N,N-Dimethylaniline → 2-Tert-butoxycarbonyloxyimino-2-(1-naphthyl)acetonitrile

HRID 596225

Reaction equation

HRID 596225 reaction equation
[OH:1][N:2]=[C:3]([C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1)[C:4]#[N:5].CN(C)C1C=CC=CC=1.Cl[C:26]([O:28]C(Cl)(Cl)Cl)=[O:27].ClC(ON=C([C:41]1[C:50]2[C:45](=CC=C[CH:49]=2)C=CC=1)C#N)=O>C1(C)C=CC=CC=1.C1C=CC=CC=1.N1C=CC=CC=1.C(O)(C)(C)C>[C:50]([O:28][C:26]([O:1][N:2]=[C:3]([C:6]1[C:15]2[C:10](=[CH:11][CH:12]=[CH:13][CH:14]=2)[CH:9]=[CH:8][CH:7]=1)[C:4]#[N:5])=[O:27])([CH3:49])([CH3:41])[CH3:45]

Participants

9

Reactant 4

HCID 949N,N-DimethylanilineHCID 10426DiphosgeneHCID 543473962-Chlorocarbonyloxyimino-2-(1-naphthyl)acetonitrileHCID 736804482-Hydroxyimino-2-(1-naphthyl)acetonitrile

Product 1

HCID 537899872-Tert-butoxycarbonyloxyimino-2-(1-naphthyl)acetonitrile

Reagents, catalysts & solvents 4

HCID 241BenzeneSolventHCID 1049PyridineSolventHCID 1140TolueneSolvent2×HCID 6386tert-ButanolSolvent

Procedure

A solution of 2-hydroxyimino-2-(1-naphthyl)acetonitrile (7.0 g.) and dimethylaniline (12.0 g.) in toluene (100 ml.) was dropwise added under ice-cooling to a solution of trichloromethyl chloroformate (phosgene dimer) (3.56 g.) in benzene (30 ml.). The mixture was stirred for 3 hours at the same temperature and allowed to stand overnight. To the resultant mixture containing 2-chlorocarbonyloxyimino-2-(1-naphthyl)acetonitrile was dropwise added a solution of tert-butyl alcohol (11.1 g.) and pyridine (12 ml.) in toluene (20 ml.) under ice-cooling, and the mixture was stirred for 6 hours at the same temperature and allowed to stand overnight. The reaction mixture was in turn washed with water, 1N hydrochloric acid, water, a sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate. The solution was concentrated under reduced pressure and to the residue were added n-hexane and methanol. The mixture was allowed to stand in a refrigerator, and the precipitated crystals were collected by filtration and recrystallized twice from methanol to give 2-tert-butoxycarbonyloxyimino-2-(1-naphthyl)acetonitrile (3.3 g.), mp 90° to 92° C.

Workup

  1. waitto stand overnight
  2. temperaturecooling
  3. stirringthe mixture was stirred for 6 hours at the same temperature
  4. waitto stand overnight
  5. washwashed with water, 1N hydrochloric acid, water
  6. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
  7. concentrationThe solution was concentrated under reduced pressure and to the residue
  8. additionwere added n-hexane and methanol
  9. filtrationthe precipitated crystals were collected by filtration
  10. customrecrystallized twice from methanol

Sources & evidence

ORD record
ord-9cc39cbc42fc430a9f344a74b6ad89c0
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Linked notes

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