Arisawa Mieko, Suzuki Takaaki, Ishikawa Tomofumi, Yamaguchi Masahiko
Department of Organic Chemistry, Graduate School of Pharmaceutical Sciences, Tohoku University, Aoba, Sendai, 980-8578, Japan.
J Am Chem Soc. 2008 Sep 17;130(37):12214-5. doi: 10.1021/ja8049996. Epub 2008 Aug 23.
In the presence of a catalytic amount of RhH(PPh3)4 and 1,2-bis(diphenylphosphino)benzene, an aromatic fluoride, an organic disulfide (0.5 equiv), and triphenylphosphine (0.5 equiv) reacted in refluxing chlorobenzene to give an aryl sulfide in high yield. Since triphenylphosphine trapped fluoride atoms forming phosphine difluoride, both organothio groups of the disulfide reacted effectively, and the fluoride substituent reacted more readily than the chloride and bromide. The reaction of hexafluorobenzene and a diaryl disulfide gave 1,4-diarylthio-2,3,5,6-tetrafluorobenzene, 1,2,4,5-tetraarylthio-3,6-difluorobenzene, and hexaarylthiobenzene in a stepwise manner; pentafluorobenzene gave 1-arylthio-2,3,5,6-tetrafluorobenzene; 1,2,3,4-tetrafluorobenzene gave 1,2-diarylthio-3,6-difluorobenzene; and 1,2,4,5-tetrafluorobenzene gave 1,4-diarylthio-2-5-difluorobenzene. The polyarylthiolation reaction of polyfluorobenzenes exhibited a strong tendency to form 1,4-difluorobenzenes.
在催化量的RhH(PPh₃)₄和1,2-双(二苯基膦基)苯存在下，一种芳族氟化物、一种有机二硫化物（0.5当量）和三苯基膦（0.5当量）在回流的氯苯中反应，以高产率得到芳基硫醚。由于三苯基膦捕获氟原子形成二氟化膦，二硫化物的两个有机硫基都能有效反应，并且氟取代基比氯和溴取代基反应更易进行。六氟苯与二芳基二硫化物反应，逐步生成1,4-二芳基硫基-2,3,5,6-四氟苯、1,2,4,5-四芳基硫基-3,6-二氟苯和六芳基硫苯；五氟苯生成1-芳基硫基-2,3,5,6-四氟苯；1,2,3,4-四氟苯生成1,2-二芳基硫基-3,6-二氟苯；1,2,4,5-四氟苯生成1,4-二芳基硫基-2,5-二氟苯。多氟苯的多芳基硫醇化反应表现出强烈的生成1,4-二氟苯的倾向。
