Benzyl chloroformate → HCID 20323724, compound

HRID 839610Notes

Reaction equation

HRID 839610 reaction equation
[CH2:1]([O:3][CH:4]([O:13][CH2:14][CH3:15])[CH2:5][NH:6][C:7]1[CH:12]=[CH:11][N:10]=[CH:9][CH:8]=1)[CH3:2].CN(C)P(=O)(N(C)C)N(C)C.[H-].[Na+].Cl[C:30]([O:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=[O:31]>CN(C)C=O.O>[CH2:1]([O:3][CH:4]([O:13][CH2:14][CH3:15])[CH2:5][N:6]([C:30]([O:32][CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)=[O:31])[C:7]1[CH:12]=[CH:11][N:10]=[CH:9][CH:8]=1)[CH3:2]

Participants

7

Reactant 4

HCID 10387Benzyl chloroformateHCID 12679HexamethylphosphoramideHCID 24758Sodium hydrideHCID 71373211N-(2,2-Diethoxyethyl)pyridin-4-amine

Product 1

HCID 20323724HCID 20323724, compoundYield 11.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent3×

Conditions

Temperature
60 °C

Procedure

A solution of 4-pyridylaminoacetaldehyde diethyl acetal (7.0 g.) in a mixture of dried dimethylformamide (20 ml.) and dried hexamethylphosphoric triamide (7.5 ml.) was dropwise added over 5 minutes under ice-cooling and stirring to a suspension of 65.5% sodium hydride (2.0 g.) in dried dimethylformamide (3 ml.). The mixture was stirred for 10 minutes at ambient temperature, for 30 minutes at 60° C and for 15 minutes under ice-cooling. A solution of benzyl chloroformate (9.0 g.) in dried dimethylformamide (2 ml.) was dropwise added thereto under stirring and ice-cooling. The resulting mixture was stirred for 20 minutes under ice-cooling and for 15 minutes at ambient temperature. After water was dropwise added to the reaction mixture, the mixture was extracted 3 times with ethyl acetate. The extract was in turn washed twice with water and once with a saturated sodium chloride aqueous solution and dried over magnesium sulfate. The solvent was distilled off under reduced pressure and the residual oil was purified by column chromatography on silica gel (60 g.) using a mixture of benzene and ethyl acetate (7 : 3) as developing solvent to give oil of N-benzyloxycarbonyl-N-(4-pyridyl)aminoacetaldehyde diethyl acetal (1.3 g.).

Workup

  1. additionwas dropwise added over 5 minutes under ice-
  2. temperaturecooling
  3. temperaturecooling
  4. stirringunder stirring
  5. temperatureice-cooling
  6. stirringThe resulting mixture was stirred for 20 minutes under ice-
  7. temperaturecooling and for 15 minutes at ambient temperature
  8. extractionthe mixture was extracted 3 times with ethyl acetate
  9. washwashed twice with water and once with a saturated sodium chloride aqueous solution
  10. dry with materialdried over magnesium sulfate
  11. distillationThe solvent was distilled off under reduced pressure
  12. customthe residual oil was purified by column chromatography on silica gel (60 g.)
  13. additiona mixture of benzene and ethyl acetate (7 : 3)

Sources & evidence

ORD record
ord-cb2217c019544f92ac214b437826121d
Source dataset
uspto-grants-1978_06
Patent number
US04096263

Reaction notes

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