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

HRID 1599816Notes

Reaction equation

HRID 1599816 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.[Br:17][CH2:18][C:19](Br)=[O:20]>O1CCOCC1>[Br:17][CH2:18][C:19]([NH:1][C:2]1[CH:10]=[CH:9][C:8]([Cl:11])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5])=[O:20]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 124762-Amino-5-chlorobenzoic acidHCID 61147Bromoacetyl bromide

Product 1

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

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2-amino-5-chlorobenzoic acid (10 g, 0.06 mol) in the mixture of anhydrous DMF (30 mL) and dioxane (30 mL) was cooled to 0° C. in a 250 mL 3-necked flask which was fitted with a magnetic stirrer, thermometer and an 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 ice-bath was removed, and then stirring was continued overnight at rt. The reaction mixture was cooled in an ice-bath and stirred for 30 min, water (80 mL) was added, and then the light yellow precipitate which formed was filtered, washed with water, and then dried in a vacuum oven (20 h, 40°-45° C.) affording 11.4 g (67%) of the title compound: mp 210°-212° C. (dec.), 1H NMR (CD3OD) δ8.58 (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) δ196.94, 169.69, 140.49, 134.86, 131.94, 129.49, 122.87, 119.47, 30.04; MS (EI, m/z) 293 (M+).

Workup

  1. customwas fitted with a magnetic stirrer
  2. custombetween 0° C. to 1° C
  3. additionAfter the addition
  4. customthe ice-bath was removed
  5. temperatureThe reaction mixture was cooled in an ice-bath
  6. stirringstirred for 30 min
  7. additionwater (80 mL) was added
  8. customthe light yellow precipitate which formed
  9. filtrationwas filtered
  10. washwashed with water
  11. customdried in a vacuum oven (20 h, 40°-45° C.)

Sources & evidence

ORD record
ord-f4bc1dba809b430fa5c6bf0a00fd8796
Source dataset
uspto-grants-1998_04
Patent number
US05741926

Reaction notes

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