Ammonium Chloride → HCID 15289535, compound

HRID 375432Notes

Reaction equation

HRID 375432 reaction equation
[C:1]1([Mg]Br)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:9]1([C:15]2([C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)[C@@H:23]3[C@@H:19]([CH2:20][N:21]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[CH2:22]3)[C:18](=[O:31])[CH2:17][CH2:16]2)[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[Cl-].[NH4+]>C(OCC)C.O1CCCC1.C(OCC)(=O)C>[C:1]1([C@:18]2([OH:31])[CH2:17][CH2:16][C:15]([C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)([C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=3)[C@@H:23]3[C@H:19]2[CH2:20][N:21]([C:24]([O:26][C:27]([CH3:29])([CH3:28])[CH3:30])=[O:25])[CH2:22]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 3

HCID 25517Ammonium ChlorideHCID 53854262HCID 53854262, compoundHCID 178418255HCID 178418255, compound

Product 1

HCID 15289535HCID 15289535, compoundYield 41.1%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A suspension of 10.78 g of phenylmagnesium bromide in 65 cm3 of diethyl ether is added dropwise to a solution of 11.66 g of (3aS,7aS)-7,7-diphenyl-2-tert-butoxycarbonylperhydroisoindol-4-one in 70 cm3 of dry tetrahydrofuran at room temperature, while stirring. The reaction mixture is stirred at room temperature for 24 hours, refluxed for 5 hours, subsequently treated with 250 cm3 of a saturated aqueous solution of ammonium chloride, diluted with 200 cm3 of ethyl acetate, washed with 200 cm3 of water (twice) and then with 200 cm3 of a saturated aqueous solution of sodium chloride, and is dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure (2.7 kPa). The residue is chromatographed on a Merck silica gel column (particle size 0.04-0.06 mm, diameter 5.3 cm, height 31.5 cm) by eluting under a pressure of 0.5 bar of nitrogen with a mixture of cyclohexane and ethyl acetate (90/10 by volume) and collecting fractions of 100 cm3. Fractions 23 to 48 are combined and concentrated to dryness under reduced pressure (2.7 kPa). 5.75 g of (3aS,4S,7aS)-4,7,7-triphenyl-2-tert-butoxycarbonylperhydroisoindol-4-ol are obtained in the form of a pale yellow foam.

Workup

  1. stirringThe reaction mixture is stirred at room temperature for 24 hours
  2. temperaturerefluxed for 5 hours
  3. washwashed with 200 cm3 of water (twice) and then with 200 cm3 of a saturated aqueous solution of sodium chloride
  4. dry with materialis dried over magnesium sulphate
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  7. customThe residue is chromatographed on a Merck silica gel column (particle size 0.04-0.06 mm, diameter 5.3 cm, height 31.5 cm)
  8. washby eluting under a pressure of 0.5 bar of nitrogen with a mixture of cyclohexane and ethyl acetate (90/10 by volume)
  9. customcollecting fractions of 100 cm3
  10. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)

Sources & evidence

ORD record
ord-cd6cc7a81d484f10b9df5e5d76f1388f
Source dataset
uspto-grants-1996_01
Patent number
US05484804

Reaction notes

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