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Ethyl bromoacetate → [2-(4-Bromo-2-fluoro-benzylcarbamoyl)-5-chloro-phenoxy]-acetic acid ethyl ester

HRID 2229529
Notes
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Reaction equation

HRID 2229529 reaction equation
[Br:1][C:2]1[CH:19]=[CH:18][C:5]([CH2:6][NH:7][C:8](=[O:17])[C:9]2[CH:14]=[CH:13][C:12]([Cl:15])=[CH:11][C:10]=2[OH:16])=[C:4]([F:20])[CH:3]=1.C([O-])([O-])=O.[K+].[K+].Br[CH2:28][C:29]([O:31][CH2:32][CH3:33])=[O:30]>CC(C)=O>[CH2:32]([O:31][C:29](=[O:30])[CH2:28][O:16][C:10]1[CH:11]=[C:12]([Cl:15])[CH:13]=[CH:14][C:9]=1[C:8](=[O:17])[NH:7][CH2:6][C:5]1[CH:18]=[CH:19][C:2]([Br:1])=[CH:3][C:4]=1[F:20])[CH3:33]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 18468196N-(4-bromo-2-fluoro-benzyl)-4-chloro-2-hydroxy-benzamide

Product 1

HCID 22093478[2-(4-Bromo-2-fluoro-benzylcarbamoyl)-5-chloro-phenoxy]-acetic acid ethyl esterYield 94%

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Conditions

Temperature
50 °C

Procedure

A solution of N-(4-bromo-2-fluoro-benzyl)-4-chloro-2-hydroxy-benzamide (3.25 g, 9.06 mmol) in acetone (45 mL, 0.2 M) was treated with aq K2CO3 (2 M, 6.8 mL, 14 mmol) and ethyl bromoacetate (1.2 mL, 11 mmol). After being heated to 50° C. for 8 h, the solution was cooled to room temperature and concentrated under reduced pressure until most of the acetone was removed. The solution was acidified to pH 1-2 with 2 N HCl, diluted with ethyl acetate and washed with saturated aq NaCl. The organic layer was dried over Na2SO4, filtered and concentrated. Purification by MPLC (10-60% ethyl acetate in heptane, 23 mL/min, 70 min) gave [2-(4-bromo-2-fluoro-benzylcarbamoyl)-5-chloro-phenoxy]-acetic acid ethyl ester as a white crystalline solid (3.78 g, 94%): mp 126-127° C.; Rf 0.61 (50% ethyl acetate in heptane); 1H NMR (DMSO-d6, 300 MHz) δ 8.90 (t, J=6 Hz, 1H), 7.82 (d, J=8.4 Hz, 1H), 7.52-7.47 (m, 1H), 7.39-7.31 (m, 2H),. 7.28 (d, J=1.8 Hz, 1H), 7.14 (dd, J=8.4 Hz, J2=1.8 Hz, 1H), 5.00, (s, 2H), 4.49 (d, J=6 Hz, 2H), 4.16 (q, J=7.2 Hz, 2H), 1.18 (t, J=6.6 Hz, 3H). ESI-LC/MS ml/z calcd for C18H16BrClFNO4: 444.7; found 446.0 (M+1)+. Anal. calcd for C18H16BrClFNO4: C, 48.62; H, 3.63; N, 3.15; Cl, 15.95. Found C, 48.57; H, 3.63; N, 3.11; Cl, 16.00.

Workup

  1. temperaturethe solution was cooled to room temperature
  2. concentrationconcentrated under reduced pressure until most of the acetone
  3. customwas removed
  4. additiondiluted with ethyl acetate
  5. washwashed with saturated aq NaCl
  6. dry with materialThe organic layer was dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by MPLC (10-60% ethyl acetate in heptane, 23 mL/min, 70 min)

Sources & evidence

ORD record
ord-9f25a2161dc64fd1ae6a19dae6d75cc6
Source dataset
uspto-grants-2002_07
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06420426B1

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes