Methyl Anthranilate → Methyl 2-((Bromoacetyl)Amino)Benzoate(WX618077)

HRID 1599825Notes

Reaction equation

HRID 1599825 reaction equation
[C:1]([O:10][CH3:11])(=[O:9])[C:2]1[C:3](=[CH:5][CH:6]=[CH:7][CH:8]=1)[NH2:4].[Br:12][CH2:13][C:14](Br)=[O:15]>CN(C=O)C.O1CCOCC1.O>[Br:12][CH2:13][C:14]([NH:4][C:3]1[CH:5]=[CH:6][CH:7]=[CH:8][C:2]=1[C:1]([O:10][CH3:11])=[O:9])=[O:15]

Participants

6

Reactant 2

HCID 8635Methyl AnthranilateHCID 61147Bromoacetyl bromide

Product 1

HCID 4062738Methyl 2-((Bromoacetyl)Amino)Benzoate(WX618077)Yield 88%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 312751,4-DioxaneSolvent

Procedure

A solution of methyl anthranilate (5 g, 0.033 mol) in anhydrous DMF (25 mL) and anhydrous dioxane (25 mL) was cooled to 0° C. in a 250 mL 3-necked flask, fitted with a magnetic stirrer and a constant addition funnel. Bromoacetyl bromide (6.7 g, 2.9 mL, 100 mol %) was added dropwise, keeping the internal temperature between 0° C. and 2° C. After the addition was complete (20-25 min), the reaction mixture was stirred at rt overnight. The reaction mixture was diluted with water (100 mL) and the white crystalline compound which precipitated was filtered, washed sequentially with 5% HBr (100 mL) and water (200 mL), and then dried in a vacuum oven at 40°-45° C. overnight. The product was triturated with ether and then dried in vacuo for 5 h, yielding 7.9 g (88%) of the title compound as a white solid: mp 81°-82° C.; 1H NMR (DMSO-d6) δ11.07 (s, 1H, NH), 8.23 (dd, 1H, J=1.2, J=8.4), 7.94 (dd, 1H, J=1.6, J=8), 7.66-7.62 (m, 1H), 7.27-7.23 (m,1H), 4.23 (s, 2H), 3.87 (s, 3H); 13C NMR (DMSO-d6) δ171.64, 167.28, 138.81, 134.03, 130.67, 124.02, 122.90, 121.22, 52.51, 30.37; MS (EI, m/z) 271 (M+), 273 (M+2+). HRMS (EI) calcd for C10 H10NO3Br 270.9844, found 270.9838. Anal. Calcd for C10 H10NO3Br: C, 44.14; H, 3.70; N, 5.15. Found: C, 44.18; H, 3.67; N, 4.94.

Workup

  1. customfitted with a magnetic stirrer and a constant addition funnel
  2. customthe internal temperature between 0° C. and 2° C
  3. additionAfter the addition
  4. custom(20-25 min)
  5. customthe white crystalline compound which precipitated
  6. filtrationwas filtered
  7. washwashed sequentially with 5% HBr (100 mL) and water (200 mL)
  8. customdried in a vacuum oven at 40°-45° C. overnight
  9. customThe product was triturated with ether
  10. customdried in vacuo for 5 h

Sources & evidence

ORD record
ord-612d588b5b3040cd91b091ca4fd07c19
Source dataset
uspto-grants-1998_04
Patent number
US05741926

Reaction notes

Loading…