Phenyl isocyanate → HCID 87588157, compound

HRID 2104202Notes

Reaction equation

HRID 2104202 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].C(N(CC)CC)C.[C:53]1([N:59]=[C:60]=[O:61])[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=1>C(Cl)Cl.C(OCC)(=O)C.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])[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]([O:31][C:60](=[O:61])[NH:59][C:53]2[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=2)[CH2:29][CH3:30])[CH:15]([CH3:18])[CH:16]=[CH:17]1)=[O:12])(=[O:3])[CH3:2]

Participants

7

Reactant 3

HCID 7672Phenyl isocyanate2×HCID 8471TriethylamineHCID 86608517HCID 86608517, compound

Product 1

HCID 87588157HCID 87588157, compoundYield 45.6%

Reagents, catalysts & solvents 3

HCID 8471TriethylamineCatalystHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

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 (100 mg, 154 μmol) was dissolved in methylene chloride (2 mL). Triethylamine (64.2 μL, 461 μmol) and phenyl isocyanate (34.0 μL, 312 μmol) were added to the reaction solution. The reaction solution was stirred at room temperature for 25.5 hours. Then, triethylamine (200 μL, 1.43 μmol) and phenyl isocyanate (98.0 μL, 900 μmol) were further added to the reaction solution, and the reaction solution was stirred at room temperature for six 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=4:1→3:1) and thin-layer chromatography (MERCK 60 F254, 0.5 mm, toluene:acetone=5:1) to obtain the title compound (54.0 mg, 70.1 μmol, 45.6%) as a colorless oil.

Workup

  1. stirringthe reaction solution was stirred at room temperature for six hours
  2. washthe dilution was washed with saturated aqueous solution of sodium hydrogencarbonate (6 mL) twice
  3. custompurified water (6 mL) twice
  4. dry with materialThe resulting organic layer was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated
  7. customThe concentrate was purified by silica gel column chromatography (MERCK Silica gel 60, 63 to 200 μm; hexane:ethyl acetate=4:1→3:1) and thin-layer chromatography (MERCK 60 F254, 0.5 mm, toluene:acetone=5:1)

Sources & evidence

ORD record
ord-1225d4640e8e4d1cab1a98262a30a589
Source dataset
uspto-grants-2009_08
Patent number
US07576204B2

Reaction notes

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