合成路线:The cyclization of methyl 5-oxo-6-heptenoate (I) with 2-methylcyclopentane-1-3-dione (II) by means of pyridine in refluxing toluene gives methyl 3-(1,5-dioxo-7a-methyl 5,6,7,7a-tetrahydroindan-4-yl)propionate (III),which is hydrolyzed with 5N HCl to the corresponding free acid (IV).Separation of the optical isomers with ephedrine affords the 3-(1,5-dioxo-7a-methyl-5,6,7,7a-tetrahydroindan 4-yl)propionic acid (V),which is reduced with NaBH4 in water to the 1beta-hydroxyacid (VI).Reduction of the double bond of (VI) with H2 over Pd/C in acetic acid gives the saturated ketoacid (VII),which is acetylated with acetic anhydride to the acetoxy Iactone (VIII).The Grignard reaction of (VIII) with propylmagnesium bromide (IX) and treatment with methanolic KOH affords 6-ethyl-3-hydroxy-3a-methyl-1,2,3,3a,4,5,8,9,9a,9b decahydro 7H benz[e]inden-7-one (X),which is finally acetylated with acetic anhydride as before.
参考文献标题:RU-38882
文献作者:Castar,J.; Prous,J.
参考来源:Drugs Fut 1986,11(10),856
合成路线:The condensation of 2-iodophenylacetic (I) with 4-fluorophenol (II) by means of K2CO3 in nitrobenzene al 160 C gives 2-(4-fluoophenoxy)phenylacetic acid (III),which by treatment with refluxing SOCl2 is converted to the corresponding acid chloride (IV).The cyclization of (IV) by means of AlCl3 in refluxing dichloroethane affords 2-fluoro-10,11-dihydro-11-oxodibenzo[b,f]oxepin (V),which is treated with 2-(dimethylamino)ethylthiol (VI) and boron trifluoride ethereate in acetic acid yielding 2-fluoro-11-[2-(dimethylamino)ethythio]dibenzo[b,f]oxepin (VII).The reaction of (VII) with phenyl chloro-formate (VIII) by means of K2CO3 in methylene chloride affords 2-fluoro-11-[2-(N-methyl-N-phenyloxycarbonylamino)ethythio]dibenzo[b,f]oxepin (IX),which is finally hydrolyzed with KOH-ethylene glycol al 155 C.
合成路线:The cyclization of methyl 5-oxo-6-heptenoate (I) with 2-methylcyclopentane-1-3-dione (II) by means of pyridine in refluxing toluene gives methyl 3-(1,5-dioxo-7a-methyl 5,6,7,7a-tetrahydroindan-4-yl)propionate (III),which is hydrolyzed with 5N HCl to the corresponding free acid (IV).Separation of the optical isomers with ephedrine affords the 3-(1,5-dioxo-7a-methyl-5,6,7,7a-tetrahydroindan 4-yl)propionic acid (V),which is reduced with NaBH4 in water to the 1beta-hydroxyacid (VI).Reduction of the double bond of (VI) with H2 over Pd/C in acetic acid gives the saturated ketoacid (VII),which is acetylated with acetic anhydride to the acetoxy Iactone (VIII).The Grignard reaction of (VIII) with propylmagnesium bromide (IX) and treatment with methanolic KOH affords 6-ethyl-3-hydroxy-3a-methyl-1,2,3,3a,4,5,8,9,9a,9b decahydro 7H benz[e]inden-7-one (X),which is finally acetylated with acetic anhydride as before.
参考文献标题:Antiandrogenic activity of a series of des-A-steroid derivatives
文献作者:Morales-Alanis,H.; Brienne,M.J.; Jacques,J.; Bouton,M.M.; Nedelec,L.; Torelli,V.; Tournemine,C.
参考来源:J Med Chem 1985,28(12),1796
合成路线:The cyclization of methyl 5-oxo-6-heptenoate (I) with 2-methylcyclopentane-1-3-dione (II) by means of pyridine in refluxing toluene gives methyl 3-(1,5-dioxo-7a-methyl 5,6,7,7a-tetrahydroindan-4-yl)propionate (III),which is hydrolyzed with 5N HCl to the corresponding free acid (IV).Separation of the optical isomers with ephedrine affords the 3-(1,5-dioxo-7a-methyl-5,6,7,7a-tetrahydroindan 4-yl)propionic acid (V),which is reduced with NaBH4 in water to the 1beta-hydroxyacid (VI).Reduction of the double bond of (VI) with H2 over Pd/C in acetic acid gives the saturated ketoacid (VII),which is acetylated with acetic anhydride to the acetoxy Iactone (VIII).The Grignard reaction of (VIII) with propylmagnesium bromide (IX) and treatment with methanolic KOH affords 6-ethyl-3-hydroxy-3a-methyl-1,2,3,3a,4,5,8,9,9a,9b decahydro 7H benz[e]inden-7-one (X),which is finally acetylated with acetic anhydride as before.
参考文献标题:Sur l'hydrogenation catalytique de structures tetrahydroindaniques,intermediaries de syntheses totales steroides
文献作者:Mohamed,M.H.; Lima,J.J.; Eberle,L.V.; Self,T.H.; Johnson,J.A.
参考来源:Bull Soc Chim France 1968,9(2),3664
合成路线:The cyclization of methyl 5-oxo-6-heptenoate (I) with 2-methylcyclopentane-1-3-dione (II) by means of pyridine in refluxing toluene gives methyl 3-(1,5-dioxo-7a-methyl 5,6,7,7a-tetrahydroindan-4-yl)propionate (III),which is hydrolyzed with 5N HCl to the corresponding free acid (IV).Separation of the optical isomers with ephedrine affords the 3-(1,5-dioxo-7a-methyl-5,6,7,7a-tetrahydroindan 4-yl)propionic acid (V),which is reduced with NaBH4 in water to the 1beta-hydroxyacid (VI).Reduction of the double bond of (VI) with H2 over Pd/C in acetic acid gives the saturated ketoacid (VII),which is acetylated with acetic anhydride to the acetoxy Iactone (VIII).The Grignard reaction of (VIII) with propylmagnesium bromide (IX) and treatment with methanolic KOH affords 6-ethyl-3-hydroxy-3a-methyl-1,2,3,3a,4,5,8,9,9a,9b decahydro 7H benz[e]inden-7-one (X),which is finally acetylated with acetic anhydride as before.
参考文献标题:Pogres en synthese totale steroide
文献作者:Cerede,J.; Amiard,G.; Velluz,L.; Nomine,G.; Torelli,V.
参考来源:CR Hebd Seances Acad Sci 1963,2573086
合成路线:The cyclization of methyl 5-oxo-6-heptenoate (I) with 2-methylcyclopentane-1-3-dione (II) by means of pyridine in refluxing toluene gives methyl 3-(1,5-dioxo-7a-methyl 5,6,7,7a-tetrahydroindan-4-yl)propionate (III),which is hydrolyzed with 5N HCl to the corresponding free acid (IV).Separation of the optical isomers with ephedrine affords the 3-(1,5-dioxo-7a-methyl-5,6,7,7a-tetrahydroindan 4-yl)propionic acid (V),which is reduced with NaBH4 in water to the 1beta-hydroxyacid (VI).Reduction of the double bond of (VI) with H2 over Pd/C in acetic acid gives the saturated ketoacid (VII),which is acetylated with acetic anhydride to the acetoxy Iactone (VIII).The Grignard reaction of (VIII) with propylmagnesium bromide (IX) and treatment with methanolic KOH affords 6-ethyl-3-hydroxy-3a-methyl-1,2,3,3a,4,5,8,9,9a,9b decahydro 7H benz[e]inden-7-one (X),which is finally acetylated with acetic anhydride as before.
参考文献标题:Nouveaux compos閟 tricycliques et proc閐?de pr閜aration
文献作者:Joly,R.; Warnant,J.; Goffinet,B.
参考来源:FR 1359675
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