【结 构 式】 |
【分子编号】49896 【品名】methyl 2-(4-hydroxy-2-methylphenoxy)acetate 【CA登记号】 |
【 分 子 式 】C10H12O4 【 分 子 量 】196.20288 【元素组成】C 61.22% H 6.16% O 32.62% |
合成路线1
该中间体在本合成路线中的序号:(IV)Alkylation of 4'-hydroxy-3'-methylacetophenone (I) with methyl bromoacetate in the presence of Cs2CO3 afforded the aryloxyacetate (II). Baeyer-Villiger rearrangement of the acetophenone moiety using meta-chloroperbenzoic acid produced the aryl ester (III), which was further converted to phenol (IV) by transesterification with methanolic NaOMe. Reaction of (IV) with dimethylthiocarbamoyl chloride gave the O-aryl thiocarbamate (V), which was thermally rearranged to the S-aryl thiocarbamate (VI) in refluxing tetradecane. Then, basic hydrolysis of the thiocarbamate function provided the thiophenol (VII). Alternatively, thiophenol (VII) was obtained by chlorosulfonation of ethyl (2-methylphenoxy)acetate (VIII), followed by reduction of the resultant sulfonyl chloride (IX) with Sn and HCl.
【1】 Maloney, P.R.; Gellibert, F.J.; Sierra, M.L.; Chao, E.Y.-H.; Haffner, C.D.; Willson, T.M.; Sznaidman, M.L.; Xu H.E.; Lambert, M.H. III; Sternbach, D.D. (Glaxo Group Ltd.); Thiazole and oxazole derivs. and their pharmaceutical use. WO 0100603 . |
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) | 49893 | 2-Methyl-4-acetophenol; 4-Hydroxy-3-methylacetophenone | 876-02-8 | C9H10O2 | 详情 | 详情 |
(II) | 49894 | methyl 2-(4-acetyl-2-methylphenoxy)acetate | C12H14O4 | 详情 | 详情 | |
(III) | 49895 | methyl 2-[4-(acetoxy)-2-methylphenoxy]acetate | C12H14O5 | 详情 | 详情 | |
(IV) | 49896 | methyl 2-(4-hydroxy-2-methylphenoxy)acetate | C10H12O4 | 详情 | 详情 | |
(V) | 49897 | methyl 2-(4-[[(dimethylamino)carbothioyl]oxy]-2-methylphenoxy)acetate | C13H17NO4S | 详情 | 详情 | |
(VI) | 49898 | methyl 2-(4-[[(dimethylamino)carbonyl]sulfanyl]-2-methylphenoxy)acetate | C13H17NO4S | 详情 | 详情 | |
(VII) | 49899 | methyl 2-(2-methyl-4-sulfanylphenoxy)acetate | C10H12O3S | 详情 | 详情 | |
(VIII) | 49900 | methyl 2-(2-methylphenoxy)acetate | C10H12O3 | 详情 | 详情 | |
(IX) | 49901 | methyl 2-[4-(chlorosulfonyl)-2-methylphenoxy]acetate | C10H11ClO5S | 详情 | 详情 |