合成路线:The condensation of diethylgermanium dihydride (I) with methyl acrylate (II) gives diethyldi-(beta-carbomethoxyethyl)germane (III),which is cyclized by treatment with potassium tert-butoxide in refluxing toluene yielding carbomethoxy-4,4-diethyl-4-germacyclohexanone (IV).The decarboxylative hydrolysis of (IV) with refluxing 20% aqueous H2SO4 affords 4,4-diethyl-4-germacyclohexanone (V),which is condensed with ethyl cyanoacetate (VI) by means of ammonium acetate acetic acid in refluxing benzene giving ethyl alpha-cyano-alpha-(4,4-diethyl-4-germacyclohexylidene)acetate (VII).The treatment of (VII) with KCN in ethanol-water,and then with refluxing aqueous HCl yields 4,4-diethyl-4-germacyclohexane-1-carboxy-1-acetic acid (VIII),which is then converted into its cyclic anhydride (IX) by reaction with refluxing acetic anhydride.The reaction of (IX) with 3-dimethylaminopropylamine (X) at 180 C gives N-(3-dimethylaminopropyl)-2-aza-8,8-diethyl-8-germaspiro[4.5]decane-1,3-dione (XI),which is finally reduced with LiAlH4 in benzene-ether.
参考文献标题:
文献作者:Rice,L.M.
参考来源:US 3825546
合成路线:The condensation of diethylgermanium dihydride (I) with methyl acrylate (II) gives diethyldi-(beta-carbomethoxyethyl)germane (III),which is cyclized by treatment with potassium tert-butoxide in refluxing toluene yielding carbomethoxy-4,4-diethyl-4-germacyclohexanone (IV).The decarboxylative hydrolysis of (IV) with refluxing 20% aqueous H2SO4 affords 4,4-diethyl-4-germacyclohexanone (V),which is condensed with ethyl cyanoacetate (VI) by means of ammonium acetate acetic acid in refluxing benzene giving ethyl alpha-cyano-alpha-(4,4-diethyl-4-germacyclohexylidene)acetate (VII).The treatment of (VII) with KCN in ethanol-water,and then with refluxing aqueous HCl yields 4,4-diethyl-4-germacyclohexane-1-carboxy-1-acetic acid (VIII),which is then converted into its cyclic anhydride (IX) by reaction with refluxing acetic anhydride.The reaction of (IX) with 3-dimethylaminopropylamine (X) at 180 C gives N-(3-dimethylaminopropyl)-2-aza-8,8-diethyl-8-germaspiro[4.5]decane-1,3-dione (XI),which is finally reduced with LiAlH4 in benzene-ether.
参考文献标题:Spirans.XXII.Synthesis of 4,4-dialkyl-4-germacyclohexanone and 8,8-dialkyl-8-germaazaspiro[4,5]decanes
文献作者:Rice,L.M.; et al.
参考来源:J Heterocycl Chem 1974,11(6),1041-47
产品链接: CAS No. 41992-22-7›› 产品链接: CAS No.41992-23-8››