Pyridine → 3-Methoxy-estra-2,5(10)-dien-17-ol
Reaction equation
[CH3:1][C@@:2]12[C@:19]([OH:23])(CC#N)[CH2:18][CH2:17][C@H:16]1[C@H:15]1[C:5](=[C:6]3[C:12]([CH2:13][CH2:14]1)=[CH:11][C:9](=[O:10])[CH2:8][CH2:7]3)[CH2:4][CH2:3]2.N1C=CC=C[CH:25]=1>>[CH3:25][O:10][C:9]1[CH2:11][C:12]2[CH2:13][CH2:14][C@@H:15]3[C@@H:5]([C:6]=2[CH2:7][CH:8]=1)[CH2:4][CH2:3][C@@:2]1([CH3:1])[C@H:16]3[CH2:17][CH2:18][CH:19]1[OH:23]Participants
Procedure
According to the German patent application DD 132,497 3-methoxy-17β-spiro-1′,2′-oxirane-estra-2,5(10)-diene is reacted with an alkali metal cyanide to yield a 17α-cyanomethyl-17β-hydroxy-3-enolether derivative. Then the so obtained compound is hydrolyzed, brominated and dehydrobrominated to furnish the dienogest of formula (I) hi 32% yield. The purity of the obtained dienogest is characterized by the melting point (204-214° C.) and optical rotation ([α]25D=290°, pyridine, c=0.5%). According to the method described in the patent application DD 80,023 3-methoxy-17β-spiro-1′,2′-oxirane-estra-2,5(10)-diene used as starting material can be synthesized by reacting dimethylsulfonium methylide and the 17-oxo derivative obtained by Oppenauer oxidation of the 17-hydroxy group of 3-methoxy-17-hydroxy-estra-2,5(10)-diene of formula (V)—latter synthesized by known methods.
Workup
- customcan be synthesized
Sources & evidence
- ORD record
- ord-7a526998ca6142e894d1713c8eda3256
- Source dataset
- uspto-grants-2012_11
- Patent number
- US08314145B2
Reaction notes
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