Acetoin → 2-Amino-4,5-dimethyl-1-(2,4,6-trimethylphenyl)-1H-pyrrole-3-carbonitrile

HRID 1884341Notes

Reaction equation

HRID 1884341 reaction equation
O[CH:2]([CH3:6])[C:3](=O)[CH3:4].[CH3:7][C:8]1[CH:14]=[C:13]([CH3:15])[CH:12]=[C:11]([CH3:16])[C:9]=1[NH2:10].[C:17](#[N:21])[CH2:18][C:19]#[N:20]>C1C=CC=CC=1.C1(C)C=CC(S(O)(=O)=O)=CC=1>[NH2:20][C:19]1[N:10]([C:9]2[C:11]([CH3:16])=[CH:12][C:13]([CH3:15])=[CH:14][C:8]=2[CH3:7])[C:2]([CH3:6])=[C:3]([CH3:4])[C:18]=1[C:17]#[N:21]

Participants

6

Reactant 3

HCID 179AcetoinHCID 69132,4,6-TrimethylanilineHCID 8010Malononitrile

Product 1

HCID 4019082-Amino-4,5-dimethyl-1-(2,4,6-trimethylphenyl)-1H-pyrrole-3-carbonitrileYield 45.3%

Reagents, catalysts & solvents 2

HCID 6101p-Toluenesulfonic acidCatalystHCID 241BenzeneSolvent

Procedure

A mixture of 3-hydroxy-2-butanone (100.000 g, 1.135 mol), 2,4,6-trimethylaniline (153.225 g, 1.135 mol) and p-toluenesulfonic acid (0.670 g) in 500 ml of benzene was refluxed using a Dean-Stark trap to remove water. After 2 hours, malononitrile (75.000 g, 1.135 mol) was added and the mixture was refluxed for an additional 10 hours until all of the starting material was consumed. The reaction mixture was cooled and precipitate formed and filtered. The solid was washed with a minimum amount of ethanol. The solid was diluted with 500 ml of benzene and product was dissolved. Some undesired product was insoluble and was filtered off. The filtrate was concentrated to give a tan solid which was recrystallized from ethanol to give 130.260 g of off-white crystals. 1H NMR (CDCl3) δ 1.68(s, 3H), 1.93(s, 6H), 2.05(s, 3H), 2.31(s, 3H), 3.62(brs, 2H), 6.95(s, 2H) ppm.

Workup

  1. temperaturewas refluxed
  2. customto remove water
  3. temperaturethe mixture was refluxed for an additional 10 hours until all of the starting material
  4. customwas consumed
  5. temperatureThe reaction mixture was cooled
  6. customprecipitate formed
  7. filtrationfiltered
  8. washThe solid was washed with a minimum amount of ethanol
  9. additionThe solid was diluted with 500 ml of benzene and product
  10. dissolutionwas dissolved
  11. filtrationwas filtered off
  12. concentrationThe filtrate was concentrated
  13. customto give a tan solid which
  14. customwas recrystallized from ethanol

Sources & evidence

ORD record
ord-6c49b06a9bcd44dda7fc2ed889adf356
Source dataset
uspto-grants-2004_07
Patent number
US06765008B1

Reaction notes

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