p-Toluenesulfonic acid → 3-Amino-1,4,5-trimethyl-1H-pyrrole-2-carbonitrile

HRID 1902476Notes

Reaction equation

HRID 1902476 reaction equation
C(N(CC)CC)C.[C:8]([CH:10]([CH3:14])[C:11](=O)[CH3:12])#[N:9].C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH3:26][NH:27][CH2:28][C:29]#[N:30].Cl>C(Cl)(Cl)Cl.O>[NH2:9][C:8]1[C:10]([CH3:14])=[C:11]([CH3:12])[N:27]([CH3:26])[C:28]=1[C:29]#[N:30]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 8471TriethylamineHCID 117641Acetonitrile, 2-(methylamino)-, hydrochloride (1:1)HCID 5369052-Methyl-3-oxobutanenitrile

Product 1

HCID 205154293-Amino-1,4,5-trimethyl-1H-pyrrole-2-carbonitrile

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Conditions

Temperature
50 °C

Procedure

10.3 ml (0.74 mole) of triethylamine, 7.2 g (0.74 mole) of 3-cyanobutan-2-one and 0.5 g of p-toluenesulfonic acid are successively added to a suspension of 7.8 g (0.74 mole) of N-methylaminoacetonitrile hydrochloride in 70 ml of chloroform, and the mixture is boiled for 5 hours, using a water separator. After it has been boiled, the mixture is washed twice with 10 ml of water each time and dried over sodium sulfate; the solvent is then stripped off in vacuo. In order to remove all of the chloroform, the residue is twice taken up in 100 ml (each time) of dry ethanol, and the mixture concentrated each time in vacuo. The resulting oil is warmed (bath temperature of 50° C.) in 100 ml of 1 N sodium ethylate/ethanol for 2 hours; some of the ethanol is removed. The mixture is then taken up in 100 ml of water and extracted several times with methylene chloride. After being dried over sodium sulfate and concentrated on a rotary evaporator, the extracts yield a solid residue, which is recrystallized from diisopropyl ether.

Workup

  1. washthe mixture is washed twice with 10 ml of water each time
  2. dry with materialdried over sodium sulfate
  3. customIn order to remove all of the chloroform
  4. concentrationthe mixture concentrated each time in vacuo
  5. customsome of the ethanol is removed
  6. extractionextracted several times with methylene chloride
  7. dry with materialAfter being dried over sodium sulfate
  8. concentrationconcentrated on a rotary evaporator
  9. customthe extracts yield a solid residue, which
  10. customis recrystallized from diisopropyl ether

Sources & evidence

ORD record
ord-5dddd74d5c0e4e388f81f9ad5bc7c671
Source dataset
uspto-grants-1982_12
Patent number
US04363816

Reaction notes

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