Tetrahydrofuran → Ethyl 7-(2-amino-4-(tert-butoxycarbonyl)phenoxy)-6,8-dichlorochroman-4-carboxylate

HRID 1021423Notes

Reaction equation

HRID 1021423 reaction equation
[C:1]([O:5][C:6]([C:8]1[CH:31]=[CH:30][C:11]([O:12][C:13]2[C:22]([Cl:23])=[C:21]3[C:16]([CH:17]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:18][CH2:19][O:20]3)=[CH:15][C:14]=2[Cl:29])=[C:10]([N+:32]([O-])=O)[CH:9]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1COCC1.[NH4+].[Cl-]>CCOC(C)=O.[Zn]>[NH2:32][C:10]1[CH:9]=[C:8]([C:6]([O:5][C:1]([CH3:2])([CH3:4])[CH3:3])=[O:7])[CH:31]=[CH:30][C:11]=1[O:12][C:13]1[C:22]([Cl:23])=[C:21]2[C:16]([CH:17]([C:24]([O:26][CH2:27][CH3:28])=[O:25])[CH2:18][CH2:19][O:20]2)=[CH:15][C:14]=1[Cl:29]

Participants

6

Reactant 3

HCID 8028TetrahydrofuranHCID 25517Ammonium ChlorideHCID 67080485Ethyl 7-(4-(tert-butoxycarbonyl)-2-nitrophenoxy)-6,8-dichlorochroman-4-carboxylate

Product 1

HCID 67080422Ethyl 7-(2-amino-4-(tert-butoxycarbonyl)phenoxy)-6,8-dichlorochroman-4-carboxylateYield 79%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of ethyl 7-(4-(tert-butoxycarbonyl)-2-nitrophenoxy)-6,8-dichlorochroman-4-carboxylate (61.593 g, 120.22 mmol), THF (500 ml), and saturated NH4Cl solution (500 ml) was purged with Argon for 10 minutes. Zn dust (78.612 g, 1202.2 mmol) was added and the mixture was stirred at ambient temperature for 1 hour under Argon atmosphere. The reaction was slightly exothermic. The mixture was diluted with EtOAc (500 ml) and filtered. The filtered solid was rinsed with EtOAc (250 ml). The filtrate was transferred to a 3 L separatory funnel. The layers were separated and the organic layer was washed with brine (250 ml). The organic layer was dried over MgSO4, filtered, and concentrated. The crude residue was purified on silica gel (EtOAc in hexanes gradient) to provide 45.6 g of the title compound as an oil (79%).

Workup

  1. customwas purged with Argon for 10 minutes
  2. filtrationfiltered
  3. washThe filtered solid was rinsed with EtOAc (250 ml)
  4. customThe filtrate was transferred to a 3 L separatory funnel
  5. customThe layers were separated
  6. washthe organic layer was washed with brine (250 ml)
  7. dry with materialThe organic layer was dried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude residue was purified on silica gel (EtOAc in hexanes gradient)

Sources & evidence

ORD record
ord-e83205facca649119175bc9af7e5dc9a
Source dataset
uspto-grants-2014_05
Patent number
US08716498B2

Reaction notes

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