N,N-Dimethylaniline → HCID 53753685, compound

HRID 2082991Notes

Reaction equation

HRID 2082991 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 added dropwise to a solution of trichloromethyl chloroformate (phosgene dimer) (16 g.) in benzene (22 ml.) under ice-cooling. The mixture was stirred for 5 hours at the same temperature and allowed to stand overnight. A solution of tert-butyl alcohol (8.9 g.) and pyridine (9.6 ml.) in dichloromethane (20 ml.) was added dropwise, under ice-cooling, to the resultant mixture containing 2-chlorocarbonyloxyimino-2-(4-chlorophenyl)-acetonitrile. The mixture was stirred for 5 hours at the same temperature and allowed to stand for 48 hours. The reaction mixture was then 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. Petroleum ether was added to the residue 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. stirringThe mixture was stirred for 5 hours at the same temperature
  4. waitto stand for 48 hours
  5. washThe reaction mixture was then washed with water, 1N hydrochloric acid, water
  6. dry with materiala sodium bicarbonate aqueous solution and water, and dried over magnesium sulfate
  7. distillationThe solvent was distilled off
  8. additionn-hexane was added to the residue
  9. filtrationAn insoluble material was filtered off
  10. concentrationthe filtrate was concentrated
  11. additionPetroleum ether was added to the residue
  12. customto precipitate crystals
  13. dissolutionThe crystals were dissolved in hot petroleum ether
  14. filtrationthe solution was filtered
  15. temperatureThe filtrate was cooled
  16. customto precipitate crystals
  17. filtrationthe crystals were collected by filtration

Sources & evidence

ORD record
ord-2ce21f8b1f5f4c96aa51acd9f8cb319b
Source dataset
uspto-grants-1978_04
Patent number
US04083848

Reaction notes

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