Hydrochloric Acid → 5-{[2-Tert-butyl-4-(2-hydroxyethoxy)-5-methylphenyl]sulfanyl}-6-hydroxy-2-[4-(2-hydroxyethoxy)phenyl]-2-(2-phenylethyl)-2,3-dihydro-4h-pyran-4-one

HRID 1003908Notes

Reaction equation

HRID 1003908 reaction equation
C([Si](C)(C)[O:6][CH2:7][CH2:8][O:9][C:10]1[CH:15]=[CH:14][C:13]([C:16]2([CH2:24][CH2:25][C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)[O:21][C:20](=[O:22])[CH:19]=[C:18]([OH:23])[CH2:17]2)=[CH:12][CH:11]=1)(C)(C)C.[C:34]([C:38]1[CH:43]=[C:42]([O:44][CH2:45][CH2:46][O:47][Si](C(C)(C)C)(C)C)[C:41]([CH3:55])=[CH:40][C:39]=1[S:56]S(C1C=CC(C)=CC=1)(=O)=O)([CH3:37])([CH3:36])[CH3:35].C([O-])([O-])=O.[K+].[K+].Cl>CO.CN(C=O)C>[C:34]([C:38]1[CH:43]=[C:42]([O:44][CH2:45][CH2:46][OH:47])[C:41]([CH3:55])=[CH:40][C:39]=1[S:56][C:19]1[C:20](=[O:22])[O:21][C:16]([C:13]2[CH:14]=[CH:15][C:10]([O:9][CH2:8][CH2:7][OH:6])=[CH:11][CH:12]=2)([CH2:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH2:17][C:18]=1[OH:23])([CH3:37])([CH3:36])[CH3:35]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 10791774Toluene-4-thiosulfonic acid S-{2-tert-butyl-4-[2-(tert-butyl-dimethyl-silanyloxy)-ethoxy]-5-methyl-phenyl}esterHCID 54682266HCID 54682266, compound

Product 1

HCID 546822895-{[2-Tert-butyl-4-(2-hydroxyethoxy)-5-methylphenyl]sulfanyl}-6-hydroxy-2-[4-(2-hydroxyethoxy)phenyl]-2-(2-phenylethyl)-2,3-dihydro-4h-pyran-4-one

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6228DimethylformamideSolvent

Procedure

To a round bottom flask equipped with a magnetic stirrer were added 6-{4-[2-(tert-butyl-dimethyl-silanyloxy)-ethoxy]-phenyl} -4-hydroxy-6-phenethyl-5,6-dihydro-pyran-2-one (prepared in Example SS; 0.260 g, 0.555 mmol), toluene-4-thiosulfonic acid S-{2-tert-butyl-4-[2-(tert-butyl-dimethyl-silanyloxy)-ethoxy]-5-methyl-phenyl) ester (prepared in Example PPP; 0.282 g, 0.555 mmol), K2CO3 (0.346 g, 2.50 mmol), and DMF (5 mL), as described in General Method 9. The mixture was stirred at room temperature for 2 days at which time MeOH (150 mL) was added and the solution taken to pH 3.0 with conc. HCl. The reaction was quenched with H2O (500 mL) and extracted with EtOAc. The organics were dried over MgSO4 and concentrated; the residue was taken up in a small amount of EtOAc and triturated with hexane. The solid was filtered and dried under high vacuum to yield the title compound, m.p. >190° C. (dec.). 1H NMR (DMSO-d6) δ 1.45 (s, 9 H), 1.68 (s, 3 H), 2.22 (br m, 4 H), 2.51 (br m, partially obscured by DMSO, 2 H), 3.34 (d of ABX q, partially obscured by H2 0, 1 H), 3.40 (d of ABX q, partially obscured by H2O, 1 H), 3.67 (br m, 2 H), 3.72 (br m, 2 H)3.91 (t, 2 H), 3.98 (t, 2 H), 6.76 (s, 1 H), 6.96 (s, 1 H), 6.99 (d, 2 H), 7.08-7.22 (m, 1 H), 7.10 (d, 2 H), 7.24 (d, 2 H), 7.30 (d, 2 H).

Workup

  1. customTo a round bottom flask equipped with a magnetic stirrer
  2. additionwas added
  3. customThe reaction was quenched with H2O (500 mL)
  4. extractionextracted with EtOAc
  5. dry with materialThe organics were dried over MgSO4
  6. concentrationconcentrated
  7. customtriturated with hexane
  8. filtrationThe solid was filtered
  9. customdried under high vacuum

Sources & evidence

ORD record
ord-630f97ae53c1485a8919d7ab0e815975
Source dataset
uspto-grants-2000_04
Patent number
US06046355

Reaction notes

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