Study On The Synthesis Of New Biomimetic Models Of Porphyrins

A series ofporphyrin compounds, as models of Cytochrome P-450, were prepared and applicated as catalysts in the oxidation reaction of cyclohaxane. Particularly, syntheses of new kinds of calixarened porphyrin compounds, tethered porphyrin compounds and theirmetalloporphyrins were studied intensively. They were described as follow: 1.Substituted porphyrin compounds were synthesized in propanoic acid, using n-hydroxybenzaldehyde (n=2,3,4), substituted benzaldehyde ( R=H, Cl, OCH 3, CH 3, et al) and pyrrole as raw materials. At the same time, monohydroxyporphyrin was prepared rapidly by means of microwave irradiation. On treatment with an excess of α,ω -dibromoalkanes (n=3,4) in the present of K 2CO 3 and dimethylformamide( DMF ), monohydroxylporphyrins were led to ω -bromoalkoxy porphyrin derivatives in high yield (90-95%), including eleven kinds of new compounds. Furthermore new tethered porphyrin compounds were synthesized. Being treated with an excess of 2-benzothiazolethiol in the present of K 2CO 3 and dimethylformamide ( DMF ), ω-bromoalkoxy porphyrin derivatives were led to fourteen kinds of new 2-benzothiazolethiol tethered porphyrins through a thiol ether linkage in 85-95% yield. Four kinds of newmetalloporphyrins (M=Fe, Co, Mn) were prepared by combination of tethered porphyrins and metal salts. 2. P-tert-butylphenol and formaldehyde were mixed together in the presence of alkali to produce p-tert-butyl-calix[n]arene(n=4,6). The tert-butyl groups of calix[n]arene(n=4,6) were removed by an AlCl 3 catalyzed transalkylation reaction. P-tert-butylcalix[4]arene and calix[4]arene were linked withω-bromoalkoxy porphyrin derivatives to prepare four kinds of new .calixarened porphyrin. compounds in 20% yield. Then these new compounds reacted with metal salts to synthesize Fe(II)porphyrins as enzyme models. Following another route, the same porphyrin compounds were obtained. Partial alkylation of p-tert-butylcalix[4]arene with an excess of α,ω -dibromoalkanes was carried out in the present of K 2CO 3. The target compounds were synthesized by linking the partial alkylation product to monohydroxylporphyrins via an ether chain in 16.4% yield. 3. 5-(4-aminophenyl)-10,15,20-triphenylporphyrin was prepared by reducing the nitro group of the 5-(4-nitrophenyl)-10,15,20- triphenylporphyrin in the present of SnCl 2. Its diazonium salt was obtained by reacting with NaNO 2 in acid. Then a kind of covalently-connected azocalix[4]arene porphyr...