Ammonium Chloride → HCID 86675506, compound

HRID 1482745Notes

Reaction equation

HRID 1482745 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][NH:10][C:11]([C:13]2[CH:14]=[CH:15][C:16]3[CH2:17][C@H:18]4[N:30]([CH3:31])[CH2:29][CH2:28][C@:24]56[C:25]=3[C:26]=2[O:27][C@H:23]5[C:22](=[O:32])[CH2:21][CH2:20][C@@:19]46[OH:33])=[O:12])=[CH:4][CH:3]=1.[Cl-].[NH4+]>[Zn].C(O)C>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][CH2:9][NH:10][C:11]([C:13]2[CH:14]=[CH:15][C:16]3[CH2:17][C@H:18]4[N:30]([CH3:31])[CH2:29][CH2:28][C@@:24]5([C:25]=3[C:26]=2[OH:27])[C@@:19]4([OH:33])[CH2:20][CH2:21][C:22](=[O:32])[CH2:23]5)=[O:12])=[CH:4][CH:3]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 71150012HCID 71150012, compound

Product 1

HCID 86675506HCID 86675506, compoundYield 79%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 702EthanolSolvent

Conditions

Temperature
40 °C

Procedure

A mixture of (5a)-N-[2-(4-bromophenyl)ethyl]-14-hydroxy-17-methyl-6-oxo-4,5-epoxymorphinan-3-carboxamide (1) (10 g, 19.6 mmol), denatured ethanol (300 mL), zinc powder (28 g, 0.43 mol) and ammonium chloride (34.5 g, 0.65 mol) was heated at reflux for 30 min and then cooled to ˜40° C. The reaction mixture was filtered through celite and washed with denatured ethanol (300 mL, 40° C.). The volatiles were removed under vacuum and the residue partitioned between dichloromethane (200 mL) and 2% aqueous ammonia (300 mL). The aqueous phase was further extracted with dichloromethane (2×200 mL) and the combined organics were dried over MgSO4 and evaporated. The residue was purified on silica eluting with dichloromethane/methanol (95:5 to 9:1) to give N-[2-(4-bromophenyl)ethyl]-4,14-dihydroxy-17-methyl-6-oxomorphinan-3-carboxamide (2) (7.95 g, 79%) as a brown solid.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 30 min
  3. filtrationThe reaction mixture was filtered through celite
  4. washwashed with denatured ethanol (300 mL, 40° C.)
  5. customThe volatiles were removed under vacuum
  6. customthe residue partitioned between dichloromethane (200 mL) and 2% aqueous ammonia (300 mL)
  7. extractionThe aqueous phase was further extracted with dichloromethane (2×200 mL)
  8. dry with materialthe combined organics were dried over MgSO4
  9. customevaporated
  10. customThe residue was purified on silica eluting with dichloromethane/methanol (95:5 to 9:1)

Sources & evidence

ORD record
ord-358765cd67a347bd808a123c6b8cf289
Source dataset
uspto-grants-2016_08
Patent number
US09415045B2

Reaction notes

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