Catechol → HCID 70357672, compound

HRID 330474Notes

Reaction equation

HRID 330474 reaction equation
C1(C(=CC=CC=1)O)O.N1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[CH3:15][C@@:16]12[CH:25]3[CH2:26][CH2:27][C@:28]4([CH3:34])[C:32](=[O:33])[CH2:31][CH2:30][C@H:29]4[C@@H:24]3CC[C@@H]1C[C@H](O)[CH2:18][CH2:17]2.[I:36]I>C(Cl)Cl>[I:36][C@@H:10]1[CH2:18][CH2:17][C@@:16]2([CH3:15])[C@H:12]([CH2:13][CH2:14][C@@H:24]3[C@@H:25]2[CH2:26][CH2:27][C@@:28]2([CH3:34])[C@H:29]3[CH2:30][CH2:31][C:32]2=[O:33])[CH2:11]1

Participants

6

Reactant 4

HCID 289CatecholHCID 807IodineHCID 1049PyridineHCID 6420080HCID 6420080, compound

Product 1

HCID 70357672HCID 70357672, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
25 °C

Procedure

3-α-methyl-5-β-androstan-17-one was synthesized by the addition of catechol phosphochloridate (35 g, 200 mmol) and pyridine (15 g, 189.6 mmol) to 3-α-hydroxy-5-β-androstan-17-one (50.1 g, 173.0 mmol) in 1000 ml of methylene dichloride. The solution was magnetically stirred for 0.5 hour at room temperature (25° C.). Iodine (70 g, 275 mmol) was then added slowly to the solution and the stirring continued for an additional 2 hours at 25° C. The solution was washed with aqueous sodium sulfite (5%), dilute HCl, water, and dried over magnesium sulfate. It is important that the sodium sulfite solution not be saturated to prevent formation of emulsions. Approximately half of the aqueous solvent was removed under reduced pressure. Ether (2000 ml) was then added, and the entire solution passed through a short column of neutral alumina to remove colored impurities. The ether/solvent was evaporated from the column effluent under reduced pressure to yield 3α-iodo- 5β-androstan-17-one. This product was pure enough to be used in the next step without recrystallization.

Workup

  1. waitthe stirring continued for an additional 2 hours at 25° C
  2. washThe solution was washed with aqueous sodium sulfite (5%), dilute HCl, water
  3. dry with materialdried over magnesium sulfate
  4. customApproximately half of the aqueous solvent was removed under reduced pressure
  5. additionEther (2000 ml) was then added
  6. customto remove colored impurities
  7. customThe ether/solvent was evaporated from the column effluent under reduced pressure

Sources & evidence

ORD record
ord-d08ad237710e4e8593b6f5511d80b542
Source dataset
uspto-grants-1990_01
Patent number
US04897390

Reaction notes

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