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

HRID 2082986Notes

Reaction equation

HRID 2082986 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 added dropwise to a solution of phosgene (5.0 g.) in benzene (50 ml.) for 30 minutes under ice-cooling. A solution of pyridine (4.0 ml.) in benzene (20 ml.) was added dropwise to the mixture. The resultant 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 then washed with 1N hydrochloric acid, water, a sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate. The solvent was distilled off and n-hexane and a small amount of methanol were added to the residue. 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 desired compound (1.5 g.). Total yield (5.0 g.).

Workup

  1. temperaturecooling
  2. filtrationan insoluble material was filtered off
  3. washThe organic layer was then washed with 1N hydrochloric acid, water
  4. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
  5. distillationThe solvent was distilled off
  6. additionn-hexane and a small amount of methanol were added to the residue
  7. filtrationAn insoluble material was filtered off
  8. concentrationthe filtrate was concentrated
  9. additionMethanol was added to the residue
  10. filtrationThe precipitates were collected by filtration

Sources & evidence

ORD record
ord-a30c196c6b8040ce806104a5fa7f8178
Source dataset
uspto-grants-1978_04
Patent number
US04083848

Reaction notes

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