m-Chloroperbenzoic acid → (S)-1-PHENYLETHYLHYDROXYLAMINE

HRID 1700838Notes

Reaction equation

HRID 1700838 reaction equation
COC1C=CC(C=[N:10][C@H:11]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH3:12])=CC=1.ClC1C=C(C=CC=1)C(OO)=[O:24].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.Cl.ON>O1CCCC1.C(OCC)(=O)C.O>[C:13]1([C@@H:11]([NH:10][OH:24])[CH3:12])[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

8

Reactant 4

HCID 70297m-Chloroperbenzoic acidHCID 443297Hydroxyamine hydrochlorideHCID 521998p-Toluenesulfonic acid monohydrateHCID 778491HCID 778491, compound

Product 1

HCID 10911281(S)-1-PHENYLETHYLHYDROXYLAMINEYield 86%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
0 °C

Procedure

A −78° C. solution of Example 2A (7.15 g, 30 mmole) in tetrahydrofuran (75 mL) was treated with a solution of 3-chloroperoxybenzoic acid (15 g, 60 mmol), warmed to 0 ° C., stirred for 2 hours, diluted with ethyl acetate (100 mL), washed sequentially with 10% (w/w) sodium thiosulfate, saturated sodium bicarbonate, and brine, dried (MgSO4), filtered, and concentrated. The concentrate was dissolved in tetrahydrofuran (100 mL), treated with p-toluene sulfonic acid monohydrate (8.15 g, 42.8 mmol), stirred for 2 hours, treated with a solution of N-hydroxylamine hydrochloride (8.7 g) in water (15 mL), and stirred for 16 hours. The mixture was diluted with ethyl acetate (100 mL), washed with saturated sodium bicarbonate and brine, dried (MgSO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 1:2 ethyl acetate/hexanes to provide 3.53g (86% yield) of the desired product. 1H NMR (300 MHz, CDCl3) δ 7.36-7.20 (m, 5H), 4.09 (q, 1H, J=6.6 Hz), 1.48 (d, 3H, J=6.6 Hz).

Workup

  1. washwashed sequentially with 10% (w/w) sodium thiosulfate, saturated sodium bicarbonate, and brine
  2. dry with materialdried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. dissolutionThe concentrate was dissolved in tetrahydrofuran (100 mL)
  6. stirringstirred for 2 hours
  7. stirringstirred for 16 hours
  8. washwashed with saturated sodium bicarbonate and brine
  9. dry with materialdried (MgSO4)
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe concentrate was purified by flash column chromatography on silica gel with 1:2 ethyl acetate/hexanes

Sources & evidence

ORD record
ord-a1504fef163d4494bbb1078f43843f5f
Source dataset
uspto-grants-2002_02
Patent number
US06350902B2

Reaction notes

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