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【结 构 式】 
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【分子编号】39582 【品名】[(2E,4E)-3-methyl-5-(2,6,6-trimethyl-3-oxo-1-cyclohexen-1-yl)-2,4-pentadienyl](triphenyl)phosphonium bromide 【CA登记号】 |
【 分 子 式 】C33H36BrOP 【 分 子 量 】559.526002 【元素组成】C 70.84% H 6.49% Br 14.28% O 2.86% P 5.54% |
合成路线1
该中间体在本合成路线中的序号：(VIII)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 |
合成路线2
该中间体在本合成路线中的序号：(VIII)The reaction of beta-ionon (X) with triethyl orthoformate (A) by means of H2SO4 in dioxane gives beta-ionon enolether (XI), which by reaction with NBS in CCl4 and hydrolysis with acetic acid is converted into 4-acetoxyonon (XII). The Grignard reaction of (XII) with vinylmagnesium bromide (B) in THF and hydrolysis with KOH in methanol gives 5-(3-hydroxy-2,6,6-trimethylcyclohex-1-en-1-yl)-3-methylpenta-1,4-dien-3-ol (XIII), which is oxidized with MnO2 in methylene chloride yielding 5-(3-oxo-2,6,6-trimethylcyclohex-1-en-1-yl)-3-methylpenta-1,4-dien-3-ol (XIV). Finally, this compound by reaction with triphenylphosphonium bromide (C) in DMF is converted into the phosphonium salt (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】 Rosenberg, M.; US 4000198 . |
| 【2】 Serradell, M.N.; Blancafort, P.; Castaner, J.; Hillier, K.; Canthazanthin. Drugs Fut 1979, 4, 7, 477. |
| 【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 |
|---|---|---|---|---|---|---|
| (B) | 16524 | bromo(vinyl)magnesium | 1826-67-1 | C2H3BrMg | 详情 | 详情 |
| (A) | 21304 | Triethyl orthoformate; 1-(Diethoxymethoxy)ethane; Diethoxymethyl ethyl ether | 122-51-0 | C7H16O3 | 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 | |
| (X) | 39584 | (E)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one | 14901-07-6 | C13H20O | 详情 | 详情 |
| (XI) | 39585 | 6-[(Z,2Z)-3-methoxy-2-butenylidene]-1,5,5-trimethyl-1-cyclohexene; methyl (Z)-1-methyl-3-(2,6,6-trimethyl-2-cyclohexen-1-ylidene)-1-propenyl ether | C14H22O | 详情 | 详情 | |
| (XII) | 39586 | 2,4,4-trimethyl-3-[(E)-3-oxo-1-butenyl]-2-cyclohexen-1-yl acetate | C15H22O3 | 详情 | 详情 | |
| (XIII) | 39587 | 3-[(1E)-3-hydroxy-3-methyl-1,4-pentadienyl]-2,4,4-trimethyl-2-cyclohexen-1-ol | C15H24O2 | 详情 | 详情 | |
| (XIV) | 39588 | 3-[(1E)-3-hydroxy-3-methyl-1,4-pentadienyl]-2,4,4-trimethyl-2-cyclohexen-1-one | C15H22O2 | 详情 | 详情 | |
| (C) | 39589 | triphenylphosphonium bromide | 6399-81-1 | C18H16BrP | 详情 | 详情 |