Chloroform → 4-Oxocyclohexyl 4-methylbenzene-1-sulfonate

HRID 1864014Notes

Reaction equation

HRID 1864014 reaction equation
[OH:1][CH:2]1[CH2:7][CH2:6][CH:5]([O:8][S:9]([C:12]2[CH:17]=[CH:16][C:15]([CH3:18])=[CH:14][CH:13]=2)(=[O:11])=[O:10])[CH2:4][CH2:3]1.C(Cl)(Cl)Cl.C1C=C[NH+]=CC=1.[O-][Cr](Cl)(=O)=O>CC(O)=O.CCOCC>[O:1]=[C:2]1[CH2:3][CH2:4][CH:5]([O:8][S:9]([C:12]2[CH:13]=[CH:14][C:15]([CH3:18])=[CH:16][CH:17]=2)(=[O:11])=[O:10])[CH2:6][CH2:7]1

Participants

6

Reactant 3

HCID 6212Chloroform2×HCID 13138782HCID 13138782, compoundHCID 178418287HCID 178418287, compound2×

Product 1

HCID 2820764-Oxocyclohexyl 4-methylbenzene-1-sulfonateYield 59.8%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 3283Diethyl EtherSolvent

Procedure

step 2—To a solution of 76 (2.23 g, 8.22 mmol) and CHCl3 (30 mL) was added PCC (1.77 g, 8.22 mmol) and CHCl3 (20 mL). One drop of HOAc was added and the mixture was stirred at RT for 2.5 days. An additional 1.77 g (8.22 mmol) of PCC was added and stirring continued at RT for an additional 6 h. The reaction was diluted with Et2O and filtered through a bed of SiO2. The cake was washed with Et2O and the filtrate was passed through a second plug of SiO2 while washing the cake with Et2O. The filtrate was stripped in vacuo and the crude material was purified by SiO2 chromatography eluting with a DCM/MeOH gradient (0 to 4% MeOH). The recovered material was re-purified by SiO2 chromatography eluting with a gradient of hexane/acetone (15 to 25% acetone) to afford 1.32 g (58%) of toluene-4-sulfonic acid 4-oxo-cyclohexyl ester (78) as a colorless oil: 1H NMR (CDCl3, 300 MHz): δ 7.83 (d, 2H), 7.37 (d, 2H), 4.92-4.86 (m, 1H), 2.78-2.53 (m, 2H), 2.46 (s, 3H), 2.34-2.13 (m, 4H), 2.03-1.83 (m, 2H).

Workup

  1. stirringstirring
  2. waitcontinued at RT for an additional 6 h
  3. filtrationfiltered through a bed of SiO2
  4. washThe cake was washed with Et2O
  5. washwhile washing the cake with Et2O
  6. customthe crude material was purified by SiO2 chromatography
  7. washeluting with a DCM/MeOH gradient (0 to 4% MeOH)
  8. customThe recovered material was re-purified by SiO2 chromatography
  9. washeluting with a gradient of hexane/acetone (15 to 25% acetone)

Sources & evidence

ORD record
ord-93618549fb61467f8d89bfa3bb2efbe6
Source dataset
uspto-grants-2009_12
Patent number
US07625891B2

Reaction notes

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