4-Toluenesulfonyl chloride → Tert-butyl 6-amino-3-bromo-2-(4-methylbenzenesulfonyloxy)benzoate

HRID 715982Notes

Reaction equation

HRID 715982 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([S:8](Cl)(=[O:10])=[O:9])=[CH:4][CH:3]=1.[NH2:12][C:13]1[C:18]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])=[C:17]([OH:26])[C:16]([Br:27])=[CH:15][CH:14]=1.C(N(CC)CC)C>CN(C1C=CN=CC=1)C.C(Cl)Cl>[NH2:12][C:13]1[C:18]([C:19]([O:21][C:22]([CH3:23])([CH3:24])[CH3:25])=[O:20])=[C:17]([O:26][S:8]([C:5]2[CH:6]=[CH:7][C:2]([CH3:1])=[CH:3][CH:4]=2)(=[O:10])=[O:9])[C:16]([Br:27])=[CH:15][CH:14]=1

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 66685946Tert-butyl 6-amino-3-bromo-2-hydroxybenzoate2×

Product 1

HCID 86712121Tert-butyl 6-amino-3-bromo-2-(4-methylbenzenesulfonyloxy)benzoateYield 80.2%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

4-Methylbenzenesulfonyl chloride (2.26 g) was added to a solution of tert-butyl 6-amino-3-bromo-2-hydroxybenzoate (Intermediate 51, 2.85 g), DMAP (1.21 g), and triethylamine (1.5 g) in DCM (40 mL) and left at room temperature for 1 hour. The resulting solution was washed with water, filtered through a phase separator and the filtrate was concentrated in vacuo. The residue was purified by chromatography on silica, eluting with a mixture of ethyl acetate and cyclohexane with a gradient of 0-15% to give tert-butyl 6-amino-3-bromo-2-(4-methylbenzenesulfonyloxyl)benzoate (3.51 g) as an off-white solid.

Workup

  1. washThe resulting solution was washed with water
  2. filtrationfiltered through a phase separator
  3. concentrationthe filtrate was concentrated in vacuo
  4. customThe residue was purified by chromatography on silica
  5. washeluting with a mixture of ethyl acetate and cyclohexane with a gradient of 0-15%

Sources & evidence

ORD record
ord-9322b16d321c4a23b183c4e7ce67b433
Source dataset
uspto-grants-2015_11
Patent number
US09187494B2

Reaction notes

Loading…