HCID 15718557, compound → HCID 15718559, compound

HRID 373036Notes

Reaction equation

HRID 373036 reaction equation
[CH3:1][O:2][C@@:3]12[CH2:9][C@@H:8]1[CH2:7][C@H:6]1[C@H:10]3[C@H:19]([CH2:20][CH2:21][C@:4]21[CH3:5])[C:18]1[CH2:17][CH2:16][C:15](=[O:22])[CH2:14][C:13]=1[CH2:12][CH2:11]3.C1C=C[NH+]=CC=1.Br[Br-]Br>N1C=CC=CC=1>[CH3:1][O:2][C@@:3]12[CH2:9][C@@H:8]1[CH2:7][C@H:6]1[C@H:10]3[C:19]([CH2:20][CH2:21][C@:4]21[CH3:5])=[C:18]1[C:13](=[CH:14][C:15](=[O:22])[CH2:16][CH2:17]1)[CH2:12][CH2:11]3

Participants

3

Reactant 1

HCID 15718557HCID 15718557, compound

Product 1

HCID 15718559HCID 15718559, compoundYield 84.8%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
-5 °C

Procedure

9.5 g of 17beta-methoxy-16alpha,17alpha-methylene-estr-5(10)-en-3-one (crude product) is dissolved in 130 ml of pyridine and then, with cooling (-5° C.), mixed with 11.5 of pyridine hydrobromide perbromide within 5 minutes. Then, the cooling is removed and the reaction solution warming slowly to room temperature is stirred for about 30 minutes, and then mixed with 3 ml of methylbutene and an excess bromation agent is consumed. Then, it is stirred for 4 hours at room temperature and then stirred into ice water, and the steroid precipitates in oily crystalline form. For complete crystallization, it is stored for 16 hours in the refrigerator and the steroid is fritted. 8 g of crystalline crude product is obtained. After extraction with methylene chloride and chromatography on neutral aluminum oxide with benzene/ethyl acetate (20:1 to 9:1), about 1 g of dienone can be obtained from the filtrate, dienone which can be crystallized from acetone/n-hexane (total yield 9 g). Melting point: 117° C. to 121° C., [α]D =-203°.

Workup

  1. customThen, the cooling is removed
  2. temperaturethe reaction solution warming slowly to room temperature
  3. additionmixed with 3 ml of methylbutene
  4. customan excess bromation agent is consumed
  5. stirringThen, it is stirred for 4 hours at room temperature
  6. stirringstirred into ice water
  7. customthe steroid precipitates in oily crystalline form
  8. customFor complete crystallization, it
  9. waitis stored for 16 hours in the refrigerator

Sources & evidence

ORD record
ord-a0f6606e8b2c48bba9712097f718e650
Source dataset
uspto-grants-1992_11
Patent number
US05162312

Reaction notes

Loading…