Org. Synth. 1955, 35, 18
DOI: 10.15227/orgsyn.035.0018
[Glyoxylic acid, n-butyl ester]
Submitted by Frank J. Wolf and John Weijlard1.
Checked by N. J. Leonard and L. A. Miller.
1. Procedure
In a 3-l. three-necked round-bottomed flask provided with a Hershberg stirrer and a thermometer are placed 1.25 l. of reagent-grade benzene and 325 g. (1.24 moles) of di-n-butyl d-tartrate (Note 1). The mixture is stirred rapidly, and 578 g. (1.30 moles) of lead tetraacetate (Note 2) is added over a period of about 25 minutes. The temperature is maintained below 30° by occasional cooling with cold water. After the addition is complete, the mixture is stirred for 1 hour, during which time the gummy salts become crystalline. The salts are removed by filtration with suction and washed with 500 ml. of benzene. The benzene and acetic acid are removed from the filtrate by distillation at 65°/50 mm. The residue is distilled at 20 mm. under nitrogen introduced through an ebullator, using a Vigreux column (2 by 30 cm.), and the fraction boiling between 65° and 79°/20 mm. (main portion at 68–74°) is collected as product. The crude n-butyl glyoxylate, which weighs 247–280 g. (77–87%), n20D 1.442–1.443, d254 1.085, is satisfactory for most purposes (Note 3).
2. Notes
1. The di-n-butyl d-tartrate used was the purest grade from Eastman Kodak Company, m.p. 20–22°.
2. Lead tetraacetate was obtained from the G. Frederick Smith Chemical Company, Columbus, Ohio. It may also be prepared by the procedure described in Inorganic Syntheses.2
3. The product undergoes autoxidation and should be stored under nitrogen. Further purification may be effected by a second fractional distillation under nitrogen at reduced pressure. The product decomposes on boiling (159–161°) at atmospheric pressure.
3. Discussion
n-Butyl glyoxylate has not been described previously. Anal. Calcd. for C6H10O3: C, 55.37; H, 7.75. Found: C, 54.95; H, 7.83. Ethyl glyoxylate has been prepared in good yield by oxidation of ethyl tartrate with red lead oxide3 or sodium bismuthate.4 These papers describe isolation of ethyl glyoxylate as carbonyl derivatives.

References and Notes
  1. Merck and Company, Rahway, New Jersey.
  2. Inorg. Syntheses, 1, 47 (1939).
  3. Hamamura, Suzumoto, and Hayashima, J. Agr. Chem. Soc. Japan, 22, 25 (1948) [C. A., 46, 10108 (1952)].
  4. Rigby, Nature, 164, 185 (1949).

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

red lead oxide

acetic acid (64-19-7)

Benzene (71-43-2)

nitrogen (7727-37-9)

Ethyl glyoxylate (924-44-7)

ethyl tartrate

sodium bismuthate (12232-99-4)

Glyoxylic acid, n-butyl ester (6295-06-3)

di-n-butyl d-tartrate

lead tetraacetate (546-67-8)