Ethyl Acetate → HCID 86608522, compound

HRID 2104201Notes

Reaction equation

HRID 2104201 reaction equation
[C:1]([O:4][CH:5]1[C:6]([OH:45])([CH3:44])[CH2:7][CH2:8][CH:9]([O:36][Si:37]([CH2:42][CH3:43])([CH2:40][CH3:41])[CH2:38][CH3:39])[CH2:10][C:11]([O:13][CH:14](/[C:19](/[CH3:35])=[CH:20]/[CH:21]=[CH:22]/[CH:23]([CH3:34])[CH2:24][CH:25]2[O:33][CH:26]2[CH:27]([CH3:32])[CH:28]([OH:31])[CH2:29][CH3:30])[CH:15]([CH3:18])[CH:16]=[CH:17]1)=[O:12])(=[O:3])[CH3:2].CN(C1C=CC=CN=1)C.ClC(O[C:59]1[CH:64]=[CH:63][C:62]([N+:65]([O-:67])=[O:66])=[CH:61][CH:60]=1)=O.[C:68]([O:71]CC)(=[O:70])C>C(Cl)Cl.C(N(CC)CC)C>[C:1]([O:4][CH:5]1[C:6]([OH:45])([CH3:44])[CH2:7][CH2:8][CH:9]([O:36][Si:37]([CH2:42][CH3:43])([CH2:38][CH3:39])[CH2:40][CH3:41])[CH:10]([C:68]([OH:71])=[O:70])[C:11]([O:13][CH:14](/[C:19](/[CH3:35])=[CH:20]/[CH:21]=[CH:22]/[CH:23]([CH3:34])[CH2:24][CH:25]2[O:33][CH:26]2[CH:27]([CH3:32])[CH:28]([O:31][C:59]2[CH:64]=[CH:63][C:62]([N+:65]([O-:67])=[O:66])=[CH:61][CH:60]=2)[CH2:29][CH3:30])[CH:15]([CH3:18])[CH:16]=[CH:17]1)=[O:12])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 218852-DimethylaminopyridineHCID 821294-Nitrophenyl chloroformate2×HCID 86608517HCID 86608517, compound

Product 1

HCID 86608522HCID 86608522, compoundYield 97.6%

Reagents, catalysts & solvents 2

HCID 8471TriethylamineCatalystHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

(8E,12E,14E)-7-acetoxy-6,21-dihydroxy-6,10,12,16,20-pentamethyl-3-triethylsiloxy-18,19-epoxytricosa-8,12,14-trien-11-olide (201 mg, 309 μmol) was dissolved in methylene chloride (2 mL). Triethylamine (220 μL, 1.58 μmol) and dimethylaminopyridine (17.0 mg, 139 μmol) were added to the reaction solution, and the reaction solution was cooled to 0° C. A solution of 4-nitrophenyl chloroformate (125 mg, 620 μmol) in methylene chloride (2 mL) was added to the solution. The reaction solution was warmed to room temperature, and then stirred for five hours. 4-nitrophenyl chloroformate (50.0 mg, 248 μmol) was further added to the reaction solution, and the solution was stirred at room temperature for two hours. The reaction solution was diluted with ethyl acetate (30 mL), and the dilution was washed with saturated aqueous solution of sodium hydrogencarbonate (6 mL) twice, purified water (6 mL) twice, and brine (6 mL). The resulting organic layer was dried over sodium sulfate, and then filtered. The filtrate was concentrated. The concentrate was purified by silica gel column chromatography (MERCK Silica gel 60, 63 to 200 μm; hexane:ethyl acetate=5:1→3:1) to obtain the title compound (246 mg, 302 μmol, 97.6%) as a colorless oil.

Workup

  1. temperatureThe reaction solution was warmed to room temperature
  2. stirringthe solution was stirred at room temperature for two hours
  3. washthe dilution was washed with saturated aqueous solution of sodium hydrogencarbonate (6 mL) twice
  4. custompurified water (6 mL) twice
  5. dry with materialThe resulting organic layer was dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated
  8. customThe concentrate was purified by silica gel column chromatography (MERCK Silica gel 60, 63 to 200 μm; hexane:ethyl acetate=5:1→3:1)

Sources & evidence

ORD record
ord-a6474963ceed4c03a75bb9d5a8f964cb
Source dataset
uspto-grants-2009_08
Patent number
US07576204B2

Reaction notes

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