Sulfuric Acid → Ethyl 2,2-di(tertiary-amylperoxy)-1-cyclopentanecarboxylate

HRID 279435

반응식

HRID 279435 반응식
[C:1]([O:6][OH:7])([CH2:4][CH3:5])([CH3:3])[CH3:2].[O:8]=[C:9]1[CH2:13][CH2:12][CH2:11][CH:10]1[C:14]([O:16][CH2:17][CH3:18])=[O:15].S(=O)(=O)(O)O>>[C:1]([O:6][O:7][C:9]1([O:8][O:6][C:1]([CH2:4][CH3:5])([CH3:3])[CH3:2])[CH2:13][CH2:12][CH2:11][CH:10]1[C:14]([O:16][CH2:17][CH3:18])=[O:15])([CH2:4][CH3:5])([CH3:3])[CH3:2]

참가 물질

4

반응물 3

HCID 1118Sulfuric Acid2회HCID 69136Ethyl 2-oxocyclopentanecarboxylateHCID 76962tert-Amyl hydroperoxide

생성물 1

HCID 22625163Ethyl 2,2-di(tertiary-amylperoxy)-1-cyclopentanecarboxylate

반응 조건

온도
-10 °C

실험 절차

Ethyl 2,2-di(tertiary-amylperoxy)-1-cyclopentanecarboxylate was prepared by the addition of 92.64% TAHP (tertiary amyl hydroperoxide) (42.16 g, 0.3750 mol) to 95% ethyl 2-oxo-1-cyclopentanecarboxylate (16.44 g, 0.1000 mol) at room temperature in a three necked 250-mL round bottomed flask equipped with a thermometer and mechanical stirrer. The solution was then cooled via a dry ice-acetone bath to −10° C. and 78% sulfuric acid (15.09 g, 0.1200 mol) added dropwise to the solution with temperature at −10° C. Upon completion of the addition of sulfuric acid, the solution was allowed to reach 5° C. where it was maintained by an ice-water bath for three hours with mechanical stirring. The reaction was transferred to a separatory funnel and the lower acidic aqueous layer separated and discarded. The organic layer was then dissolved in petroleum ether and washed with saturated NaCl solution followed by 2% NaOH solution to bring aqueous washings to a pH of 4.5 to 7.0. The organic layer was then dried over MgSO4, filtered, stripped to remove the organic solvent and then analyzed for purity by gas chromatography (66% by area). Purification by chromatography (silica gel, petroleum ether) afforded a liquid product: 13C NMR (75 MHz, CDCl3) δ 171.9 (C═O), 116.8 (O—C—O, cyclic), 81.8 (C(CH3)2), 81.4 (C(CH3)2, 59.9 (O—CH2CH3), 49.5 (CH, cyclic), 33.0 (CH2, cyclic), 31.6 (CCH2CH3, (2X)), 27.9 (CH2, cyclic), 23.8 (C(CH3)2, (2x)), 22.2 (CH2, cyclic), 13.8 (O—CH2CH3), 8.0 (CCH2CH3, (2x)); IR (neat) ν 1736, 1366, 1202, 875 cm−1; Analysis calculated for C18H34O6: C, 62.40; H, 9.89; O, 27.71; found: C, 62.40: H, 10.14; O, 26.93.

후처리

  1. customequipped with a thermometer and mechanical stirrer
  2. customto reach 5° C.
  3. temperaturewas maintained by an ice-water bath for three hours with mechanical stirring
  4. customThe reaction was transferred to a separatory funnel
  5. customthe lower acidic aqueous layer separated
  6. dissolutionThe organic layer was then dissolved in petroleum ether
  7. washwashed with saturated NaCl solution
  8. dry with materialThe organic layer was then dried over MgSO4
  9. filtrationfiltered
  10. customto remove the organic solvent
  11. customPurification by chromatography (silica gel, petroleum ether)
  12. customafforded a liquid product

출처 및 근거

ORD 기록
ord-aafe3195e4bc4b9ba4cf0613cab56fc8
출처 데이터셋
uspto-grants-2002_03
특허 번호
US06362361B1

연결된 노트

불러오는 중…