申请人:The Ohio State University Research Foundation
公开号:US03992392A1
公开(公告)日:1976-11-16
Preparing indoles and intermediates therefor by reacting an N-haloaniline with a .beta.-carbonylic hydrocarbon sulfide to form an azasulfonium halide, reacting the azasulfonium halide with a strong base to form a thio-ether indole derivative, and then reducing the thio-ether indole, e.g. with Raney nickel, to form the indole compound. When an acetal or ketal of the .beta.-carbonyl hydrocarbon sulfide is used, the azasulfonium salt is treated with a base, and then with an acid to form the thio-ether indole derivative. When an .alpha.-ethyl-.beta. -carbonylic hydrocarbon sulfide is used, the resulting azosulfonium salt reacts with strong base to form a thio-ether indolenine derivative, which on reduction with Raney nickel or complex metal hydrides yields 3-substituted indoles. The aniline may be an aminopyridine to form an aza-indole compound in the process. The azasulfonium salts and thio-ether indole or thio-ether indolenine derivatives can be isolated and recovered from their respective reaction mixtures. The thio-ether-indole and thio-ether indolenine derivatives are useful as intermediates to make the indoles without the thio-ether group. The indoles are known compounds having a wide variety of uses, e.g., in making perfumes, dyes, amino acids, pharmaceuticals, agricultural chemicals and the like.
通过将N-卤代苯胺与β-羰基烃基硫醚反应形成氮硫杂环卤化铵,再将氮硫杂环卤化铵与强碱反应形成硫醚吲哚衍生物,然后还原硫醚吲哚,例如使用Raney镍,形成吲哚化合物。当使用β-羰基烃基硫醚的缩醛或缩酮时,处理氮硫杂环盐,然后用酸处理形成硫醚吲哚衍生物。当使用α-乙基-β-羰基烃基硫醚时,生成的偶氮硫杂环盐与强碱反应形成硫醚吲哚啉衍生物,经Raney镍或复合金属氢化物还原后得到3-取代吲哚。苯胺可以是氨基吡啶,以在过程中形成氮杂吲哚化合物。可以从各自的反应混合物中分离和回收氮硫杂环盐和硫醚吲哚或硫醚吲哚啉衍生物。硫醚吲哚和硫醚吲哚啉衍生物是制备不含硫醚基的吲哚的中间体。吲哚是已知的化合物,具有广泛的用途,例如用于制造香料、染料、氨基酸、药物、农业化学品等。