Aniline → HCID 19939341, compound

HRID 35900Notes

Reaction equation

HRID 35900 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]#[C:9][C:10]([OH:12])=O)=[CH:4][CH:3]=1.S(Cl)(Cl)=O.[NH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>C1C=CC=CC=1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]#[C:9][C:10]([NH:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[O:12])=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 6115AnilineHCID 24386Thionyl ChlorideHCID 8258053-(4-Bromophenyl)propiolic acid

Product 1

HCID 19939341HCID 19939341, compoundYield 35%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Conditions

Temperature
75 °C

Procedure

A mixture of 8.50 g (37.77 mmol) (4-bromophenyl) propiolic acid (S. Chimichi, et. al., J. Heterocyclic Chem. 20, 105 (1983)), 5.39 g (45.32 mmol, 1.2 equivs.) thionyl chloride and 50 mL benzene was stirred and heated at 75° C. for 3 hrs. The reaction was allowed to cool to room temperature and solvent was evaporated. The reaction vessel was charged with 50 mL of fresh benzene and the mixture cooled in an ice bath under an atmosphere of nitrogen. Added next, dropwise in 50 mL benzene, was 7.04 g (75.54 mmol, 2 equivs.) aniline. After addition was complete, the ice bath was removed and the mixture stirred at room temperature overnight. The mixture was poured into 150 mL water and the layers were separated. The aqueous layer was extracted with three 100 mL portions of ethyl acetate. The combined organic layers were then washed sequentially with 100 mL portions of 5% aqueous hydrochloric acid, water, 5 % aqueous sodium carbonate and water. The organic layer was dried, filtered and solvent was evaporated from the filtrate. The resulting solid was recrystallized from absolute ethanol to provide 3.93 g (13.09 mmol, 35%)3-(4-bromophenyl)-N-phenylpropiolamide as a white powder, mp=159°-160.5° C. NMR (CDCl3 /TMS): 7.15 (t, 1H), 7.32-7.40 (m, 4H), 7.49 (d, 2H), 7.57 (d, 2H), 7.80 (bs, 1H). IR (KBr): 3304, 2214, 1638. High resolution mass spectrum: Calculated; 298.994575 (for 79Br isotope). Measured; 298. 994225.

Workup

  1. temperatureto cool to room temperature
  2. customsolvent was evaporated
  3. additionThe reaction vessel was charged with 50 mL of fresh benzene
  4. temperaturethe mixture cooled in an ice bath under an atmosphere of nitrogen
  5. additionAdded next, dropwise in 50 mL benzene
  6. additionAfter addition
  7. customthe ice bath was removed
  8. stirringthe mixture stirred at room temperature overnight
  9. additionThe mixture was poured into 150 mL water
  10. customthe layers were separated
  11. extractionThe aqueous layer was extracted with three 100 mL portions of ethyl acetate
  12. washThe combined organic layers were then washed sequentially with 100 mL portions of 5% aqueous hydrochloric acid, water, 5 % aqueous sodium carbonate and water
  13. customThe organic layer was dried
  14. filtrationfiltered
  15. customsolvent was evaporated from the filtrate
  16. customThe resulting solid was recrystallized from absolute ethanol

Sources & evidence

ORD record
ord-6792390546414b499cc5e48d8938a270
Source dataset
uspto-grants-1995_05
Patent number
US05411977

Reaction notes

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