Acetic Anhydride → HCID 9895874、化合物

HRID 1954273ノート

反応式

HRID 1954273 の反応式
[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]

参加物

5

反応物 3

HCID 7918Acetic AnhydrideHCID 5462737Magnesium diiodideHCID 9960530HCID 9960530、化合物

生成物 1

HCID 9895874HCID 9895874、化合物収率 76%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-0ae01d51572c46709a75a169c7d0510d
出典データセット
uspto-grants-2000_09
特許番号
US06121271

反応ノート

読み込み中…