Ammonium Chloride → Ethyl 7-(2-amino-4-(tert-butoxycarbonyl)phenoxy)-8-bromo-6-chlorochroman-4-carboxylate

HRID 1626456Notes

Reaction equation

HRID 1626456 reaction equation
[Br:1][C:2]1[C:3]([O:18][C:19]2[CH:24]=[CH:23][C:22]([C:25]([O:27][C:28]([CH3:31])([CH3:30])[CH3:29])=[O:26])=[CH:21][C:20]=2[N+:32]([O-])=O)=[C:4]([Cl:17])[CH:5]=[C:6]2[C:11]=1[O:10][CH2:9][CH2:8][CH:7]2[C:12]([O:14][CH2:15][CH3:16])=[O:13].[Cl-].[NH4+]>O1CCCC1.[Zn]>[NH2:32][C:20]1[CH:21]=[C:22]([C:25]([O:27][C:28]([CH3:29])([CH3:31])[CH3:30])=[O:26])[CH:23]=[CH:24][C:19]=1[O:18][C:3]1[C:2]([Br:1])=[C:11]2[C:6]([CH:7]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH2:8][CH2:9][O:10]2)=[CH:5][C:4]=1[Cl:17]

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 67080517Ethyl 8-bromo-7-(4-(tert-butoxycarbonyl)-2-nitrophenoxy)-6-chlorochroman-4-carboxylate

Product 1

HCID 67080476Ethyl 7-(2-amino-4-(tert-butoxycarbonyl)phenoxy)-8-bromo-6-chlorochroman-4-carboxylateYield 85.1%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of ethyl 8-bromo-7-(4-(tert-butoxycarbonyl)-2-nitrophenoxy)-6-chlorochroman-4-carboxylate (2.00 g, 3.59 mmol) in tetrahydrofuran (15 mL) at ambient temperature was added zinc dust (4.70 g, 71.8 mmol), followed by saturated ammonium chloride solution (7.5 mL). The resulting mixture was stirred at ambient temperature for 1 hour. The mixture was filtered through a glass microfibre filter to remove the insoluble zinc solids, and the solids were washed twice with tetrahydrofuran. The combined filtrate and washings were concentrated to remove most of the tetrahydrofuran, and the residue was partitioned between ethyl acetate (100 mL) and water (50 mL). The organic layer was washed with brine (50 mL), then dried over sodium sulfate and concentrated to afford the desired compound as a light brown glass (1.61 g, 85% yield).

Workup

  1. filtrationThe mixture was filtered through a glass microfibre
  2. filtrationfilter
  3. customto remove the insoluble zinc solids
  4. washthe solids were washed twice with tetrahydrofuran
  5. concentrationThe combined filtrate and washings were concentrated
  6. customto remove most of the tetrahydrofuran
  7. customthe residue was partitioned between ethyl acetate (100 mL) and water (50 mL)
  8. washThe organic layer was washed with brine (50 mL)
  9. dry with materialdried over sodium sulfate
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-5f82277bb3b3475d8572f6c35cec34ce
Source dataset
uspto-grants-2014_07
Patent number
US08785445B2

Reaction notes

Loading…