Ethyl Acetate → HCID 178477148, compound

HRID 1257722Notes

Reaction equation

HRID 1257722 reaction equation
CC(C)([O-])C.[K+].[C:7]([OH:10])(=[S:9])[CH3:8].[C:11]([O:15][C:16]([NH:18][C@@H:19]1[CH2:24][CH2:23][C@H:22](OS(C)(=O)=O)[CH2:21][CH2:20]1)=[O:17])([CH3:14])([CH3:13])[CH3:12].C(OCC)(=O)C>CN(C=O)C.O>[C:11]([O:15][C:16]([NH:18][C@H:19]1[CH2:24][CH2:23][C@H:22]([S:9][C:7](=[O:10])[CH3:8])[CH2:21][CH2:20]1)=[O:17])([CH3:14])([CH3:12])[CH3:13]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 23665647Potassium tert-butoxideHCID 178418634HCID 178418634, compoundHCID 178454080HCID 178454080, compound

Product 1

HCID 178477148HCID 178477148, compoundYield 26%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
80 °C

Procedure

To a stirred suspension of potassium tert-butoxide (0.78 g, 7.00 mmol) and DMF (10 mL), thioacetic acid (0.50 mL, 7.0 mmol) was added at 0° C. The mixture was stirred for ˜5 mins and then a solution of cis methanesulfonic acid 4 tert-butoxycarbonylamino-cyclohexyl ester (1.36 g, 4.70 mmol) in DMF (4.1 mL) was added. The mixture was heated to 80° C. for 3.75 hours and was then poured into a mixture of ethyl acetate (50 mL) and water (50 mL). The phases were separated and the aqueous phase was extracted with ethyl acetate (×2). The combined organic extracts were washed with 10% aqueous citric acid solution, saturated sodium hydrogen carbonate solution, and brine, dried with sodium sulfate and concentrated under vacuum. Purification by column chromatography on silica gel (ethyl acetate/cyclohexane, 1:6) gave 325 mg (26%) of trans thioacetic acid S-(4-tert-butoxycarbonylamino-cyclohexyl) ester as an orange solid. 1H NMR (400 MHz, CDCl3) δ: 4.38 (br s, 1H), 3.42 (br s, 1H), 3.33 (m, 1H), 2.29 (s, 3H), 2.02 (m, 5H), 1.44 (s, 9H), 1.26-1.25 (m, 3H).

Workup

  1. additionwas added at 0° C
  2. customThe phases were separated
  3. extractionthe aqueous phase was extracted with ethyl acetate (×2)
  4. washThe combined organic extracts were washed with 10% aqueous citric acid solution, saturated sodium hydrogen carbonate solution, and brine
  5. dry with materialdried with sodium sulfate
  6. concentrationconcentrated under vacuum
  7. customPurification by column chromatography on silica gel (ethyl acetate/cyclohexane, 1:6)

Sources & evidence

ORD record
ord-72fca6a4946b44a49923693232902b6d
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

Loading…