3-(4-Ethoxy-2-oxocyclohex-3-enyl)propyl-7-methoxy-2-oxo-2h-chromen-3-ylcarbamate → 3-(2,4-Dioxocyclohexyl)propyl 7-methoxy-2-oxo-2h-chromen-3-ylcarbamate

HRID 77273Notes

Reaction equation

HRID 77273 reaction equation
C([O:3][C:4]1[CH2:9][CH2:8][CH:7]([CH2:10][CH2:11][CH2:12][O:13][C:14](=[O:29])[NH:15][C:16]2[C:17](=[O:28])[O:18][C:19]3[C:24]([CH:25]=2)=[CH:23][CH:22]=[C:21]([O:26][CH3:27])[CH:20]=3)[C:6](=[O:30])[CH:5]=1)C>C1COCC1.C(Cl)Cl.Cl.O>[CH3:27][O:26][C:21]1[CH:20]=[C:19]2[C:24]([CH:25]=[C:16]([NH:15][C:14](=[O:29])[O:13][CH2:12][CH2:11][CH2:10][CH:7]3[CH2:8][CH2:9][C:4](=[O:3])[CH2:5][C:6]3=[O:30])[C:17](=[O:28])[O:18]2)=[CH:23][CH:22]=1

Participants

5

Reactant 1

HCID 589993283-(4-Ethoxy-2-oxocyclohex-3-enyl)propyl-7-methoxy-2-oxo-2h-chromen-3-ylcarbamate

Product 1

HCID 248304163-(2,4-Dioxocyclohexyl)propyl 7-methoxy-2-oxo-2h-chromen-3-ylcarbamateYield 59.4%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 962WaterSolventHCID 21919333Tetrahydrofurane dichloromethaneSolvent

Procedure

Compound 5 (240 mg, 0.58 mmol) was stirred in a mixture of THF/DCM (3/1 v/v, 4 mL) and 3N HCl (4 mL) for 1 hr. The reaction mixture was diluted with water (10 mL) and extracted with DCM (3×30 mL). The combined organic phases were dried over anhydrous MgSO4 and reduced to dryness to yield the crude product, which was purified by flash column chromatography (EtOAc/acetone 4/1) to yield 7 as an off-white solid (133 mg, 59.4%). Rf 0.62 (hexanes/EtOAc/MeOH 6/3/1); Mp. 154-156° C.; 1H NMR (300 MHz, CDCl3) δ 8.25 (1H, s), 7.42 (1H, s), 7.39 (1H, d, J=8.7 Hz), 6.88 (1H, dd, J=8.6 Hz, 2.1 Hz), 6.83 (1H, d, J=2.1 Hz), 4.23 (2H, t, J=6.5 Hz), 3.86 (3H, s), 3.44 (2H, d, J=5.1 Hz), 2.78-2.69 (1H, dt, J=16.4 Hz, 4.4 Hz), 2.67-2.51 (2H, m), 2.24-2.15 (1H, dq, J=14.1 Hz, 4.8 Hz), 2.03-1.95 (1H, m), 1.88-1.47 (6H, m); 13C NMR (75 MHz, CDCl3) δ 204.2, 203.8, 161.2, 158.9, 153.5, 151.3, 128.4, 122.0, 121.8, 113.3, 113.2, 100.9, 65.6, 58.5, 55.9, 49.1, 39.9, 26.6, 25.7, 24.8; ESI MS m/z 410 (M++Na+), 388 (M++H+); CHN calc. for C20H21NO7.0.5H2O, C: 60.59; H: 5.61; N: 3.53. found C, 61.31, H: 5.56, N: 3.48.

Workup

  1. extractionextracted with DCM (3×30 mL)
  2. dry with materialThe combined organic phases were dried over anhydrous MgSO4
  3. customto yield the crude product, which
  4. customwas purified by flash column chromatography (EtOAc/acetone 4/1)

Sources & evidence

ORD record
ord-f798a6255fe845b5b85e817fe16d352e
Source dataset
uspto-grants-2014_09
Patent number
US08841132B2

Reaction notes

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