N,N-Dimethylaniline → 2-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile

HRID 596218Notes

Reaction equation

HRID 596218 reaction equation
[OH:1][N:2]=[C:3]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[C:4]#[N:5].CN(C)C1C=CC=CC=1.[C:21]([OH:25])([CH3:24])([CH3:23])[CH3:22].[C:26](Cl)(Cl)=[O:27]>C1C=CC=CC=1.O.N1C=CC=CC=1>[C:21]([O:25][C:26]([O:1][N:2]=[C:3]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)[C:4]#[N:5])=[O:27])([CH3:24])([CH3:23])[CH3:22]

Participants

8

Reactant 4

HCID 949N,N-DimethylanilineHCID 6371PhosgeneHCID 6386tert-ButanolHCID 699982-(Hydroxyimino)-2-phenylacetonitrile

Product 1

HCID 938652-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrileYield 28.5%

Reagents, catalysts & solvents 3

HCID 241BenzeneSolvent4×HCID 962WaterSolventHCID 1049PyridineSolvent

Procedure

A solution of 2-hydroxyimino-2-phenylacetonitrile (7.3 g), dimethylaniline (6.0 g.) and tert-butyl alcohol (3.7 g.) in benzene (50 ml.) was dropwise added to a solution of phosgene (5.0 g.) in benzene (50 ml.) over 30 minutes under ice-cooling. To the mixture was dropwise added a solution of pyridine (4.0 ml.) in benzene (20 ml.) and the mixture was stirred for 1 hour at the same temperature and allowed to stand overnight. Water and benzene were added to the reaction mixture and an insoluble material was filtered off. The organic layer was in turn washed with 1N hydrochloric acid, water, a sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate. The solvent was distilled off and to the residue were added n-hexane and a small amount of methanol. An insoluble material was filtered off and the filtrate was concentrated. Methanol was added to the residue and the mixture was allowed to stand. The precipitates were collected by filtration to give 2-tert-butoxycarbonyloxyimino-2-phenylacetonitrile (3.5 g.). Mp 83° to 85° C. Water was added to the mother liquor and the mixture was allowed to stand. The precipitates were collected by filtration to give the object compound (1.5 g.). Total yield (5.0 g.).

Workup

  1. temperaturecooling
  2. waitto stand overnight
  3. filtrationan insoluble material was filtered off
  4. washwashed with 1N hydrochloric acid, water
  5. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
  6. distillationThe solvent was distilled off and to the residue
  7. additionwere added n-hexane
  8. filtrationAn insoluble material was filtered off
  9. concentrationthe filtrate was concentrated
  10. additionMethanol was added to the residue
  11. filtrationThe precipitates were collected by filtration

Sources & evidence

ORD record
ord-2bb40f82373643eb888b6183262ce988
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Reaction notes

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