SYNTHESIS AND CHEMICAL-TRANSFORMATIONS OF 1,3-DIARYLTETRAZOLIUM SALTS - PREPARATION OF MERCURY(II) AND PALLADIUM(II) COMPLEXES OF 1,3-DIARYLTETRAZOLYLENE AND REACTIONS OF 5-SUBSTITUTED 1,3-DIPHENYLTETRAZOLIUM SALTS WITH NUCLEOPHILES
SYNTHESIS AND CHEMICAL-TRANSFORMATIONS OF 1,3-DIARYLTETRAZOLIUM SALTS - PREPARATION OF MERCURY(II) AND PALLADIUM(II) COMPLEXES OF 1,3-DIARYLTETRAZOLYLENE AND REACTIONS OF 5-SUBSTITUTED 1,3-DIPHENYLTETRAZOLIUM SALTS WITH NUCLEOPHILES
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DOI：
10.1002/cber.19931260514
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发表时间：
1993-05-01
期刊：
影响因子：
--
通讯作者：
BUTSUGAN, Y
中科院分区：
文献类型：
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作者：
ARAKI, S;WANIBE, Y;BUTSUGAN, Y
1，3-二芳基四唑鎓盐5和6已通过相应的5-硫醇盐4的硝酸氧化制备。5与乙酸汞（II）反应得到（1，3-二芳基亚四唑基）汞（II）配合物7，其通过用卤素处理得到5-卤代四唑鎓盐8-10。由1，3-二苯基四唑盐Sa或6a的质子提取原位生成的1，3-二苯基四唑（16）已被四氟硼酸对-（二甲氨基）重氮苯捕获形成18/18 '。通过四（三苯基膦）钯（0）与5-氯四唑鎓盐8的氧化加成，制备了1，3-二苯基四唑撑的钯（II）配合物19。各种5-取代的四唑鎓盐对碳亲核试剂的反应性取决于C-5取代基的性质。对于负电性取代基，亲核取代在C-5处进行，而给电子取代基将亲核试剂导向N-2，产生开环产物。
1,3-Diaryltetrazolium salts 5 and 6 have been prepared by nitric acid oxidation of the corresponding 5-thiolates 4. The reaction of 5 with mercury(II) acetate gives (1,3-diaryltetra-zolylene)mercury(II) complexes 7, which provide 5-halotetrazolium salts 8-10 by treatment with halogen. 1,3-Diphenyltetrazolylene (16), generated in situ by proton abstraction of 1,3-diphenyltetrazolium salts Sa or 6a, has been trapped with p-(dimethylamino)benzenediazonium tetrafluoroborate to form 18/18'. The palladium(II) complex 19 of 1,3-diphenyltetrazolylene has been prepared by oxidative addition of tetrakis(triphenylphosphane)palladium(0) to 5-chlorotetrazolium salt 8. The reactivity of various 5-substituted tetrazolium salts toward carbon nucleophiles depends on the nature of the substituents at C-5. With electronegative substituents, nucleophilic substitution proceeds at C-5, whereas electron-donating substituents direct the nucleophiles towards N-2 yielding ring-cleaved products.