Butanal → (R)-2-(N-Phenyl-aminooxy)-butan-1-ol

HRID 500053

Reaction equation

HRID 500053 reaction equation
N1CCC[C@H]1C(O)=O.[CH:9](=[O:13])[CH2:10][CH2:11][CH3:12].[N:14]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:15].[BH4-].[Na+].P([O-])([O-])([O-])=O>C(#N)C.C(OCC)(=O)C.CO>[C:16]1([NH:14][O:15][C@H:10]([CH2:11][CH3:12])[CH2:9][OH:13])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

9

Reactant 5

HCID 261ButanalHCID 1061PhosphateHCID 11473NitrosobenzeneHCID 145742L-ProlineHCID 4311764Sodium borohydride

Product 1

HCID 11816230(R)-2-(N-Phenyl-aminooxy)-butan-1-olYield 43%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-20 °C

Procedure

At about −20° C., L-proline (4 g, 34.8 mmol) was added to solution of n-butyraldehyde (25 mL, 278 mmol) and nitrosobenzene (15 g, 140 mmol) in acetonitrile (300 mL). The mixture was stirred at about −20° C. for about 48 hours, methanol (50 mL) and sodium borohydride (16 g, 432 mmol) were added, the mixture was stirred for about 10 minutes, and phosphate buffer was added. Following standard extractive workup with ethyl acetate, the crude product was purified by column chromatography with silica gel (petroleum ether-ethyl acetate =5:1, v:v, elution) to afford the title product (10.8 g, 43%). 1H NMR (300 MHz, CDCl3) δ 7.30-7.25 (m, 2H), 7.01-6.96 (m, 3H), 3.90-3.74 (m, 3H), 1.75-1.57 (m, 2H), 1.02 (t, J=7.8 Hz, 3H); LC-MS: m/z=182 (M+H)+.

Workup

  1. stirringthe mixture was stirred for about 10 minutes
  2. customthe crude product was purified by column chromatography with silica gel (petroleum ether-ethyl acetate =5:1, v:v, elution)

Sources & evidence

ORD record
ord-9c287d615b44465c8b90e329552ec1cf
Source dataset
uspto-grants-2010_08
Patent number
US07767860B2

Linked notes

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