Cyclohexanone → 13-Ethinyl-17beta-hydroxy-10-methyl-gon-4-en-3-one

HRID 972272Notes

Reaction equation

HRID 972272 reaction equation
[C:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C@:12]4([CH3:21])[C:17](=[CH:18][CH2:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][C@@H:4]2[OH:22])[CH2:16][C@@H:15]([OH:20])[CH2:14][CH2:13]4)#[CH:2].[Al].C1(=O)CCCCC1>C1(C)C=CC=CC=1.C(OCC)(=O)C>[C:1]([C@:3]12[CH2:11][CH2:10][C@@H:9]3[C@:12]4([CH3:21])[C:17]([CH2:18][CH2:19][C@H:8]3[C@@H:7]1[CH2:6][CH2:5][C@@H:4]2[OH:22])=[CH:16][C:15](=[O:20])[CH2:14][CH2:13]4)#[CH:2]

Participants

6

Reactant 3

HCID 7967CyclohexanoneHCID 5359268AluminumHCID 13171092413-Ethinyl-10-methyl-gon-5-ene-3beta,17beta-diol

Product 1

HCID 1570448513-Ethinyl-17beta-hydroxy-10-methyl-gon-4-en-3-one

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 900 mg of the crude 13-ethinyl-10-methyl-gon-5-ene-3β,17β-diol, obtained according to Example 2E, and 540 mg of aluminium isopropylate in 135 ml of toluene and 5.4 ml of cyclohexanone is boiled under reflux, under a water separator, for 60 minutes. After cooling, the reaction mixture is diluted with ethyl acetate, washed with potassium sodium tartrate solution, water and saturated sodium chloride solution, dried and evaporated. The oily residue is chromatographed on 80 g of silica gel. Using a mixture of hexane/ethyl acetate (3:1), 13-ethinyl-10-methyl-gon-4-ene-3,17-dione is eluted, melting point 148°-150° C; [α]D25 = +63°, after which 13-ethinyl-17β-hydroxy-10-methyl-gon-4-en-3-one, melting point 147°-149° C, [α]D25 =+154°, is obtained by elution with a mixture of the same solvents in a ratio of 2:1.

Workup

  1. temperatureunder reflux, under a water separator
  2. temperatureAfter cooling
  3. washwashed with potassium sodium tartrate solution, water and saturated sodium chloride solution
  4. customdried
  5. customevaporated
  6. customThe oily residue is chromatographed on 80 g of silica gel
  7. additiona mixture of hexane/ethyl acetate (3:1), 13-ethinyl-10-methyl-gon-4-ene-3,17-dione
  8. washis eluted

Sources & evidence

ORD record
ord-444be275087b48638a3fa4234fc54db1
Source dataset
uspto-grants-1977_10
Patent number
US04052421

Reaction notes

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