Aniline → HCID 18929246, compound

HRID 1490295Notes

Reaction equation

HRID 1490295 reaction equation
[Cl:1][C:2]1[C:3]([NH:11][C:12](=[O:15])[CH2:13]Br)=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[NH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[OH-].[K+]>CN(C=O)C>[Cl:1][C:2]1[C:3]([NH:11][C:12](=[O:15])[CH2:13][NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6]

Participants

5

Reactant 3

HCID 6115AnilineHCID 14797Potassium HydroxideHCID 189292153-Chloro-2-(bromoacetamido)benzoic Acid

Product 1

HCID 18929246HCID 18929246, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 3-chloro-2-(bromoacetamido)benzoic acid from Example 39 (7.5 g, 0.026 mol), aniline (5.8 mL, 250 mol %) and anhydrous DMF (60 mL) was heated at 95°-100° C. for 20h, cooled and stirred at rt for 4h. The reaction mixture was poured into ice-water (400 mL) and the precipitated product was solubilized by adding aqueous 5% KOH (60 mL). The resulting milky homogenous solution was extracted with CH2Cl2 (3×70 mL). The combined CH2Cl2 extracts were set aside and the aqueous layer was acidified to pH=3 with aqueous 5% HBr. The resulting oil was extracted into EtOAc (3×100 mL) and the combined extract was washed with brine, dried, filtered and concentrated. Recrystallization of the resulting solid from diethyl ether afforded 3 g (38%) of the title compound as a white crystals, mp 184°-185° C.; 1H NMR (CD3OD) δ 7.85 (dd, 1H, J=1.6, J=6), 7.66 (dd, 1H, J=1.6, J=6.4), 7.33 (t, 1H, J=8), 7.16 (t, 2H, J=7.2), 6.72 (dd, 3H, J=2, J=5.6), 3.91 (s, 2H); 13C NMR (CD3OD): 203.86, 196.95, 173.19, 173.17, 168.69, 149.44, 134.30, 130.41, 130.09, 128.42, 119.31, 114.44; MS (EI, m/z) 304 (M+).

Workup

  1. temperaturecooled
  2. extractionThe resulting milky homogenous solution was extracted with CH2Cl2 (3×70 mL)
  3. extractionThe resulting oil was extracted into EtOAc (3×100 mL)
  4. extractionthe combined extract
  5. washwas washed with brine
  6. customdried
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customRecrystallization of the resulting solid from diethyl ether

Sources & evidence

ORD record
ord-19907ba33e6745368373f29710d6edbd
Source dataset
uspto-grants-1997_10
Patent number
US05681958

Reaction notes

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