Sodium Thiosulfate → HCID 21023962, compound

HRID 1446649Notes

Reaction equation

HRID 1446649 reaction equation
C(OC([O:6][CH:7]1[CH2:19][CH2:18][C:17]([O:21]C(OCC)C)([CH3:20])[CH:16]([OH:27])[CH:15]=[CH:14][CH:13]([CH3:28])[CH:12](/[C:29](/[CH3:50])=[CH:30]/[CH:31]=[CH:32]/[CH:33]([CH3:49])[CH2:34][CH:35]2[O:48][CH:36]2[CH:37]([CH3:47])[CH:38]([O:41]C(OCC)C)[CH2:39][CH3:40])[O:11][C:9](=[O:10])[CH2:8]1)C)C.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.S([O-])([O-])(=O)=S.[Na+].[Na+].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1>C(Cl)(Cl)Cl.C(OCC)(=O)C>[OH:6][CH:7]1[CH2:19][CH2:18][C:17]([OH:21])([CH3:20])[C:16](=[O:27])[CH:15]=[CH:14][CH:13]([CH3:28])[CH:12](/[C:29](/[CH3:50])=[CH:30]/[CH:31]=[CH:32]/[CH:33]([CH3:49])[CH2:34][CH:35]2[O:48][CH:36]2[CH:37]([CH3:47])[CH:38]([OH:41])[CH2:39][CH3:40])[O:11][C:9](=[O:10])[CH2:8]1

Participants

7

Reactant 4

HCID 24477Sodium ThiosulfateHCID 159087TriacetoxyperiodinaneHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 21023947(8E,12E,14E)-3,6,21-Tri(1-ethoxyethoxy)-7-hydroxy-6,10,12,16,20-pentamethyl-18,19-epoxytricosa-8,12,14-trien-11-olide

Product 1

HCID 21023962HCID 21023962, compoundYield 2%

Reagents, catalysts & solvents 2

HCID 6212ChloroformSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A solution of (8E,12E,14E)-3,6,21-tri(1-ethoxyethoxy)-7-hydroxy-6,10,12,16,20-pentamethyl-18,19-epoxytricosa-8,12,14-trien-11-olide (10 mg, 14 μmol) obtained in Example B39 in chloroform (0.5 mL) was added to a suspension of Dess-Martin reagent (60 mg, 140 μmol) in chloroform (2 mL), followed by stirring at room temperature for 3 hours. The reaction mixture was poured into a sodium thiosulfate aqueous solution, and the mixture was vigorously stirred. Then, ethyl acetate was added thereto, and the organic layer was washed with brine, dried over anhydrous sodium sulfate and evaporated. The resulting residue was dissolved in 2 mL of methanol and pyridinium p-toluenesulfonate (3 mg, 11 μmol) was added thereto, followed by stirring at room temperature for 20 hours. The solvent was removed, and the resulting residue was dissolved in ethyl acetate. The mixture was washed with a saturated sodium bicarbonate aqueous solution and brine, dried over anhydrous magnesium sulfate and evaporated. The resulting residue was purified by thin layer chromatography (MERCK Silica gel 60 F254, 0.2 mm, developing solution; hexane:ethyl acetate=1:5) and preparative HPLC (Shiseido CAPCELL PAK C18, 10 mm I.D.×250 mm, eluate; acetonitrile:water=20:80-80:20) to give the title compound (0.11 mg, 2%) as a colorless oil.

Workup

  1. stirringthe mixture was vigorously stirred
  2. washthe organic layer was washed with brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customevaporated
  5. dissolutionThe resulting residue was dissolved in 2 mL of methanol
  6. stirringby stirring at room temperature for 20 hours
  7. customThe solvent was removed
  8. dissolutionthe resulting residue was dissolved in ethyl acetate
  9. washThe mixture was washed with a saturated sodium bicarbonate aqueous solution and brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. customevaporated
  12. customThe resulting residue was purified by thin layer chromatography (MERCK Silica gel 60 F254, 0.2 mm, developing solution; hexane:ethyl acetate=1:5) and preparative HPLC (Shiseido CAPCELL PAK C18, 10 mm I.D.×250 mm, eluate; acetonitrile:water=20:80-80:20)

Sources & evidence

ORD record
ord-f23861a74ee340268442ac4040babc4d
Source dataset
uspto-grants-2010_02
Patent number
US07667052B2

Reaction notes

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