Water → HCID 18621484, compound

HRID 1861791Notes

Reaction equation

HRID 1861791 reaction equation
[H-].[H-].[H-].[H-].[Li+].[Al+3].[Cl:7][C:8]1[CH:22]=[CH:21][C:11]([CH2:12][CH:13]2[CH2:18][CH2:17][N:16]([N:19]=O)[CH2:15][CH2:14]2)=[CH:10][CH:9]=1.CCOCC.O>C1COCC1>[NH2:19][N:16]1[CH2:17][CH2:18][CH:13]([CH2:12][C:11]2[CH:10]=[CH:9][C:8]([Cl:7])=[CH:22][CH:21]=2)[CH2:14][CH2:15]1

Participants

6

Reactant 4

HCID 962WaterHCID 3283Diethyl EtherHCID 18621509HCID 18621509, compoundHCID 21226445Aluminium lithium hydride

Product 1

HCID 18621484HCID 18621484, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
25 °C

Procedure

A suspension of LiAlH4 (535 mg, 14.1 mmol) in dry THF (10 mL) was heated to refux with stirring. The mixture was removed from the heat source and a solution of 4-(4-chlorobenzyl)-1-nitrosopiperidine (1.68 g, 7.04 mmol) in dry THF (10 mL) was added with stirring so as to maintain a gentle reflux. After addition, the reaction was allowed to stir at reflux for 10 min. The reaction was allowed to cool to 25° C. and ether (60 mL) was added. Water (10 mL) was slowly added with stirring so as to destroy the excess hydride. The ether layer was separated and the aqueous portion was washed with ether. The combined ether portion was dried over Na2SO4 and the solvent was removed to give a near colorless liquid. This was filtered through a column of silica gel (2.5×10 cm) with 2% EtOH/98% CHCl3 elution to remove a low TLC Rf impurity. Solvent removal and drying in vacuo (0.005 Torr, 25° C.) gave a colorless liquid that solidified with scratching (1.20 g, 76%): mp 49-51° C.; 1H NMR (CDCl3) 1.24-1.52 (m, 3H), 1.56-1.68 (m, 2H), 2.00 (t, J=10, 2H), 2.48 (d, J=6.6, 2H), 2.86 (bs, 2H), 3.08 (d, J=11, 2H), 7.05 (d, J=8.4, 2H), 7.23 (d, J=8.4, 2H).

Workup

  1. temperaturewas heated
  2. customThe mixture was removed from the heat source
  3. stirringwith stirring so as
  4. temperatureto maintain a gentle reflux
  5. additionAfter addition
  6. stirringto stir
  7. temperatureat reflux for 10 min
  8. stirringwith stirring so as
  9. customto destroy the excess hydride
  10. customThe ether layer was separated
  11. washthe aqueous portion was washed with ether
  12. dry with materialThe combined ether portion was dried over Na2SO4
  13. customthe solvent was removed
  14. customto give a near colorless liquid
  15. filtrationThis was filtered through a column of silica gel (2.5×10 cm) with 2% EtOH/98% CHCl3 elution
  16. customto remove a low TLC Rf impurity
  17. customSolvent removal
  18. customdrying in vacuo (0.005 Torr, 25° C.)
  19. customgave a colorless liquid that solidified

Sources & evidence

ORD record
ord-d45bb45e53d749f4bac2d75f7ad2100c
Source dataset
uspto-grants-2003_03
Patent number
US06534522B2

Reaction notes

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