Dimethylformamide → 5-Chloro-2-(bromoacetamido)benzoic Acid

HRID 1490293Notes

Reaction equation

HRID 1490293 reaction equation
[NH2:1][C:2]1[CH:10]=[CH:9][C:8]([Cl:11])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].CN(C=O)C.O1CCOCC1.[Br:23][CH2:24][C:25](Br)=[O:26]>O>[Cl:11][C:8]1[CH:9]=[CH:10][C:2]([NH:1][C:25](=[O:26])[CH2:24][Br:23])=[C:3]([CH:7]=1)[C:4]([OH:6])=[O:5]

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 124762-Amino-5-chlorobenzoic acidHCID 312751,4-DioxaneHCID 61147Bromoacetyl bromide

Product 1

HCID 107800225-Chloro-2-(bromoacetamido)benzoic AcidYield 67%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of 2-amino-5-chlorobenzoic acid (10 g, 0.06 mol), anhydrous DMF (30 mL) and dioxane (30 mL) was cooled to 0° C. in a 250 mL 3- necked flask, fitted with a magnetic stirrer, thermometer and additional funnel. Bromoacetyl bromide (11.8 g, 5 mL, 100 mol %) was added dropwise over a 20 min period, keeping the internal temperature between 0° C. to 1° C. After the addition was completed, the solution was allowed to warm to room temperature and stirring was continued overnight at rt. The reaction mixture was cooled in an ice-bath, stirred for 30 min and diluted with water (80 mL). The resulting light yellow precipitate was filtered, washed with water, and dried in vacuum oven (20 h, 40°-45° C.), to afford 11.4 g (67%) of the title compound, mp 210°-212° C. (decomp.); 1H NMR (CD3OD) δ 8.58 (d, 1H, J=9.2), 8.03 (d, 1H, J=2.8), 7.55 (dd, 1H, J=2.4, J=6.4), 4.11 (s, 2H); 13C NMR (CD3OD) δ 196.94, 169.69, 140.49, 134.86, 131.94, 129.49, 122.87, 119.47, 30.04; MS (EI, m/z) 293 (M+).

Workup

  1. customfitted with a magnetic stirrer
  2. custombetween 0° C. to 1° C
  3. additionAfter the addition
  4. temperatureThe reaction mixture was cooled in an ice-bath
  5. stirringstirred for 30 min
  6. filtrationThe resulting light yellow precipitate was filtered
  7. washwashed with water
  8. customdried in vacuum oven (20 h, 40°-45° C.)

Sources & evidence

ORD record
ord-adb895ca0f674086ac58842d952b9c02
Source dataset
uspto-grants-1997_10
Patent number
US05681958

Reaction notes

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