M-Phenylenediamine → N-(3-Amino-phenyl)-4-chloro-2-hydroxy-benzamide

HRID 1354855Notes

Reaction equation

HRID 1354855 reaction equation
[Cl:1][C:2]1[CH:13]=[CH:12][C:5]2[C:6](=[O:11])OC(=O)[O:9][C:4]=2[CH:3]=1.[C:14]1([NH2:21])[CH:19]=[CH:18][CH:17]=[C:16]([NH2:20])[CH:15]=1>CN1C(=O)CCC1>[NH2:20][C:16]1[CH:15]=[C:14]([NH:21][C:6](=[O:11])[C:5]2[CH:12]=[CH:13][C:2]([Cl:1])=[CH:3][C:4]=2[OH:9])[CH:19]=[CH:18][CH:17]=1

Participants

4

Reactant 2

HCID 7935M-PhenylenediamineHCID 211038237-Chloro-2H,4H-1,3-benzodioxine-2,4-dione

Product 1

HCID 21103924N-(3-Amino-phenyl)-4-chloro-2-hydroxy-benzamide

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
110 °C

Procedure

7-Chloro-benzo[1,3]dioxine-2,4-dione (91) (0.090 g, 0.455 mmol) and benzene-1,3-diamine (397) (0.17 g, 1.57 mmol) were combined and dissolved in NMP (6 mL). The mixture was heated to 110° C. for 2 h. TLC was inconclusive, it was later determined that the desired product had same Rf as the aniline (397). LC-MS indicated complete reaction. The mixture was diluted with MeOH (2 mL) and LiOH (aqueous, 2.0 M, 4 mL). The mixture was stirred for 10 minutes. The solution was diluted with EtOAc (25 mL), washed with water (2×15 mL), saturated aqueous NaHCO3 (2×15 mL) and brine (2×15 mL) via extraction, dried over MgSO4 and concentrated to give a brown oil. Purification by flash chromatography on silica gel using a gradient of hexane and EtOAc (15–100% EtOAc in hexane) gave the desired product (398) as an off-white solid upon concentration (0.091 g, 0.347 mmol, 76% yield). LC-MS (ESI): (exact mass: 262.05) m/e=263.0 [M+1]+ (100%), 525.3 [2M+1]+ (10%).

Sources & evidence

ORD record
ord-a69213f478e546848756f5ba10ff670b
Source dataset
uspto-grants-2007_05
Patent number
US07223759B2

Reaction notes

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