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1.Study Of New Porphyrin Photosensitizes 2.Chemical Constituents Of Clerodendrum Serratum

Posted on:2007-02-20Degree:DoctorType:Dissertation
Country:ChinaCandidate:J G YinFull Text:PDF
GTID:1101360182994183Subject:Organic Chemistry
Abstract/Summary:PDF Full Text Request
Ⅰ. Study of new porphyrin photosensitizesChlorophyll-α was extracted from silkworm excrement by refluxing with acetone, then the central magnesium ion was removed by 5% H2SO4-MeOH, in the same time, the methyl pheophorbide-α (MPa) was obtained by transesterification. Mpa can be converted into methyl pyropheophorbide-a (MPPa) via demethoxyl-formyl groups at 132-position by stirring at high temperature under basic collidine (2, 4, 6-trimethyl pyridine) or acetic acid. Mppa was used as starting material for the synthesis of a series of new 131-deoxypyrophoribide derivatives by reaction of Grignard reaction to modify E ring and was carried out to complete the synthesis of derivatives of MPPa substituted with benzo-heterocycle with nitrogen atom at 3-position by modification of the vinyl group. Mppa was used as starting material for the synthesis of new bromine substituted porphin compounds, the bromines were introduced into different position of the porphin chromophore by addition reaction and substitution reaction with the bromide reagents to give different structure of porphins. MPa was used as staring material for the synthesis of new MPa compounds, the modification of function groups of MPa along N21-N23 axis, a series of new pheophorbide derivatives were synthesized and effect on their visible spectra was discussed. Methyl pyropheophorbide (Mppa) was used as starting material for the synthesis of new porphin compounds. The Z/E ketoxine isomers of methyl pyropheophorbide were obtained by reaction of carbonyl group at 131-position with hydroxylamine, the alkylation and acetyclation of E/Z ketoxines were carried out by reaction with alkyl halide and acylhalide to give Z or E O-alkyl ketoxine and O-aroyl (acetyl) ketoxine, respectively, the structures of all these compounds were characterized by HMQC and HMBC experiments. Mppa which Qy at 668 nm was used as staring material for the synthesis of a series of new Mppa derivations, the modification of function groups of MPPa along N21-N23 axis and effect on their NMR and visible spectra were discussed. Totally 52 compounds were synthesized, among them 30 are new compounds. Some new porphin derivations were evaluated for their photodynamic anti-tumor activity and all the compounds at higher concentration have stronger positive effect than clinical photodynamic anti-tumor medicine-photofrin, while compound 28 at lower concentration showed stronger positive effect than that of foscan which has been used at clinic to cure tumor.Ⅱ. Chemical constituents of medical plant Clerodendrum serratumThe genus Clerodendrum belonging to the Verbenaceae family, are widely distributed in Guangxi, Guizhou, Yunnan and Xizang province. The whole plants contain triterpenoid glycoside, and used for the treatment of ague, diarrhea, bone broken, rheumatism. We investigate the chemical constituents of Clerodendrum serratum collected from Yunnan province. From ethanol extracts, 12 compounds includingiridoid glycoside, organic acid and phenyl proponoid glycoside were isolated through CC and PTLC, and their structures were elucidated by means of MS, *H NMR, I3C NMR and DEPT spectroscopic techniques.Ill. Review of photodynamic therapy...
Keywords/Search Tags:Photosensitizes
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