Water → HCID 12790990, compound

HRID 850296Notes

Reaction equation

HRID 850296 reaction equation
CO[N:3]=[C:4]([C:12]1[CH:17]=[CH:16][C:15]([Cl:18])=[CH:14][CH:13]=1)[CH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.B.O1CCCC1.O>C1COCC1>[NH2:3][CH:4]([C:12]1[CH:13]=[CH:14][C:15]([Cl:18])=[CH:16][CH:17]=1)[CH2:5][C:6]1[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

5

Reactant 3

HCID 962WaterHCID 2723981Borane;tetrahydrofuranHCID 57395312HCID 57395312, compound

Product 1

HCID 12790990HCID 12790990, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of the oxime geometric isomer mixture 9 (2.690 g, 10.36 mmol) in dry THF (50 ml, freshly distilled from sodium benzophenone ketyl) under nitrogen at room temperature was added borane-tetrahydrofuran solution (36.0 ml, 36.0 mmol, 1.0 M solution, Aldrich) by syringe. The resulting very pale orange solution was refluxed for 16 hours, and cooled in an ice bath. Water (80 ml) was added carefully to quench, followed by 20% NaOH (80 ml). The resulting colorless bi-phasic mixture was refluxed overnight with vigorous magnetic stirring. After cooling to room temperature, hexanes (50 ml) were added and the layers separated. The aqueous portion was washed with hexanes (1×30 ml), and the combined organic portions dried over potassium carbonate. Evaporation of the solvent afforded the pure amine as 2.392 g of a clear, pale yellow syrup (99% yield): Rf 0.22 (5% methanol in CHCl3): IR (CDCl3) 3376 (w), 3068 (w), 3031 (w), 2922 (w), 2850 (w), 1602 (m), 1493 (s), 1457 (m), 1409 (w); 1H NMR (CDCl3) δ7.40-21 (m, 7H), 7.19 (d, J=8.6 Hz, 2H), 4.21 (dd, J=8.4, 5.2 Hz, 1H), 2.98 (dd, J=13.2, 5.2 Hz, 1H), 2.81 (dd, J=13.2, 8.6 Hz, 1H), 1.43 (s, 2H); low resolution mass spec. 232 (M-1, 5.0), 230 (m-1, 11), 142 (M-91, 37), 140 (M-91, 100), 91 (28).

Workup

  1. temperatureThe resulting very pale orange solution was refluxed for 16 hours
  2. temperaturecooled in an ice bath
  3. customto quench
  4. temperatureThe resulting colorless bi-phasic mixture was refluxed overnight with vigorous magnetic stirring
  5. additionhexanes (50 ml) were added
  6. customthe layers separated
  7. washThe aqueous portion was washed with hexanes (1×30 ml)
  8. dry with materialthe combined organic portions dried over potassium carbonate
  9. customEvaporation of the solvent

Sources & evidence

ORD record
ord-e9578d3c18df48a39389f450d52da965
Source dataset
uspto-grants-2000_01
Patent number
US06017910

Reaction notes

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