Acetonitrile → HCID 15867795, compound

HRID 1604107Notes

Reaction equation

HRID 1604107 reaction equation
C(#N)C.N1C=CC=CC=1.F.[CH3:11][C:12]1[CH2:26][C@@H:25]([O:27][Si](C(C)(C)C)(C)C)[C@H:24](/[CH:35]=[CH:36]/[C@@H:37]([O:45][Si](C(C)(C)C)(C)C)[CH2:38][C@H:39]([CH3:44])[CH2:40][CH2:41][CH2:42][CH3:43])[C:13]=1[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][C:20]([O:22][CH3:23])=[O:21]>N1C=CC=CC=1>[CH3:11][C:12]1[CH2:26][C@@H:25]([OH:27])[C@H:24](/[CH:35]=[CH:36]/[C@@H:37]([OH:45])[CH2:38][C@H:39]([CH3:44])[CH2:40][CH2:41][CH2:42][CH3:43])[C:13]=1[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][C:20]([O:22][CH3:23])=[O:21]

Participants

5

Reactant 3

HCID 6342AcetonitrileHCID 64774Pyridine, hydrofluoride (1:1)HCID 15867794HCID 15867794, compound

Product 1

HCID 15867795HCID 15867795, compoundYield 10%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent2×

Procedure

To a solution of ice-cooled acetonitrile (2 ml) and pyridine (0.2 mL) was added hydrogen fluoride-pyridine (0.2 mL). To this solution was added a mixture (174 mg) containing methyl (11R,12R,13E,15S,17R)-9-methyl-11,15-bis(tert-butyldimethylsiloxy)-17,20-dimethylprosta-8,13-dienoate in pyridine (0.2 mL). The ice bath was removed and the solution was agitated for 15 hours while returning it to room temperature. The reaction solution was poured into a mixture of ethyl acetate and a saturated aqueous solution of sodium hydrogencarbonate. The desired product was extracted from this mixed solution with ethyl acetate. The extract was washed with brine, then dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure, then was purified by silica gel column chromotography (30 to 50% ethyl acetate/hexane) and subjected to thin layer chromotography for separation (ethyl acetate:hexane=4:1) to obtain methyl (11R,12R,13E,15S,17R)-9-methyl-11,15-dihydroxy-17,20-dimethylprosta-8,13-dienoate (21 mg, 2 step 10%) and as a byproduct, methyl (11R,12R,13E,15S,17R)-9-trifluoromethanesulfonyloxy-11,15-dihydroxy-17,20-dimethylprosta-8,13-dienoate (48 mg, 2 step, 18%).

Workup

  1. customThe ice bath was removed
  2. customto room temperature
  3. additionThe reaction solution was poured into a mixture of ethyl acetate
  4. extractionThe desired product was extracted from this mixed solution with ethyl acetate
  5. washThe extract was washed with brine
  6. dry with materialdried over anhydrous sodium sulfate
  7. concentrationThe solution was concentrated under reduced pressure
  8. customwas purified by silica gel column chromotography (30 to 50% ethyl acetate/hexane)
  9. customsubjected to thin layer chromotography for separation (ethyl acetate:hexane=4:1)

Sources & evidence

ORD record
ord-ac059260bc424a4bad031b47d18987a2
Source dataset
uspto-grants-1999_11
Patent number
US05990346

Reaction notes

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