Chlorotrimethylsilane → HCID 11021192, compound

Temperature

0 °C

Into a mixture of 0.42 g (17.5 mmol) of Mg turnings, 1.92 g (17.7 mmol) of TMSCl and 10 mL DMF, was added 1.60 g (5.9 mmol) of bromodifluoromethyl phenyl sulfone (23). The reaction mixture was stirred at 0° C. for 30 min, and at room temperature for another 30 min until 19F NMR showed all of 23 was consumed (the yield of 20 was 76% and by-product TMSCF2TMS, 18% by 19F NMR analysis). The reaction mixture was washed with ice water followed by extraction with pentane (10 mL×4). The pentane phase was washed with cold 98% sulfuric acid (10 mL×3) to remove most of the siloxane and silanol. Then the pentane solution was washed with cold NaHCO3 aqueous solution three times until the pH paper indicated neutral pH. After drying over MgSO4 and solvent removal, the crude product was further purified by fractional distillation and then recrystallization at −20° C. to give 0.40 g crystalline product 20, m.p. 40˜42° C., yield 55%. 1H NMR (500 MHz, CDCl3): δ0.24 (s, 18H). 13C NMR (125 MHz, CDCl3): δ−4.0 (m, CH3); 126.6 (tt, 1JC-F=265.0 Hz; 2JC-F=45.9 Hz). 19F NMR (470 MHz, CDCl3): δ−122.3.

1. waitat room temperature for another 30 min until 19F NMR showed
2. customall of 23 was consumed (the yield of 20
3. washThe reaction mixture was washed with ice water
4. extractionfollowed by extraction with pentane (10 mL×4)
5. washThe pentane phase was washed with cold 98% sulfuric acid (10 mL×3)
6. customto remove most of the siloxane and silanol
7. washThen the pentane solution was washed with cold NaHCO3 aqueous solution three times until the pH paper
8. dry with materialAfter drying over MgSO4 and solvent removal
9. distillationthe crude product was further purified by fractional distillation
10. customrecrystallization at −20° C.

ORD record

ord-de1617a4e2134a638e0bb9b80d089aea

Source dataset

uspto-grants-2004_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06803477B2