Hydrogen Peroxide → 2-(3-hydroxypropyl)-8-methoxy-2,3,4,5-tetrahydro-1H-2-benzazepin-1-one

HRID 865336Notes

Reaction equation

HRID 865336 reaction equation
[CH2:1]([N:4]1[CH2:10][CH2:9][CH2:8][C:7]2[CH:11]=[CH:12][C:13]([O:15][CH3:16])=[CH:14][C:6]=2[C:5]1=[O:17])[CH:2]=[CH2:3].C1(C2CCCCCCCC2)BCCCCCCC1.[OH-].[Na+].OO.S([O-])([O-])(=[O:42])=S.[Na+].[Na+]>O1CCCC1.CCO>[OH:42][CH2:3][CH2:2][CH2:1][N:4]1[CH2:10][CH2:9][CH2:8][C:7]2[CH:11]=[CH:12][C:13]([O:15][CH3:16])=[CH:14][C:6]=2[C:5]1=[O:17]

Participants

8

Reactant 5

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 229049982-allyl-8-methoxy-2,3,4,5-tetrahydro-1H-2-benzazepin-1-oneHCID 178418648HCID 178418648, compound

Product 1

HCID 229050192-(3-hydroxypropyl)-8-methoxy-2,3,4,5-tetrahydro-1H-2-benzazepin-1-oneYield 60%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of 2-allyl-8-methoxy-2,3,4,5-tetrahydro-1H-2-benzazepin-1-one (8.0 g, 0.043 mol) in dry tetrahydrofuran (40 mL) was treated with 9-borabicyclononane (1.0M in THF) and the resulting mixture was stirred for 18 hours at room temperature. The solution was then diluted with EtOH (50 mL), cooled to 0° C. (ice bath), and treated with 15% aqueous NaOH (15 mL) followed by 30% aqueous H2O2 (10 mL). The resulting mixture was stirred for 1 hour at 0° C., then treated cautiously with saturated aqueous sodium thiosulfate (50 mL). The mixture was partitioned between ethyl acetate and brine, and the combined organic layers were concentrated in vacuo, and the residue was purified by chromatography over silica gel eluting with ethyl acetate to yield 6.5 g (60%) of 2-(3-hydroxypropyl)-8-methoxy-2,3,4,5-tetrahydro-1H-2-benzazepin-1-one as a colorless oil; 1H NMR(CDCl3) d7.19(s, 1H), 7.06(d, J=9 Hz, 1H, 6.92(dd, J=3, 9 Hz, 1H), 4.30(brs, 1H), 3.82(s, 3H), 3.71(t, J=6 Hz, 2H), 3.61(brs, 2H), 3.18(t, J=6 Hz, 2H), 2.72(t, J=6 Hz, 2H), 2.02(pentet, J=6 Hz, 2H), 1.79(pentet, J=6 Hz, 2H); 13C NMR(CDCl3) d172.25(CO), 158.51(NCO), 136.34, 129.53, 117.46, 112.94, 58.19, 55.42, 46.16, 43.30, 30.91, 29.45, 29.12; MS (FAB) m/z=250.1(MH+); HRMS (FAB, MH+) m/z=249.1364 (cald C14H19NO3 : 249.1364).

Workup

  1. temperaturecooled to 0° C. (ice bath)
  2. stirringThe resulting mixture was stirred for 1 hour at 0° C.
  3. customThe mixture was partitioned between ethyl acetate and brine
  4. concentrationthe combined organic layers were concentrated in vacuo
  5. customthe residue was purified by chromatography over silica gel eluting with ethyl acetate

Sources & evidence

ORD record
ord-5fd70794287a4ae09f8414d0f414d814
Source dataset
uspto-grants-1996_10
Patent number
US05565449

Reaction notes

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