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

HRID 596217Notes

Reaction equation

HRID 596217 reaction equation
ON=[C:3]([C:6]1[CH:11]=CC=C[CH:7]=1)C#N.CN(C)C1C=CC=CC=1.C(Cl)(Cl)=[O:22].Cl[C:26]([O:28][N:29]=[C:30]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:31]#[N:32])=[O:27]>C1C=CC=CC=1.O1CCOCC1.O.N1C=CC=CC=1.C(O)(C)(C)C>[C:6]([O:27][C:26]([O:28][N:29]=[C:30]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[C:31]#[N:32])=[O:22])([CH3:11])([CH3:7])[CH3:3]

Participants

10

Reactant 4

HCID 949N,N-DimethylanilineHCID 6371PhosgeneHCID 699982-(Hydroxyimino)-2-phenylacetonitrileHCID 536547752-Chlorocarbonyloxyimino-2-phenylacetonitrile

Product 1

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

Reagents, catalysts & solvents 5

HCID 241BenzeneSolvent3×HCID 962WaterSolventHCID 1049PyridineSolvent2×HCID 6386tert-ButanolSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of 2-hydroxyimino-2-phenylacetonitrile (7.3 g.) and dimethylaniline (6.0 g) in a mixture of benzene (50 ml) and dioxane (5 ml.) was dropwise added to a solution of phosgene (5.5 g.) in benzene (50 ml.) over 1 hour at 3° to 5° C, and the mixture was stirred for 3.5 hours at the same temperature and allowed to stand overnight. To the resultant solution containing 2-chlorocarbonyloxyimino-2-phenylacetonitrile was dropwise added, over 1 hour under ice-cooling, a solution of tert-butyl alcohol (7.4 g.) and pyridine (5.0 ml.) in benzene (20 ml.). The resultant mixture was stirred for 4 hours at the same temperature, and pyridine (3.0 ml.) was dropwise added thereto, after which the mixture was stirred for 1 hour at room temperature and allowed to stand overnight. Water was added thereto and the organic layer was separated. The organic layer was in turn washed with 1N hydrochloric acid (3 times), a sodium chloride aqueous solution, a sodium bicarbonate aqueous solution (twice) and a sodium chloride aqueous solution (twice) and concentrated. The residue was allowed to stand to give crystals. The crystals were triturated in aqueous methanol, collected by filtration, washed with n-hexane and dried to give 2-tert-butoxycarbonyloxyimino-2-phenylacetonitrile (7.0 g.), mp 84° to 86° C.

Workup

  1. waitto stand overnight
  2. additionwas dropwise added, over 1 hour under ice-
  3. temperaturecooling
  4. additionwas dropwise added
  5. stirringafter which the mixture was stirred for 1 hour at room temperature
  6. waitto stand overnight
  7. customthe organic layer was separated
  8. washwashed with 1N hydrochloric acid (3 times)
  9. concentrationa sodium chloride aqueous solution, a sodium bicarbonate aqueous solution (twice) and a sodium chloride aqueous solution (twice) and concentrated
  10. customto give crystals
  11. customThe crystals were triturated in aqueous methanol
  12. filtrationcollected by filtration
  13. washwashed with n-hexane
  14. customdried

Sources & evidence

ORD record
ord-626463952f664b868778451317e6b250
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Reaction notes

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