Sodium Hydroxide → cis-4-Tetrahydropyranyloxy 2-cyclopentenol

HRID 2546

反応式

HRID 2546 の反応式
[H-].[Al+3].[Li+].[H-].[H-].[H-].[I-].[Li+].[O:9]1[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]1[O:15][CH:16]1[CH2:20][C:19](=[O:21])[CH:18]=[CH:17]1.[OH-].[Na+]>COC(C)(C)C.C1(C)C=CC=CC=1>[O:9]1[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]1[O:15][C@@H:16]1[CH2:20][C@H:19]([OH:21])[CH:18]=[CH:17]1

参加物

7

反応物 4

HCID 14798Sodium HydroxideHCID 66321Lithium iodideHCID 128380104-(Tetrahydro-pyran-2-yloxy)-cyclopent-2-enoneHCID 21226445Aluminium lithium hydride

生成物 1

HCID 13623252cis-4-Tetrahydropyranyloxy 2-cyclopentenol収率 73.5%

試薬・触媒・溶媒 2

HCID 1140Toluene溶媒2 回HCID 15413tert-Butyl methyl ether溶媒2 回

実験手順

A slurry of lithium aluminum hydride (222 mg, 5.8 mmol), lithium iodide (3.2 g, 24 mmol), tert-butyl methyl ether (6 mL) and toluene (16 mL) is cooled to -15° C. A solution of 4-(tetrahydro-pyran-2-yloxy)-cyclopent-2-enone (2.179 g, 11.97 mmol, prepared in example 5) in tert-butyl methyl ether (2 mL) and toluene (2 mL) is added dropwise over 40 minutes. The reaction mixture is allowed to stir for 30 minutes. Then sodium hydroxide (1N, 5 mL) is added slowly to the reaction mixture. The slurry is filtered and the resulting phases separated. The aqueous phase is extracted with ethyl acetate (2×10 mL). The organic extracts are combined with the organic phase, dried over magnesium sulfate, filtered and concentrated under vacuum. The crude oil is then purified by chromatography (silica gel, 30 g, 50% ethyl acetate/hexane, 400 mL) to provide the title compound (1.62 g, 73%), cis/trans/1-2+1-4 addition, 88/8/4; 1H NMR (CDCl3) δ6.1 (m, 1H), 4.7 (m, 1H), 4.6 (m, 2H), 3.9 (m, 1H), 3.5 (m, 1H), 2.7 (m, 1H), 1.4-2.0 (m, 8H); 13C NMR (CDCl3) δ 137.2,137.1, 134.8, 133.6, 98.3, 97.8, 79.7, 79.5, 74.7, 74.5, 62.6, 62.5, 42.0, 41.1, 31.1, 30.9, 25.4, 19.6, 19.5; IR (neat) νmax 2944, 2870, 2855, 1723, 1348, 1202, 1182, 1152, 1128, 1078, 1032 cm-1 ; MS (CI) m/e (% relative intensity) 183 (M+H+, 7), 167 (M+H+ -H2O, 40), 85(100).

後処理

  1. filtrationThe slurry is filtered
  2. customthe resulting phases separated
  3. extractionThe aqueous phase is extracted with ethyl acetate (2×10 mL)
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under vacuum
  7. customThe crude oil is then purified by chromatography (silica gel, 30 g, 50% ethyl acetate/hexane, 400 mL)

出典と根拠

ORDレコード
ord-fcb0d5dcdda04901928d4fd9c09849c7
出典データセット
uspto-grants-1998_03
特許番号
US05728899

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