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Transdihydrolisuride, Terguride, SH-406, ZK-31224, VUFB-6638, Teluron, Mysalfon

特麦角脲Chemical Name: 3-(6-Methylergolin-8alpha-yl)-1,1-diethylurea
CAS No. 37686-84-3
项目整合开发状态: Launched-1994
项目研究机构: Nihon Schering (Originator), Schering AG (Originator)
合成路线:The reaction of carboxamide (I) with lead tetraacetate and K2CO3 in DMF gives the corresponding isocyanate (II),which,without isolation is treated with diethylamine (III) to afford the target diethylurea.

合成路线:Hofmann rearrangement of isolysergic acid amide (I) using lead tetraacetate produced isocyanate (II),which was further condensed with diethylamine to furnish urea (III).Hydrogenation of N-(D-6-methyl-8-isoergolenyl)-N',N'-diethylurea (III) in the presence of Raney nickel yielded a mixture of the desired isoergoline-I-yl urea along with minor amounts of its isoergoline-II-yl epimer (IV),which were separated by column chromatography.A more stereoselective hydrogenation of (III) was achieved under Birch reduction conditions using lithium amide/aniline to deprotonate the labile urea side chain.Similarly,isolysergic acid amide (I) underwent stereoselective Birch reduction to the 9,10-dihydro derivative (V),which was converted to the title compound via lead tetraacetate-promoted Hofmann rearrangement,followed by coupling with diethylamine.
📌 参考资料/链接:
参考文献标题:Process for the preparation of ergoline derivs.
文献作者:Sauer,G.; Haffer,G.(Schering AG)
参考来源:EP 0074921

📄 详细内容


合成路线:Hofmann rearrangement of isolysergic acid amide (I) using lead tetraacetate produced isocyanate (II),which was further condensed with diethylamine to furnish urea (III).Hydrogenation of N-(D-6-methyl-8-isoergolenyl)-N',N'-diethylurea (III) in the presence of Raney nickel yielded a mixture of the desired isoergoline-I-yl urea along with minor amounts of its isoergoline-II-yl epimer (IV),which were separated by column chromatography.A more stereoselective hydrogenation of (III) was achieved under Birch reduction conditions using lithium amide/aniline to deprotonate the labile urea side chain.Similarly,isolysergic acid amide (I) underwent stereoselective Birch reduction to the 9,10-dihydro derivative (V),which was converted to the title compound via lead tetraacetate-promoted Hofmann rearrangement,followed by coupling with diethylamine.

合成路线:Alternatively,D-dihydrolysergic acid-I-hydrazide (VI) was treated with nitrous acid to produce the corresponding acyl azide (VII),which was further subjected to a Curtius rearrangement in refluxing benzene.Without isolation,the obtained isocyanate (VIII) solution was treated with diethylamine to afford the title urea derivative.

参考文献标题:N-(D-6-Methyl-8-isoergoline-1-yl)-N'N'-diethylurea
文献作者:Zik醤,V.; Semonsky,M.; Rez醔ek,K.; Seda,M.; Auskov? M.(SPOFA - United Pharmaceutical Works)
参考来源:US 3953454


合成路线:Hofmann rearrangement of isolysergic acid amide (I) using lead tetraacetate produced isocyanate (II),which was further condensed with diethylamine to furnish urea (III).Hydrogenation of N-(D-6-methyl-8-isoergolenyl)-N',N'-diethylurea (III) in the presence of Raney nickel yielded a mixture of the desired isoergoline-I-yl urea along with minor amounts of its isoergoline-II-yl epimer (IV),which were separated by column chromatography.A more stereoselective hydrogenation of (III) was achieved under Birch reduction conditions using lithium amide/aniline to deprotonate the labile urea side chain.Similarly,isolysergic acid amide (I) underwent stereoselective Birch reduction to the 9,10-dihydro derivative (V),which was converted to the title compound via lead tetraacetate-promoted Hofmann rearrangement,followed by coupling with diethylamine.

参考文献标题:Process for preparing 8-alpha-substituted 6-methylergoline derivs.
文献作者:Sauer,G.(Schering AG)
参考来源:EP 0032684


合成路线:Hofmann rearrangement of isolysergic acid amide (I) using lead tetraacetate produced isocyanate (II),which was further condensed with diethylamine to furnish urea (III).Hydrogenation of N-(D-6-methyl-8-isoergolenyl)-N',N'-diethylurea (III) in the presence of Raney nickel yielded a mixture of the desired isoergoline-I-yl urea along with minor amounts of its isoergoline-II-yl epimer (IV),which were separated by column chromatography.A more stereoselective hydrogenation of (III) was achieved under Birch reduction conditions using lithium amide/aniline to deprotonate the labile urea side chain.Similarly,isolysergic acid amide (I) underwent stereoselective Birch reduction to the 9,10-dihydro derivative (V),which was converted to the title compound via lead tetraacetate-promoted Hofmann rearrangement,followed by coupling with diethylamine.

合成路线:Alternatively,D-dihydrolysergic acid-I-hydrazide (VI) was treated with nitrous acid to produce the corresponding acyl azide (VII),which was further subjected to a Curtius rearrangement in refluxing benzene.Without isolation,the obtained isocyanate (VIII) solution was treated with diethylamine to afford the title urea derivative.

参考文献标题:Ergot alkaloids.XL.Some N-(D-6-methyl-8-isoergolin-I-yl)- and N-(D-6-methyl-8-isoergolin-II-yl)-N'-substituted ureas
文献作者:Zik醤,V.; et al.
参考来源:Coll Czech Chem Commun 1972,37(8),2600


合成路线:Hofmann rearrangement of isolysergic acid amide (I) using lead tetraacetate produced isocyanate (II),which was further condensed with diethylamine to furnish urea (III).Hydrogenation of N-(D-6-methyl-8-isoergolenyl)-N',N'-diethylurea (III) in the presence of Raney nickel yielded a mixture of the desired isoergoline-I-yl urea along with minor amounts of its isoergoline-II-yl epimer (IV),which were separated by column chromatography.A more stereoselective hydrogenation of (III) was achieved under Birch reduction conditions using lithium amide/aniline to deprotonate the labile urea side chain.Similarly,isolysergic acid amide (I) underwent stereoselective Birch reduction to the 9,10-dihydro derivative (V),which was converted to the title compound via lead tetraacetate-promoted Hofmann rearrangement,followed by coupling with diethylamine.
参考文献标题:Reduction of 8alpha-substituted 9,10-didehydroergolines
文献作者:Sauer,G.; et al.
参考来源:Synthesis (Stuttgart) 1986,(12),1007


产品链接: CAS No. 37686-84-3››