Methyl iodide → HCID 178503847, compound

HRID 1257723Notes

Reaction equation

HRID 1257723 reaction equation
[C:1]([O:5][C:6]([NH:8][C@H:9]1[CH2:14][CH2:13][C@H:12]([S:15][C:16](=O)C)[CH2:11][CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C[O-].[Na+].CI>CO.C(OCC)(=O)C.O>[C:1]([O:5][C:6](=[O:7])[NH:8][C@H:9]1[CH2:10][CH2:11][C@H:12]([S:15][CH3:16])[CH2:13][CH2:14]1)([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 3

HCID 6328Methyl iodideHCID 10942334Sodium MethoxideHCID 178477148HCID 178477148, compound

Product 1

HCID 178503847HCID 178503847, compoundYield 44%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

A stirred solution of trans thioacetic acid S-(4-tert-butoxycarbonylamino-cyclohexyl) ester (1.31 g, 4.80 mmol) in methanol (31 mL) was treated with sodium methoxide (1.04 g, 19.2 mmol) followed by methyl iodide (0.45 mL, 7.2 mmol). The mixture was stirred at ambient temperature for 3 hours then diluted with ethyl acetate and water. 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 sulphate and concentrated under vacuum to give crude product. Purification by column chromatography on silica gel (10% ethyl acetate in cyclohexane) gave 516 mg (44%) of trans (4-methylsulfanyl-cyclohexyl)-carbamic acid tert-butyl ester as a white solid. 1H NMR (400 MHz, CDCl3) δ: 4.36 (br s, 1H), 3.44 (br s, 1H), 2.72-2.62 (m, 1H), 2.40 (s, 3H), 2.09 (d, 6H), 1.45 (s, 9H), 1.24-1.10 (m, 2H).

Workup

  1. customThe phases were separated
  2. extractionthe aqueous phase was extracted with ethyl acetate (×2)
  3. washThe combined organic extracts were washed with 10% aqueous citric acid solution, saturated sodium hydrogen carbonate solution, and brine
  4. dry with materialdried with sodium sulphate
  5. concentrationconcentrated under vacuum
  6. customto give crude product
  7. customPurification by column chromatography on silica gel (10% ethyl acetate in cyclohexane)

Sources & evidence

ORD record
ord-f4a51b80f8de4200b62831fd7ff6dac2
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

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