A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1952, 32, 86
DOI: 10.15227/orgsyn.032.0086
[Valeric acid, 4-methyl-, 4-nitro-, methyl ester]
Submitted by R. B. Moffett1
Checked by N. J. Leonard and B. L. Ryder.
1. Procedure
A 500-ml. three-necked flask is fitted with a stirrer, a dropping funnel, and a thermometer placed so that the bulb is near the bottom of the flask. In the flask are placed 89 g. (1 mole) of 2-nitropropane (Note 1), 50 ml. of dioxane, and 10 ml. of a 40% aqueous solution of benzyltrimethylammonium hydroxide (Triton B) (Note 2), and the contents of the flask are warmed to 70°. Eighty-six grams (1 mole) of redistilled methyl acrylate (Note 3) is added, with stirring, during 15 minutes. The temperature rises to about 100° during the addition and then drops to about 85°. The mixture is stirred and heated on a steam bath for 4 hours. After cooling, the contents of the flask are acidified with dilute hydrochloric acid and extracted with ether. The ether layer is washed twice with water, then with approximately 50 ml. of 0.1% sodium bicarbonate solution, and finally again with water. After the ethereal solution has been dried over anhydrous sodium sulfate, the drying agent is separated, the solvent is removed by distillation, and the product is distilled through a short fractionating column. A nearly colorless oil is obtained in a yield of 140–151 g. (80–86%); b.p. 79°/1 mm.; nD20 1.4408.
2. Notes
1. 2-Nitropropane from Commercial Solvents Corporation, Terre Haute, Indiana, was redistilled before use.
2. Available from Commercial Solvents Corporation or Rohm and Haas Company, Philadelphia, Pennsylvania.
3. Although the submitter knows of no case of an explosion with this type of nitro compound, it is recommended that adequate safety shields be employed during both the reaction and the distillation.
3. Discussion
Methyl γ-methyl-γ-nitrovalerate has been prepared by the Michael-type condensation of 2-nitropropane with methyl acrylate in the presence of a quaternary ammonium hydroxide2 or triethylamine.3
This preparation is referenced from:

References and Notes
  1. The Upjohn Company, Kalamazoo, Michigan.
  2. Bruson, U. S. pat. 2,342,119 and 2,390,918 [C. A., 38, 4619 (1944)].
  3. Kloetzel, J. Am. Chem. Soc., 70, 3571 (1948).

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

benzyltrimethylammonium hydroxide (Triton B)

quaternary ammonium hydroxide

hydrochloric acid (7647-01-0)

ether (60-29-7)

sodium bicarbonate (144-55-8)

sodium sulfate (7757-82-6)

methyl acrylate (96-33-3)

dioxane (123-91-1)

triethylamine (121-44-8)

Methyl γ-methyl-γ-nitrovalerate,
Valeric acid, 4-methyl-, 4-nitro-, methyl ester (16507-02-1)

2-nitropropane (79-46-9)