Sodium Hydroxide → cis-4-Tetrahydropyranyloxy 2-cyclopentenol

HRID 2393888

반응식

HRID 2393888 반응식
[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

참가 물질

7

반응물 4

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

생성물 1

HCID 13623252cis-4-Tetrahydropyranyloxy 2-cyclopentenol수율 73.5%

시약·촉매·용매 2

HCID 1140Toluene용매2회HCID 15413tert-Butyl methyl ether용매2회

실험 절차

A slurry of lithium aluminum hydride (222 mg, 5.8 mnmol), 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 mnmol, 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/l-2+l-4 addition, 88/8/4; 1H NMR (CDCl3) δ 6.1 (m, 1 H), 4.7 (m, 1 H), 4.6 (m, 2 H), 3.9 (m, 1 H), 3.5 (m, 1 H), 2 .7 (m, 1 H), 1.4-2.0 (m, 8 H) 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).

후처리

  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)
  8. customto provide

출처 및 근거

ORD 기록
ord-4f304759aa8b40d084a7bfeccf502991
출처 데이터셋
uspto-grants-1998_09
특허 번호
US05808112

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