Hydrochloric Acid → HCID 46862984, compound

HRID 1049956Notes

Reaction equation

HRID 1049956 reaction equation
[OH-].[Na+].COP([CH2:9][C:10](=[O:18])[C:11]([F:17])([F:16])[CH2:12][CH2:13][CH2:14][CH3:15])(=O)OC.[CH2:19]([O:26][C@@H:27]1[CH2:31][C:30](=[O:32])[C@H:29]([CH2:33]/[CH:34]=[CH:35]\[CH2:36][CH2:37][CH2:38][C:39]([O:41][CH2:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)=[O:40])[C@H:28]1[CH:49]=O)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1.Cl>O.O1CCCC1.[Cl-].[Zn+2].[Cl-].ClCCl>[CH2:19]([O:26][C@@H:27]1[CH2:31][C:30](=[O:32])[C@H:29]([CH2:33]/[CH:34]=[CH:35]\[CH2:36][CH2:37][CH2:38][C:39]([O:41][CH2:42][C:43]2[CH:44]=[CH:45][CH:46]=[CH:47][CH:48]=2)=[O:40])[C@H:28]1/[CH:49]=[CH:9]/[C:10](=[O:18])[C:11]([F:16])([F:17])[CH2:12][CH2:13][CH2:14][CH3:15])[C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium HydroxideHCID 11118722Dimethyl (3,3-difluoro-2-oxoheptyl)phosphonateHCID 46862669HCID 46862669, compound

Product 1

HCID 46862984HCID 46862984, compound

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 962WaterSolvent3×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a mixture of zinc chloride (25.0 mmoL) in water (15 mL) at about 10° C. was added 50% sodium hydroxide (49.0 mmoL) followed by water (5 mL). The mixture was stirred vigorously with a mechanical stirred at room temperature. To the mixture was added dimethyl(3,3-difluoro-2-oxoheptyl)phosphonate (17.0 mmoL) in tetrahydrofuran (15 mL). The mixture was stirred at room temperature for about an hour. To the mixture was added (5Z)-benzyl 7-[(1R,2R,3R)-3-benzyloxy-2-formyl-5-oxocyclopentyl]hept-5-enoate (17, R1 is phenyl, R2 and R3 are H and R7 is benzyl, 15.0 mmoL) in tetrahydrofuran (15 mL). The mixture was stirred at room temperature overnight. To the mixture was added dichloromethane (60 mL) and water (50 mL). The pH was adjusted to approximately 4 with 5 wt % hydrochloric acid. The layers were separated; the organic layer was dried over sodium sulfate, filtered through Celite® and concentrated to dryness. The residue was purified by column chromatography (40% ethyl acetate in heptanes) to yield (5Z)-benzyl 7-[(1R,2R,3R)-3-benzyloxy-2-[(E)-4,4-difluoro-3-oxooct-1-enyl]-5-oxocyclopentyl]hept-5-enoate (18, R1 is phenyl and R2, R3 are H and R7 is benzyl) as an oil (4.1 g).

Workup

  1. stirringa mechanical stirred at room temperature
  2. stirringThe mixture was stirred at room temperature for about an hour
  3. stirringThe mixture was stirred at room temperature overnight
  4. customThe layers were separated
  5. dry with materialthe organic layer was dried over sodium sulfate
  6. filtrationfiltered through Celite®
  7. concentrationconcentrated to dryness
  8. customThe residue was purified by column chromatography (40% ethyl acetate in heptanes)

Sources & evidence

ORD record
ord-e7b56fc97a08415bb653d4815c9f4875
Source dataset
uspto-grants-2016_07
Patent number
US09382272B2

Reaction notes

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