2,6-Di-tert-butyl-4-mercaptophenol → 4-(3,5-Di-tert-butyl-4-hydroxy-phenylsulfanyl)-4-ethoxycarbonylmethyl-piperidine-1-carboxylic acid tert-butyl ester

HRID 599463Notes

Reaction equation

HRID 599463 reaction equation
[C:1]([C:5]1[CH:10]=[C:9]([SH:11])[CH:8]=[C:7]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:6]=1[OH:16])([CH3:4])([CH3:3])[CH3:2].[C:17]([O:21][C:22]([N:24]1[CH2:29][CH2:28][C:27](=[CH:30][C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH2:26][CH2:25]1)=[O:23])([CH3:20])([CH3:19])[CH3:18]>N1CCCCC1.C(OCC)(=O)C>[C:17]([O:21][C:22]([N:24]1[CH2:29][CH2:28][C:27]([S:11][C:9]2[CH:8]=[C:7]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:6]([OH:16])=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:10]=2)([CH2:30][C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH2:26][CH2:25]1)=[O:23])([CH3:20])([CH3:19])[CH3:18]

Participants

5

Reactant 2

HCID 703702,6-Di-tert-butyl-4-mercaptophenolHCID 10333298tert-Butyl 4-(2-ethoxy-2-oxoethylidene)piperidine-1-carboxylate

Product 1

HCID 866354214-(3,5-Di-tert-butyl-4-hydroxy-phenylsulfanyl)-4-ethoxycarbonylmethyl-piperidine-1-carboxylic acid tert-butyl esterYield 94%

Reagents, catalysts & solvents 2

HCID 8082PiperidineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

A suspension of 2,6-di-tert-butyl-4-mercapto-phenol (1.2 g, 5.2 mmol) and 4-ethoxycarbonylmethylene-piperidine-1-carboxylic acid tert-butyl ester (1.2 g, 4.4 mmol) in 5 mL of piperidine was degassed and then heated to 90° C. for 15 h. The reaction was cooled to room temperature, toluene (10 mL) was added, and the mixture was concentrated under reduced pressure. The residue obtained was diluted with ethyl acetate (40 mL), washed with 1 N HCl (2×30 mL) and water (40 mL), dried over Na2SO4, and concentrated under reduced pressure. Chromatography (2-20% ethyl acetate/hexanes) afforded 4-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)-4-ethoxycarbonylmethyl-piperidine-1-carboxylic acid tert-butyl ester as a foamy solid (2.1 g, 94%). ESI/CI-MS m/z 506 ([M−H]−).

Workup

  1. customwas degassed
  2. temperatureThe reaction was cooled to room temperature
  3. additiontoluene (10 mL) was added
  4. concentrationthe mixture was concentrated under reduced pressure
  5. customThe residue obtained
  6. washwashed with 1 N HCl (2×30 mL) and water (40 mL)
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-4295e5b6aec4487d9fe95f8e387d9c3f
Source dataset
uspto-grants-2011_03
Patent number
US07897776B2

Reaction notes

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