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

HRID 1048034Notes

Reaction equation

HRID 1048034 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 ethyl 7-(2-amino-4-(tert-butoxycarbonyl)phenoxy)-8-bromo-6-chlorochroman-4-carboxylate 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-b3b9c0a1a40f45a0adc30b53ab472c6d
Source dataset
uspto-grants-2013_10
Patent number
US08569522B2

Reaction notes

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