Acetate → 2-Methoxyestrone

HRID 11306

Reaction equation

HRID 11306 reaction equation
[CH3:1][C@@:2]12[C:18](=[O:19])[CH2:17][CH2:16][C@H:15]1[C@H:14]1[C@@H:5]([C:6]3[CH:7]=[CH:8][C:9]([OH:20])=[CH:10][C:11]=3[CH2:12][CH2:13]1)[CH2:4][CH2:3]2.[C:21]([O-])(=[O:23])C.II>C(O)(=O)C.[Cu](Cl)Cl>[CH3:1][C@@:2]12[C:18](=[O:19])[CH2:17][CH2:16][C@H:15]1[C@H:14]1[C@@H:5]([C:6]3[C:11]([CH2:12][CH2:13]1)=[CH:10][C:9]([OH:20])=[C:8]([O:23][CH3:21])[CH:7]=3)[CH2:4][CH2:3]2

Participants

6

Reactant 3

HCID 175AcetateHCID 807IodineHCID 5870Estrone

Product 1

HCID 4406242-MethoxyestroneYield 56%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 176Acetic AcidSolvent

Procedure

To this end, 2-iodo-estrone 49 was prepared by treating oestrone with mercuric-acetate and iodine in acetic acid.40 The selective halogenation at position 2 was complete within 2 hours at room temperature with an overall yield of 56% after successive recrystallizations. 2-Iodo-estrone then reacted with a large excess of a freshly prepared solution of sodium methoxyde, in presence of copper chloride in refluxing pyridine41 and gave 2-methoxy-estrone 50 with a yield: of 75%. This method has the advantage of not involving any protecting group and gives good overall yield (42%) for the synthesis of 2-methoxy-estrone in two steps from oestrone.

Workup

  1. customafter successive recrystallizations
  2. custom2-Iodo-estrone then reacted with a large excess of a freshly prepared solution of sodium methoxyde

Sources & evidence

ORD record
ord-4e7fa853fe9144349445c73f356f4216
Source dataset
uspto-grants-2006_08
Patent number
US07098218B2

Linked notes

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