Sodium Carbonate → Benzyl (2-oxocyclohexyl)carbamate

HRID 1776229Notes

Reaction equation

HRID 1776229 reaction equation
[OH:1][CH:2]1[CH2:7][CH2:6][CH2:5][CH2:4][CH:3]1[NH:8][C:9](=[O:18])[O:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O.C(=O)([O-])[O-].[Na+].[Na+].C(=O)(O)[O-].[Na+]>CC(C)=O.O>[O:1]=[C:2]1[CH2:7][CH2:6][CH2:5][CH2:4][CH:3]1[NH:8][C:9](=[O:18])[O:10][CH2:11][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 516892Sodium BicarbonateHCID 14785668benzyl N-(2-hydroxycyclohexyl)carbamateHCID 131709961Jones' reagent

Product 1

HCID 14219048Benzyl (2-oxocyclohexyl)carbamateYield 79.4%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

To a solution of benzyl (2-hydroxycyclohexyl)carbamate (4.200 g, 16.8 mmol) in acetone (15 mL) was added Jones reagent dropwise over several minutes (with room temperature water bath cooling of reaction), and the reaction mixture was stirred at room temperature for 2.5 hrs. Solutions of saturated aqueous sodium carbonate and then saturated aqueous sodium bicarbonate were added until the solution was adjusted to neutral pH, and the resulting mixture extracted with ethyl acetate (3×). The combined organic layers were washed with saturated aqueous sodium chloride, dried (anhydrous sodium sulfate), filtered, and concentrated in vacuo. The crude product was purified by silica gel chromatography (10-50% ethyl acetate/hexanes) to give a clear liquid (3.3 g). 1H NMR (300 MHz, CDCl3) δ 7.36-7.29 (m, 5H), 5.75 (br s, 1H), 5.10 (s, 2H), 4.29-4.25 (m, 1H), 2.65 (m, 1H), 2.57-2.50 (m, 1H), 2.43-2.33 (m, 1H), 2.17-2.10 (m, 1H), 1.88-1.60 (m, 3H), 1.48-1.34 (m, 1H). ESI (m/z): 248.0 (M+H).

Workup

  1. extractionthe resulting mixture extracted with ethyl acetate (3×)
  2. washThe combined organic layers were washed with saturated aqueous sodium chloride
  3. dry with materialdried (anhydrous sodium sulfate)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude product was purified by silica gel chromatography (10-50% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-a311c89eb7f44267b93bf48f0ec9abf5
Source dataset
uspto-grants-2016_02
Patent number
US09265772B2

Reaction notes

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