Tetrafluoroboric acid → HCID 42639483、化合物

HRID 1393321ノート

反応式

HRID 1393321 の反応式
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C@@H:8]2[C@@H:13]([OH:14])[CH2:12][CH2:11][C@H:10]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C@H:9]2[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:4][CH:3]=1.[F:25][C:26]([F:47])([F:46])[C:27]1[CH:28]=[C:29]([C@@H:37](OC(=N)C(Cl)(Cl)Cl)[CH3:38])[CH:30]=[C:31]([C:33]([F:36])([F:35])[F:34])[CH:32]=1.[H+].[B-](F)(F)(F)F>CCOCC>[F:25][C:26]([F:46])([F:47])[C:27]1[CH:28]=[C:29]([C@H:37]([O:14][C@H:13]2[CH2:12][CH2:11][C@H:10]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C@@H:9]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C@@H:8]2[C:5]2[CH:4]=[CH:3][C:2]([F:1])=[CH:7][CH:6]=2)[CH3:38])[CH:30]=[C:31]([C:33]([F:34])([F:35])[F:36])[CH:32]=1

参加物

5

反応物 3

HCID 28118Tetrafluoroboric acidHCID 11611082Trichloroacetimidic acid (S)-1-[3,5-bis(trifluoromethyl)phenyl]ethyl esterHCID 42639482(1S,2S,3R,4S)-diethyl 3-(4-fluorophenyl)-4-hydroxycyclohexane-1,2-dicarboxylate

生成物 1

HCID 42639483HCID 42639483、化合物収率 59.1%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒2 回

反応条件

温度
0 °C

実験手順

To a solution of 9.09 g (26.9 mmol) of the first eluting isomer diethyl(1S,2S,3R,4S)-3-(4-fluorophenyl)-4-hydroxycyclohexane-1,2-dicarboxylate (step D) and 21.5 g (53.5 mmol) of (1S)-1-[3,5-bis(trifluoromethyl)phenyl]ethyl-2,2,2-trichloroethanimidoate (step E) in 250 mL of cyclohexane/1,2-chloroethane (3/1) under nitrogen atmosphere at −5° C. was added 0.51 mL (3.58 mmol) of 54% HBF4 in ether. The reaction mixture was stirred at −5° C. to at 0° C. for 2 hr then diluted with ether. The mixture was washed with sat. aq. NaHCO3. The organic layer was dried over drying agent, filtered and the solvent evaporated under vacuum. The residue was purified by flash column chromatography on silica gel eluting with EtOAc/hexanes (1/4) to give 9.2 g of the title compound as an oil. 1H-NMR (CDCl3): δ: δ: 7.70 (1 H, s), 7.20 (2 H, s), 7.00 (2 H, m), 6.85 (2 H, t, J=8.5 Hz), 4.43 (1 H, q, J=6.0 Hz), 4.20-4.10 (2 H, m), 3.80-3.73 (2 H, m), 3.36 (1 H, m), 2.90-2.76 (2 H, m), 2.40 (1 H, m), 2.28 (1 H, m), 1.63-1.55 (2 H, m), 1.33 (3 H, d, J=6.0 Hz), 1.25 (3 H, t, J=7.2 Hz), 0.82 (3 H, t, J=7.2 Hz). Unreacted starting alcohol could be recovered by flushing the column with EtOAc and reused in the above reaction.

後処理

  1. washThe mixture was washed with sat. aq. NaHCO3
  2. customThe organic layer was dried
  3. customover drying agent
  4. filtrationfiltered
  5. customthe solvent evaporated under vacuum
  6. customThe residue was purified by flash column chromatography on silica gel eluting with EtOAc/hexanes (1/4)

出典と根拠

ORDレコード
ord-e0611fbf4e3545bc8101d4b27bc1b800
出典データセット
uspto-grants-2008_03
特許番号
US07345083B2

反応ノート

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