Isobutyric Acid → 2,2-Dimethylhexanoic Acid

Participants

Reaction Steps

A solution of 102 g (1.02 mol) of diisopropylamine (distilled from calcium hydride) in 730 ml of dry THF was stirred under argon in an ice-bath as a full bottle (1.0 mol) of solution of n-butyllithium in hexane (Alpha, 2.4 M, ca. 417 ml) was added dropwise at a rate such that the temperature held below 8°. About halfway through the addition, the ice-bath was replaced by an ice-methanol bath to better control the temperature at 0° C. throughout the rest of the addition. The resultant mixture was kept in the cold bath and stirred for 15 minutes before a 41.6 g (0.427 mol) portion of isobutyric acid was added dropwise, again keeping the temperature below 0°. Final portions of the acid were rinsed into the reaction mixture with several ml of dry THF. After another 15 minutes a 57 ml (0.499 mol) portion of 1-iodo-butane was added dropwise. After the addition was completed, the ice-bath was removed and the resultant mixture was stirred for 2 hours. The ice-bath was used again as the resultant mixture was quenched by the dropwise addition of a solution of 200 ml of concentrated hydrochloric acid in 640 ml of water. The phases were separated and the aqueous phase was back-extracted with ether. The combined extract was washed with aqueous sodium bisulfite, dried (MgSO4) and evaporated in vacuo. The residue was distilled at 20 mm to yield 56.8 g of XXIX as an oil, bp 110°-113°; nmr 0.90 (3, broad t, J=5.7 Hz), 1.18 (6, s) and 1.0-2.0 (6, m).

Provenance & Evidence