Iodoethane → 6,8-Difluoro-7-ethoxy-4-methylcoumarin

HRID 355403ノート

反応式

HRID 355403 の反応式
[F:1][C:2]1[CH:3]=[C:4]2[C:9](=[C:10]([F:13])[C:11]=1[OH:12])[O:8][C:7](=[O:14])[CH:6]=[C:5]2[CH3:15].[CH2:16](I)[CH3:17].C(=O)([O-])[O-].[K+].[K+]>CC(C)=O>[F:1][C:2]1[CH:3]=[C:4]2[C:9](=[C:10]([F:13])[C:11]=1[O:12][CH2:16][CH3:17])[O:8][C:7](=[O:14])[CH:6]=[C:5]2[CH3:15]

参加物

5

反応物 3

HCID 6340Iodoethane2 回HCID 11430Potassium CarbonateHCID 101767076,8-Difluoro-4-methylumbelliferone

生成物 1

HCID 27626436,8-Difluoro-7-ethoxy-4-methylcoumarin収率 44.3%

試薬・触媒・溶媒 1

HCID 180Acetone溶媒

実験手順

A solution of Compound 5 (0.10 g, 0.47 mmol) and ethyl iodide (112 μL, 1.4 mmol) in acetone (10 mL) is stirred at reflux with potassium carbonate (207 mg, 1.5 mmol) for 72 hours, during which additional ethyl iodide (2×200 μL) is added at 24 and 48 hours. After cooling, the reaction mixture is filtered and the filtrate is concentrated to a colorless solid. This solid is purified by preparative TLC (silica gel, 1000 μm plate, eluting with ethyl acetate/hexanes 1:1) to give 50 mg of nonfluorescent Compound 7 as a colorless solid. UV-vis (MeCN): 298 nm, ε=7,770 cm-1M-1 ; 279 nm, ε=11,080 cm-1 M-1. Rf (ethyl acetate/hexanes 3:2) 0.75. 1H NMR (CDCl3) 7.10 (dd, 1H), 6.28 (s, 1H), 4.38 (q, 2H), 2.39 (s, 3H), 1.42 (t, 3H). 19F NMR (CDCl3) 132.2 (t, 1F), 146.9 (d, 1F). Anal. calcd for C12H10O3F2 : C, 60.00; H, 4.20; N, 0.00; Found: C, 59.98; H, 4.27; N, 0.01.

後処理

  1. additionis added at 24 and 48 hours
  2. temperatureAfter cooling
  3. filtrationthe reaction mixture is filtered
  4. concentrationthe filtrate is concentrated to a colorless solid
  5. customThis solid is purified by preparative TLC (silica gel, 1000 μm plate, eluting with ethyl acetate/hexanes 1:1)

出典と根拠

ORDレコード
ord-7960fd29e085417792121641bccad6d4
出典データセット
uspto-grants-1998_11
特許番号
US05830912

反応ノート

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