Acetic Acid → HCID 58593377, compound

HRID 916998Notes

Reaction equation

HRID 916998 reaction equation
[C:1]([C:5]1[CH:10]=[C:9]([S:11][C:12]([S:15][C:16]2[CH:21]=[C:20]([C:22]([CH3:25])([CH3:24])[CH3:23])[C:19]([O:26][CH2:27][CH2:28][CH:29]3[CH:33]([CH2:34][CH2:35][OH:36])[O:32]C(OCC)[O:30]3)=[C:18]([C:40]([CH3:43])([CH3:42])[CH3:41])[CH:17]=2)([CH3:14])[CH3:13])[CH:8]=[C:7]([C:44]([CH3:47])([CH3:46])[CH3:45])[C:6]=1[OH:48])([CH3:4])([CH3:3])[CH3:2].C(O)(=O)C.O>CO>[C:40]([C:18]1[CH:17]=[C:16]([S:15][C:12]([S:11][C:9]2[CH:10]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[C:6]([OH:48])=[C:7]([C:44]([CH3:47])([CH3:46])[CH3:45])[CH:8]=2)([CH3:14])[CH3:13])[CH:21]=[C:20]([C:22]([CH3:25])([CH3:24])[CH3:23])[C:19]=1[O:26][CH2:27][CH2:28][CH:29]([OH:30])[CH:33]([OH:32])[CH2:34][CH2:35][OH:36])([CH3:43])([CH3:42])[CH3:41]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 962WaterHCID 86602766HCID 86602766, compound

Product 1

HCID 58593377HCID 58593377, compoundYield 65%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

2,6-Di-tert-butyl-4-[1-(3,5-di-tert-butyl-4-{2-[2-ethoxy-5-(2-hydroxy-ethyl)-[1,3]dioxo-lan-4-yl]-ethoxy}-phenylsulfanyl)-1-methyl-ethylsulfanyl]-phenol (Ex-13D, 4.0 g, 5.7 mmol) was dissolved in methanol (60 mL). Acetic acid (2.8 mL) and water (2.8 mL) were added and the resultant mixture was stirred at reflux for 3 h. The reaction mixture was concentrated under reduced pressure and the residue was diluted with water (100 mL) and extracted with dichloromethane (3×100 mL). The combined organic extracts were dried over sodium sulfate and concentrated to an off-white foam. The residue was dissolved in methanol (60 mL) and potassium carbonate (1.6 g) was added. The mixture was stirred at room temperature for 1.5 h and concentrated under reduced pressure and the residue was diluted with water (100 mL). The solution was extracted with dichloromethane (3×100 mL), dried over sodium sulfate, and concentrated to a white foam. Following silica gel chromatography (2:1 ethyl acetate:hexanes) gave 2.2 g (65%) of 6-{2,6-di-tert-butyl-4-[1-(3,5-di-tert-butyl-4-hydroxy-phenylsulfanyl)-1-methyl-ethylsulfanyl]-phenoxy}-hexane-1,3,4-triol as a white solid, mp 75–77° C. 1H-NMR (300 MHz, CDCl3) δ7.54 (s, 2H), 7.45 (s, 2H), 5.36 (s, 1H), 3.92–3.99 (m, 4H), 3.78 (brs, 2H), 2.99 (d, 1H, J=3.8 Hz, 2.78 (d, 1H, J=3.8 Hz), 2.15 (t, 1H, J=4.6 Hz), 2.02–2.11 (m, 2H), 1.83–1.85 (m, 2H), 1.43–1.44 (m, 42H). HRMS (ESI) calcd for C37H60O5S2 (M+Na), 671.3780; found, 671.3775. Anal. calcd. for C37H60O5S2: C, 68.47, H, 9.32, S, 9.88; Found: C, 68.62, H, 9.49, S, 9.59.

Workup

  1. temperatureat reflux for 3 h
  2. concentrationThe reaction mixture was concentrated under reduced pressure
  3. additionthe residue was diluted with water (100 mL)
  4. extractionextracted with dichloromethane (3×100 mL)
  5. dry with materialThe combined organic extracts were dried over sodium sulfate
  6. concentrationconcentrated to an off-white foam
  7. dissolutionThe residue was dissolved in methanol (60 mL)
  8. additionpotassium carbonate (1.6 g) was added
  9. concentrationconcentrated under reduced pressure
  10. additionthe residue was diluted with water (100 mL)
  11. extractionThe solution was extracted with dichloromethane (3×100 mL)
  12. dry with materialdried over sodium sulfate
  13. concentrationconcentrated to a white foam

Sources & evidence

ORD record
ord-dbd5e905c44941d5ad5563781f1e3d46
Source dataset
uspto-grants-2007_09
Patent number
US07271274B2

Reaction notes

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