Sodium Hydroxide → HCID 20512083, compound

HRID 1164385Notes

Reaction equation

HRID 1164385 reaction equation
[C:1]([CH:4]1[CH2:9][C:8]([CH3:11])([CH3:10])[NH:7][C:6]([CH3:13])([CH3:12])[CH2:5]1)([OH:3])=O.S(Cl)(Cl)=O.[CH2:18]([NH:21][CH2:22][CH:23]=[CH2:24])[CH:19]=[CH2:20].[OH-].[Na+]>ClCCl.O>[CH2:18]([N:21]([CH2:22][CH:23]=[CH2:24])[C:1]([CH:4]1[CH2:9][C:8]([CH3:11])([CH3:10])[NH:7][C:6]([CH3:13])([CH3:12])[CH2:5]1)=[O:3])[CH:19]=[CH2:20]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 24386Thionyl ChlorideHCID 31279DiallylamineHCID 1034464-Piperidinecarboxylic acid, 2,2,6,6-tetramethyl-

Product 1

HCID 20512083HCID 20512083, compoundYield 42%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

4-Carboxy-2,2,6,6-tetramethylpiperidine (100 grams; 0.5405 mole) is added to thionyl chloride (300 mls) in portions and the reaction mixture is heated at reflux for 3 hours. The thionyl chloride is then removed by distillation, the last traces being removed by azeotropic distillation with toluene. The residual acid chloride is slurried in dichloromethane (300 mls), and a solution of diallylamine (105 grams; 1.081 mole) in dichloromethane (100 mls) is slowly added thereto while stirring and allowing the temperature to rise. Upon completion of the addition, the reaction mixture is heated at reflux for 18 hours, cooled to room temperature, and treated successively with 100 mls of water, and 5 N sodium hydroxide, while stirring, to adjust the pH to about 11. The organic phase is separated, and washed with dilute aqueous sodium hydroxide having a pH of 11. The aqueous phase is separated and the organic phase is washed twice with 100-ml portions of very dilute aqueous hydrogen peroxide (5 mls of 30% hydrogen peroxide diluted to 100 mls with water). After the second washing, the organic phase is washed twice with water, treated with activated carbon, dried over anhydrous magnesium sulfate, filtered and evaporated under vacuum to remove dichloromethane and unreacted diallylamine. The residue is then distilled under vacuum to obtain 60 grams of the desired product, bp 118°-128° C. at 0.05 mm of mercury, mp 64°-67° C.

Workup

  1. temperaturethe reaction mixture is heated
  2. temperatureat reflux for 3 hours
  3. customThe thionyl chloride is then removed by distillation
  4. customthe last traces being removed by azeotropic distillation with toluene
  5. additionUpon completion of the addition
  6. temperaturethe reaction mixture is heated
  7. temperatureat reflux for 18 hours
  8. stirringwhile stirring
  9. customThe organic phase is separated
  10. washwashed with dilute aqueous sodium hydroxide having a pH of 11
  11. customThe aqueous phase is separated
  12. washthe organic phase is washed twice with 100-ml portions of very dilute aqueous hydrogen peroxide (5 mls of 30% hydrogen peroxide diluted to 100 mls with water)
  13. washAfter the second washing, the organic phase is washed twice with water
  14. additiontreated with activated carbon
  15. dry with materialdried over anhydrous magnesium sulfate
  16. filtrationfiltered
  17. customevaporated under vacuum
  18. customto remove dichloromethane and unreacted diallylamine
  19. distillationThe residue is then distilled under vacuum

Sources & evidence

ORD record
ord-b31dfeccf4d64f4cb24852ded1288297
Source dataset
uspto-grants-1983_01
Patent number
US04369274

Reaction notes

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