Acrylonitrile → Tri-o-tolylphosphine

Participants

Reaction Conditions

Reaction Steps

A stock solution of 0.0561 g (2.5×10-4 mol) of palladium acetate and 0.304 g (10-3 mol) of tri-o-tolylphosphine in 100 ml of N,N-dimethylformamide (DMF) is prepared under argon. 1 ml of stock solution [containing 0.000561 g (2.5×10-6 mol) of palladium acetate, Pd content=0.01 mol %, and 0.00304 g (10-5 mol) of tri-o-tolylphosphine], 4.63 g (25 mmols) of 4-bromobenzaldehyde, 2.08 ml (31.25 mmols) of acrylonitrile and 2.56 g (31.25 mmols) of anhydrous sodium acetate are then added, under argon, to 9 ml of DMF, and the mixture is stirred at 120° C. for 6 hours. The mixture is then poured into 100 ml of water, which is extracted with twice 25 ml of methylene dichloride, and the extract is dried for 15 minutes with 5 g of magnesium sulfate. After the methylene dichloride and a little DMF have been removed on a rotary evaporator, the crude product is distilled in vacuo. 3.2 g (20 mmols) of 4-formylcinnamonitrile are obtained in the form of a nearly white solid; yield 81% of theory (conversion figure 8100); melting point 92°-98° C.; boiling point 157°-163° C./133 Pa. Analysis for C10H7NO (molecular weight 157.17): calculated C 76.42: H 4.49; N 8.91, found C 76.35; H 4.60; N 9.01. The product is a mixture of isomers consisting of approx. 77% of trans-isomer and 23% of cis-isomer.

Provenance & Evidence