Ethyl Acetate → N-(2-((tert-butyl(dimethyl)silyl)oxy)ethyl)-N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-2-nitrobenzenesulfonamide

HRID 85560Notes

Reaction equation

HRID 85560 reaction equation
[O:1]=[S:2]1(=[O:23])[CH2:7][CH2:6][N:5]([CH2:8][CH2:9][NH:10][S:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[N+:20]([O-:22])=[O:21])(=[O:13])=[O:12])[CH2:4][CH2:3]1.C(=O)([O-])[O-].[Cs+].[Cs+].Br[CH2:31][CH2:32][O:33][Si:34]([C:37]([CH3:40])([CH3:39])[CH3:38])([CH3:36])[CH3:35].C(OCC)(=O)C>CN(C=O)C.O>[Si:34]([O:33][CH2:32][CH2:31][N:10]([CH2:9][CH2:8][N:5]1[CH2:6][CH2:7][S:2](=[O:1])(=[O:23])[CH2:3][CH2:4]1)[S:11]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=1[N+:20]([O-:22])=[O:21])(=[O:12])=[O:13])([C:37]([CH3:40])([CH3:39])[CH3:38])([CH3:36])[CH3:35]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 10796Cesium carbonateHCID 3608067(2-Bromoethoxy)-tert-butyldimethylsilaneHCID 68358008N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-2-nitrobenzenesulfonamide

Product 1

HCID 68275942N-(2-((tert-butyl(dimethyl)silyl)oxy)ethyl)-N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-2-nitrobenzenesulfonamideYield 98%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

N-(2-(1,1-dioxido-4-thiomorpholinyl)ethyl)-2-nitrobenzenesulfonamide (0.400 g, 1.10 mmol) was combined with cesium carbonate (0.538 g, 1.65 mmol) in DMF (5 mL). The slurry was stirred at rt for 30 min, then to it was added (2-bromoethoxy)(tert-butyl)dimethylsilane (0.527 g, 2.20 mmol). The resulting mixture was stirred at rt for 18 h. Dilution with ethyl acetate (60 mL) and water (40 mL) followed by shaking gave a separation of phases. The organic phase was isolated, washed with water (2×30 mL) and brine (25 mL), dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to a residue. Purification by silica gel chromatography (gradient 100% DCM to 100:1 DCM:MeOH) gave the title compound as a yellow solid (0.560 g, 98% yield). LCMS: m/z 522 (M+H+), retention time 2.22 min (method 11). 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 0.01 (s, 6H) 0.86 (s, 9H) 2.75 (t, J=5.95 Hz, 2H) 3.05 (s, 8H) 3.44 (t, J=5.49 Hz, 2H) 3.57 (t, J=6.41 Hz, 2H) 3.70 (t, J=5.49 Hz, 2H) 7.63-7.78 (m, 3H) 8.02-8.11 (m, 1H).

Workup

  1. stirringThe resulting mixture was stirred at rt for 18 h
  2. stirringby shaking
  3. customgave
  4. customa separation of phases
  5. customThe organic phase was isolated
  6. washwashed with water (2×30 mL) and brine (25 mL)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo to a residue
  10. customPurification by silica gel chromatography (gradient 100% DCM to 100:1 DCM:MeOH)

Sources & evidence

ORD record
ord-8dbf128ee7064e898d61a563a65a8d20
Source dataset
uspto-grants-2014_09
Patent number
US08846647B2

Reaction notes

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