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

HRID 1578206Notes

Reaction equation

HRID 1578206 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 1 N 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 1 N 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-cc4f67b166bb48c5acdfdbfd4410932f
Source dataset
uspto-grants-1981_09
Patent number
USRE030752

Reaction notes

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