Water → HCID 22665451, compound

HRID 1278801Notes

Reaction equation

HRID 1278801 reaction equation
Br[CH2:2][C:3]([O:5]C)=[O:4].C(=O)([O-])[O-].[K+].[K+].[Br:13][C:14]1([N+:37]([O-:39])=[O:38])[CH:19]=[C:18]([C:20]2[C:32]3[C:31]([CH3:33])=[C:30]([CH3:34])[S:29][C:28]=3[C:27]([Br:35])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)[CH:17]=[CH:16][CH:15]1[OH:36].O>CN(C=O)C>[Br:13][C:14]1([N+:37]([O-:39])=[O:38])[CH:19]=[C:18]([C:20]2[C:32]3[C:31]([CH3:33])=[C:30]([CH3:34])[S:29][C:28]=3[C:27]([Br:35])=[C:26]3[C:21]=2[CH:22]=[CH:23][CH:24]=[CH:25]3)[CH:17]=[CH:16][CH:15]1[O:36][CH2:2][C:3]([OH:5])=[O:4]

Participants

6

Reactant 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 60984Methyl bromoacetateHCID 22665456HCID 22665456, compound

Product 1

HCID 22665451HCID 22665451, compoundYield 68.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Methyl bromoacetate (0.150 mL, 1.58 mmol) was added to a stirred suspension of potassium carbonate (0.223 g, 1.61 mmol), 2-bromo-4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-2-nitro-phenol (0.400 g, 0.789 mmol) in DMF (2.8 mL). After 15 h, the reaction mixture was added to water and extracted with ethyl acetate. Silica gel was added to the ethyl acetate and the solvent was removed. The adsorbate was flashed (9:1 petroleum ether: ethyl actetate) to provide the title compound as a yellow solid (0.305 g, 67%). This solid (0.050 g, 0.086 mmol) was dissolved in 1:1 THF:methanol (2 mL) and treated with aqueous potassium hydroxide (1.0 N, 0.30 mL, 0.30 mmol). After 25 min the reaction mixture was diluted with water, acidified with 10% aqeous HCl and extracted with ether. The ether phase was dried (sodium sulfate), concentrated and recrystallized from petroleum ether:ether to provide the title compound as a white solid (0.025 g, 51%): mp 228-229° C.: NMR (DMSO-d6); δ 8.23 (d, J=9 Hz, 1H), 8.14 (d, J=2 Hz, 1H), 8.04 (d, J=2 Hz, 1H), 7.69 (ddd, J=8, 7, 1, 1H), 7.54 (ddd, J=8, 7, 1 Hz, 1H), 7.48 (d, J=8 Hz, 1H), 4.87 (d, J=6 Hz, 1H), 4.82 (d, J=6 Hz, 1H), 2.46 (s, 3H), 1.62 (s, 3H); MS (+FAB): 2 bromine isotope pattern 563 (40%), 565 (100%), 567 (50%); Anal. Calc. for C22H15Br2NO5S: C, 46.75, H, 2.68, N, 2.48. Found: C, 45.18, H, 2.66, N, 2.38.

Workup

  1. extractionextracted with ethyl acetate
  2. additionSilica gel was added to the ethyl acetate
  3. customthe solvent was removed

Sources & evidence

ORD record
ord-3bcf095797e9479c9403b79daacb1b73
Source dataset
uspto-grants-2002_09
Patent number
US06444670B2

Reaction notes

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