Diphenylamine → HCID 18544379, compound

Participants

Reaction Conditions

Reaction Steps

A mixture of 2,7 dibromo-9,9-diprop-2-enylfluorene (40.4 g, 0.1 mol), diphenylamine (8.5 g, 0.05 mol), bis(dibenzylideneacetone)palladium(0) (0.3 g, 0.522 mmol), bis(diphenylphosphino)ferrocene (0.32 g, 0.57 mmol) sodium t-butoxide (5.6 g, 0.058 mol) and toluene (350 mL) was heated at 93° C. for 18 hours under nitrogen, and cooled. The mixture was diluted with toluene and water, and the toluene phase was dried and concentrated. The residue was chromatographed over 850 g of alumina. Elution with heptane led to the recovery of unreacted dibromo-diallylfluorene, 13.38 g, 33%, m.p. 134-137° C. Elution with 10% toluene-heptane yielded the desired product, m.p. 151-153° C., 11.74 g, 48% yield. Two successive recrystallizations from hexanes did not raise the m.p., 150.4-152.8° C. Mass Spec: m/z 491,493 (M+). IR (KBr): 3068, 2977,1639,1589,1489 cm−1. Anal. Calcd. for C31H26BrN; C, 75.61%; H, 5.32%; N, 2.84%; Br, 16.23%. Found: C, 75.56%; H, 5.27%; N, 2.68%. (Br- 17.1%). This reaction also produced some 2,7-bis(diphenylamino)-9,9-diallylfluorene, 1.09 g, m.p. 179-183° C. Mass Spec: m/z 580 (M+).

Provenance & Evidence