Acetic Anhydride → HCID 9895874, compound

HRID 1954273Notes

Reaction equation

HRID 1954273 reaction equation
[Br:1][C:2]1[C:11]2[S:12][C:13]([CH3:16])=[C:14]([CH3:15])[C:10]=2[C:9]([C:17]2[CH:36]=[C:35]([CH3:37])[C:20]([O:21][S:22]([C:25]3[CH:33]=[CH:32][C:28]([C:29]([OH:31])=[O:30])=[C:27]([OH:34])[CH:26]=3)(=[O:24])=[O:23])=[C:19]([CH3:38])[CH:18]=2)=[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]=[CH:7]2.[C:39](OC(=O)C)(=[O:41])[CH3:40].[I-].[Mg+2].[I-]>C(OCC)C>[C:39]([O:34][C:27]1[CH:26]=[C:25]([S:22]([O:21][C:20]2[C:35]([CH3:37])=[CH:36][C:17]([C:9]3[C:10]4[C:14]([CH3:15])=[C:13]([CH3:16])[S:12][C:11]=4[C:2]([Br:1])=[C:3]4[C:8]=3[CH:7]=[CH:6][CH:5]=[CH:4]4)=[CH:18][C:19]=2[CH3:38])(=[O:24])=[O:23])[CH:33]=[CH:32][C:28]=1[C:29]([OH:31])=[O:30])(=[O:41])[CH3:40]

Participants

5

Reactant 3

HCID 7918Acetic AnhydrideHCID 5462737Magnesium diiodideHCID 9960530HCID 9960530, compound

Product 1

HCID 9895874HCID 9895874, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

A stirred suspension containing 4-[4-(9-bromo-2,3-dimethyl-naphtho[2,3-b]thiophen-4-yl)-2,6-dimethyl-phenoxysulfonyl]-2-hydroxy-benzoic acid (0.350 g, 0.572 mmol), acetic anhydride (4.55 mL) and magnesium iodide (0.159 g, 0.572 mmol) in anhydrous ethyl ether (10.0 mL, 0.05M) was refluxed for 0.5 h. The reaction was cooled to ambient temperature, quenched with H2O (150 mL), extracted with ether and concentrated. The crude product was dissolved in THF:H2O (1:1, 10 mL) and refluxed for 1 h. The reaction was cooled to ambient temperature, diluted with H2O (50 mL) and extracted with ether and EtOAc. The combined organic extracts were concentrated and purified on 2% H3PO4 /MeOH treated silica gel, eluting with a 20 & 25% EtOAc/pet. ether step gradient to give 0.298 g (76%) of the title compound as a white solid; 1H NMR (DMSO-d6) δ 1.58 (s, 3 H), 2.15 (s, 6 H), 2.30 (s, 3 H), 2.45 (s, 3 H), 7.20 (s, 2 H), 7.46-7.54 (m, 2 H), 7.67 (t, 1 H), 7.94 (d, 1 H), 8.05 (dd, 1 H), 8.20-8.25 (m, 2 H), 13.75-13.95 (br.s., 1 H). mass spectrum (-ESI), m/z 651/653 (M-H).

Workup

  1. temperaturewas refluxed for 0.5 h
  2. customquenched with H2O (150 mL)
  3. extractionextracted with ether
  4. concentrationconcentrated
  5. dissolutionThe crude product was dissolved in THF:H2O (1:1, 10 mL)
  6. temperaturerefluxed for 1 h
  7. temperatureThe reaction was cooled to ambient temperature
  8. additiondiluted with H2O (50 mL)
  9. extractionextracted with ether and EtOAc
  10. concentrationThe combined organic extracts were concentrated
  11. custompurified on 2% H3PO4 /MeOH
  12. additiontreated silica gel
  13. washeluting with a 20 & 25% EtOAc/pet. ether step gradient

Sources & evidence

ORD record
ord-0ae01d51572c46709a75a169c7d0510d
Source dataset
uspto-grants-2000_09
Patent number
US06121271

Reaction notes

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