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【结 构 式】 
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【分子编号】23542 【品名】ethyl 3-oxo-4-phenoxybutanoate 【CA登记号】 |
【 分 子 式 】C12H14O4 【 分 子 量 】222.24076 【元素组成】C 64.85% H 6.35% O 28.8% |
合成路线1
该中间体在本合成路线中的序号：(III)The reaction of phenol (I) with ethyl 4-chloroacetoacetate (II) by means of KOH in DMSO gives ethyl 4 phenoxyacetoacetate (III), which by treatment with NH3 is converted into ethyl 3-amino-4-phenoxycrotonate (IV). The cyclization of (IV) with propargyl aldehyde (V) in hot toluene affords ethyl 2-(phenoxymethyl)nicotinate (VI), which is cyclized again by means of polyphosphoric acid (PPA) to yield 5,11-dihydro[1]benzoxepino[3,4-b)pyridin-5-one (VII). The reduction of (VII) with NaBH4 in ethanol gives the corresponding alcohol (VIII), which is finally condensed with N,N-diethylethylene diamine (IX) by means of SOCl2 in dichloromethane.
| 【1】 Harakawa, H.; Kumazawa, T.; Tanaka, H.; Oijo, Y.; Shuto, K.; Ishii, A.; Nakamizo, N.; Obase, H.; Oka, T.; Synthesis and antiulcer activity of 5,11-dihydro[1. J Med Chem 1988, 31, 4, 779. |
| 【2】 Kumazawa, T.; Oiji, Y.; Shuto, K.; Tanaka, H. (Kyowa Hakko Kogyo Co., Ltd.); Benzepino[3,4-b]pyridine derivs.. EP 0129879; JP 1985006690; JP 1985078985; JP 1985089419; US 4547496 . |
| 【3】 Castaner, J.; Prous, J.; KW-5805. Drugs Fut 1988, 13, 11, 954. |
| 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) | 23540 | Phenol | 108-95-2 | C6H6O | 详情 | 详情 |
| (II) | 23541 | ethyl 4-chloro-3-oxobutanoate；Ethyl 4-chloro-3-oxobutanoate；Ethyl 4-chloroacetoacetate | 638-07-3 | C6H9ClO3 | 详情 | 详情 |
| (III) | 23542 | ethyl 3-oxo-4-phenoxybutanoate | C12H14O4 | 详情 | 详情 | |
| (IV) | 23543 | ethyl (Z)-3-amino-4-phenoxy-2-butenoate | C12H15NO3 | 详情 | 详情 | |
| (V) | 23544 | propiolaldehyde | C3H2O | 详情 | 详情 | |
| (VI) | 23545 | ethyl 2-(phenoxymethyl)nicotinate | C15H15NO3 | 详情 | 详情 | |
| (VII) | 23546 | [1]benzoxepino[3,4-b]pyridin-5(11H)-one | C13H9NO2 | 详情 | 详情 | |
| (VIII) | 23547 | 5,11-dihydro[1]benzoxepino[3,4-b]pyridin-5-ol | C13H11NO2 | 详情 | 详情 | |
| (IX) | 23548 | N-(5,11-dihydro[1]benzoxepino[3,4-b]pyridin-5-yl)-N-[2-(dimethylamino)ethyl]amine; N(1)-(5,11-dihydro[1]benzoxepino[3,4-b]pyridin-5-yl)-N(2),N(2)-dimethyl-1,2-ethanediamine | C17H21N3O | 详情 | 详情 |