Peracetic Acid → 2-(Prop-2-en-1-yl)cyclododecan-1-one

HRID 1263035Notes

Reaction equation

HRID 1263035 reaction equation
[CH2:1]([CH:4]1[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][C:5]1=[O:16])[CH:2]=[CH2:3].[C:17]1([SH:23])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1.[C:24]([O:27]O)(=[O:26])[CH3:25].B(F)(F)F.CC[O:35]CC.[OH-:38].[Na+]>>[CH2:1]([CH:4]1[CH2:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][C:5]1=[O:16])[CH:2]=[CH2:3].[C:17]1([S:23]([CH2:13][CH2:12][CH2:11][CH:10]2[O:27][C:24](=[O:26])[CH2:25][CH2:3][CH2:2][CH2:1][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9]2)(=[O:35])=[O:38])[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

7

Reactant 5

HCID 6585Peracetic Acid2×HCID 7969ThiophenolHCID 8000Boron trifluoride etherateHCID 14798Sodium HydroxideHCID 124038542-(Prop-2-en-1-yl)cyclododecan-1-one

Product 2

HCID 124038542-(Prop-2-en-1-yl)cyclododecan-1-oneHCID 2045662913-[3-(Benzenesulfonyl)propyl]-1-oxacyclotridecan-2-one

Procedure

22.0 g (100 mmole) of 2-allyl-cyclododecanone--Helv. Chim. Acta 54, 2889 (1971)--in admixture with 13.2 g (12.2 mmole) of thiophenol and 0.3 g of α,α'-azoisobutyronitrile were heated at 100° for 10 hours, an additional amount of 0.6 g of α,α'-azoisobutyronitrile being added over this period, portionwise, to the reaction mixture. After elimination of the excess of thiophenol and unreacted 2-allyl-cyclododecanone (2.25 g) by distillation (170°/0.05 Torr) the reaction mixture was diluted with 300 ml of trichloroethane and cooled to 0°. 90.4 g (475 mmole) of 40% peracetic acid were then progressively added to the above solution under good stirring (reaction temperature: 30°-40°). After addition of 7.5 g (53 mmole) of BF3.Et2O, the resulting mixture was further stirred for 10 days at 50°, 4 portions each of 11.3 g (60 mmole) of 40% peracetic acid being added thereto over this period. After cooling to 20°, the reaction mixture was poured onto crushed ice and then brought to pH 8 by the addition of 10% aqueous sodium hydroxide. After washing with a 10% solution of NaHSO3 in water, then with H2O, the organic phase was dried over Na2SO4 and evaporated. The obtained residue was finally purified by column chromatography (silicagel-eluent: 50/50 mixture of petrol ether and ethyl acetate) to afford 27.7 g (81% yield based on transformed 2-allyl-cyclododecanone) of the title compound (purity 90%).

Workup

  1. distillationAfter elimination of the excess of thiophenol and unreacted 2-allyl-cyclododecanone (2.25 g) by distillation (170°/0.05 Torr) the reaction mixture
  2. additionwas diluted with 300 ml of trichloroethane
  3. temperaturecooled to 0°
  4. custom(reaction temperature: 30°-40°)
  5. stirringthe resulting mixture was further stirred for 10 days at 50°
  6. waitover this period
  7. temperatureAfter cooling to 20°
  8. additionthe reaction mixture was poured
  9. customonto crushed ice
  10. washAfter washing with a 10% solution of NaHSO3 in water
  11. dry with materialwith H2O, the organic phase was dried over Na2SO4
  12. customevaporated
  13. customThe obtained residue was finally purified by column chromatography (silicagel-eluent: 50/50 mixture of petrol ether and ethyl acetate)

Sources & evidence

ORD record
ord-2106c1b91c4141498225ca1a1fa3e0c5
Source dataset
uspto-grants-1984_06
Patent number
US04454351

Reaction notes

Loading…