Reacción #1365702

ord-10b6824bcbc0490f9bb5c5e5887e5132

Ecuación de reacción

CCOC(=O)[C@@H]1C(=O)N(C)C(=O)C[C@H]1c1ccc(F)cc1
(+/−)trans 3-ethoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione
[Cl-].[Li+]
LiCl
O
Water
[Cl-].[Li+]
LiCl
[Na+].[OH-]
NaOH
CCOC(=O)[C@@H]1C(=O)N(C)C(=O)C[C@H]1c1ccc(F)cc1
(+/−)trans 3-ethoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione
O
H2O
CN1CC[C@@H](c2ccc(F)cc2)[C@H](CO)C1
(+/−) trans-4-(4′-fluorophenyl)-3-hydroxymethyl-N-methylpiperidine

Condiciones de reacción

Condiciones detalladas
See reaction.notes.procedure_details.

Tratamiento posterior

  1. 1
    Otrothe temperature below 15° C
  2. 2
    workup.ADDITIONAfter addition
  3. 3
    Otroreaction
  4. 4
    Temperaturathe reaction is heated to >40° C. for 2 hr
  5. 5
    TemperaturaThe reaction is then cooled to <5° C.
  6. 6
    Otrothe temperature below 15° C
  7. 7
    OtroThe solid inorganic salts are removed by filtration
  8. 8
    LavadoThese solids are washed with additional THF or toluene
  9. 9
    ConcentraciónThe filtered solution is then concentrated

Procedimiento

To a cooled mixture of NaAlH4 (0.22 mol) in toluene is added LiCl (0.11 mol) in THF. Note: LiCl can be added to the reactor prior to the addition of NaAlH4 or after the addition of the substrate, (+/−)trans 3-ethoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione. Next, (+/−)trans 3-ethoxycarbonyl-4-(4′-fluorophenyl)-N-methyl-piperidine-2,6-dione (0.083 mol) is added in THF (65 ml) holding the temperature below 15° C. After addition is completed, reaction is allowed to warm to room temperature. After 30 minutes at room temperature, the reaction is heated to >40° C. for 2 hr. The reaction is then cooled to <5° C. and toluene (50 ml) is added. Water (9 ml) is then added slowly holding the temperature below 15° C. Additional H2O or aqueous NaOH is used as necessary. The solid inorganic salts are removed by filtration. These solids are washed with additional THF or toluene. The filtered solution is then concentrated to give (+/−) trans-4-(4′-fluorophenyl)-3-hydroxymethyl-N-methylpiperidine in essentially the same yield and similar impurity profile as with LiAlH4 as shown by HPLC analysis. The product can be recovered by standard procedures such as trituration with a less polar solvents.

Fuente

DOI: 10.6084/m9.figshare.5104873.v1Patente: US06444190B2uspto-grants-2002_09