Water → HCID 19362820, compound

HRID 2293967Notes

Reaction equation

HRID 2293967 reaction equation
CO[N:3]=[C:4]([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([Br:12])=[CH:8][CH:7]=1.B.O1CCCC1.O>C1COCC1>[NH2:3][CH:4]([C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[CH2:5][C:6]1[CH:11]=[CH:10][C:9]([Br:12])=[CH:8][CH:7]=1

Participants

5

Reactant 3

HCID 962WaterHCID 2723981Borane;tetrahydrofuranHCID 85675369HCID 85675369, compound

Product 1

HCID 19362820HCID 19362820, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of the mixture of oxime isomers 8 (4.92 g, 16.2 mmol) in 75 ml THF (freshly distilled from sodium benzophenone ketyl) under nitrogen was added borane-tetrahydrofuran complex (1.0M in THF, 55.0 ml, 55.0 mmol) by syringe at room temperature. The resulting pale orange solution was brought to reflux and held there for 16 hours. With cooling by an ice bath, water (125 ml) was carefully added to quench, followed by 20% NaOH (125 ml).The resulting biphasic solution was refluxed with vigorous magnetic stirring overnight. After cooling to room temperature, hexanes (60 ml) were added and the layers were separated. The aqueous portion was extracted with hexanes (2×50 ml). The combined organic portions were dried over potassium carbonate and concentrated in vacuo to a cloudy, colorless syrup. This syrup was purified by column chromatography on 20 g neutral alumina (activity I) using a 20% ethyl acetate-hexanes to 4% diethylamine-chloroform elution gradient. The amine 13 was isolated as 3.985 g of a clear, colorless syrup (89% yield): Rf 0.18 (2% diethylamine in CHCl3); 1H NMR (CDCl3) δ7.41 (d, J=8.2 Hz, 2H), 7.35-7.28 (m, 5H), 7.03 (d, J=8.2 Hz, 2H), 4.18 (dd, J=8.2, 5.3 Hz, 1H), 2.97 (dd, J=13.3, 53 Hz, 1H), 2.83 (dd, J=13.3, 8.3 Hz, 1H), 1.45 br s, 2H); low resolution mass Spec. 277 (M+, 1.5), 275 (M+, 1.5), 261 (2.2), 259 (2.2), 171, (4.5), 169 (4.5), 106 (100), 79 (45).

Workup

  1. distillationfreshly distilled from sodium benzophenone ketyl) under nitrogen
  2. temperatureto reflux
  3. temperatureWith cooling by an ice bath
  4. customto quench
  5. customresulting biphasic solution
  6. temperaturewas refluxed with vigorous
  7. customthe layers were separated
  8. extractionThe aqueous portion was extracted with hexanes (2×50 ml)
  9. dry with materialThe combined organic portions were dried over potassium carbonate
  10. concentrationconcentrated in vacuo to a cloudy, colorless syrup
  11. customThis syrup was purified by column chromatography on 20 g neutral alumina (activity I)
  12. washto 4% diethylamine-chloroform elution gradient

Sources & evidence

ORD record
ord-26e092272ef44dfba49eea8282e68f14
Source dataset
uspto-grants-1997_11
Patent number
US05688789

Reaction notes

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