Benzonitrile → Diphenylacetylene

A solution of phenylacetylene (0.439 ml; 0.409 g; 4.00 mmol) in THF (2 ml) was treated at 0° C. with n-butyllithium (1.6 ml; 4.0 mmol; 2.5 M in hexanes) and the resulting solution was allowed to warm to room temperature for 10 min. The solution was cooled to 0° C., then treated with a solution of ZnBr2 (0.901 g; 4.00 mmol) in THF (2 ml) and allowed to warm to room temperature for 30 min. Solvent was removed in vacuo, then THF (2 ml) was added. This solution was then added to a room temperature solution of benzonitrile (0.204 ml; 0.206 g; 2.00 mmol), dichlorobis(trimethylphosphine)nickel (0.0282 g; 5 mol %), trimethylphosphine (0.20 ml; 0.20 mmol; 1.0 M in THF), and tridecane (0.244 ml; 0.184 g; 1.00 mmol) in THF (2 ml). The reaction mixture was then heated to 65° C. and stirred for 44 h; then a sample was withdrawn and quenched in a mixture of 1 M sodium citrate (aq) and MTBE. GC analysis of the organic phase of the hydrolyzed reaction sample showed the presence of 1.43 mmol (72% yield) of diphenylacetylene and 0.36 mmol of benzonitrile remaining in the reaction mixture.

1. temperatureThe solution was cooled to 0° C.
2. temperatureto warm to room temperature for 30 min
3. customSolvent was removed in vacuo
4. additionTHF (2 ml) was added
5. temperatureThe reaction mixture was then heated to 65° C.
6. customthen a sample was withdrawn
7. customquenched in a mixture of 1 M sodium citrate (aq) and MTBE

ORD record

ord-6f02debe8b59483386212d73f863b302

Source dataset

uspto-grants-2006_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07105707B2