Ammonia → HCID 54403606, compound

HRID 1282341Notes

Reaction equation

HRID 1282341 reaction equation
ClC1C=CC(C(C2N(C)C(CC(OCC)=O)=CC=2)=O)=CC=1.[NH2-].[Na+].N.C(I)C.[Cl-].[NH4+].Cl.[Cl:31][C:32]1[CH:53]=[CH:52][C:35]([C:36]([C:38]2[N:42]([CH3:43])[C:41]([CH:44]([CH2:50][CH3:51])[C:45]([O:47]CC)=[O:46])=[CH:40][CH:39]=2)=[O:37])=[CH:34][CH:33]=1.[OH-].[Na+]>C(O)C.CCOCC>[Cl:31][C:32]1[CH:53]=[CH:52][C:35]([C:36]([C:38]2[N:42]([CH3:43])[C:41]([CH:44]([CH2:50][CH3:51])[C:45]([OH:47])=[O:46])=[CH:40][CH:39]=2)=[O:37])=[CH:34][CH:33]=1

Participants

11

Reactant 8

HCID 222Ammonia2×HCID 313Hydrochloric AcidHCID 6340Iodoethane2×HCID 14798Sodium HydroxideHCID 24533Sodium amideHCID 25517Ammonium ChlorideHCID 18424207HCID 18424207, compoundHCID 18424323HCID 18424323, compound

Product 1

HCID 54403606HCID 54403606, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 3283Diethyl EtherSolvent2×

Procedure

A solution of 6.5 g (0.021 mole) of ethyl 5-(p-chlorobenzoyl)-1-methylpyrrole-2-acetate in 60 ml. of ether is added to a suspension of 1.25 g. (0.032 mole) of sodamide in 150 ml. of refluxing liquid ammonia. After 10 minutes, 4.98 g. (0.032 mole) of ethyl iodide is added. The mixture is stirred for 1.5 hours, and an additional 1.0 g. (0.0064 mole) of ethyl iodide is added. Stirring is continued for 30 minutes and ammonium chloride is then added to neutralize any anion. The mixture is allowed to warm to room temperature and the ammonia allowed to escape. Ether is added, and the mixture poured into dilute hydrochloric acid. The ether layer is separated, and the aqueous layer is washed with ether. The combined ether solutions are washed successively with sodium bisulfite solution and brine and then dried over anhydrous magnesium sulfate. The solvent is evaporated in vacuo to give about 7.4 g. of a yellow oily residue containing ethyl 5-(p-chlorobenzoyl)-α-ethyl-1-methylpyrrole-2-acetate, which is used as such in the following transformation to acid procedure. A 6.9 g. sample of the oily residue is dissolved in 30 ml. of ethanol and 11.4 ml. of 1N sodium hydroxide is added. The mixture is refluxed for 1 hour. The solvent is then evaporated in vacuo, and the residue partitioned between ether and water. The aqueous layer is separated and acidified with dilute hydrochloric acid. The precipitated oil, which is separated, crystallizes on scratching to give a solid, 5-(p-chlorobenzoyl)-α-ethyl-1-methylpyrrole-2-acetic acid, which is collected and dried, m.p. 108-112° C. After successive recrystallizations from ether-methylcyclohexane, benzene-hexane, methylcyclohexane and ether-hexane, the m.p. is 110-114° C. Analysis: Calcd. for C16H16ClNO3: C, 62.84;H, 5.27; N, 4.58% Found: C, 63.01; H, 5.36; N, 4.61%

Workup

  1. stirringStirring
  2. waitis continued for 30 minutes
  3. customThe ether layer is separated
  4. washthe aqueous layer is washed with ether
  5. washThe combined ether solutions are washed successively with sodium bisulfite solution and brine
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe solvent is evaporated in vacuo
  8. customto give about 7.4 g
  9. dissolutionsample of the oily residue is dissolved in 30 ml
  10. temperatureThe mixture is refluxed for 1 hour
  11. customThe solvent is then evaporated in vacuo
  12. customthe residue partitioned between ether and water
  13. customThe aqueous layer is separated
  14. customThe precipitated oil, which is separated
  15. customcrystallizes

Sources & evidence

ORD record
ord-005dfb238f6342f895d2c0bc97177b9b
Source dataset
uspto-grants-2002_09
Patent number
US06455703B2

Reaction notes

Loading…