Methoxymethylbutanol → N-hydroxy-3-methoxy-3-methylbutan-1-imine

HRID 475534

Reaction equation

HRID 475534 reaction equation
CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O.[CH3:23][O:24][C:25]([CH3:30])([CH3:29])[CH2:26][CH2:27]O.COC(C)(C)CC=O.Cl.[OH:40][NH2:41]>C(OCC)(=O)C.N1C=CC=CC=1.C(Cl)(Cl)Cl>[OH:40][N:41]=[CH:27][CH2:26][C:25]([O:24][CH3:23])([CH3:30])[CH3:29]

Participants

8

Reactant 4

HCID 62118MethoxymethylbutanolHCID 159087TriacetoxyperiodinaneHCID 443297Hydroxyamine hydrochlorideHCID 111709493-Methoxy-3-methylbutanal

Product 1

HCID 86670070N-hydroxy-3-methoxy-3-methylbutan-1-imineYield 38.2%

Reagents, catalysts & solvents 3

HCID 1049PyridineSolventHCID 6212ChloroformSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

Dess-Martin reagent (15.0 g) was added to a chloroform solution (35 ml) of 3-methoxy-3-methyl-1-butanol (3.3 g) under ice cooling and stirred at room temperature for 5 hours. Chloroform was added to the reaction mixture and the organic layer was washed with an aqueous solution of 20 wt. % sodium thiosulfate, a saturated aqueous solution of sodium hydrogencarbonate and saturated brine. The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure, thereby obtaining a crude product containing 3-methoxy-3-methylbutanal. Hydroxyamine hydrochloride (3.5 g) was added to a pyridine solution of the obtained crude product (30 ml) under ice cooling and stirred at room temperature overnight under nitrogen atmosphere. Ethyl acetate was added to the reaction mixture and the organic layer was washed with water, 1M-hydrochloric acid aqueous solution and saturated brine. The organic layer was dried over magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (KP-Sil, Biotage, ethyl acetate/n-hexane=10 to 50%), thereby obtaining (N-hydroxy-3-methoxy-3-methylbutan-1-imine (1.4 g) as a colorless oily substance.

Workup

  1. washthe organic layer was washed with an aqueous solution of 20 wt. % sodium thiosulfate
  2. dry with materialThe organic layer was dried over magnesium sulfate
  3. distillationthe solvent was distilled off under reduced pressure
  4. customobtaining a crude product
  5. customobtained crude product (30 ml) under ice cooling
  6. stirringstirred at room temperature overnight under nitrogen atmosphere
  7. washthe organic layer was washed with water, 1M-hydrochloric acid aqueous solution and saturated brine
  8. dry with materialThe organic layer was dried over magnesium sulfate
  9. distillationthe solvent was distilled off under reduced pressure
  10. customThe residue was purified by column chromatography (KP-Sil, Biotage, ethyl acetate/n-hexane=10 to 50%)

Sources & evidence

ORD record
ord-69f858a680a946669bf50bcfe03079b8
Source dataset
uspto-grants-2014_01
Patent number
US08637557B2

Linked notes

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