Sulfuric Acid → HCID 18714308, compound

HRID 279432Notes

Reaction equation

HRID 279432 reaction equation
[C:1]([O:5][OH:6])([CH3:4])([CH3:3])[CH3:2].[O:7]=[C:8]1[CH2:13][CH2:12][CH2:11][CH2:10][CH:9]1[C:14]([O:16][CH2:17][CH3:18])=[O:15].S(=O)(=O)(O)O>>[C:1]([O:5][O:6][C:8]1([O:7][O:5][C:1]([CH3:4])([CH3:3])[CH3:2])[CH2:13][CH2:12][CH2:11][CH2:10][CH:9]1[C:14]([O:16][CH2:17][CH3:18])=[O:15])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 3

HCID 1118Sulfuric Acid2×HCID 6410tert-Butyl hydroperoxideHCID 95543Ethyl 2-oxocyclohexanecarboxylate

Product 1

HCID 18714308HCID 18714308, compound

Conditions

Temperature
-10 °C

Procedure

Ethyl 2,2-di(tertiary-butylperoxy)-1-cyclohexanecarboxylate was prepared by the addition of 92.28% TBHP (tertiary butyl hydroperoxide) (24.41 g, 0.2500 moles) to 95% ethyl 2-oxo-1-cyclohexanecarboxylate (17.92 g, 0.1000 moles) at room temperature in a three necked 250-mL round bottomed flask equipped with a thermometer and mechanical stirrer. The solution was then cooled to −10° C. via a dry ice-acetone bath and 78% sulfuric acid (15.09 g, 0.1200 moles) 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 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 and filtered through a Buchner funnel to give a resulting peroxide (24.92 g, 74.92%). The resulting peroxide crystallized and was subsequently re-crystallized with hexanes, analyzed for purity by Gas Chromatography, as presented in Example 1, (95% by area) and it's 10 hr half life temperature was determined to be 93.31° C. by G.C.: m.p. 36-38°; 13C NMR (75 MHz, CDCl3) δ 171.8 (C═O), 106.1 (O—C—O, cyclic), 79.0 (C(CH3)3), 78.9 (C(CH3)3, 59.5 (CH2CH3), 44.3 (CH, Cyclic), 27.6 (CH2, cyclic), 26.3 ((CH3)3), 26.2 ((CH3)3), 2.17 (CH2, cyclic), 21.4 (CH2, cyclic), 13.8 (CH3CH2—O); IR (NaCl, CHCl3) ν 1735, 1370, 1200, 880 Cm−1; Analysis calculated for C17H32O6: C, 61.42; H, 9.70; O, 28.88; found: C, 61.05; H, 9.82: O, 28.22.

Workup

  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

Sources & evidence

ORD record
ord-15dc367966314ba88f89693c82e47d6d
Source dataset
uspto-grants-2002_03
Patent number
US06362361B1

Reaction notes

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