Tetrabutylammonium Fluoride → [6-[[2-Chloro-5-(trifluoromethyl)phenoxy]methyl]dithiin-3-yl]methanol

HRID 265319ノート

反応式

HRID 265319 の反応式
[Si]([O:8][CH2:9][C:10]1[S:11][S:12][C:13]([CH2:16][O:17][C:18]2[CH:23]=[C:22]([C:24]([F:27])([F:26])[F:25])[CH:21]=[CH:20][C:19]=2[Cl:28])=[CH:14][CH:15]=1)(C(C)(C)C)(C)C.[F-].C([N+](CCCC)(CCCC)CCCC)CCC>C1COCC1.C(O)(=O)C>[OH:8][CH2:9][C:10]1[S:11][S:12][C:13]([CH2:16][O:17][C:18]2[CH:23]=[C:22]([C:24]([F:25])([F:26])[F:27])[CH:21]=[CH:20][C:19]=2[Cl:28])=[CH:14][CH:15]=1

参加物

5

反応物 2

HCID 2724141Tetrabutylammonium FluorideHCID 103224233-[(Tert-butyldimethylsilyloxy)methyl]-6-[(2-chloro-5-trifluoromethyl-phenyloxy)methyl]-1,2-dithiin

生成物 1

HCID 6481178[6-[[2-Chloro-5-(trifluoromethyl)phenoxy]methyl]dithiin-3-yl]methanol収率 57%

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a stirred solution of the 3-[(tert-butyldimethylsilyloxy)methyl]-6-[(2-chloro-5-trifluoromethyl-phenyloxy)methyl]-1,2-dithiin obtained above (290 mg, 0.62 mmol) in 8 mL of THF was added a solution of 4 mL of 1M tetrabutylammonium fluoride in THF and 2.5 mL of acetic acid. The reaction mixture was stirred for 5 h until TLC analysis showed the reaction to be complete. The reaction mixture was partitioned between 30 mL of water and 50 mL of ethyl acetate. The organic phase was washed with 3% aqueous sodium bicarbonate (50 mL). The aqueous layer was extracted with ethyl acetate (3×50 mL) and then the combined organic layer was washed with water, dried over magnesium sulfate and concentrated to a small volume. The residue was chromatographed over a silica gel column (ethyl acetate-hexane, 1:3) to yield 120 mg (57%) of the title compound as a yellow solid. The compound was further purified by reverse phase HPLC (PRP-1 column, acetonitrile:water gradient), mp 94.2°-96° C.; 1H NMR (CDCl3):δ7.51 (d, J=8.4, 1 H), 7.22 (dd, J=6.8, J=2.0, 1 H), 7.16 (d, J=l.2, 1 H), 6.55 (d, J=6.0, 1 H), 6.5 (d, J=6.0, 1 H), 4.79 (s, 2 H), 4.31 (d, 2 H, J=5.6) 1.80 (t, J=6.0, 1 H); 13C NMR(CDCl3):δ153.69, 136.86, 136.49, 130.98, 130.85, 128.30, 127.54, 124.77, 119.13, 118.28, 111.03, 70.73, 64.53, MS (EI):354 (M+). Anal. calcd for C13H10ClF3O2S2 :C, 44.01; H, 2.84. Found:C, 43.74; H, 2.94.

後処理

  1. customthe reaction
  2. customThe reaction mixture was partitioned between 30 mL of water and 50 mL of ethyl acetate
  3. washThe organic phase was washed with 3% aqueous sodium bicarbonate (50 mL)
  4. extractionThe aqueous layer was extracted with ethyl acetate (3×50 mL)
  5. washthe combined organic layer was washed with water
  6. dry with materialdried over magnesium sulfate
  7. concentrationconcentrated to a small volume
  8. customThe residue was chromatographed over a silica gel column (ethyl acetate-hexane, 1:3)

出典と根拠

ORDレコード
ord-de3ce1491b4b46d8bcca9d91cb2ba7d8
出典データセット
uspto-grants-1997_07
特許番号
US05648354

反応ノート

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