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【结 构 式】 
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【分子编号】54389 【品名】3-(aminomethyl)-2,6-di(tert-butyl)-4-hydroxyphenyl acetate 【CA登记号】 |
【 分 子 式 】C17H27NO3 【 分 子 量 】293.40632 【元素组成】C 69.59% H 9.28% N 4.77% O 16.36% |
合成路线1
该中间体在本合成路线中的序号：(IV)The condensation of 4-acetoxy-3,5-di-tert-butylphenol (I) with 2-chloro-N-(hydroxymethyl)acetamide (II) by means of H2SO4 in Ac-OH gives 4-acetoxy-3,5-di-tert-butyl-2-(2-chloroacetamidomethyl)phenol (III), which is hydrolyzed with HCl in ethanol to yield 4-acetoxy-2-/aminomethyl)-3,5-di-tert-butylphenol (IV). The oxidation of (IV) by means of hexamethylenetetramine (HMTA) affords the aldehyde (V), which is submitted to a Grignard condensation with 6-undecylmagnesium bromide (VI) in THF, followed by dehydration with conc. HCl to provide 4-acetoxy-3,5-di-tert-butyl-2-(2-pentyl-1-heptenyl)phenol (VII). The cyclization of (VII) by means of BF3/Et2O in dichloromethane gives the dihydrobenzofuran (VIII), which is finally deacetylated by reduction with LiAlH4 in THF to provide the target phenol.
| 【1】 Kato, Y.; et al.; Synthesis and reactivity of novel dihydrobenzofuranol antioxidants on various active oxygen species. 17th Symp Med Chem (Nov 19 1997, Tsukuba) 1997, Abst 1-P-20. |
| 【2】 Yoshida, M.; Kato, Y.; Tamura, K.; Ohba, Y.; Cynshi, O. (Chugai Pharmaceutical Co. Ltd.); 4-Alkoxy-2,6-di-tert-butylphenol derivs.. EP 0665208; US 5574178; WO 9408930 . |
| 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) | 54387 | 2,6-di(tert-butyl)-4-hydroxyphenyl acetate | C16H24O3 | 详情 | 详情 | |
| (II) | 23020 | 2-chloro-N-(hydroxymethyl)acetamide | 2832-19-1 | C3H6ClNO2 | 详情 | 详情 |
| (III) | 54388 | 2,6-di(tert-butyl)-3-{[(2-chloroacetyl)amino]methyl}-4-hydroxyphenyl acetate | C19H28ClNO4 | 详情 | 详情 | |
| (IV) | 54389 | 3-(aminomethyl)-2,6-di(tert-butyl)-4-hydroxyphenyl acetate | C17H27NO3 | 详情 | 详情 | |
| (V) | 54390 | 2,6-di(tert-butyl)-3-formyl-4-hydroxyphenyl acetate | C17H24O4 | 详情 | 详情 | |
| (VI) | 54391 | bromo(1-pentylhexyl)magnesium | C11H23BrMg | 详情 | 详情 | |
| (VII) | 54392 | 2,6-di(tert-butyl)-4-hydroxy-3-(2-pentyl-1-heptenyl)phenyl acetate | C28H46O3 | 详情 | 详情 | |
| (VIII) | 54393 | 4,6-di(tert-butyl)-2,2-dipentyl-2,3-dihydro-1-benzofuran-5-yl acetate | C28H46O3 | 详情 | 详情 |