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

HRID 1578210Notes

Reaction equation

HRID 1578210 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.Cl[C:22](OC(Cl)(Cl)Cl)=[O:23].[C:29]([OH:33])([CH3:32])([CH3:31])[CH3:30]>C1C=CC=CC=1.O1CCOCC1.O.N1C=CC=CC=1>[C:29]([O:33][C:22]([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:23])([CH3:32])([CH3:31])[CH3:30]

Participants

9

Reactant 4

HCID 949N,N-DimethylanilineHCID 6386tert-ButanolHCID 10426DiphosgeneHCID 699982-(Hydroxyimino)-2-phenylacetonitrile

Product 1

HCID 938652-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrileYield 69.4%

Reagents, catalysts & solvents 4

HCID 241BenzeneSolvent3×HCID 962WaterSolventHCID 1049PyridineSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of 2-hydroxyimino-2-phenylacetonitrile (14.6 g) and dimethylaniline (13.2 g.) in a mixture of benzene (80 ml.) and dioxane (8 ml.) was added to a solution of trichloromethyl chloroformate (phosgene dimer) (11 g.) in benzene (50 ml.) under ice-cooling. The and the mixture was stirred for 3 hours at the same temperature and allowed to stand overnight. A solution of tert-butyl alcohol (14.8 g.) and pyridine (16.0 ml.) in benzene (20 ml.) was added dropwise, under ice-cooling, to the mixture containing 2-chlorocrabonyloxyimino-2-phenylacetonitrile. The reaction mixture was stirred for 6 hours and the reaction temperature was gradually elevated to room temperature and allowed to stand overnight. Water was added to the reaction mixture and the organic layer was separated. The organic layer was then washed with 1 N hydrochloric acid, a sodium chloride aqueous solution, a sodium bicarbonate aqueous solution and water and then dried. The solvent was distilled off and methanol was added to the residue. The mixture was cooled with, ice-water and the precipitates were collected by filtration and washed with a small amount of cooled methanol to give 2-tert-butoxycarbonyloxyimino-2-phenylacetonitrile (9.5 g.). The desired compound (9.4 g.) was further obtained from the mother liquor. Amounts of the desired compounds obtained above were combined and recrystallized from methanol to give the pure compound (14.6 g.), mp 84° to 86° C.

Workup

  1. temperaturecooling
  2. waitto stand overnight
  3. temperaturecooling, to the mixture
  4. stirringThe reaction mixture was stirred for 6 hours
  5. customwas gradually elevated to room temperature
  6. waitto stand overnight
  7. customthe organic layer was separated
  8. washThe organic layer was then washed with 1 N hydrochloric acid
  9. dry with materiala sodium chloride aqueous solution, a sodium bicarbonate aqueous solution and water and then dried
  10. distillationThe solvent was distilled off
  11. additionmethanol was added to the residue
  12. temperatureThe mixture was cooled with, ice-water
  13. filtrationthe precipitates were collected by filtration
  14. washwashed with a small amount of cooled methanol

Sources & evidence

ORD record
ord-efd11bff512c432e8ace1ecd180b9fe1
Source dataset
uspto-grants-1981_09
Patent number
USRE030752

Reaction notes

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