A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted...A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2\|nitration increased with the electronegativity of the central metal. When Cu(NO 3 ) 2 · 3H 2O was used as nitrating reagent, almost quantitative yields of 2\|nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO 3 ) 2 ·10H 2 O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.展开更多
文摘A series of 2\|nitro\|5,10,15,20\|tetra(4\|methoxyphenyl) porphyrinato metals were regioselectively synthesized with nitrate salts as nitrating reagent in acetic acid/acetic anhydride for preparation of 2\|substituted porphyrin. The influence of nitrate salts and complex metal ion to the reaction were investigated. The extent of 2\|nitration increased with the electronegativity of the central metal. When Cu(NO 3 ) 2 · 3H 2O was used as nitrating reagent, almost quantitative yields of 2\|nitro porphyrin were obtained in the case of Cu(Ⅱ) or Ni(Ⅱ) chelates, while Zn(Ⅱ) or Mn(Ⅲ) chelates gave 50% and 30% yields respectively. If Zn(NO 3 ) 2 ·10H 2 O was used as nitrating agent, no product was found for Cu(Ⅱ) or Ni(Ⅱ) chelates, 12% was found for Zn(Ⅱ) chelates. The other metal ion and nitrate salts were also found in quite different influence.
