Ethyl Acetate → 2-Bromo-4-(1,1-dioxo-hexahydro-1lambda6-thiopyran-4-yl)-phenylamine

HRID 1428027Notes

Reaction equation

HRID 1428027 reaction equation
[O:1]=[S:2]1(=[O:15])[CH2:7][CH2:6][CH:5]([C:8]2[CH:13]=[CH:12][C:11]([NH2:14])=[CH:10][CH:9]=2)[CH2:4][CH2:3]1.[Br:16]N1C(=O)CCC1=O.CCOC(C)=O>C(Cl)Cl.CO.C(Cl)Cl>[Br:16][C:12]1[CH:13]=[C:8]([CH:5]2[CH2:6][CH2:7][S:2](=[O:15])(=[O:1])[CH2:3][CH2:4]2)[CH:9]=[CH:10][C:11]=1[NH2:14]

Participants

6

Reactant 3

HCID 8857Ethyl AcetateHCID 67184N-bromobutanimideHCID 591285934-(1,1-Dioxo-hexahydro-1lambda6-thiopyran-4-yl)-phenylamine

Product 1

HCID 591285552-Bromo-4-(1,1-dioxo-hexahydro-1lambda6-thiopyran-4-yl)-phenylamineYield 66%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 21226129Dichloromethane methanolSolvent

Procedure

To a suspension of 4-(1,1-dioxo-hexahydro-1λ6-thiopyran-4-yl)-phenylamine (as prepared in the previous step, 174 mg, 0.77 mmol) in 20 mL of 3:1 DCM/MeOH at 0° C. was added N-bromosuccinimide (NBS) (137 mg, 0.77 mmol) in 5 mL of DCM under Ar. The mixture was warmed to RT and stirred for 1 h under Ar. Treated with 100 mL of EtOAc, the mixture was washed with H2O (2×20 mL), brine (20 mL) and dried (Na2SO4). Removal of the solvent under reduced pressure followed by flash chromatography of the residue on silica gel (2-3% EtOAc/DCM) gave 155 mg (66%) of the title compound as a white solid. 1H-NMR (CDCl3; 400 MHz): δ 7.28 (d, 1H, J=2.0 Hz), 6.97 (dd, 1H, J=8.3, 2.0 Hz), 6.73 (d, 1H, J=8.3 Hz), 4.07 (br s, 2H), 3.09-3.14 (m, 4H), 2.66 (dddd, 1H, J=12.1, 12.1, 3.3, 3.3 Hz), 2.26-2.39 (m, 2H), 2.12-2.21 (m, 2H). Mass spectrum (ESI, m/z): Calcd. for C11H14BrNO2S, 304.0 (M+H). found 304.1.

Workup

  1. washthe mixture was washed with H2O (2×20 mL), brine (20 mL)
  2. dry with materialdried (Na2SO4)
  3. customRemoval of the solvent under reduced pressure

Sources & evidence

ORD record
ord-adf87cf275cb46828a156587a0566f54
Source dataset
uspto-grants-2015_01
Patent number
US08933091B2

Reaction notes

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