Anthranilic Acid → HCID 10611190, compound

HRID 1490311Notes

Reaction equation

HRID 1490311 reaction equation
[C:1]([OH:10])(=[O:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[NH2:4].CN(C=O)C.[Br:16][CH2:17][C:18](Br)=[O:19]>O1CCOCC1>[Br:16][CH2:17][C:18]([NH:4][C:3]1[CH:5]=[CH:6][CH:7]=[CH:8][C:2]=1[C:1]([OH:10])=[O:9])=[O:19]

Participants

5

Reactant 3

HCID 227Anthranilic AcidHCID 6228DimethylformamideHCID 61147Bromoacetyl bromide2×

Product 1

HCID 10611190HCID 10611190, compoundYield 87.8%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of anthranilic acid (50 g, 364.6 mmol) in anhyd DMF (125 mL) and dioxane (125 mL) in a 1 L Morton flask equipped with a mechanical stirrer and a constant addition funnel was cooled with an ice-bath to 0° C. Freshly distilled bromoacetyl bromide (73.6 g, 31.77 mL, 364.6 mmol) was added dropwise keeping the internal temperature between 0°-1.5° C. over a 2.5 hour period. After addition of the bromoacetyl bromide was completed, the ice-bath was removed and stirring at rt was continued for 5 h. The reaction mixture was cooled in an ice-bath and slowly diluted with water (300 mL). A white precipitate formed, which was filtered, washed sequentially with 5% HBr solution (500 mL) and water (500 mL), and then dried in a vacuum desiccator. Further drying in a vacuum oven at 60° C. afforded 82.61 g (87.8%) of the title compound as a white powder, mp 164.6°-167.6° C. [lit 165.5°-172° C. (Hoffman LaRoche U.S. Pat. No. 3,244,698)]; 1H NMR (DMSO-d6) δ 13.7 (bs, 1H), 11.60 (s, 1H), 8.44 (d, J=8.0, 1H), 8.00 (dd, J=8.0, J=1.6, 1H), 7.62 (dt, J=8.0, J=1.6, 1H), 7.21 (t, J=8.0, 1H); 4.26 (s, 2H); 13C NMR (DMSO-d6) δ 169.20, 165.05, 139.95, 134.08, 131.13, 123.46, 120.02, 117.09, 30.67; MS (EI, m/z) 256.9 (M+), 258.9 (M30 2+).

Workup

  1. custombetween 0°-1.5° C.
  2. customover a 2.5 hour
  3. customthe ice-bath was removed
  4. temperatureThe reaction mixture was cooled in an ice-bath
  5. additionslowly diluted with water (300 mL)
  6. customA white precipitate formed
  7. filtrationwhich was filtered
  8. washwashed sequentially with 5% HBr solution (500 mL) and water (500 mL)
  9. customdried in a vacuum desiccator
  10. customFurther drying in a vacuum oven at 60° C.

Sources & evidence

ORD record
ord-46490365f5294f44a71391d56b95e689
Source dataset
uspto-grants-1997_10
Patent number
US05681958

Reaction notes

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