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【结 构 式】 
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【分子编号】30539 【品名】6,6-dimethyl-1-hepten-4-yn-3-ol 【CA登记号】 |
【 分 子 式 】C9H14O 【 分 子 量 】138.20956 【元素组成】C 78.21% H 10.21% O 11.58% |
合成路线1
该中间体在本合成路线中的序号：(IX)The condensation of propenal (VII) with tert-butylacetylene (VIII) by means of butyllithium gives 6,6-dimethylhept-1-en-4-yn-3-ol (IX), which is rearranged with HBr to the allyl isomer 6,6-dimethylhept-2-en-4-yn-1-yl bromide (X). Finally, this compound is condensed with amine (IV) by means of Na2CO3 in DMF.
| 【1】 Stutz, A.; SF-86327 and related compounds: Synthetic methods. Int Con Chemother 1983, 116, 5-8. |
| 【2】 Stutz, A. (Novartis AG); Propenylamines, pharmaceutical compositions containing them and their use as pharmaceuticals. EP 0024587; JP 56032440; JP 63313753; Us 4755534 . |
| 【3】 Serradell, M.N.; Castaner, J.; SF-86327. Drugs Fut 1984, 9, 6, 425. |
| 中间体序号 | 中间体编号 | 品名 | CAS号 | 分子式 | 供应商 | 用于合成 |
|---|---|---|---|---|---|---|
| (IV) | 10108 | N-Methyl(1-naphthyl)methanamine; N-Methyl-N-(1-naphthylmethyl)amine; 1-Methyl-1-naphthalenemethylamine | 65473-13-4 | C12H13N | 详情 | 详情 |
| (VII) | 17668 | acrylaldehyde; Acrolein | 107-02-8 | C3H4O | 详情 | 详情 |
| (VIII) | 30538 | 4,4-dimethyl-2-pentyne | 999-78-0 | C7H12 | 详情 | 详情 |
| (IX) | 30539 | 6,6-dimethyl-1-hepten-4-yn-3-ol | C9H14O | 详情 | 详情 | |
| (X) | 30540 | (E)-1-bromo-5,5-dimethyl-1-hexen-3-yne | C8H11Br | 详情 | 详情 |
合成路线2
该中间体在本合成路线中的序号：(I)The rearrangement of 6,6-dimethylhept-1-en-4-yn-3-ol (I) (scheme 09027805a, intermediate (IX)) to 1-bromo-6,6-dimethylhept-2(E)-en-4-yne (scheme 09027805a, intermediate (X)) with HBr reports a stereoselectivity E/Z of only 3/1. An exhaustive study of this halogenation/rearrangement reaction has been performed. This reaction ((I) to chloride (II)) has been improved up to and E/Z ratio of 9/1 with reaction yields of 95%, the reaction conditions being BCl3 (1.25 molar ratio) in hexane, with a reaction temperature of 25 C.
| 【1】 Chou, S.Y.; et al.; A stereoselective synthesis of (E)-1-halo-6,6-dimethyl-2-hepten-4-yne: A key intermediate for terbinafine. Tetrahedron Lett 2000, 41, 20, 3895. |