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Org. Synth. 1956, 36, 77
DOI: 10.15227/orgsyn.036.0077
SEBACIL
[1,2-Cyclodecanedione]
Submitted by A. T. Blomquist and Albert Goldstein1.
Checked by N. J. Leonard and J. C. Little.
1. Procedure
Fifty-one grams (0.30 mole) of sebacoin (Note 1), 25 ml. of methanol, 120 g. of cupric acetate monohydrate (0.60 mole), and 300 ml. of 50% aqueous acetic acid are mixed in a 1-l. flask equipped with an efficient mechanical stirrer and a reflux condenser. The mixture is heated over a free flame until refluxing occurs. The color of the mixture changes from blue to red at approximately 75°. Refluxing is continued for 1 minute. The mixture is then allowed to cool, with stirring, to about 40° (Note 2). The mixture is filtered through filter aid ("Celite") on a sintered glass funnel to remove cuprous oxide, and the filtrate is transferred to a 2-l. separatory funnel (Note 3). Saturated aqueous sodium chloride solution. (310 ml.) is added to the filtrate, which is then extracted with three 150-ml. portions of ether. The combined ether extracts are washed with three 250-ml. portions of saturated salt solution, four 250-ml. portions of 5% sodium bicarbonate solution (foaming!), and once again with 250 ml. of saturated salt solution. The ether solution is then dried over 20 g. of anhydrous sodium or magnesium sulfate. The ether is removed by distillation at atmospheric pressure, and the residue is transferred to a 100-ml. flask and distilled under vacuum. The yield of sebacil is 44.4–45.1 g. (88–89%), b.p. 104–106°/10 mm. (Note 4).
2. Notes
1. The sebacoin-sebacil mixture obtained from the sebacoin preparation (p. 840) was used.
2. The sebacil may tend to crystallize during filtration if the reaction mixture is too cool.
3. The "Celite"-cuprous oxide mixture is extracted with three 50-ml. portions of ether, and the combined extracts are used as the first ether portion for the extraction of the sebacil-containing aqueous solution.
4. 1,2-Cyclononanedione has been prepared from 2-hydroxycyclononanone in 67–72% yield by this procedure.2
3. Discussion
1,2-Cyclodecanedione has also been prepared by oxidation of sebacoin with chromium trioxide in acetic acid.3,4 Cupric acetate in acetic acid has been used for oxidation of an α-hydroxyketone by Ruggli and Zeller.5

References and Notes
  1. Cornell University, Ithaca, New York.
  2. Blomquist, Liu, and Bohrer, J. Am. Chem. Soc., 74, 3643 (1952).
  3. Blomquist, Burge, and Sucsy, J. Am. Chem. Soc., 74, 3636 (1952).
  4. Prelog, Schenker, and Günthard, Helv. Chim. Acta, 35, 1610 (1952).
  5. Ruggli and Zeller, Helv. Chim. Acta, 28, 741 (1945).

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

sodium or magnesium sulfate

Sebacoin

sebacoin-sebacil

Celite

acetic acid (64-19-7)

methanol (67-56-1)

ether (60-29-7)

sodium bicarbonate (144-55-8)

sodium chloride (7647-14-5)

cuprous oxide

cupric acetate (142-71-2)

chromium trioxide (1333-82-0)

cupric acetate monohydrate (6046-93-1)

1,2-Cyclodecanedione,
Sebacil (96-01-5)

1,2-Cyclononanedione

2-hydroxycyclononanone