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【结 构 式】 
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【分子编号】33245 【品名】2-(1-hydroxy-5-isopropyl-6,7-dimethoxy-3-methyl-2-naphthyl)-5-isopropyl-6,7-dimethoxy-3-methyl-1-naphthol 【CA登记号】 |
【 分 子 式 】C32H38O6 【 分 子 量 】518.65012 【元素组成】C 74.11% H 7.38% O 18.51% |
合成路线1
该中间体在本合成路线中的序号：(VII)The condensation of 3,4-dimethoxy-2-isopropylbenzaldehyde (I) with diethyl succinate (II) by means of NaH in refluxing benzene gives 2-(2-isopropyl-3,4-dimethoxybenzylidene)succinic acid monoethyl ester (III), which is cyclized by treatment with acetic anhydride and sodium acetate in refluxing acetic acid and hydrolyzed with NaOH in refluxing methanol yielding acid (IV). The reduction of (IV) with LiAlH4 in ether affords 3-hydroxymethyl-5-isopropyl-6,7-dimethoxy-1-naphthol (V), which is hydrogenated with H2 over Pd/C in methanol with some HCl giving 3-methyl-5-isopropyl-6,7-dimethoxy-1-naphthol (VI). Thermal dimerization of (VI) by heating at 215 C yields 2,2'-bis(3-methyl-5-isopropyl-6,7-dimethoxy-1-naphthol) (VII).
| 【1】 Cashaw, J.L.; Edwards, J.D.Jr.; Studies in the naphtalene series. III. Synthesis of apogossypol hexamethyl ether. J Am Chem Soc 1957, 79, 2283. |
| 【2】 Edwards, J.D.Jr.; Total synthesis of gossypol. J Am Chem Soc 1958, 80, 3798. |
| 【3】 El-Nockrashy; J Am Oil Chem Soc 1963, 40, 1, 14. |
| 【4】 Leeson, P.; Gossypol. Drugs Fut 1979, 4, 5, 338. |
| 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) | 33240 | 2-isopropyl-3,4-dimethoxybenzaldehyde | C12H16O3 | 详情 | 详情 | |
| (II) | 12313 | diethyl succinate | 123-25-1 | C8H14O4 | 详情 | 详情 |
| (III) | 33241 | (E)-3-(ethoxycarbonyl)-4-(2-isopropyl-3,4-dimethoxyphenyl)-3-butenoic acid | C18H24O6 | 详情 | 详情 | |
| (IV) | 33242 | 4-hydroxy-8-isopropyl-6,7-dimethoxy-2-naphthoic acid | C16H18O5 | 详情 | 详情 | |
| (V) | 33243 | 3-(hydroxymethyl)-5-isopropyl-6,7-dimethoxy-1-naphthol | C16H20O4 | 详情 | 详情 | |
| (VI) | 33244 | 5-isopropyl-6,7-dimethoxy-3-methyl-1-naphthol | C16H20O3 | 详情 | 详情 | |
| (VII) | 33245 | 2-(1-hydroxy-5-isopropyl-6,7-dimethoxy-3-methyl-2-naphthyl)-5-isopropyl-6,7-dimethoxy-3-methyl-1-naphthol | C32H38O6 | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(VII)Intermediate (VII) is methylated with dimethylsulfate and KOH in refluxing aqueous dioxane affording apogossypol hexamethyl ether (VIII) . The cleavage of the methoxy groups with BBr3 and aqueous NaOH yields apogossypol (IX), which by reaction with N,N'-diphenylformamidine (X) affords gossypol bis(N-phenylimine) (XI), which is finally hydrolyzed.
| 【1】 Cashaw, J.L.; Edwards, J.D.Jr.; Studies in the naphtalene series. III. Synthesis of apogossypol hexamethyl ether. J Am Chem Soc 1957, 79, 2283. |
| 【2】 Edwards, J.D.Jr.; Total synthesis of gossypol. J Am Chem Soc 1958, 80, 3798. |
| 【3】 El-Nockrashy; J Am Oil Chem Soc 1963, 40, 1, 14. |
| 【4】 Leeson, P.; Gossypol. Drugs Fut 1979, 4, 5, 338. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (VII) | 33245 | 2-(1-hydroxy-5-isopropyl-6,7-dimethoxy-3-methyl-2-naphthyl)-5-isopropyl-6,7-dimethoxy-3-methyl-1-naphthol | C32H38O6 | 详情 | 详情 | |
| (VIII) | 33246 | 1-isopropyl-6-(5-isopropyl-1,6,7-trimethoxy-3-methyl-2-naphthyl)-2,3,5-trimethoxy-7-methylnaphthalene; 1-isopropyl-6-(5-isopropyl-1,6,7-trimethoxy-3-methyl-2-naphthyl)-3,5-dimethoxy-7-methyl-2-naphthyl methyl ether | C34H42O6 | 详情 | 详情 | |
| (IX) | 33247 | 5-isopropyl-3-methyl-2-(1,6,7-trihydroxy-5-isopropyl-3-methyl-2-naphthyl)-1,6,7-naphthalenetriol | C28H30O6 | 详情 | 详情 | |
| (X) | 33248 | N,N'-diphenyliminoformamide | 622-15-1 | C13H12N2 | 详情 | 详情 |
| (XI) | 33249 | 5-isopropyl-3-methyl-8-[(phenylimino)methyl]-2-[1,6,7-trihydroxy-5-isopropyl-3-methyl-8-[(phenylimino)methyl]-2-naphthyl]-1,6,7-naphthalenetriol | C42H40N2O6 | 详情 | 详情 |