Acetic Acid → HCID 178495749, compound

HRID 916999Notes

Reaction equation

HRID 916999 reaction equation
C(C1C=C(S[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][C@H:28]3[C@H:32]([CH2:33][O:34][CH3:35])[O:31]C(OCC)[O:29]3)=[C:18]([C:39]([CH3:42])([CH3:41])[CH3:40])[CH:17]=2)([CH3:14])[CH3:13])C=C(C(C)(C)C)C=1O)(C)(C)C.[C:48]([OH:51])(=O)[CH3:49]>CO.O>[C:39]([C:18]1[CH:17]=[C:16]([SH:15]([CH:12]([CH3:13])[CH3:14])[S:15][C:16]2[CH:21]=[C:49]([C:22]([CH3:20])([CH3:23])[CH3:24])[C:48]([OH:51])=[C:18]([C:39]([CH3:42])([CH3:40])[CH3:41])[CH:17]=2)[CH:21]=[C:20]([C:22]([CH3:24])([CH3:25])[CH3:23])[C:19]=1[O:26][CH2:27][C@H:28]([OH:29])[C@@H:32]([OH:31])[CH2:33][O:34][CH3:35])([CH3:42])([CH3:41])[CH3:40]

Participants

5

Reactant 2

HCID 176Acetic AcidHCID 86602767HCID 86602767, compound

Product 1

HCID 178495749HCID 178495749, compoundYield 99%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 962WaterSolvent2×

Procedure

2,6-Di-tert-butyl-4-{1-[3,5-di-tert-butyl-4-(2-ethoxy-5(s)-methoxymethyl-[1,3]dioxolan-4(S)-ylmethoxy)-phenylsulfanyl]-1-methyl-ethylsulfanyl}-phenol (Ex-15A, 0.72 g, 1.1 mmol) was dissolved in methanol (3 mL). Acetic acid (0.14 mL) and water (0.14 mL) were added and the resultant mixture was stirred at reflux for 3 h. The reaction mixture was diluted with water (10 mL) and extracted with dichloromethane (3×10 mL). The combined organic extracts were dried over sodium sulfate and concentrated to an off-white foam. The residue was dissolved in methanol (3 mL) and potassium carbonate (0.085 g) was added. The mixture was stirred at room temperature for 30 min and diluted with water (10 mL). The solution was extracted with dichloromethane (3×10 mL), dried over sodium sulfate, and concentrated to a white foam. Silica gel chromatography (3:1 ethyl acetate: hexanes) gave 0.18 g (99%) of 1-{2,6-di-tert-butyl-4-[1-(3,5-di-tert-butyl-4-hydroxyphenylsulfanyl)-1-methylethylsulfanyl]phenoxy}-4-methoxybutane-2(S),3(S)-diol as a white solid, mp 62–64° C. 1H-NMR (CDCl3) δ 7.55 (s, 2H), 7.45 (s, 2H), 5.36 (s, 1H), 4.25–4.26 (m, 1H), 3.86–3.90 (m, 3H), 3.59–3.61 (m, 2H), 3.41 (s, 3H), 2.79 (d, 1H, J=4.8 Hz), 2.63 (d, 1H, J=4.8 Hz), 1.42–1.45 (m, 42H). HRMS (ESI) calcd for C36H58O5S2 (M+Na), 657.3624; Found, 657.3630. Anal. calcd. for C36H58O5S2: C, 68.10, H, 9.21, S, 10.10; Found: C, 68.47, H, 9.38, S, 9.85.

Workup

  1. temperatureat reflux for 3 h
  2. extractionextracted with dichloromethane (3×10 mL)
  3. dry with materialThe combined organic extracts were dried over sodium sulfate
  4. concentrationconcentrated to an off-white foam
  5. dissolutionThe residue was dissolved in methanol (3 mL)
  6. additionpotassium carbonate (0.085 g) was added
  7. additiondiluted with water (10 mL)
  8. extractionThe solution was extracted with dichloromethane (3×10 mL)
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated to a white foam

Sources & evidence

ORD record
ord-d023d3bc886f4fef892e1398b9fdeb41
Source dataset
uspto-grants-2007_09
Patent number
US07271274B2

Reaction notes

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