Acetone → HCID 53949067, compound

HRID 370708Notes

Reaction equation

HRID 370708 reaction equation
C[C@]12CC[C@H]3[C@@H](C=CC4[C@]3(C)CCC(=O)C=4)[C@@H]1CCC2=O.CC(C)=O.[OH:26][C@H:27]1[C@@:43]2([CH3:44])[C@@H:39]([CH2:40][CH2:41][C:42]2=[O:45])[C@H:38]2[C@@H:29]([C@:30]3([CH3:47])[C:35]([CH2:36][CH2:37]2)=[CH:34][C:33](=[O:46])[CH2:32][CH2:31]3)[CH2:28]1>CCCCCC.C(OCC)(=O)C>[OH:26][C@H:27]1[C@@:43]2([CH3:44])[C@@H:39]([CH2:40][CH2:41][C:42]2=[O:45])[C@H:38]2[C@@H:29]([C@:30]3([CH3:47])[C:35]([CH:36]=[CH:37]2)=[CH:34][C:33](=[O:46])[CH2:32][CH2:31]3)[CH2:28]1

Participants

5

Reactant 3

HCID 180AcetoneHCID 12452Androsta-4,6-diene-3,17-dioneHCID 12183443HCID 12183443, compound

Product 1

HCID 53949067HCID 53949067, compound

Reagents, catalysts & solvents 1

HCID 21226206Ethyl acetate hexaneSolvent

Procedure

Product C is seen to contain compounds of low polarity. A portion (26 g) is chromatographed on silica gel using a gradient of acetone in chloroform to separate the components. From the eluate comprising 10% acetone a fraction containing IV is obtained. This is re-chromatographed on silica gel with equal parts of hexane and ethyl acetate as eluent and provides a fraction which on recrystallising the product from aqueous ethanol gives pure IV, seen to be androsta-4,6-diene-3,17-dione, melting point 171.5°-172.5° C. (0.65 g). Similarly an eluate comprising 15% acetone is seen to contain a mixture of products, V and VI. On re-chromatography as above with hexane-ethyl acetate the compound V elutes first and on recrystallising this product from aqueous ethanol gives pure V, shown to be 12β-hydroxyandrost-4-ene-3,17-dione, melting point 169°-70° C. (8.2 g). The product VI elutes soon after and on recrystallising the product from aqueous ethanol gives pure VI, 12β-hydroxyandrosta-4,6-diene-3,17-dione, melting point 195°-6° C. (0.75 g). Similarly, an eluate comprising 20-25% acetone is seen to contain a mixture of II and VII. On re-chromatography as before, component II elutes first and then VII. On recovering this latter component and re-crystallising from aqueous ethanol gives pure VII, seen to be 12α-hydroxyandrosta-1,4-diene-3,17-dione melting point 202°-3° C. (0.34 g). Similarly the eluate comprising 30-35% acetone is seen to contain III and VIII. On re-chromatography of this product with ethyl acetate-hexane the first component eluting is VIII. On recovering this product and recrystallising from aqueous ethanol pure VIII is obtained, shown to be 7α-hydroxyandrost-4-ene-3,17-dione melting point 248°-50° C. (0.22 g). Similarly the eluate comprising 35-40% acetone is seen to contain IX and X, eluting separately. The first product is recovered and on recrystallising from aqueous ethanol pure IX is obtained shown to be 12β,17β-dihydroxyandrost-4-ene-3,17-dione melting point 118°-19° C. (1.6 g). The second product is also recovered and on recrystallising from aqueous ethanol pure X is obtained, shown to be 12β,17β-dihydroxyandrosta-1,4-diene-3-one, melting point 174°-5° C. (0.79 g).

Workup

  1. customon recrystallising this product from aqueous ethanol
  2. customgives pure V
  3. customon recrystallising the product from aqueous ethanol

Sources & evidence

ORD record
ord-02f7bd73ffe14d1c999f152017f5630e
Source dataset
uspto-grants-1985_07
Patent number
US04528272

Reaction notes

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