Sulfuric Acid → HCID 18714309, compound

HRID 279433Notes

Reaction equation

HRID 279433 reaction equation
[C:1]([O:5][OH:6])([CH3:4])([CH3:3])[CH3:2].[O:7]=[C:8]1[CH2:12][CH2:11][CH2:10][CH:9]1[C:13]([O:15][CH2:16][CH3:17])=[O:14].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])[CH2:12][CH2:11][CH2:10][CH:9]1[C:13]([O:15][CH2:16][CH3:17])=[O:14])([CH3:4])([CH3:3])[CH3:2]

Participants

4

Reactant 3

HCID 1118Sulfuric Acid2×HCID 6410tert-Butyl hydroperoxideHCID 69136Ethyl 2-oxocyclopentanecarboxylate

Product 1

HCID 18714309HCID 18714309, compound

Conditions

Temperature
-10 °C

Procedure

Ethyl 2,2-di(tertiary-butylperoxy)-1-cyclopentanecarboxylate was prepared by the addition of 92.28% TBHP (tertiary butyl hydroperoxide) (24.41 g, 0.2500 moles) to 95% ethyl 2-oxo-cyclopentanecarboxylate (16.44 g, 0.1000 mol) in a three necked 250-mL round bottomed flask equipped with a thermometer and mechanical stirrer at room temperature. The solution was cooled to −10° C. via a dry ice-acetone bath and 70% sulfuric acid (16.81 g, 0.1200 mol) was 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, filtered through a Buchner funnel and analyzed for purity by gas chromatography (87.98% by area). Purification by chromatography (silica gel, 90:10 petroleum ether/diethyl ether) afforded a liquid product: 13C NMR (75 MHz, CDCl3) δ 171.8 (C═O), 116.8 (O—C—O, cyclic), 79.6 (C(CH3)3, 79.2 (C(CH3)3, 59.8 (O—CH2CH3), 49.5 (CH, cyclic), 32.9 (CH2, cyclic), 27.7 (CH2, cyclic) 26.2 ((CH3)3), 26.1 ((CH3)3), 22.1 (CH2, cyclic) 13.8 (CH2CH3); IR (neat) ν 1735, 1364, 1198, 878 cm−1; Analysis calculated for C16H30O6; C, 60.36, H, 9.50; O, 30.15; found: C, 60.36; H, 9.58; O, 29.11.

Workup

  1. customequipped with a thermometer and mechanical stirrer at room temperature
  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, 90:10 petroleum ether/diethyl ether)
  10. customafforded a liquid product

Sources & evidence

ORD record
ord-271ca74bcf27477cba992ce8781622f6
Source dataset
uspto-grants-2002_03
Patent number
US06362361B1

Reaction notes

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