Sodium hydride → 6-Bromo-4-methyl-7-trifluoromethyl-2-(2-trimethylsilanyl-ethoxymethyl)-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one

To a 0° C. solution of 6-bromo-4-methyl-7-trifluoromethyl-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one (0.364 g, 1.0 mmol) in THF (50 mL) was added sodium hydride (60% in mineral oil, 0.080 g, 2 mmol) and the reaction mixture was stirred for 0.5 h. (2-(chloromethoxy)ethyl)trimethylsilane (0.250 g, 1.5 mmol) was added and the mixture was stirred at ambient temperature for 2 h. The reaction was quenched with water (100 mL) and the aqueous mixture was extracted with EtOAc (2×30 mL). The combined organic layers were washed with brine (30 mL), dried over Na2SO4, filtered and evaporated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 3-20% EtOAc in petroleum ether) to give 6-bromo-4-methyl-7-trifluoromethyl-2-(2-trimethylsilanyl-ethoxymethyl)-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one as a white solid (0.330 g, 67%). 1H NMR (CDCl3, 400 MHz): δ 7.32 (s, 1H), 7.16 (s, 1H), 5.11 (q, J=8.8 Hz, 2H), 4.75 (d, J=12.6 Hz, 1H), 4.69 (q, J=6.4 Hz, 1H), 4.57 (d, J=12.6 Hz, 1H), 3.65 (t, J=8.4 Hz, 2H), 1.51 (d, J=6.8 Hz, 3H), 0.99 (t, J=8.4 Hz, 2H), 0.01 (s, 9H).

1. additionwas added
2. customThe reaction was quenched with water (100 mL)
3. extractionthe aqueous mixture was extracted with EtOAc (2×30 mL)
4. washThe combined organic layers were washed with brine (30 mL)
5. dry with materialdried over Na2SO4
6. filtrationfiltered
7. customevaporated in vacuo
8. customThe residue was purified by column chromatography on silica gel (eluting with 3-20% EtOAc in petroleum ether)

ORD-Eintrag

ord-053b9899f3de4a0f862ae38b00529a06

Quelldatensatz

uspto-grants-2015_08

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09115151B2