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【结 构 式】 
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【分子编号】39026 【品名】ethyl 2-cyano-2-(1,1-diethyl-4-germinanylidene)acetate 【CA登记号】 |
【 分 子 式 】C14H23GeNO2 【 分 子 量 】309.95216 【元素组成】C 54.25% H 7.48% Ge 23.43% N 4.52% O 10.32% |
合成路线1
该中间体在本合成路线中的序号：(VII)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.
| 【1】 Rice, L.M.; US 3825546 . |
| 【2】 Rice, L.M.; et al.; Spirans. XXII. Synthesis of 4,4-dialkyl-4-germacyclohexanone and 8,8-dialkyl-8-germaazaspiro[4,5]decanes. J Heterocycl Chem 1974, 11, 6, 1041-47. |
| 【3】 Castaner, J.; Spirogermanium Hydrochloride. Drugs Fut 1980, 5, 3, 149. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (I) | 39022 | diethyl-lambda(2)-germane | C4H12Ge | 详情 | 详情 | |
| (II) | 14156 | methyl acrylate | 96-33-3 | C4H6O2 | 详情 | 详情 |
| (III) | 39023 | methyl 3-[diethyl(3-methoxy-3-oxopropyl)germyl]propanoate | C12H24GeO4 | 详情 | 详情 | |
| (IV) | 39024 | methyl 1,1-diethyl-4-oxo-3-germinanecarboxylate | C11H20GeO3 | 详情 | 详情 | |
| (V) | 39025 | 1,1-diethyl-4-germinanone | C9H18GeO | 详情 | 详情 | |
| (VI) | 11877 | Cyanoacetic acid ethyl ester; Ethyl 2-cyanoacetate; Ethyl cyanoacetate; Ethyl isocyanacetate | 105-56-6 | C5H7NO2 | 详情 | 详情 |
| (VII) | 39026 | ethyl 2-cyano-2-(1,1-diethyl-4-germinanylidene)acetate | C14H23GeNO2 | 详情 | 详情 | |
| (VIII) | 39027 | 4-(carboxymethyl)-1,1-diethyl-4-germinanecarboxylic acid | C12H22GeO4 | 详情 | 详情 | |
| (IX) | 39028 | 8,8-diethyl-2-oxa-8-germaspiro[4.5]decane-1,3-dione | C12H20GeO3 | 详情 | 详情 | |
| (X) | 25248 | N-(3-aminopropyl)-N,N-dimethylamine; N(1),N(1)-dimethyl-1,3-propanediamine | 109-55-7 | C5H14N2 | 详情 | 详情 |
| (XI) | 39029 | 2-[3-(dimethylamino)propyl]-8,8-diethyl-2-aza-8-germaspiro[4.5]decane-1,3-dione | C17H32GeN2O2 | 详情 | 详情 |