Water → HCID 3052630, compound

HRID 850294Notes

Reaction equation

HRID 850294 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]([Cl:12])=[CH:8][CH:7]=1.B.O1CCCC1.O>C1COCC1>[Cl:12][C:9]1[CH:8]=[CH:7][C:6]([CH2:5][CH:4]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[NH2:3])=[CH:11][CH:10]=1

Participants

5

Reactant 3

HCID 962WaterHCID 2723981Borane;tetrahydrofuranHCID 85675368HCID 85675368, compound

Product 1

HCID 3052630HCID 3052630, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of oxime geometric isomers 7 (840 mg, 3.23 mmol) in 30 ml dry THF (freshly distilled from sodium/benzophenone ketyl) under nitrogen was added borane-tetrahydrofuran complex (1.0 M in THF, 16.2 ml, 16.2 mmol) by syringe at room temperature. The resulting pale yellow solution was refluxed overnight, and cooled in an ice bath. Water (25 ml) was carefully added to quench, followed by 20% NaOH (25 ml). The resulting bi-phasic solution was refluxed with vigorous magnetic stirring overnight. After cooling to room temperature, hexanes (40 ml) were added, and the layers were separated. The aqueous portion was extracted with hexanes (1×40 ml). The combined organic portions were dried over potassium carbonate and concentrated in vacuo to a cloudy, pale yellow syrup. This syrup was purified by column chromatography on 18 g neutral alumina (activity I) using chloroform as eluant to afford the amine as 455.6 mg of a colorless, slightly cloudy syrup (61% yield): Rf 0.36 (5% Et2NH/CHCl3); IR (CDCl3) 3376 (w), 3316 (w), 3031 (w), 2928 (m), 2856 (w), 1602 (m), 1493 (m), 1451 (m); 1H NMR (CDCl3) δ7.38-7.28 (m, 5H), 7.26 (d, J=8.3 Hz, 2H), 7.09 (d, J=8.3 Hz, 2H), 4.18 (dd, J=8.3, 5.4 Hz, 1H), 2.98 (dd, J=13.4, 5.4 Hz, 1H), 2.84 (dd, J=13.4, 8.4 Hz), 1.50 (br s, 2H); low resolution mass spec. 232 (M+, 22), 215 (37), 125 (54), 106 (100), 89 (49), 79 (100).

Workup

  1. temperatureThe resulting pale yellow solution was refluxed overnight
  2. temperaturecooled in an ice bath
  3. customto quench
  4. temperatureThe resulting bi-phasic solution was refluxed with vigorous
  5. additionhexanes (40 ml) were added
  6. customthe layers were separated
  7. extractionThe aqueous portion was extracted with hexanes (1×40 ml)
  8. dry with materialThe combined organic portions were dried over potassium carbonate
  9. concentrationconcentrated in vacuo to a cloudy, pale yellow syrup
  10. customThis syrup was purified by column chromatography on 18 g neutral alumina (activity I)

Sources & evidence

ORD record
ord-243e2af8f54d4e519830db72da2ae032
Source dataset
uspto-grants-2000_01
Patent number
US06017910

Reaction notes

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