2-Chloroaniline → 4-Chloro-2-(2-chloro-phenylamino)-benzoic acid

HRID 1887801Notes

Reaction equation

Br[C:2]1[CH:10]=[C:9]([Cl:11])[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[Cl:12][C:13]1[CH:19]=[CH:18][CH:17]=[CH:16][C:14]=1[NH2:15].C(=O)([O-])[O-].[K+].[K+].C(OCCO)C>[Cu].[Cu-]=O.O>[Cl:11][C:9]1[CH:8]=[CH:7][C:3]([C:4]([OH:6])=[O:5])=[C:2]([NH:15][C:14]2[CH:16]=[CH:17][CH:18]=[CH:19][C:13]=2[Cl:12])[CH:10]=1

Participants

Conditions

Temperature: 130 °C

Procedure

In a 250 mL round bottom flask, 2-bromo-4-chloro-benzoic acid (10 g, 42.5 mmol), 2-chloroaniline (8.49 g, 7.0 mL, 66.6 mmol), potassium carbonate (9.39 g, 68.0 mmol), copper (0.092 g, 1.44 mmol) and copper (I) oxide (0.126 g, 0.88 mmol) were combined with 2-ethoxyethanol (20 mL). The mixture was heated to 130° C. for 4 hr. The mixture was cooled to room temp. and 150 mL of water was added. The slurry was stirred at room temperature for 2 days. The slurry was filtered and rinsed with 2-ethoxyethanol. The pH of the filtrate was adjusted to 7 using 4N HCl and the solid was filtered off. The green solid was then air-dried for 4 hr. to give 4-chloro-2-(2-chloro-phenylamino)-benzoic acid (3.5 g, 29% yield). The material was used in the next step without further purification. MS calcd. for C13H9Cl2N3O2 [(M−H)−1]280.0, obsd. 280.0.

Workup

temperatureThe mixture was cooled to room temp.
filtrationThe slurry was filtered
washrinsed with 2-ethoxyethanol
filtrationthe solid was filtered off
customThe green solid was then air-dried for 4 hr

Sources & evidence

ORD record: ord-b35787b782354c4e86e6c609679dcbe5
Source dataset: uspto-grants-2013_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08501732B2

Reaction notes

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