Trimethylsilyl iodide → 4-Amino-2-chloro-6-fluorobenzyl acetate

HRID 83904Notes

Reaction equation

HRID 83904 reaction equation
[C:1]([O:4][CH2:5][C:6]1[C:11]([F:12])=[CH:10][C:9]([NH:13]C(OC(C)(C)C)=O)=[CH:8][C:7]=1[Cl:21])(=[O:3])[CH3:2].C[Si](I)(C)C>CC#N>[C:1]([O:4][CH2:5][C:6]1[C:11]([F:12])=[CH:10][C:9]([NH2:13])=[CH:8][C:7]=1[Cl:21])(=[O:3])[CH3:2]

Participants

4

Reactant 2

HCID 85247Trimethylsilyl iodideHCID 667410364-(Tert-butoxycarbonylamino)-2-chloro-6-fluorobenzyl acetate

Product 1

HCID 667403684-Amino-2-chloro-6-fluorobenzyl acetate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of 4-(tert-butoxycarbonylamino)-2-chloro-6-fluorobenzyl acetate (8.5 g, 24 mmol) in CH3CN (300 mL) was added trimethylsilyl iodide (4.12 mL, 28 mmol) at 0° C. under N2.2 After stirring 15 min, the reaction mixture was quenched with 5% Na2S2O3 (10 mL) in ice-bath, concentrated in vacuo, and extracted with EtOAc. The combined extracts were washed with H2O and brine successively, dried over anhyd MgSO4, concentrated and purified by column chromatography (Hex/DCM=1:1) to afford 4-amino-2-chloro-6-fluorobenzyl acetate as yellow solid. 1H NMR (400 MHz, CDCl3) δ 6.55-6.49 (m, 1H), 6.33-6.27 (m, 1H), 5.15 (d, 2H), 3.97 (d, 2H), 2.07 (s, 3H).

Workup

  1. customthe reaction mixture was quenched with 5% Na2S2O3 (10 mL) in ice-bath
  2. concentrationconcentrated in vacuo
  3. extractionextracted with EtOAc
  4. washThe combined extracts were washed with H2O and brine successively
  5. dry with materialdried over anhyd MgSO4
  6. concentrationconcentrated
  7. custompurified by column chromatography (Hex/DCM=1:1)

Sources & evidence

ORD record
ord-e9f042995ddb4a79b1e725c0e551699c
Source dataset
uspto-grants-2014_09
Patent number
US08846739B2

Reaction notes

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