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

HRID 597682Notes

Reaction equation

HRID 597682 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 added dropwise to a solution of phosgene (5.5 g.) in benzene (50 ml.) over 1 hour at 3° to 5° C. The mixture was stirred for 3.5 hours at the same temperature and allowed to stand overnight. A solution of tert-butyl alcohol (7.4 g.) and pyridine (5.0 ml.) in benzene (20 ml.) was added dropwise for 1 hour under ice-cooling to the resultant solution containing 2-chlorocarbonyloxyimino2-phenylacetonitrile. The resultant mixture was stirred for 4 hours at the same temperature, and pyridine (3.0 ml.) was added dropwise thereto. The mixture was then 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 then 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 obtain 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 added dropwise
  3. stirringThe mixture was then stirred for 1 hour at room temperature
  4. waitto stand overnight
  5. customthe organic layer was separated
  6. washThe organic layer was then washed with 1N hydrochloric acid (3 times)
  7. concentrationa sodium chloride aqueous solution, a sodium bicarbonate aqueous solution (twice) and a sodium chloride aqueous solution (twice) and concentrated
  8. customto obtain crystals
  9. customThe crystals were triturated in aqueous methanol
  10. filtrationcollected by filtration
  11. washwashed with n-hexane
  12. customdried

Sources & evidence

ORD record
ord-0d6adaba6c0e49959324a819e5adcb75
Source dataset
uspto-grants-1977_03
Patent number
US04014915

Reaction notes

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