9H-Fluoren-9-one, 3,6-bis(diphenylamino)- synthesis

Yield:1338442-27-5 80%

Reaction Conditions:

with tri-tert-butyl phosphine;bis(dibenzylideneacetone)-palladium⁽⁰⁾;sodium t-butanolate in toluene; for 18 h;Reflux;Inert atmosphere;Buchwald-Hartwig Coupling;

Steps:

4.2.2. Synthesis of 3,6-bis(diphenylamino)-9H-fluoren-9-one (FO1)

A mixture of 3,6-dibromo-9-fluorenone (0.500 g, 1.48 mmol), diphenylamine(0.440 g, 3.25 mmol) and sodium tert-butoxide (0.936 g,9.75 mmol) was added to a suspension of Pd(dba)2 (0.042 g,0.074 mmol) and PtBu3 (0.11 mL, 0.11 mmol, 1M in toluene) in anhydrousand deoxygenated toluene (22 mL), was heated to reflux undernitrogen for 18 h. After cooling to room temperature, the mixture wasfiltered on Celite and the solvent was removed under pressure. Theresidue was dissolved in dichloromethane and washed with water. Thecombined organic phase was dried on Na2SO4 and concentrated byrotary evaporation. The residue was purified by column chromatography(silica gel, hexane/CH2Cl2:1/1) to give the product as an orangesolid in a yield of 80%. 1H NMR (400 MHz, CDCl3): δ 7.48 (d,J=8.2 Hz, 2H), 7.31 (d, J=7.1 Hz, 4H), 7.29 (d, J=7.3 Hz, 4H),7.14-7.09 (m, 12H), 7.02 (d, J=1.9 Hz, 2H), 6.78 (dd, J=2.0, 8.2 Hz,2H). 13C NMR (100 MHz, CDCl3): δ 190.70, 153.24, 146.53, 145.04,129.39, 128.31, 125.41, 124.96, 124.21, 121.10, 113.14. LCMS (APCI)calcd for C37H26N2O [M + H+] 515.20; found 515.10. FT-IR (KBr):ν1686, 1587, 1489, 1384, 1327, 1280, 1256, 1108. Elemental analysiscalcd for C37H26N2O: C, 86.35; H, 5.09; N, 5.44; O, 3.11. Found C,86.57; H, 5.25; N, 5.31.

References:

Manni, Francesca;Fabiano, Eduardo;Clarkson;Accorsi, Gianluca;Fieramosca, Antonio;Nobile, Concetta;Saracino, Michela;Zanelli, Alberto;Farran, Angeles;Sanvitto, Daniele;Gigli, Giuseppe;Capodilupo, Agostina-Lina [Dyes and Pigments,2019,vol. 171,art. no. 107780]