Ethylene Glycol → 1,4,8-Trioxaspiro[4.5]dec-6-ylacetaldehyde

HRID 73634

반응식

HRID 73634 반응식
C(C1C(=O)CC[O:6]C1)C=C.C(O)CO.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH2:27]([CH:30]1[CH2:39][O:38][CH2:37][CH2:36][C:31]21[O:35][CH2:34][CH2:33][O:32]2)[CH:28]=C.I([O-])(=O)(=O)=O.[Na+]>C1(C)C=CC=CC=1.C1COCC1.O.[Os](=O)(=O)(=O)=O>[O:35]1[C:31]2([CH2:36][CH2:37][O:38][CH2:39][CH:30]2[CH2:27][CH:28]=[O:6])[O:32][CH2:33][CH2:34]1

참가 물질

10

반응물 5

HCID 174Ethylene GlycolHCID 521998p-Toluenesulfonic acid monohydrateHCID 210779083-allyltetrahydro-4H-pyran-4-oneHCID 23667635Sodium periodateHCID 665794486-(Prop-2-en-1-yl)-1,4,8-trioxaspiro[4.5]decane

생성물 1

HCID 772311511,4,8-Trioxaspiro[4.5]dec-6-ylacetaldehyde

시약·촉매·용매 4

HCID 30318Osmium Tetroxide촉매HCID 962Water용매HCID 1140Toluene용매HCID 8028Tetrahydrofuran용매

반응 조건

온도
120 °C

실험 절차

A mixture of 3-(prop-2-en-1-yl)tetrahydro-4H-pyran-4-one (1.00 g, 7.13 mmol), ethylene glycol (0.597 mL, 10.70 mmol) and p-toluenesulfonic acid monohydrate (0.136 g, 0.713 mmol) in toluene (30 mL) was heated to 120° C. overnight. The reaction was then cooled to rt and concentrated. The residue was purified via column chromatography and used in the next step. To a mixture of 6-(prop-2-en-1-yl)-1,4,8-trioxaspiro[4.5]decane (0.840 g, 4.56 mmol) and osmium tetraoxide (2.5 wt % in T-BuOH, 0.551 mL, 0.046 mmol) in THF (15 mL) and water (5 mL) at rt was added sodium periodate (2.15 g, 1.19 mmol) portionwise over 5 min. The mixture was stirred at rt for 2 hr. The reaction was then quenched with sat'd. aq. sodium sulfite. The mixture was extracted 3× with Et2O. The combined organics were dried (anhd. Na2SO4), filtered, and concentrated. The residue was purified by column chromatography to give the title compound. 1H NMR (500 MHz, CDCl3) δ 9.71 (s, 1H), 3.81-3.99 (m, 6H), 3.64-3.70 (m, 1H), 3.47 (dd, 1H, J=8.6 Hz, 11.5 Hz), 2.49-2.57 (m, 2H), 2.18-2.26 (m, 1H), 1.65-1.82 (m, 2H).

후처리

  1. temperatureThe reaction was then cooled to rt
  2. concentrationconcentrated
  3. customThe residue was purified via column chromatography
  4. customThe reaction was then quenched with sat'd
  5. extractionThe mixture was extracted 3× with Et2O
  6. dry with materialThe combined organics were dried (anhd. Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography

출처 및 근거

ORD 기록
ord-69baf18d8b26484bb4e36d096cf9c749
출처 데이터셋
uspto-grants-2014_09
특허 번호
US08829196B2

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