A Facile Preparation, Characteristic Properties, and Crystal Structure of {4-[(E)-2-(3-Guaiazulenyl)diazenyl]phenyl}(3-guaiazulenyl)methylium Hexafluorophosphate

作者：Takekuma Shin ichi^*; Seki Atsuki; Minematsu Toshie

来源：Bulletin of the Chemical Society of Japan, 2014, 87(4): 511-527.

DOI：10.1246/bcsj.20130230

Reaction of 4-[(E)-2-(3-guaiazulenyl)diazenyl]benzene-1-carbaldehyde with guaiazulene (=7-isopropyl-1,4-dimethylazulene) in methanol in the presence of 65% hexafluorophosphoric acid at 25 degrees C for 2 h gives the title new mono-carbenium ion compound with an equivalent of HPF6, in 97% isolated yield, which upon reduction with NaBH4 in a mixed solvent of ethanol and acetonitrile at 25 C for 30 mm affords the corresponding new H--reduction product, {4-[(E)-2-(3-guaiazulenyl)diazenyl]phenyl}(3-guaiazulenyl)methane, in 93% isolated yield. Along with the above basic studies, the difference between the delocalized pi-electron system (i.e., the formation of the resonance structures) of the title compound, possessing an (E)-diazene linkage (-N=N-), and that of the structurally related new compound, possessing an (E)-ethene linkage (-CH=CH-), i.e., {4-[(E)-2-(3-guaiazulenyl)ethenyl]phenyl}(3-guaiazulenyl)methylium hexafluorophosphate, is reported in detail.

• 出版日期2014-4-15