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

HRID 596221Notes

Reaction equation

HRID 596221 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]([O:24]C(Cl)(Cl)Cl)=[O:23].ClC(ON=[C:34]([C:37]1[CH:42]=CC=C[CH:38]=1)C#N)=O>C1C=CC=CC=1.O1CCOCC1.O.N1C=CC=CC=1.C(O)(C)(C)C>[C:37]([O:24][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])([CH3:34])([CH3:38])[CH3:42]

Participants

10

Reactant 4

HCID 949N,N-DimethylanilineHCID 10426DiphosgeneHCID 699982-(Hydroxyimino)-2-phenylacetonitrileHCID 536547752-Chlorocarbonyloxyimino-2-phenylacetonitrile

Product 1

HCID 938652-(tert-Butoxycarbonyloxyimino)-2-phenylacetonitrile

Reagents, catalysts & solvents 5

HCID 241BenzeneSolvent3×HCID 962WaterSolventHCID 1049PyridineSolventHCID 6386tert-ButanolSolventHCID 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 dropwise added to a solution of trichloromethyl chloroformate (phosgene dimer) (11 g.) in benzene (50 ml.) under ice-cooling, and the mixture was stirred for 3 hours at the same temperature and allowed to stand overnight. To the mixture containing 2-chlorocarbonyloxyimino-2-phenylacetonitrile was dropwise added a solution of tert-butyl alcohol (14.8 g.) and pyridine (16.0 ml.) in benzene (20 ml.) under ice-cooling. The reaction mixture was stirred for 6 hours together with gradual elevation of the reaction temperature 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 in turn washed with 1N 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 by 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.). From the mother liquor the object compound (9.4 g.) was further obtained. Both of the object 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
  4. stirringThe reaction mixture was stirred for 6 hours together with gradual elevation of the reaction temperature to room temperature
  5. waitto stand overnight
  6. customthe organic layer was separated
  7. washwashed with 1N hydrochloric acid
  8. dry with materiala sodium chloride aqueous solution, a sodium bicarbonate aqueous solution and water and then dried
  9. distillationThe solvent was distilled off
  10. additionmethanol was added to the residue
  11. temperatureThe mixture was cooled by ice-water
  12. filtrationthe precipitates were collected by filtration
  13. washwashed with a small amount of cooled methanol

Sources & evidence

ORD record
ord-e00b6ec187be40cd9fd4eb21ae163dcf
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Reaction notes

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