Ammonium Chloride → HCID 15289535, compound

HRID 2211405Notes

Reaction equation

HRID 2211405 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-butoxycarbonyl-perhydroisoindol-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 and then treated with 250 cm3 of an aqueous saturated solution of ammonium chloride, diluted with 200 cm3 of ethyl acetate, washed with 200 cm3 of water (twice) and then with 200 cm3 of an aqueous saturated solution of sodium chloride, dried over magnesium sulphate, filtered and concentrated to dryness under reduced pressure (2.7 kPa). The residue is chromatographed over 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-butoxycarbonyl-perhydroisoindol-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 an aqueous saturated solution of sodium chloride
  4. dry with materialdried over magnesium sulphate
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure (2.7 kPa)
  7. customThe residue is chromatographed over 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-2fe6d72228814e09a54bcbcb4effd3df
Source dataset
uspto-grants-1995_10
Patent number
US05463077

Reaction notes

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