Aniline → HCID 67267939, compound

HRID 598165Notes

Reaction equation

HRID 598165 reaction equation
NC1C=CC=CC=1.[CH3:8][C:9]1[CH:14]=[C:13]([CH3:15])[CH:12]=[CH:11][C:10]=1[N:16]=[CH:17][C:18]([O:20][CH2:21][CH3:22])=[O:19].S([CH2:33][N+:34]#[C-:35])(C1C=CC(C)=CC=1)(=O)=O.C(=O)([O-])[O-].[K+].[K+]>C(OCC)(=O)C.COCCOC.C(O)C>[CH3:8][C:9]1[CH:14]=[C:13]([CH3:15])[CH:12]=[CH:11][C:10]=1[N:16]1[C:17]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:35][N:34]=[CH:33]1

Participants

8

Reactant 4

HCID 6115AnilineHCID 11430Potassium CarbonateHCID 161915Tosylmethyl isocyanideHCID 67267243HCID 67267243, compound

Product 1

HCID 67267939HCID 67267939, compoundYield 62%

Reagents, catalysts & solvents 3

HCID 702EthanolSolventHCID 80711,2-DimethoxyethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

To 10 g (83 mmol) of 2,4-dimethylaniline in 200 mL of methanol was added 80 mL (50% solution in toluene, 410 mmol) of ethyl gyloxalate. The mixture was heated to 70° C. for 7 h and then allowed to stand at room temperature overnight. The reaction was concentrated in vacuo, dissolved in dichloromethane and concentrated onto silica gel. The product was eluted with a 93-100% ethyl acetate/hexanes gradient mixture to give 8.0 g (47%) of ethyl 2-(2,4-dimethylphenylimino)acetate as an oil containing approximately 20% starting aniline by LCMS analysis. This material was used without further purification. MS Calcd.: 205. Found: 206 (M+H). To 7.2 g (35 mmol) of ethyl 2-(2,4-dimethylphenylimino)acetate, 11 g (56 mmol) of tosylmethylisocyanide and 9.7 g (70 mmol) of potassium carbonate was added 200 mL of a 2:1 ethanol:1,2-dimethoxyethane mixture. The resulting slurry was heated to 90° C. for 1 h. The cooled mixture was diluted with 300 mL of ethyl acetate and filtered through GFF paper. The resulting filter cake was washed with an additional 500 mL of ethyl acetate and the resulting filtrate was added to the previous filtrate. The combined filtrates were then concentrated in vacuo to give a brown semisolid. The crude material thus obtained was then purified by flash chromatography eluting with a 45% ethyl acetate/hexanes mixture to give 4.3 g (62%) of the title compound as a tan solid.

Workup

  1. additioncontaining approximately 20%
  2. customThis material was used without further purification
  3. filtrationfiltered through GFF paper
  4. filtrationThe resulting filter cake
  5. washwas washed with an additional 500 mL of ethyl acetate
  6. additionthe resulting filtrate was added to the previous filtrate
  7. concentrationThe combined filtrates were then concentrated in vacuo
  8. customto give a brown semisolid
  9. customThe crude material thus obtained
  10. customwas then purified by flash chromatography
  11. washeluting with a 45% ethyl acetate/hexanes mixture

Sources & evidence

ORD record
ord-0ba61148f63541f4be023be1bb5e8396
Source dataset
uspto-grants-2011_03
Patent number
US07897607B2

Reaction notes

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