5-Bromosalicylic acid → 5-bromo-N-(3,4-dichlorophenyl)-2-hydroxybenzamide

HRID 1383290Notes

Reaction equation

HRID 1383290 reaction equation
[Br:1][C:2]1[CH:10]=[C:6]([C:7]([OH:9])=O)[C:5]([OH:11])=[CH:4][CH:3]=1.[Cl:12][C:13]1[CH:14]=[C:15]([CH:17]=[CH:18][C:19]=1[Cl:20])[NH2:16].P(Cl)(Cl)Cl>ClC1C=CC=CC=1>[Br:1][C:2]1[CH:10]=[C:6]([C:7]([NH:16][C:15]2[CH:17]=[CH:18][C:19]([Cl:20])=[C:13]([Cl:12])[CH:14]=2)=[O:9])[C:5]([OH:11])=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 69725-Bromosalicylic acidHCID 72573,4-DichloroanilineHCID 24387Phosphorus trichloride

Product 1

HCID 52713095-bromo-N-(3,4-dichlorophenyl)-2-hydroxybenzamideYield 46.2%

Reagents, catalysts & solvents 1

HCID 7964ChlorobenzeneSolvent

Procedure

A slurry of 5-bromosalicylic acid (15 g, 69 mmol) and 3,4-dichloroaniline (19.85 g, 73 mmol) and phosphorous trichloride (4.74 g 34.5 mmol) in 300 ml of chlorobenzene was refluxed for 3 hr. The hot solution was filtered through a glasswool plug and allowed to stand at room temperature for 18 hr. The crystals which deposited were collected by filtration and washed with fresh chlorobenzene and then methylene chloride to give after drying 19 g (76%) of product mp 230-233°. HPLC tr 19.25 min (Vydac HS5215 C18 ODS, 2.1×150 mm, 0.2 mL/min, gradient, A: water−0.1% trifluoroacetic acid B: acetonitrile−0.1% trifluoroacetic acid, 90-10% A during 20 min, UV detection at 214 nm). Recrystallization from chlorobenzene and then acetone gave 11.5 g of crystals, mp 237-2380°. The structure was verified by X-ray crystallography.

Workup

  1. filtrationThe hot solution was filtered through a glasswool plug
  2. filtrationThe crystals which deposited were collected by filtration
  3. washwashed with fresh chlorobenzene
  4. custommethylene chloride to give
  5. dry with materialafter drying 19 g (76%) of product mp 230-233°
  6. waitHPLC tr 19.25 min (Vydac HS5215 C18 ODS, 2.1×150 mm, 0.2 mL/min, gradient, A: water−0.1% trifluoroacetic acid B: acetonitrile−0.1% trifluoroacetic acid, 90-10% A during 20 min
  7. customRecrystallization from chlorobenzene

Sources & evidence

ORD record
ord-752bcabf1b5f42a68f9b4dc1752e7350
Source dataset
uspto-grants-2001_07
Patent number
US06255298B1

Reaction notes

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