Fluorosulfuric acid, (1-methylethylidene)di-4,1-phenylene ester synthesis

Yield:38184-64-4 100%

Reaction Conditions:

Stage #1: BPAwith triethylamine in dichloromethane at 20; for 0.166667 h;
Stage #2: with sulfuryl fluoride in dichloromethane at 20;Sealed tube;

Steps:

2.A.i 2A(i). Preparation of propane-2,2-diylbis(4,l-phenylene) difluorosulfonate (BPA- ()S()₂F) from WO 2014/089078 to Dong et al.

2A(i). Preparation of propane-2,2-diylbis(4,l-phenylene) difluorosulfonate (BPA- ()S()₂F) from WO 2014/089078 to Dong et al. A 2-liter single-neck round-bottom flask was charged with bisphenol A (114.9 g, 0.5 mol), CH₂CI₂ (DCM; 1 L) and triethylamine (Et₃N; 174 mL, 1.25 mol, 2.5 equivalents). The mixture was stirred at room temperature for 10 minutes (min). The reaction flask was then sealed with a septum, the atmosphere above the solution was removed with gentle vacuum, and SO₂F₂ gas (sulfuryl fluoride, VIKA E) was introduced by needle from a balloon filled with the gas. For large scale reactions such as this, depletion of the sulfuryl fluoride from the balloon is easily observed, and more reagent is introduced with a fresh balloon when required. For small scale reactions, SO₂F₂ is used in excess. These reactions can be easily followed by thin layer chromatography (TLC). The reaction mixture was vigorously stirred at room temperature for about 2 to 4 hours, monitoring by GC-MS and TLC. After completion, the solvent was removed by rotary evaporation, the residue was dissolved in ethyl acetate (EtOAc; 1 L), and the solution was washed with IN HC1 (2 x 500 mL) and brine (2 x 500 mL). The organic phase was dried over anhydrous Na₂S0₄ and concentrated. The resulting solid was dried under high vacuum at about 60 °C overnight to afford BPA-OS0₂F as a white crystalline solid in quantitative yield (typically about 197 g, 100% yield). Melting point (MP) 48-49 °C. 1H NMR (400 MHz, CDC1₃) δ 7.34- 7.32 (m, 2H), 7.28-7.26 (m, 2H), 1.72 (s, 3H); ¹³C NMR (101 MHz, CDC1₃) δ 150.4, 148.2, 128.7, 120.5, 42.9, 28.4, 30.7; ¹⁹F NMR (376 MHz, CDC1₃) δ +37.0; GC-MS (t_R): 7.2 min; EI- MS (m/z): 392 [M]⁺.

References:

WO2016/209920,2016,A1 Location in patent:Page/Page column 36