Partially fluorinated heterocyclic compounds. Part 26[1]. An investigation into the mode of cyclisation in the reaction of lithium 1,3,4,5,6,7,8-heptafluoro-2-naphthalenethiolate with dimethyl acetylenedicarboxylate
作者:Gerald M. Brooke
DOI:10.1016/s0022-1139(00)82726-8
日期:1989.6
Octafluoronaphthalene reacted with sodium hydrosulphide to give 1,3,4,5,6,7,8-heptafluoro-2-naphthalenethiol (4). The lithium salt of (4) and dimethyl acetylenedicarboxylate gave dimethyl 4,5,6,7,8,9-hexafluoronaphtho[2,1-b]thiophen-1,2- dicarboxylate (6) and dimethyl 4,5,6,7,8,9-hexafluoronaphtho[2,3-b] thiophen-2,3-dicarboxylate (7) in the ratio of 92:8 respectively via intramolecular cyclisation
八氟萘与硫化氢钠反应生成1,3,4,5,6,7,8-七氟-2-萘硫醇(4)。(4)的锂盐和乙炔二羧酸二甲酯形成4,5,6,7,8,9-六氟萘二甲基[2,1-b]噻吩1,2-二羧酸二甲酯(6)和4,5,6二甲基,通过分子内环化反应分别以92:8的比例合成7,8,9-六氟萘[2,3-b]噻吩-2,3-二羧酸酯(7)。通过水解和脱羧,将化合物(6)转化为4,5,6,7,8,9-六氟萘并[2,1-b]噻吩(8)。甲醇中的甲醇钠取代了1,3,4,5,6,7,8-七氟-2-萘甲基硫化物中的6-F氟(12)。通过在中间体(5)中的1-F处取代氟来优选形成(6),表明对局部能的考虑提高了该取向反应的选择性。