tert-Butyl bromoacetate → HCID 15896050, compound

HRID 1955102Notes

Reaction equation

HRID 1955102 reaction equation
[CH2:1]([NH:9][S:10]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)(=[O:12])=[O:11])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[Li+].C[Si]([N-][Si](C)(C)C)(C)C.Br[CH2:31][C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33]>C1COCC1.[NH4+].[Cl-].C(OCC)(=O)C>[C:35]([O:34][C:32](=[O:33])[CH2:31][N:9]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])[S:10]([C:13]1[CH:18]=[CH:17][C:16]([CH3:19])=[CH:15][CH:14]=1)(=[O:11])=[O:12])([CH3:38])([CH3:37])[CH3:36]

Participants

7

Reactant 3

HCID 79177tert-Butyl bromoacetateHCID 2733832Lithium HexamethyldisilazideHCID 3090479Benzenesulfonamide, 4-methyl-N-octyl-

Product 1

HCID 15896050HCID 15896050, compoundYield 53%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
-78 °C

Procedure

N-Octyl-toluene-4-sulfonamide (7.0 g, 0.025 mol) was dissolved in dry THF (200 ml) and cooled to -78° C. A 1M solution of LHMDS in THF (27.2 ml, 0.028 mol) was then added over 10 minutes. The reaction mixture was allowed to warm to -40° C. with stirring over 30 minutes. Neat tert-butyl bromoacetate (4.8 ml, 0.03 mol) was added over 5 minutes and the reaction mixture was allowed to warm to ambient temperature overnight. The reaction mixture was diluted with saturated aqueous NH4Cl (200 ml) and ethyl acetate (200 ml). The organic layer was separated and washed consecutively with 1M HCl, 0.5M Na2CO3 and brine, dried over Na2SO4, filtered and concentrated in vacuo. The resulting crude oil was purified by flash chromatography (silica gel, 6% ethyl acetate in hexane) to give the title compound as a white solid (5.2 g, 53%). 1H NMR: δ (CDCl3), 7.72 (2H, d, J=8.3 Hz), 7.27 (2H, d, J=8.4 Hz), 3.94 (2H, s), 3.23 (2H, dd, J=7.5, 7.6 Hz), 2.42 (3H, s), 1.60-1.42 (2H, m), 1.39 (9H, s), 1.34-1.17 (10H, m), 0.88 (3H, t, J=6.9 Hz).

Workup

  1. temperatureto warm to -40° C.
  2. temperatureto warm to ambient temperature overnight
  3. customThe organic layer was separated
  4. washwashed consecutively with 1M HCl, 0.5M Na2CO3 and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe resulting crude oil was purified by flash chromatography (silica gel, 6% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-60b06511e8754d299e8e2a127e540664
Source dataset
uspto-grants-2000_09
Patent number
US06124333

Reaction notes

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