Oxalyl chloride → HCID 67486306, compound

HRID 1755142Notes

Reaction equation

HRID 1755142 reaction equation
[CH3:1][O:2][C:3](=[O:22])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10][CH:11]([C:15]2[CH:20]=[CH:19][C:18]([Br:21])=[CH:17][CH:16]=2)[C:12]([OH:14])=O)=[CH:6][CH:5]=1.C(Cl)(=O)C(Cl)=O.[C:29]1([NH2:35])[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=1.[O:36]1[C:41]2=[CH:42][CH:43]=[CH:44][C:40]2=[CH:39][CH:38]=[CH:37]1>C(Cl)Cl>[CH3:1][O:2][C:3](=[O:22])[C:4]1[CH:5]=[CH:6][C:7]([CH2:10][CH:11]([C:12](=[O:14])[N:35]([C:37]2[O:36][C:41]3=[CH:42][CH:43]=[CH:44][C:40]3=[CH:39][CH:38]=2)[C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:15]2[CH:20]=[CH:19][C:18]([Br:21])=[CH:17][CH:16]=2)=[CH:8][CH:9]=1

Participants

5

Reactant 3

HCID 65578Oxalyl chlorideHCID 67211264HCID 67211264, compoundHCID 67486196HCID 67486196, compound

Product 1

HCID 67486306HCID 67486306, compoundYield 69%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

To a stirred suspension of 4-[2-(4-bromo-phenyl)-2-carboxy-ethyl]benzoic acid methyl ester (0.4 g, 1.10 mmol) in anhydrous CH2Cl2 (10 mL), was added oxalyl chloride (0.28 g, 2.7 mmol) at room temperature. The reaction mixture was stirred for 14 h, concentrated under reduced pressure and coevaporated with CH2Cl2 (2×10 mL. The crude material was dried under vacuum for 3 h. The crude acid chloride (0.4 g, 1.04 mmol) was treated with 4-benzofuran phenyl amine (Step E above, 0.26 g, 1.25 mmol) and N,N-diispropylethylamine (0.6 mL, 3.12 mmol) in CH2Cl2 at 0° C. The resulting mixture was stirred for 14 h at room temperature and concentrated under reduced pressure. The residue was treated with MeOH and the precipitate was filtered and washed with cold MeOH to give 4-[2-(4-benzofuran-2yl-phenylcarbamoyl)-2-(4-bromo-phenyl)-ethyl]-benzoic acid methyl ester as a brownish solid (0.4 g, 69%): 1H NMR (300 MHz, CDCl3): δ 7.82 (d, J=8.1 Hz, 2H), 7.68 (d, J=8.7 Hz, 2H), 7.38-7.47 (m, 5H), 7.09-7.20 (m, 7H), 6.87 (s, 1H), 3.81 (s, 3H), 3.53-3.64 (m, 2H), 3.0 (dd, J=6.6, 12.9 Hz, 1H); LC-MS m/z=554 [C31H42NBrO4+H]+; TLC conditions: Uniplate silica gel, 250 microns; mobile phase=ethyl acetate/hexanes (2:1); Rf=0.4.

Workup

  1. concentrationconcentrated under reduced pressure
  2. dry with materialThe crude material was dried under vacuum for 3 h
  3. stirringThe resulting mixture was stirred for 14 h at room temperature
  4. concentrationconcentrated under reduced pressure
  5. additionThe residue was treated with MeOH
  6. filtrationthe precipitate was filtered
  7. washwashed with cold MeOH

Sources & evidence

ORD record
ord-321ce89ab0df4550bb06ab415a63ffdc
Source dataset
uspto-grants-2015_10
Patent number
US09169201B2

Reaction notes

Loading…