69-7)