Acetone → 13-Ethinyl-10-methyl-gon-4-ene-3,17-dione

HRID 972269Notes

Reaction equation

HRID 972269 reaction equation
[C:1]1(C)C=[CH:5][C:4](S(O)(=O)=O)=[CH:3][CH:2]=1.C1C[O:27][CH:21]2[C@:22]34OCCOC3([CH2:15][CH2:16][C@H:17]4[C@@H:18]3[CH2:36][CH:35]=[C:34]4[C@:29]([CH3:37])(CC[CH2:32][CH2:33]4)[C@H:19]3[CH2:20]2)O1.CC(C)=[O:40]>O>[C:2]([C@:3]12[CH2:32][CH2:33][C@@H:34]3[C@:29]4([CH3:37])[C:17]([CH2:16][CH2:15][C@H:35]3[C@@H:36]1[CH2:18][CH2:5][C:4]2=[O:40])=[CH:22][C:21](=[O:27])[CH2:20][CH2:19]4)#[CH:1]

Participants

5

Reactant 3

HCID 180AcetoneHCID 6101p-Toluenesulfonic acidHCID 13171092317,17-Bis-(ethylenedioxy)-10-methyl-gon-5-ene

Product 1

HCID 1570448413-Ethinyl-10-methyl-gon-4-ene-3,17-dione

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

20 mg of p-toluenesulphonic acid are added to a solution of 327 mg of 13-ethinyl-3,3;17,17-bis-(ethylenedioxy)-10-methyl-gon-5-ene in 15 ml of acetone and 0.5 ml of water and the mixture is heated under reflux for 5 hours. The reaction mixture is concentrated to about 5 ml, diluted with ethyl acetate, washed with water and saturated sodium chloride solution, dried and evaporated. Chromatography on silica gel using a mixture of hexane/ethyl acetate (3:1) as the eluant gives only 13-ethinyl-10-methyl-gon-4-ene-3,17-dione, which is recrystallised from ether/hexane; melting point 148°-150° C, [α]D25 = +63°.

Workup

  1. temperatureunder reflux for 5 hours
  2. concentrationThe reaction mixture is concentrated to about 5 ml
  3. additiondiluted with ethyl acetate
  4. washwashed with water and saturated sodium chloride solution
  5. customdried
  6. customevaporated
  7. additionChromatography on silica gel using a mixture of hexane/ethyl acetate (3:1) as the eluant

Sources & evidence

ORD record
ord-a1e4ec8057d243db8ed1f0349f7db6fe
Source dataset
uspto-grants-1977_10
Patent number
US04052421

Reaction notes

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