Carbon Dioxide → 3-Ethylpentanoic acid

Participants

Reaction Steps

Into a 2 L 3-necked flask equipped with a condenser attached to a nitrogen inlet tube, a mechanical stirrer, and a 500 mL addition funnel, was added magnesium turnings (18.7 g, 0.769 mol), which were crushed in a mortar and pestle. The reaction was placed under argon. Enough THF was added to just cover the magnesium turnings. With the mechanical stirrer turned off, 2-ethyl-1-bromobutane (155.5 g 0.70 mol) was placed in the addition funnel and about 2-3 mL was added to the magnesium turnings. This area of the THF solution was then heated with a heat gun until vigorous boiling occurred. The remaining 2-ethyl-1-bromobutane was diluted with THF (200 mL) and added dropwise to the stirred reaction mixture at a rate that maintained a gentle reflux. The addition was completed in approximately 3-4 h. After 24 h, the gray slurry was diluted with THF (500 mL), and gently heated with a hot water bath until a homogeneous solution was formed. The warm solution was then poured into two 4 L Nalgene beakers each containing crushed solid carbon dioxide (1 L). The slush was stirred well with a Teflon rod and allowed to stand at room temperature. After 18 h, the solutions were diluted with ethyl acetate (500 mL), and washed with 2N hydrochloric acid (500 mL). The aqueous layer was saturated with sodium chloride and extracted once more with ethyl acetate (500 mL). The combined ethyl acetate layers were dried (Na2SO4). Concentration under reduced pressure gave a wet residue, which was taken up in methylene chloride (600 mL), dried (Na2SO4), and concentrated at 56° C. under reduced pressure to give the title compound as an oil (91 g, 99.8%): 1H NMR (DMSO-d6, 500 MHz): δ11.95 (broad s, 1H), 2.11 (d, J=6.9 Hz, 2H), 1.60 (septet, J=6.5 Hz, 1H), 1.28 (m, 4H), 0.81 (t, J=7.5 Hz, 6H); MS(−ESI): [M—H]−, 129 (100%); Anal. Calc. for C7H14O2: C, 64.58; H, 10.84. Found: C, 64.61; H, 11.11.

Provenance & Evidence