Aniline → HCID 18929250, compound

HRID 582664Notes

Reaction equation

HRID 582664 reaction equation
[Cl:1][C:2]1[C:7]([C:8]([OH:10])=[O:9])=[C:6]([NH:11][C:12](=[O:15])[CH2:13]Br)[CH:5]=[CH:4][CH:3]=1.[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:7]([C:8]([OH:10])=[O:9])=[C:6]([NH:11][C:12](=[O:15])[CH2:13][NH:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 6115AnilineHCID 14797Potassium HydroxideHCID 18929201HCID 18929201, compound

Product 1

HCID 18929250HCID 18929250, compoundYield 82%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 6-chloro-2-(bromoacetamido)benzoic acid from Example 42 (7 g, 0.024 mol), aniline (5.6 g, 6 mL, 250 mol %) and DMF (40 mL) was heated at 100° C. for 5 h. The reaction mixture was cooled to rt, poured onto ice and the resulting crystalline product was solubilized by adding 5% KOH (70 mL, pH=9). The resulting milky homogenous solution was extracted with CH2Cl2 (3×100 mL), and the aqueous layer was acidified to pH=3 with 5% HBr and extracted with EtOAc (4×100 mL). Combined EtOAc washings were dried and concentrated. Recrystallization of the resulting solid from EtOAc/Hex, afforded 6 g (82%) of the title compound as white crystals, 176-178.2° C.; 1H NMR (DMSO-d6) δ 9.93 (s, 1H, COOH), 7.97 (d, 1H, J=8), 7.42 (t, 1H, J=8), 7.30 (d, 1H, J=7.6), 7.12 (t, 2H, J=7.2), 6.65 (t, 3H, J=7.2), 3.82 (s, 2H); 13C NMR (DMSO-d6) δ 170.19, 166.30, 148.15, 136.56, 131.12, 130.53, 128.98, 125.51, 121.39, 117.23, 112.71, 48.13; MS (EI, m/z) 304 (M+)

Workup

  1. additionpoured onto ice
  2. extractionThe resulting milky homogenous solution was extracted with CH2Cl2 (3×100 mL)
  3. extractionextracted with EtOAc (4×100 mL)
  4. dry with materialCombined EtOAc washings were dried
  5. concentrationconcentrated
  6. customRecrystallization of the resulting solid from EtOAc/Hex

Sources & evidence

ORD record
ord-9db803662b7f4522a84ffc9a62755062
Source dataset
uspto-grants-1999_07
Patent number
US05925647

Reaction notes

Loading…