Ammonium Chloride → Ethyl 2-(5-amino-4-fluoro-2-(2-(trimethylsilyl)ethynyl)phenyl)acetate

HRID 1930307Notes

Reaction equation

HRID 1930307 reaction equation
[F:1][C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][C:5]([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:4]([C:17]#[C:18][Si:19]([CH3:22])([CH3:21])[CH3:20])[CH:3]=1.[NH4+].[Cl-]>CO.C1COCC1.[Zn]>[NH2:8][C:7]1[C:2]([F:1])=[CH:3][C:4]([C:17]#[C:18][Si:19]([CH3:20])([CH3:21])[CH3:22])=[C:5]([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])[CH:6]=1

Participants

5

Reactant 2

HCID 25517Ammonium ChlorideHCID 69088386Ethyl 2-(4-fluoro-5-nitro-2-(2-(trimethylsilyl)ethynyl)phenyl)acetate

Product 1

HCID 68983308Ethyl 2-(5-amino-4-fluoro-2-(2-(trimethylsilyl)ethynyl)phenyl)acetateYield 90.2%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a stirring suspension of ethyl 2-(4-fluoro-5-nitro-2-(2-(trimethylsilyl)ethynyl)phenyl)acetate (0.66 g, 2.04 mmol) in MeOH/THF (1:1, 20 mL) was added NH4Cl (1.09 g, 20.4 mmol), followed by Zn dust (1.33 g, 20.4 mmol). After stirring 1.5 h, the mixture was filtered through C elite, and rinsed forward with MeOH. The combined filtrates were concentrated, diluted with brine and extracted with THF (2×). The combined organic layers were washed with brine (1×), dried (MgSO4), filtered and concentrated to afford ethyl 2-(5-amino-4-fluoro-2-(2-(trimethylsilyl)ethynyl)phenyl)acetate (0.54 g, 90% yield). 1H NMR (400 MHz, DMSO-d6): δ 6.86 (d, J=12.0 Hz, 1H), 6.47 (d, J=8.8 Hz, 1H), 5.47 (brs, 2H), 3.88 (d, J= 6.8 Hz, 2H), 3.43 (s, 2H), 1.00 (d, J=6.8 Hz, 3H), 0.00 (s, 9H); MS (ESI) m/z: 294.0 (M+H+).

Workup

  1. filtrationthe mixture was filtered through C elite
  2. washrinsed forward with MeOH
  3. concentrationThe combined filtrates were concentrated
  4. additiondiluted with brine
  5. extractionextracted with THF (2×)
  6. washThe combined organic layers were washed with brine (1×)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-04414c3f3e024e76bff1ee895f4c0c50
Source dataset
uspto-grants-2012_05
Patent number
US08188113B2

Reaction notes

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