HCID 23560772, compound → HCID 23560799, compound

HRID 2270794Notes

Reaction equation

HRID 2270794 reaction equation
[Br:1][C:2]1[CH:11]=[C:10]([C:12]([NH:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[C:18]([N+:22]([O-])=O)[CH:17]=2)=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]>O.C(O)(=O)C.[Fe]>[NH2:22][C:18]1[CH:17]=[C:16]([CH2:15][NH:14][C:12]([C:10]2[CH:9]=[CH:8][C:3]([C:4]([O:6][CH3:7])=[O:5])=[C:2]([Br:1])[CH:11]=2)=[O:13])[CH:21]=[CH:20][CH:19]=1

Participants

5

Reactant 1

HCID 23560772HCID 23560772, compound

Product 1

HCID 23560799HCID 23560799, compoundYield 87%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Conditions

Temperature
25 °C

Procedure

Iron powder (135 mg, 2.4 mmol) was added to a suspension of 2-bromo-4-[[[(3-nitrophenyl)methyl]amino]carbonyl]benzoic acid, methyl ester (Example 16; 125 mg, 3.18 mmol) in water (530 μL) and acetic acid (111 μL) at 25° C. The reaction was heated to reflux for 30 min and then cooled to 25° C. The suspension was diluted with water (20 mL), stirred for 15 min, and filtered through Celite. The filter cake was washed well with water (100 mL). The filtrate was extracted with ethyl acetate (50 mL) followed by ethyl acetate containing 2% methanol (50 mL). The organic layers were combined, dried (MgSO4), filtered, and concentrated. The residue was diluted with 10% methanol in dichloromethane and stirred with Celite. After 1 h, the suspension was filtered and washed well with 10% methanol in dichloromethane. Concentration of the filtrate afforded 4-[[[(3-aminophenyl)methyl]amino]carbonyl]-2-bromobenzoic acid, methyl ester (100 mg, 87%) as an off-white solid.

Workup

  1. temperatureThe reaction was heated
  2. temperatureto reflux for 30 min
  3. filtrationfiltered through Celite
  4. washThe filter cake was washed well with water (100 mL)
  5. extractionThe filtrate was extracted with ethyl acetate (50 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. additionThe residue was diluted with 10% methanol in dichloromethane
  10. stirringstirred with Celite
  11. waitAfter 1 h
  12. filtrationthe suspension was filtered
  13. washwashed well with 10% methanol in dichloromethane

Sources & evidence

ORD record
ord-bdb9b3fba1894a0bbe1bee998a07f6d8
Source dataset
uspto-grants-2001_12
Patent number
US06331640B1

Reaction notes

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