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【结 构 式】 
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【分子编号】39579 【品名】3-[(E)-5-hydroxy-3-methyl-3-penten-1-ynyl]-2,4,4-trimethyl-2-cyclohexen-1-one 【CA登记号】 |
【 分 子 式 】C15H20O2 【 分 子 量 】232.3226 【元素组成】C 77.55% H 8.68% O 13.77% |
合成路线1
该中间体在本合成路线中的序号：(V)The reaction of 3-methyl-2-trans-penten-4-yn-1-ol (I) with ethyl vinyl ether (II) by means of p-toluenesulfonic acid gives 1-(1-ethoxyethoxy)-3-methyl-4-trans-penten-1-yne (III), which is condensed with 2,6,6-trimethyl-3-isobutoxycyclohex-2-en-1-one (IV) by means of butyllithium in ether at -60 C to afford 5-(2,6,6-trimethyl-3-oxocyclohexen-1-yl)-3-methyl-2-trans-penten-4-yn-1-ol (V). The reduction of (V) with H2 over a Lindlar catalyst in toluene yields 5-(2,6,6-trimethyl-3-oxocyclohexen-1-yl)-3-methyl-2,4-pentadien-1-ol (VI), which is converted into the corresponding pentadienyl bromide (VII) by reaction with PBr3 in ether. The reaction of (VII) with triphenylphosphine in refluxing benzene affords 5-(2,6,6-trimethyl-3-oxocyclohexen-1-yl)-3-methyl-2,4-pentadien-1-triphenylphosphonium bromide (VIII) , which is finally condensed in a Wittig reaction with 2,7-dimethyl-2,4,6-octatriene-1,8-dial (IX) by means of sodium methoxide in dichloromethane.
| 【1】 Serradell, M.N.; Blancafort, P.; Castaner, J.; Hillier, K.; Canthazanthin. Drugs Fut 1979, 4, 7, 477. |
| 【2】 Rosenberg, M.; US 4000198 . |
| 【3】 Rigassi, N.; Schwieter, U.; DE 2037935 . |
| 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) | 39576 | (E)-3-methyl-2-penten-4-yn-1-ol | 6153-06-6 | C6H8O | 详情 | 详情 |
| (II) | 18762 | 1-Ethoxyethylene; Ethyl vinyl ether；Ethoxyethene | 109-92-2 | C4H8O | 详情 | 详情 |
| (III) | 39577 | 5-(1-ethoxyethoxy)-3-methyl-1-penten-4-yne; 1-ethoxyethyl 3-methyl-4-penten-1-ynyl ether | C10H16O2 | 详情 | 详情 | |
| (IV) | 39578 | 3-isobutoxy-2,6,6-trimethyl-2-cyclohexen-1-one | C13H22O2 | 详情 | 详情 | |
| (V) | 39579 | 3-[(E)-5-hydroxy-3-methyl-3-penten-1-ynyl]-2,4,4-trimethyl-2-cyclohexen-1-one | C15H20O2 | 详情 | 详情 | |
| (VI) | 39580 | 3-[(1E,3E)-5-hydroxy-3-methyl-1,3-pentadienyl]-2,4,4-trimethyl-2-cyclohexen-1-one | 29538-78-1 | C15H22O2 | 详情 | 详情 |
| (VII) | 39581 | 3-[(1E,3E)-5-bromo-3-methyl-1,3-pentadienyl]-2,4,4-trimethyl-2-cyclohexen-1-one | C15H21BrO | 详情 | 详情 | |
| (VIII) | 39582 | [(2E,4E)-3-methyl-5-(2,6,6-trimethyl-3-oxo-1-cyclohexen-1-yl)-2,4-pentadienyl](triphenyl)phosphonium bromide | C33H36BrOP | 详情 | 详情 | |
| (IX) | 39583 | (2E,4E,6E)-2,7-dimethyl-2,4,6-octatrienedial | C10H12O2 | 详情 | 详情 |