Isopropanol → Methyl 3-oxocyclohexane-1-carboxylate

Ruthenium (IV) oxide hydrate (1.47 g, 11.1 mmol) and sodium bromate (100 g, 664 mmol) were combined in diethyl ether (600 mL) and water (300 mL). The resulting black mixture was stirred for 10 min and then cooled in an ice bath. Methyl 3-hydroxycyclohexanecarboxylate (35 g, 221 mmol) was dissolved in ether (to bring total volume to 100 mL) and was added dropwise to the ice cold reaction mixture. The temperature was not allowed to go above 30° C. The reaction mixture was stirred for 1 h with the reaction temperature at ˜15° C. Isopropanol was carefully added to the reaction mixture at a rate necessary to keep the reaction temperature at ˜27° C. The layers were separated and the organic layers were washed with ether. The combined organics were washed with saturated aqueous NaHCO3 solution and brine. The organics were then dried over MgSO4, filtered, and concentrated to provide methyl 3-oxocyclohexanecarboxylate (34.5 g, 100% yield) which was used without further purification. 1H NMR (400 MHz, CDCl3) δ 3.68 (s, 3H), 2.79 (m, 1H), 2.52 (d, J=7.78 Hz, 2H), 2.23-2.42 (m, 2H), 1.98-2.15 (m, 2H), 1.82 (d, J=10.29 Hz, 1H), 1.61-1.77 (m, 1H).

1. temperaturecooled in an ice bath
2. customto go above 30° C
3. stirringThe reaction mixture was stirred for 1 h with the reaction temperature at ˜15° C
4. customat ˜27° C
5. customThe layers were separated
6. washthe organic layers were washed with ether
7. washThe combined organics were washed with saturated aqueous NaHCO3 solution and brine
8. dry with materialThe organics were then dried over MgSO4
9. filtrationfiltered
10. concentrationconcentrated

ORD-Eintrag

ord-d4772c99cde24cd8876d2da570c96d18

Quelldatensatz

uspto-grants-2015_11

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09187464B2