4,4-diphenylbutan-2-one

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

Procedure: The 1,2-epoxy-4,4-diarylbutane starting materials can alternatively be prepared by reaction of dimethylsulfonium methylide or dimethyloxosulfonium methylide with an appropriate diarylalkyl aldehyde or a diarylalkyl ketone. For example, reaction of an aldehyde such as 3,3-diphenylpropanal with either dimethylsulfonium methylide or dimethyloxosulfonium methylide in approximately equimolar amounts provides 1,2-epoxy-4,4-diphenylbutane. Similarly, reaction of a diarylalkyl ketone such as methyl-(2,2-diphenylethyl) ketone with either dimethylsulfonium methylide or dimethyloxosulfonium methylide provides 1,2-epoxy-4,4-diphenyl-2-methylbutane. Such reactions typically are carried out in a solvent such as dimethyl sulfoxide or tetrahydrofuran, and normally at a reduced temperature of about 0° C. Dimethylsulfonium methylide is prepared by reaction of trimethylsulfonium iodide with methylsulfinylcarbanion, while demethyloxosulfonium methylide is prepared by reaction of trimethyloxosulfonium iodide with sodium hydride. Such reactions are more fully discussed by Corey et al., J. Am. Chem. Soc., 84, 867(1962) and J. Am. Chem. Soc., 84, 3782 (1962).

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

Procedure: The 1,2-epoxy-4,4-diarylbutane starting materials can alternatively be prepared by reaction of dimethylsulfonium methylide or dimethyloxosulfonium methylide with an appropriate diarylalkyl aldehyde or a diarylalkyl ketone. For example, reaction of an aldehyde such as 3,3-diphenylpropanal with either dimethylsulfonium methylide or dimethyloxosulfonium methylide in approximately equimolar amounts provides 1,2-epoxy-4,4-diphenylbutane. Similarly, reaction of a diarylalkyl ketone such as methyl-(2,2-diphenylethyl) ketone with either dimethylsulfonium methylide or dimethyloxosulfonium methylide provides 1,2-epoxy-4,4-diphenyl-2-methylbutane. Such reactions typically are carried out in a solvent such as dimethyl sulfoxide or tetrahydrofuran, and normally at a reduced temperature of about 0° C. Dimethylsulfonium methylide is prepared by reaction of trimethylsulfonium iodide with methylsulfinylcarbanion, while dimethyloxosulfonium methylide is prepared by reaction of trimethyloxosulfonium iodide with sodium hydride. Such reactions are more fully discussed by Corey et al., J. Am. Chem. Soc., 84, 867(1962) and J. Am. Chem. Soc., 84, 3782 (1962).

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

Procedure: The title compound, mp 146°-148° C., was prepared from 4,4-diphenylbutan-2-one (3.50 g, 0.015 mol), 2.6-diisopropylphenyl isocyanate (3.17 g, 0.015 mol) and lithium diisopropylamide (0.015 mol) using the procedure described in Example 1.

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

Procedure: To a solution of β-oxo-δ-phenyl-benzene pentanoic acid ethyl ester (8.0 g, 0.026 mol) in 47.5 mL xylenes (15.0 eq), 1,4-diazabicyclo[2.2.2]octane (30.28 g, 0.269 mol, 10 eq) was added and the reaction mixture was first heated to reflux for 5 hours and then stirred at room temperature for 16 hours (D. H. Miles, et al, J. Org. Chem. 39, 2647 (1974)). The reaction mixture was then acidified (pH 1) with approximately 10 mL 5% HCl. This heterogeneous mixture was then filtered through Celite, thoroughly washing the bed of Celite with ether. The organic layer was washed with water, dried (MgSO4), and concentrated in vacuo to give a crude oil. Purification by flash chromatography (silica gel, 15% EtOAc/hexane) yielded 4.0 g (0.018 mol, 70%) of the desired product. the reaction mixture was first heated to reflux for 5 hours This heterogeneous mixture was then filtered through Celite thoroughly washing the bed of Celite with ether The organic layer was washed with water dried (MgSO4) concentrated in vacuo to give a crude oil Purification by flash chromatography (silica gel, 15% EtOAc/hexane)