Isobutyronitrile → HCID 19384563, compound

Participants

Reaction Steps

To a stirring solution of 25.1 g of isobutyronitrile and 61.0 g of 2-(2-bromoethyl)-1,3-dioxolane in 300 ml of anhydrous ether was slowly added 310 ml of a 1.5M solution of lithiumdiisopropylamide mono(tetrahydrofuran) in cyclohexane at 0°-5° C. After removal of the cooling bath, the reaction mixture was stirred for 4 hours at room temperature, treated with a saturated solution of ammonium chloride and worked up with ether. The organic phase was washed with water, dried over anhydrous magnesium sulfate and concentrated to give 61 g of a crude oil. Purification of this material on a silica gel column (eluting system:ether-hexane 4:1) afforded 47.9 g (77.9%) of α, α-dimethyl-1,3-dioxolane -2-butanenitrile. A solution of 47.9 g of α,α-dimethyl-1,3dioxolane-2-butanenitrile in 500 ml of anhydrous ethyl ether was treated with 200 ml of 1.4M methyllithium solution in ether at 0°-5° C. The reaction mixture was stirred for 2 hours at room temperature, treated with a saturated ammonium chloride solution and worked up with ether. The ethereal solution was washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo to give 39.2 g of a crude yellow oil. This material was treated with 70 ml of 4N-sulfuric acid and refluxed for 13 hours. After being cooled, the mixture was extracted with ether. The organic phase was washed with water, a saturated solution of sodium bicarbonate, water, dried over anhydrous magnesium sulfate and concentrated to give 23.1 g (65.8%) of 6,6-dimethyl-2-cyclohexen-1-one as an orange oil. This material was used without further purification.

Provenance & Evidence