2-hex-5-enyloxirane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 16 ml of an n-butyllithium solution (40 mmol, 16 ml, 2.5 M in hexane) were added dropwise to a solution of 6.64 g (40 mmol) of fluorene in 80 ml of diethyl ether at room temperature and the reaction mixture was stirred for another hour. A solution of 4.8 g (38 mmol) of 1,2-epoxy-7-octene in 20 ml of diethyl ether was then slowly added thereto. After the reaction mixture had been stirred for another hour, 7.6 g (40 mmol) of p-toluenesulfonyl chloride was slowly added as a solid. Separately from this first reaction mixture, a solution of a mixture of 7.4 g (40 mmol) of 2-methyl-3H-cyclopenta[b][1]benzothiophene/2-methyl-1H-cyclopenta[b][1]benzothiophene in 70 ml of diethyl ether was admixed with 16 ml of an n-butyllithium solution (40 mmol, 16 ml, 2.5 M in hexane) and the mixture was stirred for another hour. The second reaction mixture was added dropwise to the first reaction mixture comprising 2-(9H-fluoren-9-yl)oct-7-enyl p-toluenesulfonate, the resulting mixture was stirred for 18 hours and subsequently subjected to an aqueous work-up. After phase separation, the organic phase was washed with water, dried over magnesium sulfate and the solvent was removed under reduced pressure. This gave 17.6 g of a deep orange oil which was chromatographed on silica gel (dichloromethane/hexane 1:9). This gave 3.07 g of (1a) (yield 17.5%) as a viscous yellow oil. After the reaction mixture had been stirred for another hour the mixture was stirred for another hour The second reaction mixture the resulting mixture was stirred for 18 hours After phase separation the organic phase was washed with water dried over magnesium sulfate the solvent was removed under reduced pressure This gave 17.6 g of a deep orange oil which was chromatographed on silica gel (dichloromethane/hexane 1:9)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 16 ml of an n-butyllithium solution (40 mmol, 16 ml, 2.5 M in hexane) were added dropwise to a solution of 6.64 g (40 mmol) of fluorene in 80 ml of diethyl ether at room temperature and the reaction mixture was stirred for another hour. A solution of 4.8 g (38 mmol) of 1,2-epoxy-7-octene in 20 ml of diethyl ether was then slowly added thereto. After the reaction mixture had been stirred for another hour, 7.6 g (40 mmol) of p-toluenesulfonyl chloride was slowly added as a solid. Separately from this first reaction mixture, a solution of a mixture of 7.4 g (40 mmol) of 2-methyl-3H-cyclopenta[b][1]benzothiophene/2-methyl-1H-cyclopenta[b][1]benzothiophene in 70 ml of diethyl ether was admixed with 16 ml of an n-butyllithium solution (40 mmol, 16 ml, 2.5 M in hexane) and the mixture was stirred for another hour. The second reaction mixture was added dropwise to the first reaction mixture comprising 2-(9H-fluoren-9-yl)oct-7-enyl p-toluenesulfonate, the resulting mixture was stirred for 18 hours and subsequently subjected to an aqueous work-up. After phase separation, the organic phase was washed with water, dried over magnesium sulfate and the solvent was removed under reduced pressure. This gave 17.6 g of a deep orange oil which was chromatographed on silica gel (dichloromethane/hexane 1:9). This gave 3.07 g of (1a) (yield 17.5%) as a viscous yellow oil. After the reaction mixture had been stirred for another hour the mixture was stirred for another hour The second reaction mixture the resulting mixture was stirred for 18 hours After phase separation the organic phase was washed with water dried over magnesium sulfate the solvent was removed under reduced pressure This gave 17.6 g of a deep orange oil which was chromatographed on silica gel (dichloromethane/hexane 1:9)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The significance of the conjugated epoxyalkene system in the reactants of this invention is demonstrated by the hydrogenation of 3,4-epoxy-1-butene and 1,2-epoxy-7-octene under mild conditions of 50°-55° C. and 4.6 bars hydrogen pressure using a sulfur-modified Raney-nickel catalyst. Such hydrogenation of 3,4-epoxy-1-butene gives 74% crotyl alcohol and 23% 3-buten-1-ol whereas the hydrogenation of 1,2-epoxy-7-octene (wherein the double bond and epoxy groups are separated by four carbon atoms) gives a mixture of starting material, 1,2-epoxyoctane, and isomers of the starting material.