Water → 197915-50-7

HRID 1003917Notes

Reaction equation

HRID 1003917 reaction equation
CC(OC(=O)[NH:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][CH2:15][C:16]2([CH:24]([CH3:26])[CH3:25])[CH2:21][C:20]([OH:22])=[CH:19][C:18](=[O:23])[O:17]2)=[CH:10][CH:9]=1)(C)C.C([O-])([O-])=O.[K+].[K+].[C:34]([C:38]1[CH:43]=[C:42]([CH2:44][OH:45])[C:41]([CH3:46])=[CH:40][C:39]=1[S:47]S(C1C=CC(C)=CC=1)(=O)=O)([CH3:37])([CH3:36])[CH3:35].O>C(Cl)Cl.CC(O)=O.CCOC(C)=O>[NH2:7][C:8]1[CH:9]=[CH:10][C:11]([CH2:14][CH2:15][C:16]2([CH:24]([CH3:25])[CH3:26])[O:17][C:18](=[O:23])[C:19]([S:47][C:39]3[CH:40]=[C:41]([CH3:46])[C:42]([CH2:44][OH:45])=[CH:43][C:38]=3[C:34]([CH3:37])([CH3:36])[CH3:35])=[C:20]([OH:22])[CH2:21]2)=[CH:12][CH:13]=1

Participants

8

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 10499026S-[2-Tert-butyl-4-(hydroxymethyl)-5-methylphenyl] 4-methylbenzenesulfonothioateHCID 70251287HCID 70251287, compound

Product 1

HCID 54676890197915-50-7

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of {4-[2-(4-hydroxy-2-isopropyl-6-oxo-3,6-dihydro-2H-pyran-2-yl)-ethyl]-phenyl}-carbamic acid 1,1-dimethylethyl ester (0.26 g, 0.69 mmol; prepared in Example QQQQQ) in CH2Cl2 was cooled to 5° C. and treated with a steady stream of gaseous HCI for 5 minutes. The solution was concentrated, and the residue was triturated with ether. The crude material was dissolved in DMF (5 mL) and treated with 1.0 g (7.0 mmol) of K2CO3 and 0.25 g (0.69 mmol) of toluene-4-thiosulfonic acid S-(2-tert-butyl-4-hydroxymethyl-5-methyl-phenyl) ester (prepared in Example FFF). The reaction mixture was stirred overnight at room temperature. Water (30 mL) and EtOAc (50 mL) were added; the mixture was cooled in an ice bath and acidified to pH 5.5 with AcOH. The organic layer was separated, washed with brine, dried (MgSO4), and concentrated. The product was chromatographed on silica gel, eluting with CHCl3 :MeOH (90:10) to give the title compound, m.p. 139-141° C. 1H NMR (DMSO-d6) δ 0.88 (m, 6 H), 1.42 (s, 9 H), 1.87 (m, 5 H), 2.14 (m, 1 H), 2.40 (m, partially obscured by DMSO, 2 H), 2.66 (d of ABXq, 1 H), 2.88 (d, of ABXq, 1 H), 4.30 (s, 2 H), 4.90 (br s, 1 H), 6.43 (d, 2 H), 6.64 (s, 1 H), 6.77 (d, 2 H), 7.20 (s, 1 H).

Workup

  1. customwas cooled to 5° C.
  2. additiontreated with a steady stream of gaseous HCI for 5 minutes
  3. concentrationThe solution was concentrated
  4. customthe residue was triturated with ether
  5. dissolutionThe crude material was dissolved in DMF (5 mL)
  6. temperaturethe mixture was cooled in an ice bath
  7. customThe organic layer was separated
  8. washwashed with brine
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated
  11. customThe product was chromatographed on silica gel
  12. washeluting with CHCl3 :MeOH (90:10)

Sources & evidence

ORD record
ord-3f5c1696f86744dbaaaa57361b4a0b1b
Source dataset
uspto-grants-2000_04
Patent number
US06046355

Reaction notes

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