Trimethylolethane → (5-Methyl-2-oxo-1,3-dioxan-5-yl)methyl perfluorophenyl carbonate

To a 100 mL round bottom flask, 1,1,1-tris(hydroxymethyl)ethane (2.0 g, 16.7 mmol) was combined with bis(pentafluorophenyl)carbonate (15.1 g, 38.3 mmol, 2.3 eq.) and cesium fluoride (0.76 g, 5.0 mmol, 0.3 eq.) in anhydrous tetrahydrofuran (THF) (11.9 mL) and stirred for four hours at room temperature. Initially the reaction was heterogeneous, but after one hour the reaction formed a clear homogeneous solution. The reaction was concentrated in vacuo (100 mm Hg, 30° C.) and the residue was dissolved in methylene chloride (˜50 mL). Upon standing (˜10 min), the pentafluorophenol byproduct precipitated from solution and was recovered by filtration. The mother liquor was washed with aqueous sodium bicarbonate (3×50 mL) until the pH of aqueous layer was ˜8 and then with brine (1×50 mL). The organic layer was separated and dried over anhydrous sodium sulfate. The solution was concentrated to give the crude product that was purified by recrystallization. The crude product was dissolved in ethyl acetate (24 mL) at 65° C. n-Hexane (35 mL) was added at the same temperature, and the resulting solution was allowed to cool to room temperature. After stirring the solution overnight, the white crystalline product TMCPFP was separated by filtration (4.0 g, 67% yield). m.p. 130-131° C. 1H NMR (CDCl3, 400 Hz) 1.22 (s, 3H), 4.23 (d, 2H, J=11 Hz), 4.37 (s, 2H), 4.38 (d, 2H, J=11 Hz). 19F NMR (CDCl3, 376 Hz) −154.3-154.3 (m, 2F), −157.8 (t, 1F, J=22 Hz), −162.6˜-162.7 (m, 2F). 13C NMR (CDCl3, 100 Hz) 16.8, 32.6, 70.3, 73.0, 125.4, 137.9, 140.1, 141.3, 147.4, 151.1.

1. customafter one hour the reaction formed a clear homogeneous solution
2. concentrationThe reaction was concentrated in vacuo (100 mm Hg, 30° C.)
3. dissolutionthe residue was dissolved in methylene chloride (˜50 mL)
4. custom(˜10 min)
5. customthe pentafluorophenol byproduct precipitated from solution
6. filtrationwas recovered by filtration
7. washThe mother liquor was washed with aqueous sodium bicarbonate (3×50 mL) until the pH of aqueous layer
8. customThe organic layer was separated
9. dry with materialdried over anhydrous sodium sulfate
10. concentrationThe solution was concentrated

ORD record

ord-93b560e3bed74d4ebd22fb4f9bdce38b

Source dataset

uspto-grants-2013_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08389746B2