N,N-Dimethylaniline → HCID 53753685, compound

HRID 596223Notes

Reaction equation

HRID 596223 reaction equation
[OH:1][N:2]=[C:3]([C:6]1[CH:11]=[CH:10][C:9]([Cl:12])=[CH:8][CH:7]=1)[C:4]#[N:5].CN(C)C1C=CC=CC=1.Cl[C:23]([O:25]C(Cl)(Cl)Cl)=[O:24].ClC(ON=[C:35]([C:38]1[CH:43]=CC(Cl)=C[CH:39]=1)C#N)=O>ClCCl.C1C=CC=CC=1.N1C=CC=CC=1.C(O)(C)(C)C.O1CCCC1.O1CCOCC1>[C:38]([O:25][C:23]([O:1][N:2]=[C:3]([C:6]1[CH:11]=[CH:10][C:9]([Cl:12])=[CH:8][CH:7]=1)[C:4]#[N:5])=[O:24])([CH3:35])([CH3:39])[CH3:43]

Participants

11

Reactant 4

HCID 949N,N-DimethylanilineHCID 10426DiphosgeneHCID 54050016HCID 54050016, compoundHCID 73187595HCID 73187595, compound

Product 1

HCID 53753685HCID 53753685, compound

Reagents, catalysts & solvents 6

HCID 241BenzeneSolventHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent2×HCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolventHCID 312751,4-DioxaneSolvent

Procedure

A suspension of 2-hydroxyimino-2-(4-chlorophenyl)acetonitrile (6.75 g.) and dimethylaniline (4.5 g.) in a mixture of dichloromethane (70 ml.), dioxane (10 ml.) and tetrahydrofuran (10 ml.) was dropwise added to a solution of trichloromethyl chloroformate (phosgene dimer) (16 g.) in benzene (22 ml.) under ice-cooling, and the mixture was stirred for 5 hours at the same temperature and allowed to stand overnight. To the resultant mixture containing 2-chlorocarbonyloxyimino-2-(4-chlorophenyl)acetonitrile was dropwise added a solution of tert-butyl alcohol (8.9 g.) and pyridine (9.6 ml.) in dichloromethane (20 ml.) under ice-cooling, and the mixture was stirred for 5 hours at the same temperature and allowed to stand for 48 hours. 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 solvent was distilled off and n-hexane was added to the residue. An insoluble material was filtered off and the filtrate was concentrated. To the residue was added petroleum ether and the mixture was allowed to stand to precipitate crystals. The crystals were dissolved in hot petroleum ether and the solution was filtered. The filtrate was cooled to precipitate crystals and the crystals were collected by filtration to give 2-tert-butoxycarbonyloxyimino-2-(4-chlorophenyl)acetonitrile (1.6 g.). These crystals were recrystallized from methanol to give the pure compound (0.7 g.), mp 91° to 92° C.

Workup

  1. temperaturecooling
  2. waitto stand overnight
  3. temperaturecooling
  4. stirringthe mixture was stirred for 5 hours at the same temperature
  5. waitto stand for 48 hours
  6. washwashed with water, 1N hydrochloric acid, water
  7. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
  8. distillationThe solvent was distilled off
  9. additionn-hexane was added to the residue
  10. filtrationAn insoluble material was filtered off
  11. concentrationthe filtrate was concentrated
  12. additionTo the residue was added petroleum ether
  13. customto precipitate crystals
  14. dissolutionThe crystals were dissolved in hot petroleum ether
  15. filtrationthe solution was filtered
  16. temperatureThe filtrate was cooled
  17. customto precipitate crystals
  18. filtrationthe crystals were collected by filtration

Sources & evidence

ORD record
ord-7d6045f1253e4a25a5cdc53a64ceb46e
Source dataset
uspto-grants-1977_03
Patent number
US04010178

Reaction notes

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