Triethylamine → 2-(4-Methoxycarbonylphenylthio)-2-tert.butoxycarbonylcyclohexanone

HRID 467340Notes

Reaction equation

HRID 467340 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([S:11]Cl)=[CH:7][CH:6]=1)=[O:4].[C:13]([O:17][C:18]([CH:20]1[CH2:25][CH2:24][CH2:23][CH2:22][C:21]1=[O:26])=[O:19])([CH3:16])([CH3:15])[CH3:14].C(N(CC)CC)C>C(Cl)Cl>[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([S:11][C:20]2([C:18]([O:17][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:19])[CH2:25][CH2:24][CH2:23][CH2:22][C:21]2=[O:26])=[CH:7][CH:6]=1)=[O:4]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 12431017tert-Butyl 2-oxocyclohexane-1-carboxylateHCID 15584701Methyl 4-(chlorosulfanyl)benzoate

Product 1

HCID 197556512-(4-Methoxycarbonylphenylthio)-2-tert.butoxycarbonylcyclohexanoneYield 56.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

A solution 10.8 g (53.2 mmol) of 4-methoxycarbonylphenylsulphenic acid chloride in 20 ml of methylene chloride (analytically pure) is added dropwise to a solution of 11.4 g (57 mmol) of 2-tert.butoxycarbonylcyclohexanone and 7.5 g (75 mmol) of triethylamine in 150 ml of methylene chloride. When the dropwise addition has ended the mixture is subsequently stirred for 15 mins. and is then diluted with methylene chloride and the organic phase is washed with 2N sulphuric acid and a saturated bicarbonate solution, dried with sodium sulphate and concentrated by evaporation. 20.5 g of a crude product are thus obtained, which is chromatographed on 2 kg of silica gel (Merck Si 60, 0.04-0.063 nm) using petroleum ether/ether 8:20 as the mobile solvent. A fraction is thus obtained which, after being concentrated by evaporation, yields 11 g of a solid product.

Workup

  1. additionWhen the dropwise addition
  2. washthe organic phase is washed with 2N sulphuric acid
  3. dry with materiala saturated bicarbonate solution, dried with sodium sulphate
  4. concentrationconcentrated by evaporation
  5. custom20.5 g of a crude product are thus obtained
  6. customwhich is chromatographed on 2 kg of silica gel (Merck Si 60, 0.04-0.063 nm)
  7. customA fraction is thus obtained which
  8. concentrationafter being concentrated by evaporation

Sources & evidence

ORD record
ord-71f89223f9314c70b89c795bc001e085
Source dataset
uspto-grants-1992_10
Patent number
US05159097

Reaction notes

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