Sodium hydride → O-[4-(tert-butyl-diphenyl-silanyloxy)-butyl]-N-methyl-N-Boc-hydroxylamine

HRID 2093239Notes

Reaction equation

HRID 2093239 reaction equation
[C:1]([N:8]([CH3:10])[OH:9])([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2].[H-].[Na+].Br[CH2:14][CH2:15][CH2:16][CH2:17][O:18][Si:19]([C:32]([CH3:35])([CH3:34])[CH3:33])([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>CN(C=O)C>[C:32]([Si:19]([C:20]1[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=1)([C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[O:18][CH2:17][CH2:16][CH2:15][CH2:14][O:9][N:8]([CH3:10])[C:1]([O:3][C:4]([CH3:7])([CH3:6])[CH3:5])=[O:2])([CH3:33])([CH3:34])[CH3:35]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 272414tert-Butyl hydroxy(methyl)carbamateHCID 14362384(4-Bromobutoxy)(tert-butyl)diphenylsilane

Product 1

HCID 86638814O-[4-(tert-butyl-diphenyl-silanyloxy)-butyl]-N-methyl-N-Boc-hydroxylamine

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

N-Boc-N-methylhydroxylamine (a) (0.74 g, 5 mmol) was dissolved in 10 ml DMF, treated with NaH (200 mg, 60% dispersion in mineral oil, 4.75 mmol), and stirred for 1 h under an argon atmosphere. The mixture was cooled to 0° C., treated with a solution of 4-bromo-butoxy)-tert-butyl-diphenyl-silane (b) (1.56 g, 4 mmol) in DMF (10 mL) and stirred at 0° C. for an additional 3 hours. The solvents were removed under reduced pressure, and the residue was dissolved in EtOAc (150 mL) and poured into a separatory funnel. The organic layer was washed with 0.1 M NaOH (5×50 mL), H20 (50 ml), 0.1 M KHSO4, and brine (50 ml) and the dried with MgSO4. After removal of the solvent, the residue was chromatographed on silicagel (Hexane:EtOAc 10:1) to yield 0.588 g (24%). The product was identified by electrospray mass spectrometry (ESI-MS)(MH+ calculated 457.26; found 457.8)

Workup

  1. stirringstirred at 0° C. for an additional 3 hours
  2. customThe solvents were removed under reduced pressure
  3. dissolutionthe residue was dissolved in EtOAc (150 mL)
  4. additionpoured into a separatory funnel
  5. washThe organic layer was washed with 0.1 M NaOH (5×50 mL), H20 (50 ml), 0.1 M KHSO4, and brine (50 ml)
  6. dry with materialthe dried with MgSO4
  7. customAfter removal of the solvent
  8. customthe residue was chromatographed on silicagel (Hexane:EtOAc 10:1)
  9. customto yield 0.588 g (24%)

Sources & evidence

ORD record
ord-d5ba3aebd1914af484b43e649e90473b
Source dataset
uspto-grants-2013_05
Patent number
US08444955B2

Reaction notes

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