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【结 构 式】 
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【分子编号】38912 【品名】methoxy(2-methyl-6-nitro-1a,7b-dihydro-2H-oxireno[2,3-c]chromen-2-yl)methyl methyl ether; 2-(dimethoxymethyl)-2-methyl-6-nitro-1a,7b-dihydro-2H-oxireno[2,3-c]chromene 【CA登记号】 |
【 分 子 式 】C13H15NO6 【 分 子 量 】281.26524 【元素组成】C 55.51% H 5.38% N 4.98% O 34.13% |
合成路线1
该中间体在本合成路线中的序号：(IX)The cyclization of 2-hydroxyacetophenone (I) with pyruvic aldehyde dimethylacetal (II) by means of pyridine in refluxing toluene gives 2-(dimethoxymethyl)-2-methyl-3,4-dihydro-2H-1-benzopyran-4-one (III), which is nitrated with ammonium nitrate and TFA yielding the 6-nitro derivative (IV). The reduction of (IV) with NaBH4 in methanol affords the benzopyranol (V), which is treated with MsCl and DIEA to provide the mesylate (VI). The reaction of (VI) with DBU in refluxing toluene gives 2-(dimethoxymethyl)-2-methyl-6-nitro-2H-1-benzopyran (VII), which is treated with NBS in DMSO to yield the bromohydrin (VIII). Epoxidation of (VIII) with NaOH in dioxane/water affords the epoxide (IX), which is treated with 2-pyrrolidinone (X) and potassium tert-butoxide in tert-butanol to furnish 1-[2-(dimethoxymethyl)-3-hydroxy-2-methyl-3,4-dihydro-2H-1-benzpyran-4-yl]pyrrolidin-2-one (XI). The trans-acetalization of (XI) with ethylene glycol (XII) and TsOH in refluxing toluene gives the 1,3-dioxolanyl derivative (XIII), which is finally dehydrated to the target compound with NaOH in refluxing dioxane.
| 【1】 Yoo, S.-E.; Yi, K.Y.; Jeong, N.C.; Suh, J.H.; Kim, S.-J.; Shin, H.-S.; Lee, B.H.; Jung, K.S. (Korea Research Institute of Chemical Technology); Spiro-benzopyran derivs. and useful for treating asthma and hypertension. EP 0514935; US 5300511; US 5493029 . |
| 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) | 29654 | 2-hydroxyacetophenone; 1-(2-hydroxyphenyl)-1-ethanone | 118-93-4 | C8H8O2 | 详情 | 详情 |
| (II) | 25433 | 1,1-dimethoxyacetone | 6342-56-9 | C5H10O3 | 详情 | 详情 |
| (III) | 38906 | 2-(dimethoxymethyl)-2-methyl-2,3-dihydro-4H-chromen-4-one | C13H16O4 | 详情 | 详情 | |
| (IV) | 38907 | 2-(dimethoxymethyl)-2-methyl-6-nitro-2,3-dihydro-4H-chromen-4-one | C13H15NO6 | 详情 | 详情 | |
| (V) | 38908 | 2-(dimethoxymethyl)-2-methyl-6-nitro-4-chromanol | C13H17NO6 | 详情 | 详情 | |
| (VI) | 38909 | 2-(dimethoxymethyl)-2-methyl-4-[[methyl(dimethylene)-lambda(6)-sulfanyl]oxy]-6-nitrochromane; methoxy(2-methyl-4-[[methyl(dimethylene)-lambda(6)-sulfanyl]oxy]-6-nitro-3,4-dihydro-2H-chromen-2-yl)methyl methyl ether | C16H23NO6S | 详情 | 详情 | |
| (VII) | 38910 | methoxy(2-methyl-6-nitro-2H-chromen-2-yl)methyl methyl ether; 2-(dimethoxymethyl)-2-methyl-6-nitro-2H-chromene | C13H15NO5 | 详情 | 详情 | |
| (VIII) | 38911 | 3-bromo-2-(dimethoxymethyl)-2-methyl-6-nitro-4-chromanol | C13H16BrNO6 | 详情 | 详情 | |
| (IX) | 38912 | methoxy(2-methyl-6-nitro-1a,7b-dihydro-2H-oxireno[2,3-c]chromen-2-yl)methyl methyl ether; 2-(dimethoxymethyl)-2-methyl-6-nitro-1a,7b-dihydro-2H-oxireno[2,3-c]chromene | C13H15NO6 | 详情 | 详情 | |
| (X) | 27397 | 2-Pyrrolidinone | 616-45-5 | C4H7NO | 详情 | 详情 |
| (XI) | 38913 | 1-[2-(dimethoxymethyl)-3-hydroxy-2-methyl-6-nitro-3,4-dihydro-2H-chromen-4-yl]-2-pyrrolidinone | C17H22N2O7 | 详情 | 详情 | |
| (XII) | 11295 | Polyethylene glycol;1,2-Ethanediol;Monoethylene glycol; Ethylene glycol | 107-21-1 | C2H6O2 | 详情 | 详情 |
| (XIII) | 38914 | 1-[2-(1,3-dioxolan-2-yl)-3-hydroxy-2-methyl-6-nitro-3,4-dihydro-2H-chromen-4-yl]-2-pyrrolidinone | C17H20N2O7 | 详情 | 详情 |