The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.
5,15-Di-bithienyl porphyrin (1) and its Cu(Ⅱ), Zn (Ⅱ) complexes (2 and 3)[1] were polymerized according to Scheme 1 by chemical oxidation using FeCl3 as oxidant for making organic conductor, and the linear porphyrin-thiophene copolymers were obtained. The structures of the copolymers were identified by elemental analysis and IR spectra. The conductivity of poly 5,15-di-bithienyl porphyrin (4) doped with FeCl3 was measured to reach over 10-6 S/cm, which was in the range of semiconductor and higher than that of other porphyrin-thiophene copolymers prepared by Shimidzu. The higher conductivity may be due to the better conjugation between the thienyl group and the porphyrin ring. The thienylporphyrins 7 and 8 could not be polymerized under the similar conditions, but could be polymerized by electrochemical oxidation (working electrode: gold-plate electrode; counter electrode: platinum; reference: standard calomel electrode SEC; solvent: 0.1 mol·dm-3 n-Bu4NClO4 in dry MeCN).……
