Diethylamine → Vinyl ketone 6-(m-methoxyphenyl)-1-hexen-3-one
Reaktionsgleichung
C(N(CC)[CH2:4][CH2:5][C:6](=[O:18])[CH2:7][CH2:8][CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([O:16][CH3:17])[CH:11]=1)C.C(NCC)C>>[CH3:17][O:16][C:12]1[CH:11]=[C:10]([CH2:9][CH2:8][CH2:7][C:6](=[O:18])[CH:5]=[CH2:4])[CH:15]=[CH:14][CH:13]=1.[CH:11]([C:12]([CH:13]=[CH2:14])=[O:16])=[CH2:10]Komponenten
Versuchsvorschrift
Referring now to FIG. 1, wherein the compounds are assigned Roman numerals for identification schematically, the sequence of reactions involved in the synthesis of a specific embodiment, namely, 13β,17α-diethyl-17β-hydroxygon-4-en-3-one, is illustrated. 3-(m-Methoxyphenyl)propanol (I) is heated with phosphorus tribromide in benzene after dropwise addition in the cold to form 3-(m-methoxyphenyl)propyl bromide (II). This halogen compound (II) dissolved in tetrahydrofuran is condensed with sodium acetylide in liquid ammonia to obtain 5-(m-methoxyphenyl)-1-pentyne (III). Compound III is allowed to stand under nitrogen with water, 30% formalin, acetic acid, diethylamine, dioxan, and cuprous chloride at 70° C for about 12 hours, whereby there is obtained 1-diethylamino-6-(m-methoxyphenyl)-2-hexyne (IV), which is in turn hydrated in the presence of a mercury salt and sulfuric acid to form 1-diethylamino-6-(m-methoxyphenyl)-3-hexanone (V). The ketamine (V) may eliminate diethylamine on distillation to give the vinyl ketone 6-(m-methoxyphenyl)-1-hexen-3-one (VI). Either the ketamine (V) or the ketone (VI), or mixtures thereof, is then reacted with 2-ethyl-1,3-cyclopentanedione (VII) under Michael condensation conditions, e.g. refluxing in methanolic potassium hydroxide to form 2-ethyl-2-[6-(m-methoxyphenyl)-3-oxohexyl]-1,3-cyclopentanedione (VIII).
Aufarbeitung
- distillationon distillation
Quellen und Nachweise
- ORD-Eintrag
- ord-cd8a9a500f9c45a0877deb0ff2656968
- Quelldatensatz
- uspto-grants-1977_01
- Patentnummer
- US04002746
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