CN100420689C - Porphyrin derivate with macrosubstituent, preparation process thereof and use as small molecule antioxidant - Google Patents

Porphyrin derivate with macrosubstituent, preparation process thereof and use as small molecule antioxidant Download PDF

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CN100420689C
CN100420689C CNB021165564A CN02116556A CN100420689C CN 100420689 C CN100420689 C CN 100420689C CN B021165564 A CNB021165564 A CN B021165564A CN 02116556 A CN02116556 A CN 02116556A CN 100420689 C CN100420689 C CN 100420689C
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porphyrin
pyridyl
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巩宪昌
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Sinopharm Yixin Pharmaceutical Co Ltd
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Abstract

The present invention discloses a porphyrin derivative with large substituent groups, pharmaceutical acceptable salts thereof and a preparation method thereof. The porphyrin derivative is M-5, 10, 15, 20-tetra [(N)-substituted-n-phenyl or heterocyclic radical] porphyrin, wherein n represents 2, 3 and 4 site substitution, and M is one of Fe, Mn, Co, Ni, Cu, Zn, Sn, Cr and V metal ions. The porphyrin derivative has larger steric hindrance, and can effectively avoid the combination of porphyrin and DNA, reduce interconversion of different isomers, reduce the toxicity of porphyrin and increase medicinal practicability. The porphyrin derivative can be used as a small-molecular antioxidant for regulating the intercellular or intracellular concentration of peroxides in human bodies, preventing human bodies from being damaged by peroxy radicals or other peroxides derived by the peroxy radicals, and preventing and treating diseases caused by harmful peroxides.

Description

Have the derivatives of porphyrin, its preparation method of large-substituent and as the application of small molecule antioxidant
Technical field
The present invention relates to a kind ofly replace derivatives of porphyrin, its preparation method and as the application of small molecule antioxidant, particularly have the derivatives of porphyrin, its preparation method of large-substituent and as small molecule antioxidant between mediator's somatocyte or the application aspect the cell endoperoxides substrate concentration.
Background technology
Superoxide is a kind of product in the human body normal physiological metabolism process.Be present in the human body cell and comprise O with intercellular superoxide 2 -, OH -, ONOO -And H 2O 2Because superoxide has the height chemical activity, can react with the material of forming human body cell such as cytolemma and karyomit(e), thereby cause the generation of disease.
Oxygen has activity, can participate in important metabolic processes, plays an important role to earning a bare living.But oxygen also can cause the infringement to organism.In vivo, oxygen is converted into the multiple superoxide that can damage deoxynucleotide, protein and phospholipid.The result that these reactions are accumulated can weaken the function of cell, even causes disease.Research thinks, superoxide is in chronic bronchitis, cerebral thrombosis, and asthma, the infringement that the oxygen supply again that is caused by heart failure causes, rheumatic arthritis, senile dementia, Parkinson's formula disease, even in the multiple disease such as aging, play a role.
Free radical is the high-energy unstable compound that a class contains unpaired electron.The intravital harmful superoxide of people comprises O 2 -, OH , ONOO -And H 2O 2This class superoxide results from the intravital physiological response of body, for example the process of oxygen supply and radiation treatment again.ONOO -Be O 2 -And NO -The effect product.OH -It is a kind of free radical that often produces in the process of radiation treatment.This free radical is the most active free radical in the chemistry.It can react with the intravital chemical substance of body and cause chain reaction.Thereby it in addition can react with the group on the deoxynucleotide and destroy the heredity of cell and duplicate.Radiation treatment might originate in the generation of free radical to the toxic action of human body.Again oxygen supply can produce a large amount of peroxy radicals for the tissue that is damaged.
There are three kinds can decompose the natural Green Tea Extract enzyme of free radical in the human body.A kind of being present in the tenuigenin, a kind of being present in the plastosome, a kind of being present in the cell matrix.Above-mentioned three kinds of Green Tea Extract enzymes all be molecular weight at the polymer substance more than 10000, be present in the human body cell or human body cell between, but can not pass cytolemma.When the content of free radical in the human body hanged down, these naturally occurring endonuclease capables effectively decomposed these free radicals, thereby played the effect of protection human body.But when the content of free radical in the human body was higher, these naturally occurring enzymes were merely able to effectively decompose the part free radical.The remaining free radical that can not be decomposed will cause bigger injury to human body.
The following reaction of endonuclease capable catalysis of naturally occurring Green Tea Extract in the human body:
2O 2 -+2H +→O 2+H 2O 2
This reaction can be removed oxyradical and be generated hydrogen peroxide.Though hydrogen peroxide is not a kind of free radical, the toxic effect of pair cell.Hydrogen peroxide can further be removed by intravital other enzyme of body.
Antioxidase plays an important role in the process that protection body resistance free radical is invaded.But this enzyme itself is a kind of polymer, in blood circulation the transformation period very short, can not enter cell, cost is high again, these have limited its feasibility as medicine.
Effectively remove in the human body and can not in time be had two kinds by the method for zymolytic superoxide of natural Green Tea Extract.A kind of is to add a kind of pouncing on to obtain agent.When superoxide forms in a flash, both pounced on and obtained the agent molecule elimination.Pounce on the quantity that obtains agent molecule with the quantity of free radical 1: 1 relation normally.A kind of method in addition is to add a kind of small molecule antioxidant (catalyzer), when superoxide form in a flash both by catalytic decomposition.Adopting the advantage of micromolecule catalyst is just can reach the purpose of removing a large amount of superoxide with a spot of medicine.
The porphyrin compound of manganese and iron has been used to study the feasibility as small molecule antioxidant.Duke University and Princeton University are the pioneer Kachadourian of this respect research, R. wait the people at InorganicChemistry, 1999,38, " Syntheses and Superoxide DismutingActivities of Partially (1-4)-Chlorinated Derivatives of Manganese (III) meso-Tetrakis (N-ethylpyridinium-2-yl) porphyrin " disclosed among the 391-396; Ferrer-Sueta, Deng the people at Chemical Research in Toxicology, 1999,12, " CatalyticScavenging of Peroxynitrite by Isomeric Mn (III) N-Methylpyridylporphyrinsin the Presence of Reductants " disclosed among the 442-449; Lee, people such as J are at Journal of the American ChemicalSociety, 1998,120, " Mechanisms of Iron PorphyrinReactions with Peroxynitrite " disclosed among the 7493-7501, in addition Lee, J. wait the people also at Journal of the AmericanChemical Society, 1998,120, " Manganese Porphyrins asRedox-Coupled Peroxynitrite Reductases " disclosed among the 6053-6061..Above-mentioned result of study shows that the porphyrin compound of manganese and iron has the performance of good antiperoxide, better biocompatibility and very little toxicity.
In sum, if can develop a kind of steady quality, have good medicine kinetic property and effectively the antioxidant of decompose hydroperoxide will keep healthy to human beings'health and make major contribution.
Summary of the invention
The object of the present invention is to provide a kind of derivatives of porphyrin that has large-substituent, described derivatives of porphyrin has bigger steric hindrance, can stop combining of porphyrin and DNA effectively, reduced the mutual conversion between the different isomerization body simultaneously, thereby reduced the toxicity of porphyrin, and increased with the practicality of porphyrin mixture of isomers as medicine.
Another object of the present invention is to provide a kind of preparation method who has the derivatives of porphyrin of large-substituent, this method is simple, yield is high, be fit to scale operation.
A further object of the present invention be to provide a kind of derivatives of porphyrin that has a large-substituent as small molecule antioxidant between mediator's somatocyte or the application aspect the cell endoperoxides substrate concentration.The derivatives of porphyrin of described large-substituent can protect human body to avoid peroxy radical and by the injury of other superoxide of peroxy radical deutero-, and is used for preventing and treats the disease that the existence owing to harmful superoxide causes.
To achieve these goals, the skill flitch case of the present invention's employing is: a kind of Supreme Being has the derivatives of porphyrin of large-substituent, and described derivatives of porphyrin has following structure:
Figure C0211655600071
Wherein A, B, C, D are
In at least a.
In the compound in structural formula I, at least one is the phenyl of phenyl or replacement.
Wherein in the compound in structural formula I, R is-(CH 2) n-X, n=0-10, radicals X comprises OH, and one or more the combination in the following groups:
Figure C0211655600082
-(C mH 2m) j(OC mH 2m) pOZ ' (work as m=2 in this structural formula, j=1, during p=2, Z ' can not be methyl) ,-(C mH 2m) j(OC mH 2m) pOH (m is not equal to 2 in this structural formula) ,-(C mH 2m) j(NH-C mH 2m) pNH 2,-(C mH 2m) j(NH-C mH 2m) pNH-Z ' ,-(C mH 2m) j(NH-C mH 2m) pN-Z 2' or-(C mH 2m) j(NH-C mH 2m) pN-Z 3' +
Wherein, when radicals X is 0 ,-(CH 2) n-X is a cycloalkyl.
Wherein radicals X also comprises one or more the combination in the following groups:
-(CH 2) jCH 3
Figure C0211655600083
-COOH ,-CONH 2,-PO 3H 2, ,-SO 3H ,-NH 2,-OH ,-SH ,-(C mH 2m) j(OC mH 2m) pOZ ' ,-(C mH 2m) j(OC mH 2m) pOH ,-CH=CH 2,-CONH 2,-CO 2CH 2CH 3,-(C mH 2m) j(NH-C mH 2m) pNH 2,-(C mH 2m) j(NH-C mH 2m) pNH-Z ' ,-(C mH 2m) j(NH-C mH 2m) pN-Z 2' or-(C mH 2m) j(NH-C mH 2m) pN-Z 3' +
Wherein R is-C qH 2q+1Perhaps-(C qH 2q) CH=CH 2
-C mH 2mBe meant that the total number of carbon atoms is m, hydrogen atom adds up to straight chain, branched-chain alkyl and the cycloalkyl of 2m;-C qH 2q+1Be meant that the total number of carbon atoms is q, hydrogen atom adds up to straight chain and the branched-chain alkyl of 2q+1, j, p, q, m=0-10.
Group Y and Y ' are CH 2, O, NH, among the S one, group Z is selected from-C ,-O ,-N, among-the S one, group Z ', Z 2', Z 3' be-C qH 2q+1Perhaps-(C qH 2q) CH=CH 2, j wherein, p, q, m=0-10.
M is a kind of in the metal ion of following metal: Fe, Mn, Co, Ni, Cu, Zn, Sn, Cr, or V.
Among the present invention, have compound in structural formula I, preferred R is cycloalkyl-(CH 2) n, alkyl-(CH 2) nH, the how pure monomethyl ether base of second-(C mH 2m) j(OC mH 2m) pOCH 3Or a kind of in the hydroxyl, m, j, p, n=1-8.
Preferably, the metal porphyrin derivative that has large-substituent of the present invention has following structure:
Figure C0211655600091
Figure C0211655600111
Have a structural formula 1-3 among the present invention shown in the structural formula I, in the compound shown in the 5-19, R1-R4 is a kind of in cyclohexyl, pentamethylene base, tetramethylene base, diethylene glycol monomethyl ether base, methyl or the hydroxyl.
The present invention comprises that also the hydrochloride, vitriol, acetate, phosphoric acid salt of the metal porphyrin derivative that has large-substituent shown in structural formula I and the structural formula 1-19 and other can be at the salt of medically using.
Described hydrochloride is preferably two---nine villaumites.
Small molecule antioxidant of the present invention can have four kinds of different isomer.Under different temperature, the ratio difference of these four kinds of isomer.These four kinds of isomer can transform mutually.Under suitable condition, utilize HPLC can separate these isomer.Small molecule antioxidant of the present invention can be any isomer, also can be several mixture of isomers.
The different metal that has the metal porphyrin derivative of large-substituent of the present invention has different character, can with different harmful peroxide reactions.The complex compound that preferably has large-substituent porphyrin and iron among the present invention.
Among the present invention, the metal porphyrin derivative that has different large-substituents has different functions.Different substituting groups can change the distribution coefficient of porphyrins in water and oil phase, thereby changes its curative effect in the disease treatment process.
The metal porphyrin derivative that has different large-substituents of the present invention has less toxicity.The substituting group that these texture ratios are bigger, particularly cycloalkyl pyridine have bigger steric hindrance, can stop combining of porphyrin and DNA effectively, thereby have reduced the toxicity of porphyrin.Adopting the bigger substituent additional advantage of texture ratio is the mutual conversion that has reduced between the different isomerization body, thereby has increased with the practicality of porphyrin mixture of isomers as medicine.With respect to the chain substituting group, the advantage of cyclic substituents is the better principle of work of the enzyme of the Green Tea Extract that exists of simulating nature.
The Base Metal derivatives of porphyrin that has big replacement of the present invention can be used as small molecule antioxidant, by reducing O 2 -Free radical, OH -Free radical, ONOO -And H 2O 2Content in human body cell or tissue reaches the purpose of treatment disease.The metal porphyrin derivative that has large-substituent of the present invention, can be used for reducing or prevent since the formation of cerebral thrombosis to the damage of human brain, thereby reach the purpose of treatment cerebral thrombosis.The present invention is equally applicable to treat chronic bronchitis, asthma, the infringement that the oxygen supply again that is caused by heart failure causes, rheumatic arthritis, senile dementia, Parkinson's formula disease, AIDS even aging.The metal porphyrin derivative that has a large-substituent of the present invention can the intravital harmful superoxide of catalytic decomposition people and can be passed through cytolemma and enter human body cell.
The synthetic method that has the derivatives of porphyrin of large-substituent of the present invention, wherein:
When 1) A-D was for replacement 2,3 or 4 pyridines, the preparation method was:
1. 10.7 gram n-pyridyl formaldehyde are dissolved in 1 liter of propionic acid, add 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (n '-pyridyl) porphyrin;
2. 2-4 gram 5,10,15, in 20-four (n '-pyridyl) the porphyrin 10-30 milliliter alkyl chloride, reflux 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excessive alkyl chloride and promptly get 5,10,15,20-four [(N-alkyl)-n-pyridyl] porphyrin tetrachloro salt;
3. the 1.8-6 gram 5,10,15, and 20-four [(N-alkyl)-n-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds the chloro metallic compound then.Gained mixture under protection of nitrogen gas backflow 2-5 hour.Add ammoniacal liquor and remove excessive chloro metallic compound, under vacuum, steam water and promptly get M-5,10,15,20-four [(N-alkyl)-n-pyridyl] porphyrin four or pentachloro-salt; Wherein n represents 2,3,4 replacements;
2) E-H is 4 '-C or N or O)-during glucosyl group, the preparation method is:
28 gram (4 '-C or N or O)-glucosyl groups)-and phenyl aldehyde and 6.7 restrains and to be dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Under vacuum, steam propionic acid, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10,15,20-four [(4 '-C or N or O)-glucosyl group]-phenyl] porphyrin.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram chloro metallic compounds.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive chloro metallic compound, under vacuum, steam methyl alcohol and promptly get iron-5,10,15,20-four [(4 '-C or N or O)-glucosyl group]-phenyl] porphyrin;
When 3) A-D was for replacement 2,3 or 4 pyridines and substituted-phenyl, the preparation method was:
5.4 gram n-pyridyl formaldehyde and 5.4 gram substituted benzaldehydes are dissolved in 1 liter of propionic acid, add 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure porphyrin.The gained porphyrin is dissolved in the 10-30 milliliter haloalkane, when 60 spend, refluxed 4 hours.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excessive haloalkane.Products therefrom is dissolved in 100 ml waters, adds the chloro metallic compound then.Gained mixture under protection of nitrogen gas backflow 2-5 hour.Add ammoniacal liquor and remove excessive chloro metallic compound, under vacuum, steam water and promptly get the purpose product.
4) A-D is for replacing 4 pyridines, and substituting group is 2, and during the 4-pyridinium salt, the preparation method is
1 gram 5,10,15,20-four (4 '-pyridyl) porphyrin is dissolved in 50 ml methanol, adds 10 gram 2 or 4-iodo-N-methyl-pyridine hydrochlorides then.At room temperature stirred 24 hours, and filtered out throw out.Throw out is water-soluble, add 0.5 gram chloro metallic compound then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive chloro metallic compound, under vacuum, steam water and promptly get the purpose product.
The present invention has the synthetic of metal porphyrin derivative of large-substituent can be with reference to Drain, C.M. wait the people at J.Chem.Soc., Chem.Commun.1997 is among the 2117-2118 " Synthesis of meso substitutedporphyrins in air without solvents or catalysts "; And Adler, A.D. wait the people at J.Am.Chem.Soc.1964,86, open " Mechanistic investigationof porphyrin synthesis.I.Preliminary studies on ms-Tetraphenylporphyrin " disclosed method among the 3145-3149.
The preparation method of structural formula 1-3 compound of the present invention is:
1. 10.7 gram n-pyridyl formaldehyde are dissolved in 1 liter of propionic acid, add 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (n '-pyridyl) porphyrin;
2. 2-4 gram 5,10,15, in 20-four (n '-pyridyl) the porphyrin 10-30 milliliter alkyl chloride, reflux 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excessive chlorocyclohexane and promptly get 5,10,15,20-four [(N-alkyl)-n-pyridyl] porphyrin four-villaumite;
3. the 1.8-6 gram 5,10,15, and 20-four [(N-alkyl)-n-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds the chloro metallic compound then.Gained mixture under protection of nitrogen gas backflow 2-5 hour.Add ammoniacal liquor and remove excessive chloro metallic compound, under vacuum, steam water and promptly get M-5,10,15,20-four [(N-alkyl)-n-pyridyl] porphyrin four or pentachloro-salt; Wherein n represents 2,3,4 replacements.
The synthetic method of other compounds is seen embodiment, and wherein the synthetic method of the compound of structural formula 6-17 is similar.The synthetic method of structural formula 18-19 compound is similar.
The following way of synthetic general employing of the metal complex of porphyrin: porphyrin is dissolved in the chloroform, adds the vitriol of excessive respective metal then, under protection of nitrogen gas, refluxed 2 hours then.Under vacuum, steam the metal complex that chloroform promptly gets porphyrin.
In actual applications, the small molecule antioxidant that has the metal porphyrin derivative of large-substituent of the present invention can be divided into two kinds of oral and injections.As oral, can be made into sheet or capsule, the ratio of active ingredient can be between 0.1-80%.As injection, water is as solvent usually.The usage quantity of medicine is between 0.01-100mg/Kg/ days.Be used for treating diseases such as cerebral thrombosis, heart failure as small molecule antioxidant.
Describe the present invention in detail below in conjunction with the drawings and specific embodiments, described embodiment is used to describe the present invention, rather than restriction the present invention.
Description of drawings
Fig. 1 is with CT-DNA titration 5,10-two [(N-methyl)-4 '-pyridyl]-15, the ultra-violet absorption spectrum of 20-two (4 '-tolyl) porphyrin two villaumites in water.
Embodiment
Embodiment 1: iron-5,10,15, synthetic (structural formula 1) of 20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (2 '-pyridyl) porphyrin 1.74 grams.Productive rate 10%.
1 gram 5,10,15,20-four (2 '-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclohexanes, refluxes 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excessive chlorocyclohexane and promptly get 5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt 1.8 grams, productive rate 99%.
1.8 restrain 5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds 0.33 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt 1.79 grams, productive rate 95%.UV spectrum (aqueous solution, nanometer): 410,585.Mass spectrum: 201[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 65.01; H, 5.80; Cl, 14.99; Fe, 4.72; N, 9.48.Measured value: C, 64.7; H, 5.70; Cl, 15.5; Fe, 4.75; N, 9.35.
Embodiment 2: copper-5,10,15, synthetic (structural formula 2) of 20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt
10.7 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (3 '-pyridyl) porphyrin 2.6 grams.Productive rate 15%.
2 grams 5,10,15,20-four (3 '-pyridyl) porphyrin is dissolved in 30 milliliters of chloro tetramethylene, refluxes 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excess chlorine and promptly get 5,10,15,20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt 3.1 grams, productive rate 99% for tetramethylene.
3 grams 5,10,15,20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds 0.33 gram dichloride copper then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive dichloride copper, under vacuum, steam water and promptly get copper-5,10,15,20-four [(N-tetramethylene base)-3 '-pyridyl] porphyrin tetrachloro salt 3.03 grams, productive rate 95%.UV spectrum (aqueous solution, nanometer): 420,565.Mass spectrum: 214.5[(M-4Cl -) 4+/4]。Ultimate analysis: theoretical value: C, 64.52; H, 5.03; Cl, 13.60; Cu, 6.10; N, 10.75.Measured value: C, 64.7; H, 5.13; Cl, 13.32, Cu, 6.05; N, 10.80
Embodiment 3: cobalt-5,10,15, synthetic (structural formula 3) of 20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin pentachloro-salt
10.7 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, pure 5,10,15,20-four (4 '-pyridyl) porphyrin 4.3 grams, productive rate 25%.
4 grams 5,10,15,20-four (4 '-arsenic pyridine base) porphyrin is dissolved in 30 milliliters of chloro tetramethylene, refluxes 4 hours when 60 spend.After reaction is finished, the solution cool to room temperature.Under vacuum, steam excess chlorine and promptly get 5,10,15,20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin tetrachloro salt 6.1 grams, productive rate 99% for tetramethylene.
6 grams 5,10,15,20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin tetrachloro salt is dissolved in 100 ml waters, adds 1.2 gram cobalt dichlorides then.The gained mixture refluxed in air 12 hours.Add ammoniacal liquor and remove excessive cobalt dichloride, under vacuum, steam water and promptly get cobalt-5,10,15,20-four [(N-tetramethylene base)-4 '-pyridyl] porphyrin pentachloro-salt 6.05 grams, productive rate 92%.UV spectrum (aqueous solution, nanometer): 417,551.Mass spectrum: 179[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 62.67; H, 4.88; Cl, 16.52; Co, 5.49; N, 10.44.Measured value: C, 62.70; H, 4.85; Cl, 16.6; Co, 5.35; N, 10.50.
Embodiment 4: iron-5,10,15, synthetic (structural formula 4) of 20-four [(4 '-C-glucosyl group)-phenyl] porphyrin
28 gram (4 '-C-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Steam propionic acid under vacuum, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10,15,20-four [(4 '-C-glucosyl group)-phenyl] porphyrin 2.6 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10,15,20-four [(4 '-C-glucosyl group)-phenyl] porphyrin 2.4 grams.Mass spectrum: 1319[(M-Fe+3H) +/ 1].Ultimate analysis: theoretical value: C, 63.35; H, 5.02; Fe, 4.09; N, 4.10; 0,23.44; Measured value: C, 62.73; H, 5.12; Fe, 4.1; N, 3.95; 0,24.1.
The synthetic of (4 '-C-glucosyl group)-phenyl aldehyde can be with reference to Pasetto, P. wait the people at J.Chem.Soc., Chem.Commun.2001, disclosed synthetic method in " Synthesis of hydrolytically stable porphyrinC-and S-glycoconjugates in high yields " among the 81-82.
Embodiment 5: manganese-5,10-two [(N-methyl)-4 '-pyridyl]-15, synthetic (structural formula 6) of 20-two (4 '-tolyl) porphyrin acetate
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin 0.54 gram.Productive rate 20%.
0.5 restrain 5,10-two [4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.66 gram, productive rate 92%.
0.6 restrain 5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.4 gram manganese acetate then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive manganese acetate, under vacuum, steam water and promptly get manganese-5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin acetate 0.52 gram, productive rate 95%.UV spectrum (aqueous solution, nanometer): 435,605.Mass spectrum: 364[(M-2CH 3COO -) 2+/ 2].Ultimate analysis: theoretical value: C, 71.00; H, 5.00; Mn, 6.50; N, 9.94; 0,7.57 measured value: C, 70.5; H, 4.95; Mn, 6.45; N, 9.84; 0,8.26.
Embodiment 6: iron-5,15-two [(N-methyl)-4 '-pyridyl]-10, synthetic (structural formula 7) of 20-two (4 '-tolyl) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin 0.1 gram.Productive rate 3.5%.
0.1 restrain 5,15-two [4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.13 gram, productive rate 90%.
0.1 restrain 5,15-two [(N-methyl)-4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-4 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin three villaumites 0.08 gram, productive rate 90%.UV spectrum (aqueous solution, nanometer): 411,580.Mass spectrum: 364[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.2; H, 4.10; Cl, 13.5; Fe, 7.7; N, 9.5.
Embodiment 7 :-4 '-pyridyl iron-5-[(N-methyl)]-10,15, synthetic (structural formula 8) of 20-three (4 '-tolyl) porphyrin two villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with chloroform and separate, isolate pure 5-(4 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin 0.82 gram.Productive rate 30%.
0.8 gram 5-(4 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get the 5-[(N-methyl)-4 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine 0.92 gram, productive rate 95%.
0.9-4 '-pyridyl gram 5-[(N-methyl)]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine is dissolved in 50 ml waters, adds 2 then.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin two villaumites 0.72 gram, productive rate 80%.UV spectrum (methyl alcohol, nanometer): 431,595.Mass spectrum 356[(M-2Cl -) 2+/ 2].Ultimate analysis: theoretical value: C, 70.78; H, 4.55; Cl, 8.89; Fe, 7.00; N, 8.78 measured values: C, 69.8; H, 4.40; Cl, 9.35; Fe, 7.50; N, 8.95.
Embodiment 8: iron-5,10, synthetic (structural formula 9) of 15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 5.3 gram phenyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with the mixed solution of 90% chloroform and 10% methyl alcohol and separate, isolate pure 5,10,15-three (4 '-pyridyl)-20-(4 '-tolyl) porphyrin 0.52 gram.Productive rate 20%.
0.5 restrain 5,10,15-three (4 '-pyridyl)-20-(4 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine 0.71 gram, productive rate 85%.
0.7 restrain 5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine are dissolved in 50 ml waters, add 2.5 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt 0.47 gram, productive rate 85%.UV spectrum (aqueous solution, nanometer): 415,590.Mass spectrum: 182[(M-4Cl -) 4+/ 4].Ultimate analysis: theoretical value: C, 61.95; H, 4.16; Cl, 16.25; Fe, 6.40; N, 11.24; Measured value: C, 62.2; H, 4.26; Cl, 16.39; Fe, 6.30; N, 10.85.
Embodiment 9: manganese-5,10-two [(N-methyl)-2 '-pyridyl]-15, synthetic (structural formula 10) of 20-two (2 '-tolyl) porphyrin acetate
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin 0.5 gram.Productive rate 18%.
0.5 restrain 5,10-two [2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin two salt compounded of iodine 0.64 gram, productive rate 90%.
0.6 restrain 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.4 gram manganese acetate then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive manganese acetate, under vacuum, steam water and promptly get manganese-5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin acetate 0.52 gram, productive rate 95%.UV spectrum (aqueous solution, nanometer): 437,610.Mass spectrum: 364[(M-2CH 3COO -) 2+/ 2].Ultimate analysis: theoretical value: C, 71.00; H, 5.00; Mn, 6.50; N, 9.94; 0,7.57 measured value: C, 70.3; H, 4.95; Mn, 6.65; N, 9.9; 0,8.2.
Embodiment 10: iron-5,15-two [(N-methyl)-2 '-pyridyl]-10, synthetic (structural formula 11) of 20-two (2 '-tolyl) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin 0.2 gram.Productive rate 7%.
0.2 restrain 5,15-two [2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (2 '-tolyl) porphyrin two salt compounded of iodine 0.26 gram, productive rate 90%.
0.2 restrain 5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin three villaumites 0.08 gram, productive rate 90%.UV spectrum (aqueous solution, nanometer): 411,580.Mass spectrum: 243[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.2; H, 4.10; Cl, 13.5; Fe, 7.7; N, 9.5.
Embodiment 11 :-2 '-pyridyl iron-5-[(N-methyl)]-10,15, synthetic (structural formula 12) of 20-three (2 '-tolyl) porphyrin two villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with chloroform and separate, isolate pure 5-(2 '-pyridyl)-10,15,20-three (2 '-tolyl) porphyrin 0.8 gram.Productive rate 29%.
0.8 gram 5-(2 '-pyridyl)-10,15,20-three (2 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get the 5-[(N-methyl)-2 '-pyridyl]-10,15,20-three (2 '-tolyl) porphyrin one salt compounded of iodine 0.9 gram, productive rate 93%.
0.9-2 '-pyridyl gram 5-[(N-methyl)]-10,15,20-three (2 '-tolyl) porphyrin one salt compounded of iodine is dissolved in 50 ml waters, adds 2 then.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-2 '-pyridyl]-10,15,20-three (2 '-tolyl) porphyrin two villaumites 0.7 gram, productive rate 77%.UV spectrum (methyl alcohol, nanometer): 430,596.Mass spectrum 356[(M-2Cl -) 2+/ 2].Ultimate analysis: theoretical value: C, 70.78; H, 4.55; Cl, 8.89; Fe, 7.00; N, 8.78 measured values: C, 69.6; H, 4.60; Cl, 9.32; Fe, 7.53; N.8.95.
Embodiment 12: iron-5,10, synthetic (structural formula 13) of 15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin tetrachloro salt
8.1 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 then.0 gram o-methyl-benzene formaldehyde and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin 2.5 grams.With gained 2.5 grams 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin three salt compounded of iodine 3.0 gram.3。0 gram 5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin three salt compounded of iodine are dissolved in 100 ml waters, add 4 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(2 '-tolyl) porphyrin tetrachloro salt 2.1 gram, overall yield 9.6％。UV spectrum (aqueous solution, nanometer): 410,582.Mass spectrum: 182.5[(M-4Cl -) 3+/4]。Ultimate analysis: theoretical value: C, 61.95; H, 4.16; Cl, 16.25; Fe, 6.40; N, 11.24 measured values: C, 62.5; H, 4.17; Cl, 16.03; Fe, 7.5; N, 9.8.
Embodiment 13: iron-5,10-two [(N-methyl)-3 '-pyridyl]-15, synthetic (structural formula 14) of 20-two (4 '-tolyl) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin 0.4 gram.Productive rate 14%.
0.4 restrain 5,10-two [3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.52 gram, productive rate 90%.
0.5 restrain 5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin three villaumites 0.2 gram, productive rate 90%.UV spectrum (aqueous solution, nanometer): 409,582.Mass spectrum: 243[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.3; H, 4.0; Cl, 13.7; Fe, 7.5; N, 9.5.
Embodiment 14: iron-5,15-two [(N-methyl)-3 '-pyridyl]-10, synthetic (structural formula 15) of 20-two (4 '-tolyl) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin 0.25 gram.Productive rate 9%.
0.25 restrain 5,15-two [3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (4 '-tolyl) porphyrin two salt compounded of iodine 0.325 gram, productive rate 90%.
0.3 restrain 5,15-two [(N-methyl)-3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin two salt compounded of iodine are dissolved in 50 ml waters, add 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-3 '-pyridyl]-10,20-two (4 '-tolyl) porphyrin three villaumites 0.13 gram, productive rate 95%.UV spectrum (aqueous solution, nanometer): 413,585.Mass spectrum: 243[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 66.17; H, 4.35; Cl, 12.74; Fe, 6.69; N, 10.06 measured values: C, 65.7; H, 4.0; Cl, 13.3; Fe, 7.2; N, 9.6.
Embodiment 15 :-3 '-pyridyl iron-5-[(N-methyl)]-10,15, synthetic (structural formula 16) of 20-three (4 '-tolyl) porphyrin two villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Products therefrom is the mixture of 6 kinds of different porphyrins.Carry out silicagel column with chloroform and separate, isolate pure 5-(3 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin 1.0 grams.Productive rate 36%.
1 gram 5-(3 '-pyridyl)-10,15,20-three (4 '-tolyl) porphyrin is dissolved in 20 milliliters of methyl iodide, at room temperature stirs 24 hours.Under vacuum, steam excess iodine methane and promptly get the 5-[(N-methyl)-3 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine 1.2 grams, productive rate 94%.
1.2-3 '-pyridyl gram 5-[(N-methyl)]-10,15,20-three (4 '-tolyl) porphyrin one salt compounded of iodine is dissolved in 50 ml waters, adds 2 then.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10,15,20-three (4 '-tolyl) porphyrin two villaumites 1.1 grams, productive rate 90%.UV spectrum (methyl alcohol, nanometer): 427,594.Mass spectrum 356[(M-2Cl -) 2+/ 2].Ultimate analysis: theoretical value: C, 70.78; H, 4.55; Cl, 8.89; Fe, 7.00; N, 8.78 measured values: C, 69.4; H, 4.80; Cl, 9.52; Fe, 7.45; N.8.83.
Embodiment 16: iron-5,10, synthetic (structural formula 17) of 15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt
8.1 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin 3 grams.With gained 3 grams 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane and promptly get 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine 3.2 grams.3.2 restrain 5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin three salt compounded of iodine are dissolved in 100 ml waters, add 5 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(4 '-tolyl) porphyrin tetrachloro salt 2.5 grams, overall yield 11.4%.UV spectrum (aqueous solution, nanometer): 412,583.Mass spectrum: 182.5[(M-4Cl -) 3+/4]。Ultimate analysis: theoretical value: C, 61.95; H, 4.16; Cl, 16.25; Fe, 6.40; N, 11.24 measured values: C, 62.3; H, 4.10; Cl, 16.13; Fe, 7.7; N, 9.77.
Embodiment 17: iron-5,10,15,20-four [N-[(N-methyl)-2 '-pyridyl]-4 '-pyridyl] synthetic (structural formula 18) of porphyrin nine villaumites
1 gram 5,10,15,20-four (4 '-pyridyl) porphyrin is dissolved in 50 ml methanol, adds 10 gram 2-chloro-N-methyl-pyridine iodates then.At room temperature stirred 24 hours, and filtered out throw out.Throw out is water-soluble, add 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15, and 20-four [the N-[(N-methyl)-2 '-pyridyl]-4 '-pyridyl] porphyrin nine villaumites 0.7 gram.UV spectrum (aqueous solution, nanometer): 408,575.Mass spectrum: 116[(M-9Cl -) 9+/ 9].Ultimate analysis: theoretical value: C, 56.35; H, 3.84; Cl, 23.39; Fe, 4.09; N, 12.32; Measured value: C, 56.9; H, 3.66; Cl, 23.33, Fe, 3.75; N, 12.36.
Synthesizing of 2-chloro-N-methyl-pyridine iodate: 10 gram 2-chloro-pyridines are dissolved in 100 milliliters of methyl iodide stirring at room 24 hours.Steam methyl iodide then, promptly get product.
Embodiment 18: iron-5,10,15,20-four [N-[(N-methyl)-4 '-pyridyl]-4 '-pyridyl] synthetic (structural formula 19) of porphyrin nine villaumites
1 gram 5,10,15,20-four (4 '-pyridyl) porphyrin is dissolved in 50 ml methanol, adds 10 gram 4-chloro-N-methyl-pyridine iodates then.At room temperature stirred 24 hours, and filtered out throw out.Throw out is water-soluble, add 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15, and 20-four [the N-[(N-methyl)-4 '-pyridyl]-4 '-pyridyl] porphyrin nine villaumites 1.1 grams.UV spectrum (aqueous solution, nanometer): 408,575.Mass spectrum: 116[(M-9Cl -) 9+/ 9].Ultimate analysis: theoretical value: C, 56.35; H, 3.84; Cl, 23.39; Fe, 4.09; N, 12.32; Measured value: C, 57.1; H, 3.63; Cl, 23.16; Fe, 3.95; N, 12.16.
Synthesizing of 4-chloro-N-methyl-pyridine iodate: 10 gram 4-chloro-pyridines are dissolved in 100 milliliters of methyl iodide stirring at room 24 hours.Steam methyl iodide then, promptly get product.
Embodiment 19: iron-5,10,15, synthetic (structural formula 1) of 20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin pentachloro-salt
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of chloro diethylene glycol monomethyl ethers, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15,20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin pentachloro-salt 5 grams.UV spectrum (aqueous solution, nanometer): 408,585.Mass spectrum: 217[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 57.09; H, 5.43; Cl, 14.04; Fe, 4.42; N, 8.88; 0,10.14.Measured value: C, 57.27; H, 5.35; Cl, 14.02; Fe, 4.34; N, 8.64; 0,10.38.
Synthesizing of chloro diethylene glycol monomethyl ether: 10 gram diethylene glycol monomethyl ethers are dissolved in 1 liter of chloroform, add phosphorus trichloride 20 grams, stirring at room 10 hours.Steam chloroform then. carry out the silicagel column separation with chloroform and promptly get product.
Embodiment 20: iron-5,10-two [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl]-15, synthetic (structural formula 1) of 20-two [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (2-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 20 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5,10-two [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl]-15,20-two [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt. products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl]-15,20-two [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt 4.5 grams.UV spectrum (aqueous solution, nanometer): 410,587.Mass spectrum: 209[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 60.92; H, 5.61; Cl, 14.50; Fe, 4.57; N, 9.17; 0,5.24.Measured value: C, 60.77; H, 5.81; Cl, 14.30; Fe, 4.52; N, 9.14; 0,5.47.
Embodiment 21 :-2 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15, synthetic (structural formula 1) of 20-three [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (2-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 10 milliliters of chlorocyclopentanes and 30 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-2 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-2 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-2 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt 4 grams.UV spectrum (aqueous solution, nanometer): 412,588.Mass spectrum: 198[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 64.76; H, 5.69; Cl, 15.17; Fe, 4.78; N, 9.59.Measured value: C, 64.96; H, 5.57; Cl, 15.39; Fe, 4.68; N, 9.39.
Embodiment 22 :-2 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15-two [(N-cyclohexyl)-2 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] synthetic (structural formula 1) of porphyrin pentachloro-salt
3 the gram 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclopentanes, in the mixture of 10 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes in, at room temperature stirred 24 hours.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-2 '-pyridyl]-10,15-two [(N-cyclohexyl)-2 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-2 '-pyridyl]-10,15-two [(N-cyclohexyl)-2 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin pentachloro-salt 4.8 grams.UV spectrum (aqueous solution, nanometer): 411,588.Mass spectrum: 202[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 62.66; H, 5.60; Cl, 14.92; Fe, 4.70; N, 9.43; 0,2.69.Measured value: C, 61.62; H, 6.10; Cl, 14.96; Fe, 5.21; N, 9.49; 0,2.62.
Embodiment 23: iron-5,10-two [(N-diethylene glycol monomethyl ether base)-3 '-pyridyl]-15, synthetic (structural formula 2) of 20-two [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (3-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 20 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5,10-two [(N-diethylene glycol monomethyl ether base)-3 '-pyridyl]-15,20-two [(N-cyclohexyl)-3 '-pyridyl] porphyrin tetrachloro salt. products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-diethylene glycol monomethyl ether base)-3 '-pyridyl]-15,20-two [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt 4.2 grams.UV spectrum (aqueous solution, nanometer): 410,587.Mass spectrum: 209[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 60.92; H, 5.61; Cl, 14.50; Fe, 4.57; N, 9.17; 0,5.24.Measured value: C, 61.17; H, 5.31; Cl, 14.80; Fe, 4.52; N, 8.74; 0.5.47.
Embodiment 24 :-3 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15, synthetic (structural formula 2) of 20-three [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (3-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 10 milliliters of chlorocyclopentanes and 30 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-3 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-3 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-3 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-3 '-pyridyl] porphyrin pentachloro-salt 5.2 grams.UV spectrum (aqueous solution, nanometer): 412,588.Mass spectrum: 198[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 64.76; H, 5.69; Cl, 15.17; Fe, 4.78; N, 9.59.Measured value: C, 65.36; H, 5.58; Cl, 14.99; Fe, 4.37; N, 9.69.
Embodiment 25 :-3 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15-two [(N-cyclohexyl)-3 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-3 '-pyridyl] synthetic (structural formula 2) of porphyrin pentachloro-salt
3 the gram 5,10,15,20-four (3-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclopentanes, in the mixture of 10 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes in, at room temperature stirred 24 hours.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-3 '-pyridyl]-10,15-two [(N-cyclohexyl)-3 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-3 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-3 '-pyridyl]-10,15-two [(N-cyclohexyl)-3 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-3 '-pyridyl] porphyrin pentachloro-salt 4.8 grams.UV spectrum (aqueous solution, nanometer): 411,588.Mass spectrum: 202[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 62.66; H, 5.60; Cl, 14.92; Fe, 4.70; N, 9.43; 0,2.69.Measured value: C, 62.62; H, 6.60; Cl, 13.96; Fe, 5.41; N, 9.29; 0,2.12.
Embodiment 26: iron-5,10-two [(N-diethylene glycol monomethyl ether base)-4 '-pyridyl]-15, synthetic (structural formula 3) of 20-two [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (4-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 20 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5,10-two [(N-diethylene glycol monomethyl ether base)-4 '-pyridyl]-15,20-two [(N-cyclohexyl)-4 '-pyridyl] porphyrin tetrachloro salt. products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-diethylene glycol monomethyl ether base)-4 '-pyridyl]-15,20-two [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt 4.4 grams.UV spectrum (aqueous solution, nanometer): 410,587.Mass spectrum: 209[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 60.92; H, 5.61; Cl, 14.50; Fe, 4.57; N, 9.17; 0,5.24.Measured value: C, 61.2; H, 5.13; Cl, 14.72; Fe, 4.65; N, 8.70; 0,5.60.
Embodiment 27 :-4 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15, synthetic (structural formula 3) of 20-three [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt
3 grams 5,10,15,20-four (3-pyridyl) porphyrin at room temperature stirred 24 hours in being dissolved in the mixture of 10 milliliters of chlorocyclopentanes and 30 milliliters of chlorocyclohexanes.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-4 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-4 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-4 '-pyridyl]-10,15,20-three [(N-cyclohexyl)-4 '-pyridyl] porphyrin pentachloro-salt 5.5 grams.UV spectrum (aqueous solution, nanometer): 412,588.Mass spectrum: 198[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 64.76; H, 5.69; Cl, 15.17; Fe, 4.78; N, 9.59.Measured value: C, 65.22; H, 5.87; Cl, 14.92; Fe, 4.32; N, 9.67.
Embodiment 28 :-4 '-pyridyl iron-5-[(N-pentamethylene base)]-10,15-two [(N-cyclohexyl)-4 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-4 '-pyridyl] synthetic (structural formula 3) of porphyrin pentachloro-salt
3 the gram 5,10,15,20-four (4-pyridyl) porphyrin is dissolved in 10 milliliters of chlorocyclopentanes, in the mixture of 10 milliliters of chloro diethylene glycol monomethyl ethers and 20 milliliters of chlorocyclohexanes in, at room temperature stirred 24 hours.Carry out silicagel column with methyl alcohol and separate, isolate 5-[(N-pentamethylene base)-4 '-pyridyl]-10,15-two [(N-cyclohexyl)-4 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-4 '-pyridyl] porphyrin tetrachloro salt.Products therefrom is dissolved in 20 ml waters, adds 1.5 gram iron trichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-pentamethylene base)-4 '-pyridyl]-10,15-two [(N-cyclohexyl)-4 '-pyridyl]-20-[(N-diethylene glycol monomethyl ether base)-4 '-pyridyl] porphyrin pentachloro-salt 4 grams.UV spectrum (aqueous solution, nanometer): 411,588.Mass spectrum: 202[(M-5Cl -) 5+/ 5].Ultimate analysis: theoretical value: C, 62.66; H, 5.60; Cl, 14.92; Fe, 4.70; N, 9.43; 0,2.69.Measured value: C, 61.98; H, 6.75; Cl, 13.55; Fe, 5.43; N, 9.49; 0,2.8.
Embodiment 29: iron-5, synthetic (structural formula 6) of 10-two [(N-methyl)-4 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.15 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-4 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.1 gram.UV spectrum (aqueous solution, nanometer): 411,583.Mass spectrum: 243.3[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 64.75; H, 4.04; Cl, 12.17; Fe, 6.76; N, 10.09; 0,1.91.
Embodiment 30: iron-5,10-two [(N-methyl)-4 '-pyridyl]-15, synthetic (structural formula 6) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [4 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin 0.25 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-4 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin three villaumites 0.22 gram.UV spectrum (aqueous solution, nanometer): 412,585.Mass spectrum: 244[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 62.92; H, 3.71; Cl, 13.13; Fe, 6.27; N, 10.12; 0,3.85.
Embodiment 31: iron-5, synthetic (structural formula 7) of 15-two [(N-methyl)-4 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [4 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.17 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-4 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.2 gram.UV spectrum (aqueous solution, nanometer): 411,583.Mass spectrum: 243.3[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 65.2; H, 4.11; Cl, 12.56; Fe, 6.34; N, 10.22; 0,1.57.
Embodiment 32: iron-5,15-two [(N-methyl)-4 '-pyridyl]-10, synthetic (structural formula 7) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [4 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin 0.22 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-4 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin three villaumites 0.27 gram.UV spectrum (aqueous solution, nanometer): 412,585.Mass spectrum: 244[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 62.59; H, 3.88; Cl, 12.84; Fe, 6.66; N, 10.42; 0,3.61.
Embodiment 33 :-4 '-pyridyl iron-5-[(N-methyl)]-10-(4 '-tolyl)-15, synthetic (structural formula 8) of 20-two (p-hydroxybenzene) porphyrin two villaumites
2.7 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[4 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin 0.05 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin two villaumites 0.04 gram.UV spectrum (aqueous solution, nanometer): 413,585.Mass spectrum: 365[(M-2Cl -) 2+/ 2].Ultimate analysis: theoretical value: C, 67.43; H, 4.02; Cl, 8.85; Fe, 6.97; N, 8.74; 0,3.99; Measured value: C, 68.13; H, 3.92; Cl, 8.17; Fe, 6.54; N, 9.28; 0,3.96.
Embodiment 34 :-4 '-pyridyl iron-5-[(N-methyl)]-10-(p-hydroxybenzene)-15, synthetic (structural formula 8) of 20-two (4 '-tolyl) porphyrin two villaumites
2.7 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[4 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin 0.04 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-4 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin two villaumites 0.02 gram.UV spectrum (aqueous solution, nanometer): 413,584.Mass spectrum: 364[(M-2Cl -) 2+/ 2].Ultimate analysis: theoretical value: C, 69.10; H, 4.29; Cl, 8.87; Fe, 6.98; N, 8.76; 0,2.00; Measured value: C, 68.92; H, 4.39; Cl, 8.53; Fe, 6.95; N, 9.09; 0,2.12.
Embodiment 35: iron-5,10, synthetic (structural formula 9) of 15-three [(N-methyl)-4 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt
8.1 gram 4-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three (4 '-pyridyl)-20-(p-hydroxybenzene) porphyrin 2.7 grams.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 1.3 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-4 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt 2.5 grams.UV spectrum (aqueous solution, nanometer): 412,585.Mass spectrum: 183[(M-4Cl -) 4+/ 4].Ultimate analysis: theoretical value: C, 60.44; H, 3.92; Cl, 16.22; Fe, 6.39; N, 11.21; 0,1.83; Measured value: C, 59.81; H, 3.73; Cl, 17.28; Fe, 6.32; N, 10.95; 0,1.91.
Embodiment 36: iron-5, synthetic (structural formula 10) of 10-two [(N-methyl)-2 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [2 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.17 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-2 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.12 gram.UV spectrum (aqueous solution, nanometer): 410,583.Mass spectrum: 243.3[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 64.05; H, 4.54; Cl, 12.31; Fe, 6.76; N, 10.09; 0,1.97.
Embodiment 37: iron-5,10-two [(N-methyl)-2 '-pyridyl]-15, synthetic (structural formula 10) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [2 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin 0.15 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-2 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin three villaumites 0.12 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 244[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 63.1; H, 3.8; Cl, 13.21; Fe, 6.32; N, 10.24; 0,3.33.
Embodiment 38: iron-5, synthetic (structural formula 11) of 15-two [(N-methyl)-2 '-pyridyl]-10-(2 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [2 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.11 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-2 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.23 gram.UV spectrum (aqueous solution, nanometer): 410.5,583.Mass spectrum: 243.3[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 64.57; H, 4.09; Cl, 12.71; Fe, 6.67; N, 10.04; 0,1.91; Measured value: C, 65.11; H, 4.21; Cl, 12.43; Fe, 6.21; N, 10.44; 0,1.60.
Embodiment 39: iron-5,15-two [(N-methyl)-2 '-pyridyl]-10, synthetic (structural formula 11) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [2 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin 0.27 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin three villaumites 0.11 gram.UV spectrum (aqueous solution, nanometer): 411,587.Mass spectrum: 244[(M-3Cl -) 3+/ 3].Ultimate analysis: theoretical value: C, 62.99; H, 3.84; Cl, 12.68; Fe, 6.66; N, 10.02; 0,3.81; Measured value: C, 62.95; H, 3.88; Cl, 12.48; Fe, 6.66; N, 10.24; 0,3.16.
Embodiment 40 :-2 '-pyridyl iron-5-[(N-methyl)]-10-(4 '-tolyl)-15, synthetic (structural formula 12) of 20-two (p-hydroxybenzene) porphyrin two villaumites
2.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[2 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin 0.04 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-2 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin two villaumites 0.022 gram.UV spectrum (aqueous solution, nanometer): 413,585.Mass spectrum: 365[(M-2Cl -) 2+/ 2].
Embodiment 41 :-2 '-pyridyl iron-5-[(N-methyl)]-10-(p-hydroxybenzene)-15, synthetic (structural formula 12) of 20-two (4 '-tolyl) porphyrin two villaumites
2.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[2 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin 0.045 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-2 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin two villaumites 0.03 gram.UV spectrum (aqueous solution, nanometer): 411,586.Mass spectrum: 364[(M-2Cl -) 2+/ 2].
Embodiment 42: iron-5,10, synthetic (structural formula 13) of 15-three [(N-methyl)-2 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt
8.1 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three (2 '-pyridyl)-20-(p-hydroxybenzene) porphyrin 3 grams.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 1.3 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-2 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt 2.8 grams.UV spectrum (aqueous solution, nanometer): 409,585.Mass spectrum: 183[(M-4Cl -) 4+/ 4].
Embodiment 43: iron-5, synthetic (structural formula 14) of 10-two [(N-methyl)-3 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [3 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.18 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-3 '-pyridyl]-15-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.15 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 243.3[(M-3Cl -) 3+/ 3].
Embodiment 44: iron-5,10-two [(N-methyl)-3 '-pyridyl]-15, synthetic (structural formula 14) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10-two [3 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin 0.15 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10-two [(N-methyl)-3 '-pyridyl]-15,20-two (p-hydroxybenzene) porphyrin three villaumites 0.14 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 244[(M-3Cl -) 3+/ 3].
Embodiment 45: iron-5, synthetic (structural formula 15) of 15-two [(N-methyl)-3 '-pyridyl]-10-(2 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [3 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin 0.17 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-3 '-pyridyl]-10-(4 '-tolyl)-20-(p-hydroxybenzene) porphyrin three villaumites 0.27 gram.UV spectrum (aqueous solution, nanometer): 411,583.Mass spectrum: 243.3[(M-3Cl -) 3+/ 3].
Embodiment 46: iron-5,15-two [(N-methyl)-3 '-pyridyl]-10, synthetic (structural formula 15) of 20-two (p-hydroxybenzene) porphyrin three villaumites
5.4 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,15-two [3 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin 0.35 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,15-two [(N-methyl)-3 '-pyridyl]-10,20-two (p-hydroxybenzene) porphyrin three villaumites 0.16 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 244[(M-3Cl -) 3+/ 3].
Embodiment 47 :-3 '-pyridyl iron-5-[(N-methyl)]-10-(4 '-tolyl)-15, synthetic (structural formula 16) of 20-two (p-hydroxybenzene) porphyrin two villaumites
2.7 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3.0 gram p-tolyl aldehydes then, 6 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[3 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin 0.034 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.3 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-3 '-pyridyl]-10-(4 '-tolyl)-15,20-two (p-hydroxybenzene) porphyrin two villaumites 0.032 gram.UV spectrum (aqueous solution, nanometer): 411,585.Mass spectrum: 365[(M-2Cl -) 2+/ 2].
Embodiment 48 :-3 '-pyridyl iron-5-[(N-methyl)]-10-(p-hydroxybenzene)-15, synthetic (structural formula 16) of 20-two (4 '-tolyl) porphyrin two villaumites
2.7 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6 gram p-tolyl aldehydes then, 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5-[3 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) 0.04 gram.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 0.5 gram iron trichloride then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5-[(N-methyl)-3 '-pyridyl]-10-(p-hydroxybenzene)-15,20-two (4 '-tolyl) porphyrin two villaumites 0.04 gram.UV spectrum (aqueous solution, nanometer): 411,586.Mass spectrum: 364[(M-2Cl -) 2+/ 2].
Embodiment 49: iron-5,10, synthetic (structural formula 17) of 15-three [(N-methyl)-3 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt
8.1 gram 3-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 3 gram p-Hydroxybenzaldehydes and 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate pure 5,10,15-three (3 '-pyridyl)-20-(p-hydroxybenzene) porphyrin 3 grams.The gained porphyrin is dissolved in 10 milliliters of methyl iodide, at room temperature stirred 24 hours.Under vacuum, steam excess iodine methane. products therefrom is dissolved in 50 ml waters, adds 1.3 gram iron trichlorides then.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive iron trichloride, under vacuum, steam water and promptly get iron-5,10,15-three [(N-methyl)-3 '-pyridyl]-20-(p-hydroxybenzene) porphyrin tetrachloro salt 2.5 grams.UV spectrum (aqueous solution, nanometer): 410,585.Mass spectrum: 183[(M-4Cl -) 4+/ 4].
Embodiment 50: iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15, synthetic (structural formula 4) of 20-two [(4 '-N-glucosyl group)-phenyl] porphyrin
14 gram (4 '-C-glucosyl group)-phenyl aldehydes, 14 gram (4 '-N-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Under vacuum, steam propionic acid, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.5 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.45 gram.Mass spectrum: 1321[(M-Fe+3H) +/ 1].
The synthetic of (4 '-N-glucosyl group)-phenyl aldehyde can be with reference to Pasetto, P. wait the people at J.Chem.Soc., Chem.Commun.2001, disclosed synthetic method in " Synthesis of hydrolytically stable porphyrinC-and S-glycoconjugates in high yields " among the 81-82.
Embodiment 51: iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15, synthetic (structural formula 4) of 20-two [(4 '-0-glucosyl group)-phenyl] porphyrin
14 gram (4 '-C-glucosyl group)-phenyl aldehydes, 14 gram (4 '-0-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Under vacuum, steam propionic acid, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-0-glucosyl group)-phenyl] porphyrin 0.47 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10-two [(4 '-C-glucosyl group)-phenyl]-15,20-two [(4 '-0-glucosyl group)-phenyl] porphyrin 0.42 gram.Mass spectrum: 1323[(M-Fe+3H) +/ 1].
The synthetic of (4 '-0-glucosyl group)-phenyl aldehyde can be with reference to Pasetto, P. wait the people at J.Chem.Soc., Chem.Commun.2001, disclosed synthetic method in " Synthesis of hydrolytically stable porphyrinC-and S-glycoconjugates in high yields " among the 81-82.
Embodiment 52: iron-5,10-two [(4 '-0-glucosyl group)-phenyl]-15, synthetic (structural formula 4) of 20-two [(4 '-N-glucosyl group)-phenyl] porphyrin
14 gram (4 '-0-glucosyl group)-phenyl aldehydes, 14 gram (4 '-N-glucosyl group)-phenyl aldehydes and 6.7 restrain and are dissolved in 1 liter of propionic acid after pyrroles mix, and reflux was cooled to room temperature in 2 hours then in air.Under vacuum, steam propionic acid, carry out silicagel column with the mixed solution of 80% chloroform and 20% methyl alcohol and separate, isolate 5,10-two [(4 '-0-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.6 restrains.The gained porphyrin is dissolved in 50 ml methanol, adds 3 gram ferrous chloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Filter out excessive ferrous chloride, under vacuum, steam methyl alcohol and promptly get iron-5,10-two [(4 '-0-glucosyl group)-phenyl]-15,20-two [(4 '-N-glucosyl group)-phenyl] porphyrin 0.55 gram.Mass spectrum: 1325[(M-Fe+3H) +/ 1].
Embodiment 53: cobalt-5,10,15, synthetic (structural formula 1) of 20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of chloro diethylene glycol monomethyl ethers, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 2.5 gram cobalt dichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive cobalt dichloride, under vacuum, steam water and promptly get cobalt-5,10,15,20-four [(N-diethylene glycol monomethyl ether base)-2 '-pyridyl] porphyrin 3 grams.Mass spectrum: 271 (M 4+/ 4).
Embodiment 54: cobalt-5,10,15, synthetic (structural formula 1) of 20-four [(N-5 '-imidazolyl)-2 '-pyridyl] porphyrin
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of 5-chloro imidazoles, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 2.5 gram cobalt dichlorides.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive cobalt dichloride, under vacuum, steam water and promptly get cobalt-5,10,15,20-four [(N-5 '-imidazolyl)-2 '-pyridyl] porphyrin 2.7 grams.Mass spectrum: 236 (M 4+/ 4).
Embodiment 55: zinc-5,10,15, synthetic (structural formula 1) of 20-four [(N-(N-ethylethylenediamine base)-2 '-pyridyl] porphyrin
10.7 gram 2-pyridyl formaldehyde is dissolved in 1 liter of propionic acid, adds 6.7 gram pyrroles then.Gained mixture reflux in air was cooled to room temperature in 1 hour then.Under vacuum, steam propionic acid.Carry out silicagel column with chloroform and separate, isolate 5,10,15,20-four (2-pyridyl) porphyrin 3.5 grams.3.5 grams 5,10,15,20-four (2-pyridyl) porphyrin is dissolved in 10 milliliters of iodo N-ethylethylenediamine bases, at room temperature stirs 24 hours.The gained reactant is dissolved in 20 ml waters, adds 2.5 gram zinc dichloride.The gained mixture refluxed 2 hours under protection of nitrogen gas.Add ammoniacal liquor and remove excessive zinc dichloride, under vacuum, steam water and promptly get zinc-5,10,15,20-four [(N-(N-ethylethylenediamine base)-2 '-pyridyl) porphyrin 2.7 grams.Mass spectrum: 304 (M 4+/ 4).
Embodiment 56: the effect of small molecule antioxidant and DNA
Because small molecule antioxidant of the present invention all has positive charge, so they can both work with the DNA that has negative charge.When with DNA titration a kind of small molecule antioxidant of the present invention, the uv-absorbing generation red shift of porphyrin.Fig. 1 is with CT-DNA titration 5,10-two [(N-methyl)-4 '-pyridyl]-15, the ultra-violet absorption spectrum of 20-two (4 '-tolyl) porphyrin two villaumites in water.Along with the adding of DNA, porphyrin obviously descends and red shift in the absorption of Soret band.
Embodiment 57: the cobalt complex of porphyrin synthetic
At first the porphyrin with 1 gram is dissolved in 100 milliliters the chloroform, adds the rose vitriols of 2 grams then.Under protection of nitrogen gas, reaction refluxed 2 hours, then cool to room temperature.Cross and miss unreacted rose vitriol, under vacuum, steam chloroform then, promptly obtain the cobalt complex of porphyrin.
Experimental example 1: iron-5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt in the focal cerebral ischemia model to the provide protection of rat brain
24 bull Sprague-Dawley rats are become four groups by 6 one components.Cause the rat brain thrombus with the method for the artery in the brain being separated ligation, inject iron-5,10,15,20-four [(N-cyclohexyl)-2 '-pyridyl] porphyrin pentachloro-salt to two groups of rats wherein by the amount of 1 mg/kg after 5 minutes.The cerebral infarct size that compares four groups of rats after one hour.The average cerebral infarct size of medication group rat be control rats average cerebral infarct size 1/2nd.
Experimental example 2: iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin three villaumites in rat anoxia anoxia model to the provide protection of rat brain
24 bull Sprague-Dawley rats are become four groups by 6 one components.Inject iron-5,15-two [(N-methyl)-2 '-pyridyl]-10,20-two (2 '-tolyl) porphyrin three villaumites to two groups of rats wherein by the dosage of 2 mg/kg.After one hour rat is placed in the bottle that fills nitrogen, takes out rapidly after one minute, observe the rats death number.The rats death number of medication group is 1/3rd of a control group.
Cerebral thrombosis is meant the constricted flow of blood in brain.Again dredge blood flow after the operation, can cause further infringement to brain, this is called again the infringement that oxygen supply causes.Many scientists think, cerebral thrombosis and again the infringement that causes of oxygen supply have at least a part to cause by free radical.The derivatives of porphyrin that has large-substituent of the present invention can be used as small molecule antioxidant and is used for treating cerebral thrombosis, alleviates because the death of the brain cell that causes of cerebral thrombosis and the infringement that causes of oxygen supply again, and consumption is a 0.5-100 mg/kg body weight.
Acute myocardial infarction, so-called heart failure.It is to cause heart tissue death to cause owing to the coronary flow of supplying heart blood is obstructed.Long-term or nonvolatil blood flow is obstructed and makes and finally cause myocardial cell's death by the part myocardial anoxia.If by nature or medical procedure get involved, blood flow is by very fast mediation, the infringement that infarct causes may be removed or alleviate.But the mediation again of blood flow also can damage myocardial cell and adjacent tissue cell thereof.This injury is called the ischemic infringement that causes of oxygen supply again.Studies have shown that free radical all plays an important role in blood flow the is obstructed infringement that causes and the ischemic infringement that oxygen supply causes again.Therefore, the derivatives of porphyrin that has large-substituent of the present invention can reduce tissue injury as small molecule antioxidant, and patient in heart failure is benefited.
Owing in the process of radiation treatment, produce a large amount of free radicals, thereby human body produced very big side effect.The derivatives of porphyrin that has large-substituent of the present invention can be treated owing to human body is accepted the sequela that radiation treatment causes as small molecule antioxidant.
Chronic bronchitis, asthma, rheumatic arthritis, senile dementia, Parkinson's formula disease, the shock that causes by septicemia, disease such as aging is also directly relevant with a large amount of generations of free radical.So the derivatives of porphyrin that has a large-substituent of the present invention also can be used for treating these diseases as small molecule antioxidant.
Experimental example 3: have the distribution coefficient of the derivatives of porphyrin of large-substituent at oil phase and aqueous phase
Measuring method: in 10 milliliters test tube, add 3 milliliters n-Octanol, add the 1-2 milligram derivatives of porphyrin that has different substituents of the present invention then.After the derivatives of porphyrin dissolving that has large-substituent, add 3 milliliters water again.Acutely shake test tube, place then and spend the night.Mensuration has the absorbancy of the derivatives of porphyrin of large-substituent at oil phase and aqueous phase respectively, and both ratio is distribution coefficient.Table 1 is that some of this invention have the distribution coefficient of the derivatives of porphyrin of large-substituent at oil phase and aqueous phase.
Table 1: small molecule antioxidant is at the distribution coefficient of oil phase and aqueous phase
Porphyrin R R’ R” R’” K (n-Octanol/water)
1 OH Me Me PyMe+ ＞2500
2 OH Me PyMe+ PyMe+ 7.23
3 OH PyMe+ Me PyMe+ 16.5
4 OH OH PyMe+ PyMe+ 4.02
5 OH PyMe+ OH PyMe+ 6.25
6 OH OH OH PyMe+ ＞2500
7 Me Me PyMe+ PyMe+ ＞100
8 Me PyMe+ Me PyMe+ 38.5
As can be seen from Table 1, the derivatives of porphyrin that has a large-substituent of the present invention is different at the distribution coefficient of oil phase and aqueous phase, according to this characteristic, the derivatives of porphyrin of different substituents can be used for the treatment of different diseases.

Claims (7)

1. derivatives of porphyrin that has large-substituent is derivatives of porphyrin or its pharmacy acceptable salt with following structure:
Figure C021165560002C1
Wherein A, B, C, D are
Figure C021165560002C2
In at least a, and at least one is
Figure C021165560002C3
R represents-(CH 2) n-X, n=0-10, radicals X is selected from 0, H, and one or more the combination in the following groups;
Figure C021165560002C4
-(C mH 2m) j(OC mH 2m) pOZ’、-(C mH 2m) j(OC mH 2m) pOH、
-(C mH 2m) j(NH-C mH 2m) pNH 2、-(C mH 2m) j(NH-C mH 2m) pNH-Z’、
-(C mH 2m) j(NH-C mH 2m) pN-Z 2' or-(C mH 2m) j(NH-C mH 2m) pN-Z 3' +
Figure C021165560003C1
-COOH、-CONH 2、-PO 3H 2、-SO 3H、-NH 2、-OH、-SH、-CH＝CH 2、-CO 2CH 2CH 3；
When X was 0, R was cycloalkyl-(CH 2) n, its n=3-10; When X was H, R was alkyl-(CH 2) nH, n=1-10;
Among the A-D, group Y and Y ' are selected from CH 2, O, among NH, the S one, group Z is selected from C, O, N, among the S one, group Z ' is selected from-C qH 2q+1Perhaps-(C qH 2q) CH=CH 2, j wherein, p, q, m=0-10;
M is a kind of in the metal ion of following metal: Fe, Mn, Co, Ni, Cu, Zn, Sn, Cr, or V.
2. the derivatives of porphyrin that has large-substituent according to claim 1, R is-(CH 2) n ,-(C mH 2m) j(OC mH 2m) pOCH 3,-CH 3A kind of among the ,-OH, j wherein, p, n, m=0-10.
3. the derivatives of porphyrin that has large-substituent according to claim 1 and 2 is following structure:
Figure C021165560004C1
In the said structure formula, R 1-R 4For-(CH 2) nH or-a kind of among the OH, n=1-8.
4. the derivatives of porphyrin that has large-substituent according to claim 3, wherein R 1-R 4Be methyl.
5. the derivatives of porphyrin that has large-substituent according to claim 1 and 2, the salt of described pharmaceutically acceptable derivatives of porphyrin is hydrochloride, vitriol, acetate or the phosphoric acid salt of derivatives of porphyrin.
6. the described synthetic method that has the derivatives of porphyrin of large-substituent of claim 1 comprises the steps:
5.4 gram n-pyridyl formaldehyde and 5.4 gram substituted benzaldehydes are dissolved in 1 liter of propionic acid; add 6.7 gram pyrroles then; gained mixture reflux in air was cooled to room temperature in 1 hour then; under vacuum, steam propionic acid; carrying out silicagel column with chloroform separates; isolate pure porphyrin; the gained porphyrin is dissolved in the 10-30 milliliter haloalkane; when 60 spend, refluxed 4 hours; after reaction is finished; the solution cool to room temperature steams excessive haloalkane under vacuum, products therefrom is dissolved in 100 ml waters; add the chloro metallic compound then; gained mixture under protection of nitrogen gas backflow 2-5 hour adds ammoniacal liquor and removes excessive chloro metallic compound, steams water and promptly get the purpose product under vacuum.
Any one described derivatives of porphyrin that has a large-substituent of claim 1-5 as small molecules oxidation inhibitor accept sequela, AIDS that radiation treatment causes as preparation treatment cerebral thrombosis, chronic bronchitis, asthma, rheumatic arthritis, senile dementia, Parkinson's formula disease, the shock that causes by septicemia, owing to human body, wear out and disease medicament in heart failure on purposes.
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US7807825B2 (en) 2004-02-09 2010-10-05 Duke University Substituted porphyrins
JP2007530695A (en) * 2004-03-29 2007-11-01 イノテック ファーマシューティカルズ コーポレイション Pyridyl-substituted porphyrin compounds and methods of use thereof
CN101235036A (en) * 2007-02-02 2008-08-06 济南赛文医药技术有限公司 Porphyrin derivative and application for the same as small molecule antioxidant
WO2009123569A1 (en) * 2008-03-31 2009-10-08 Agency For Science, Technology And Research Method for treating neurological disorders with imidazolium and imidazolinium compounds
JP6041360B2 (en) * 2011-07-22 2016-12-07 バイオリテック ウンターネーメンスベタイリグンクス ツヴァイ アクツィエンゲゼルシャフト Sugar-substituted dihydroxy-chlorins and β-functionalized chlorins for antibacterial photodynamic therapy
CN104513250B (en) * 2014-12-23 2016-11-23 南开大学 The synthetic method of a kind of water-soluble porphyrin and photocatalytic applications thereof
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CN106939004A (en) * 2017-01-23 2017-07-11 河南师范大学 The method of mixed solvent system synthesizing cationic type water-soluble porphyrin and metal porphyrinses
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CN110028514B (en) * 2019-05-30 2021-07-02 湖南科技大学 5,10,15, 20-tetraaryl-2, 3-imidazole fused-21-carbon chlorophyll compound and preparation method thereof
CN111607100A (en) * 2020-06-10 2020-09-01 苏州大学 Crystalline material based on iron-based porphyrin ligand, preparation and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994339A (en) * 1993-10-15 1999-11-30 University Of Alabama At Birmingham Research Foundation Oxidant scavengers
US6087493A (en) * 1997-02-05 2000-07-11 Regents Of The University Of Texas System Porphyrin compounds as telomerase inhibitors
US6103714A (en) * 1994-09-20 2000-08-15 Duke University Oxidoreductase activity of manganic porphyrins
CN1295574A (en) * 1998-03-31 2001-05-16 阿斯特里德·沙斯塔克 Porphyrins and their use as photosensitizer

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5994339A (en) * 1993-10-15 1999-11-30 University Of Alabama At Birmingham Research Foundation Oxidant scavengers
US6103714A (en) * 1994-09-20 2000-08-15 Duke University Oxidoreductase activity of manganic porphyrins
US6087493A (en) * 1997-02-05 2000-07-11 Regents Of The University Of Texas System Porphyrin compounds as telomerase inhibitors
CN1295574A (en) * 1998-03-31 2001-05-16 阿斯特里德·沙斯塔克 Porphyrins and their use as photosensitizer

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
四中位(邻烷基)-苯基卟啉.... 桂明德等.高等学校化学学报，第15卷第10期. 1994 *
尾式金属卟啉配合物的研究(III). 黄锦汪等.高等学校化学学报，第16卷第2期. 1995 *
水溶性[5-邻(乙氧羰基甲氧基苯基)-10,15,20-Tri(4-N-甲基吡啶基)卟啉铜(II)配合物的合成.... 韩高义等.无机化学学报，第16卷第6期. 2000 *

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