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【结 构 式】 
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【分子编号】31106 【品名】4,5-dimethyl-1,3-dioxol-2-one 【CA登记号】37830-90-3 |
【 分 子 式 】C5H6O3 【 分 子 量 】114.10084 【元素组成】C 52.63% H 5.3% O 42.07% |
合成路线1
该中间体在本合成路线中的序号：(I)The bromination of 4,5-dimethyl-1,3-dioxolen-2-one (I) with N-bromo-succinimide (NBS) and azobisisobutyronitrile (AIBN) in CCl4 gives 4-methyl-5-bromomethyl-1,3-diioxolen-2-one (II), which is then condensed with ampicillin (III) by means of KHCO3 and benzaldehyde in DMF.
| 【1】 Sakamoto, F.; Ikeda, S.; Tsukamoto, G.; Utsumi, I. (Kanebo Pharmaceuticals, Ltd.); Novel ampicillin esters and production thereof. EP 0039086; EP 0039477; EP 0061206; US 4389408 . |
| 【2】 Serradell, M.N.; Castaner, J.; Blancafort, P.; KB-1585. Drugs Fut 1983, 8, 11, 920. |
| 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) | 31106 | 4,5-dimethyl-1,3-dioxol-2-one | 37830-90-3 | C5H6O3 | 详情 | 详情 |
| (II) | 13462 | 4-(Bromomethyl)-5-methyl-1,3-dioxol-2-one | 80715-22-6 | C5H5BrO3 | 详情 | 详情 |
| (III) | 31107 | (2S,5R,6R)-6-[[(2R)-2-amino-2-phenylethanoyl]amino]-3,3-dimethyl-7-oxo-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid | 69-53-4 | C16H19N3O4S | 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 acylating reagent (V) was prepared as follows. Allylic bromination of 4,5-dimethyl-1,3-dioxolene-2-one (I) with N-bromosuccinimide afforded bromide (II). This was converted to alcohol (IV) via formation of the formate ester (III), followed by acidic hydrolysis. Reaction of (IV) with p-nitrophenyl chloroformate and pyridine furnished carbonate (V). The acylation of pseudomycin B (VI) with carbonate (V) produced a mixture of mono-, di- and triacylated compounds from which the desired tricarbamate was isolated by reverse-phase preparative HPLC.
| 【1】 Sun, X.; et al.; Synthesis and evaluation of oxodioxolenylmethyl carbamate prodrugs of pseudomycins. J Med Chem 2001, 44, 16, 2671. |
| 【2】 Chen, S.H.; Sun, X.D.; Rodriguez, M.J. (Eli Lilly and Company); Pseudomycin prodrugs. WO 0105813 . |
| 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) | 31106 | 4,5-dimethyl-1,3-dioxol-2-one | 37830-90-3 | C5H6O3 | 详情 | 详情 |
| (II) | 13462 | 4-(Bromomethyl)-5-methyl-1,3-dioxol-2-one | 80715-22-6 | C5H5BrO3 | 详情 | 详情 |
| (III) | 50467 | (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl formate | C6H6O5 | 详情 | 详情 | |
| (IV) | 50468 | 4-(hydroxymethyl)-5-methyl-1,3-dioxol-2-one | C5H6O4 | 详情 | 详情 | |
| (V) | 25503 | (5-methyl-2-oxo-1,3-dioxol-4-yl)methyl 4-nitrophenyl carbonate | C12H9NO8 | 详情 | 详情 | |
| (VI) | 50469 | (2S)-2-((3S,6S,12S,15S,18S,21S,24R,27S)-18-(4-aminobutyl)-15,24-bis(2-aminoethyl)-21-(carboxymethyl)-3-[(1S)-2-chloro-1-hydroxyethyl]-9-[(Z)ethylidene]-12-[(1S)-1-hydroxyethyl]-27-[[(3R)-3-hydroxytetradecanoyl]amino]-2,5,8,11,14,17,20,23,26-nonaoxo-1-oxa-4,7,10,13,16,19,22,25-octaazacyclooctacosan-6-yl)-2-hydroxyethanoic acid | C51H87ClN12O19 | 详情 | 详情 |