Phosphine oxide, [1,2-bis(methylene)-1,2-ethanediyl]bis[diphenyl- (9CI) synthesis

Yield:-

Reaction Conditions:

with copper(II) bis(trifluoromethanesulfonate);Cs₂CO₃ in 1,2-dichloro-ethane at 60;Inert atmosphere;Glovebox;

Steps:

General procedure (GP 1)

General procedure: To a 100 mL flask with a stirrer bar was charged with CuOTf2 (0.18 g, 10 mol %), Cs2CO3 (4.885 g, 3equiv), SPO (2.02 g, 2 equiv) and but-2-yne-1,4-diyl dimethanesulfonate (1.2114 g, 5 mmol). 1,2-DCE(50 mL) was then added, the reaction mixture was heated at 60 oC overnight followed by the addition ofWater (50 mL). The mixture was separated and the aqueous phase was extracted with CH2Cl2 (30 mL ×3). The combined organic phase was sequentially washed with brine, dried over Mg2SO4, filtered. Thefiltrate was concentrated under reduced pressure to give the crude product which was purified byrecrystallization (PE/EtOAc = 40/1) to afford Diene 1-Diene 10 as white solids.(1a) 1H NMR (500 MHz, Chloroform-d) δ 7.78 - 7.65 (m, 8H), 7.52 (t, J = 7.4 Hz,4H), 7.44 (t, J = 7.0 Hz, 8H), 6.65 (d, J = 40.2 Hz, 2H), 5.54 (d, J = 19.5 Hz, 2H). 31PNMR (202 MHz, Chloroform-d) δ 32.6. 13C NMR (126 MHz, Chloroform-d) δ 138.03(dd, J = 95.2, 2.7 Hz), 135.86 (t, J = 7.6 Hz), 132.02, 131.95 (t, J = 5.0 Hz), 131.19(dd, J = 107.4, 3.0 Hz), 128.53 (t, J = 6.3 Hz). HRMS (ESI) calcd for C28H25O2P2+[M+H]+ 455.1330, Found 455.1337

References:

Sun, Ying-Ying;Zhang, Bin;Yu, Liangbin;Cui, Ranran;Zhao, Qingyang;Zhang, Qing-Wei [Chinese Chemical Letters,2022,vol. 33,# 12,p. 5084 - 5087] Location in patent:supporting information