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

HRID 279434

反応式

HRID 279434 の反応式
[C:1]([O:6][OH:7])([CH2:4][CH3:5])([CH3:3])[CH3:2].[O:8]=[C:9]1[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]1[C:15]([O:17][CH2:18][CH3:19])=[O:16].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])[CH2:14][CH2:13][CH2:12][CH2:11][CH:10]1[C:15]([O:17][CH2:18][CH3:19])=[O:16])([CH2:4][CH3:5])([CH3:3])[CH3:2]

参加物

4

反応物 3

HCID 1118Sulfuric Acid2 回HCID 76962tert-Amyl hydroperoxideHCID 95543Ethyl 2-oxocyclohexanecarboxylate

生成物 1

HCID 22625161Ethyl 2,2-di(tertiary-amylperoxy)-1-cyclohexanecarboxylate

反応条件

温度
-10 °C

実験手順

Ethyl 2,2-di(tertiary-amylperoxy)-1-cyclohexanecarboxylate was prepared by the addition of 92.64% TAHP (tertiary amyl hydroperoxide) (42.16 g, 0.3750 mol) to 95% ethyl 2-oxo-1-cyclohexanecarboxylate (17.92 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 cooled to −10° C. via a dry ice-acetone bath and 78% sulfuric acid (15.09, 0.1200 mol) was added dropwise to the solution with the 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 washed with saturated NaCl solution until the aqueous washings had a pH of 4.5 or greater. The organic layer was then dried over MgSO4, filtered through a Buchner funnel and analyzed for purity by gas chromatography (53% by area). Purification by chromatography (silica gel, 95:5 petroleum ether/diethyl ether) afforded a liquid product: 13C NMR (75 MHz, CDCl3) δ 171.8 (C═O), 106.0 (O—C—O, cyclic), 81.1 (C—(CH3)2CH2), 81.0 (C(CH3)2CH2), 59.6 (O—CH2CH3), 44.0 (CH, cyclic), 3.16 (CH3—CH2—C), 31.5 (CH3CH2—C), 26.0 (CH2, cyclic), 23.6 (C(CH3)2, (2x)), 21.8 (CH2, cyclic), 22.0 (CH2, cyclic), 13.8 ((O—CH2CH3) (2X)), 8.0 ((CCH2CH3) (2x)); IR (neat) ν 1736, 1364, 1220, 872 cm−1.

後処理

  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. washThe organic layer was then washed with saturated NaCl solution until the aqueous washings
  7. dry with materialThe organic layer was then dried over MgSO4
  8. filtrationfiltered through a Buchner funnel
  9. customPurification by chromatography (silica gel, 95:5 petroleum ether/diethyl ether)
  10. customafforded a liquid product

出典と根拠

ORDレコード
ord-d0c362f45d844def9c5b7764ac0f3238
出典データセット
uspto-grants-2002_03
特許番号
US06362361B1

関連ノート

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