Nitromethane → Ethyl 4-hydroxy-4-(nitromethyl)-1-piperidinecarboxylate

HRID 559136Notes

Reaction equation

HRID 559136 reaction equation
[O:1]=[C:2]1[CH2:7][CH2:6][N:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:4][CH2:3]1.[N+:13]([CH3:16])([O-:15])=[O:14].C[O-].[Na+]>CO>[OH:1][C:2]1([CH2:16][N+:13]([O-:15])=[O:14])[CH2:3][CH2:4][N:5]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[CH2:6][CH2:7]1

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 34767Ethyl 4-oxo-1-piperidinecarboxylateHCID 10942334Sodium Methoxide

Product 1

HCID 22708806Ethyl 4-hydroxy-4-(nitromethyl)-1-piperidinecarboxylateYield 62.9%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a stirred and cooled mixture of ethyl 4-oxo-1-piperidinecarboxylate (85.5 g), nitromethane (33.6 g) in methanol (240 ml), sodium methoxide (10 g) is added dropwise. Upon completion, stirring is continued for 2 hours at about 10° C. and further overnight at room temperature. The reaction mixture is evaporated at room temperature, crushed ice is added to the oily residue and the whole is acidified with acetic acid. The product is extracted with trichloromethane, the extract is dried, filtered and evaporated. The oily residue solidifies on triturating in petroleumether. The product is filtered off and dried, yielding 73 g of ethyl 4-hydroxy-4-(nitromethyl)-1-piperidinecarboxylate (interm. 5).

Workup

  1. temperaturecooled
  2. additionis added dropwise
  3. stirringUpon completion, stirring
  4. customThe reaction mixture is evaporated at room temperature
  5. customcrushed ice
  6. additionis added to the oily residue
  7. extractionThe product is extracted with trichloromethane
  8. customthe extract is dried
  9. filtrationfiltered
  10. customevaporated
  11. customon triturating in petroleumether
  12. filtrationThe product is filtered off
  13. customdried

Sources & evidence

ORD record
ord-47867c8e472049fdbf96fe1279cd21e5
Source dataset
uspto-grants-2011_11
Patent number
US08063070B2

Reaction notes

Loading…