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Oxidation of Porphyrinogen with Traditional Chinese Medicines and New Methods for Synthesis of Porphyrin Derivatives

Author: HeBaiYin
Tutor: ChenJianNan
School: Guangzhou University of Traditional Chinese Medicine
Course: Of Pharmacy
Keywords: porphyrin oxidize herbal medicine synthesize protonated
CLC: R284
Type: Master's thesis
Year: 2011
Downloads: 32
Quote: 0
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Abstract


Porphyrins are macrocyclic aromatic compounds which have 18 atoms and 18πelectrons. They have many unique optical and biological activities. Porphyrins like chlorophyll and hemocrystallin are widely distributed in living organism. Porphyrins are currently used in catalysis, analysis, solar power, diagnosis and photodynamic therapy(PDT) of some diseases such as cancers. Although porphyrins are widely used in modern science, their synthesis is diffcult and costly. To find a easyer and cheaper way to snythesize porphyrins has great importance.There were many researchers have reported that the oxidizating capability of some herbal medicines especially those contain quinone like compounds, are related with their pharmacology and toxicology activities such as anti-cancer activity and hepatotoxicity. Those herbal mecidines can serve as oxidizers to oxidize porphyrinogen to produce porphyrin. This reaction can provide a chemical parameter to compare the oxidization capability of those herbal medicines under the same chemical condition.Modern pharmacology experiments prove that porphyrins can be enriched in cancer tissue. If connecting some anti-cancer drug with porphyrin properly, porphyrin might become a carrier to deliver the drugs directly to the tumor.Base on above result, this reseach focus on following aspects:i. Porphyrinogen oxidized by herbal medicineAccording to Lindsey porphyrin synthesis method, porphyrinogen synthesize was using Redroot Gromwell, Indian Madder Root, Rhubarb, Tuber Fleece flower Root, Giant Knotweed Rhizome and Rhein (90%) as oxidants to oxidize porphyrinogen in anisole-pyridine environment, In order to investigate the oxidization capability of those herbal medicines, the TPP yield and percentage of TPC in products were determined by using HPLC. Higher TPP yield and lower percentage of TPC in products means greater oxidization capability.Our experimental results showed that those herbal medicines could oxidize porphyrinogen into TPC and TPP. Their oxidization intensity is as follow:Tuber Fleece flower Root>Giant Knotweed Rhizome>Rhubarb>Indian Madder Root>Redroot Gromwell.Artemisinin could also oxidize porphyrinogen under different chemical conditionsLindsey porphyrin synthesis method was employed to snythsize porphyrinogen, with Artemisinin as oxidant to react in anisole-pyridine, anisole-propionic acid and anisole environment to study the oxidation property of Artemisinin under different conditions.Our experimental data proved that Artemisinin could oxidize porphyrinogen into TPC and TPP. It’s oxidation capability was stronger under basic condition than acidic condition.ii. Study on the raction mechanism of porphyrinogen oxidized by nitrobenzeneNitrobenzene was used as oxidant to produce TPP, and the TPC content was tracked during reaction by using HPLC during the reaction.The aniline formed in this reaction was examed.Our experimental data showed that nitrobenzene can produce TPP without any TPC inside. HPLC data proved that nitrobenzene oxidizes porphyrinogen into porphyrin, and nitrobenzene was reduced into aniline.iii. Research of new methods for porphyrin synthesisThis research studied porphyrin synthesis in substituted benzoic acids and some low temperature melting salts such as:pyridine-trifluoroacetic acid salt, pyridine-propionic acid salt and aluminium trichloride-sodium chloride mixture.Using substituted benzoic acid as solvent and catalyst could synthesize 5,10,15, 20-tetraphenyl-21H,23H-porphyrin,5,10,15,20-tetrakis (4-methoxyphenyl)-21H, 23H-porphyrin & 5,10,15,20-tetrakis (4-Chlorophenyl)-21H,23H-porphyrin effciently. When the relation between solvent’s melting point (Y)and pKa (X) could satisfact the equation:D=Y-36.25X<0, the porphyrin’s yield could up to 35%-47%; If D>0, the yield was very low.The acid was melted under 130℃, the reactants was added with electromagnetic stirring, and the reaction was last for about 50min. After the reaction, the system was cooled down, and ethanol was added, and porphyrin was separated from solvent. The porphyrin yield was about 35%-47%. If was the solvent processed by boiling water properly after the reaction, more than 70% could be recycled.Using pyridine-trifluoroacetic acid salt, pyridine-propionic acid salt could produce about 20% porphyrin, and more than half of the product was protonated.But if use aluminum chloride-sodium chloride as solvent, the yield was very low.iv. porphyrin’s protonation phenomenonPorphyrin was dissoved in 0.2% Trifluoroacetic acid-chloroform and 0.2% Trifluoroacetic acid-ethanol to study its UV-Vis spectrurm and dissoving property in ethanol.When porphyrin interacted with acid, pyrrole’s N inside the porphyrin would reacted with H+ to form protonated porphyrin. When it was protonated, porphyrin would have many new distinctive properties. Most important two were the red shift of its UV-Vis spectrum and the dissolving capability in ethanol.The UV-Vis spectrum of protonated porphyrin had its distinctive red shift phenomenon, especially the absorption peak at 640nm-650nm, it was not only red shifted but also intensified. The spectrum was similar to that of Chlorin’s. The red shift was related to the substituents on benzene in porphyrin’s molecule. There was an exponential relationship between theΔλand substituents’Hammettσvalue.This research using porphyrinogen oxidition reaction as an indicator to investigate some herbal mecidines’oxidization capability, Our experimental data provided a chemical parameter for their pharmacology and toxicology activity study.In summary, porphyrin can be synthesize efficiently in some substituted benzoic acid, and after proper processe, more than 70% solvent could be recycled. Snythesizing porphyrin in salt could provide a new way to produce some special porphyrins, which can not be dissolved in dichloromethane or sensitive to acid.Porphyrin using as PDT photosensitizer has two major weakness:Poor dissolving capability in water or ethanol, and weak absorption in 650nm or beyond. These drawbacks limited the clinical use of porphyrin.The protonated porphyrin could be dissolved in ethanol, and inhance the absorption at 650nm or beyond was enhanced. These properties could provide some new idea to improve the clinical use of porphyrin in PDT.

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