CN1238355C - Metalloporphyrin synthesizing method - Google Patents
Metalloporphyrin synthesizing method Download PDFInfo
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- CN1238355C CN1238355C CN 200310110537 CN200310110537A CN1238355C CN 1238355 C CN1238355 C CN 1238355C CN 200310110537 CN200310110537 CN 200310110537 CN 200310110537 A CN200310110537 A CN 200310110537A CN 1238355 C CN1238355 C CN 1238355C
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Abstract
The present invention discloses a synthesizing method of metal porphyrin, particularly a method using pyrrole and aromatic aldehyde as raw materials to synthesize metal aryl porphyrin and mu-oxygen bimetal aryl porphyrin. In the method, zinc salts are used as a template center, pyrrole and aromatic aldehyde are used as raw materials to firstly synthesize the mixture of aryl porphine and zinc aryl porphyrin; then the mixture of the aryl porphine and the zinc aryl porphyrin reacts with other metal salts under an acidic or neutral condition to synthesize metal aryl porphyrin; finally, mu-oxygen bimetal aryl porphyrin is synthesized in one step by reaction under an alkaline condition. Compared with the existing method for synthesizing the metal aryl porphyrin, the synthesizing method of the metal aryl porphyrin disclosed by the present invention can improve the synthesizing yield of the metal aryl porphyrin by (10 to 15%) to 920 to 40%). The synthesizing method of the mu-oxygen bimetal aryl porphyrin disclosed by the present invention can make the two-step process of the existing synthesizing method become a one-step process. The synthesizing yield of the mu-oxygen bimetal aryl porphyrin can be improved by 30 to 40%, and yield can reach 90 to 95%. Thus, the synthesizing cost of the metal aryl porphyrin and the mu-oxygen bimetal aryl porphyrin can be greatly reduced.
Description
Technical field
The present invention relates to a kind of metalloporphyrin synthetic method, especially a kind of is the method for the synthetic metal aryl-porphyrin of raw material and μ-oxygen bimetal aryl-porphyrin with pyrroles and aromatic aldehyde.
Background technology
Oxidation has the selectivity katalysis to metal aryl-porphyrin and μ-oxygen bimetal aryl-porphyrin to hydrocarbon-air.But metal aryl-porphyrin and μ-oxygen bimetal aryl-porphyrin does not have industrial preparative method at present.Need following two-step reaction in the laboratory from pyrroles and the synthetic metal aryl-porphyrin of aromatic aldehyde at present:
And by the reaction yield of the synthetic porphines of pyrroles and aromatic aldehyde less than 20%, the production cost height.
Need pass through following reaction from the synthetic μ of porphines-oxygen bimetal aryl-porphyrin at present:
Reaction also needed for two steps, metalloporphyrin also needs to separate and purify, and, generate in the reaction process of μ-oxygen bimetallic porphyrin at metalloporphyrin and NaOH, the a large amount of NaOH that add can make the metal ion in the metalloporphyrin come off, cause the yield of μ-oxygen bimetallic porphyrin not high, and the product separation difficulty.
Summary of the invention
The objective of the invention is to overcome the defective of above-mentioned prior art, a kind of yield height is provided, production cost is low, and product separates the synthetic method that is easy to metal aryl-porphyrin and μ-oxygen bimetal aryl-porphyrin.
The object of the present invention is achieved like this: adopting zinc salt in the organic solvent that refluxes is template center, is raw material with pyrroles and aromatic aldehyde, at first synthesizing aryl porphines and zinc aryl-porphyrin mixture; With aryl porphines and zinc aryl-porphyrin mixture and other metal-salt, under acidity or neutrallty condition, react synthetic metal aryl-porphyrin then; Under alkaline condition, react one-step synthesis μ-oxygen bimetal aryl-porphyrin.
Synthetic μ-oxygen bimetal aryl-porphyrin except that the mixture that can use aryl porphines and zinc aryl-porphyrin is done the raw material, can also use aryl porphines or zinc aryl-porphyrin to make raw material respectively separately.
The synthetic route of the present invention's metal aryl-porphyrin and μ-oxygen bimetal aryl-porphyrin is as follows:
Method of the present invention concrete operations as follows:
(1) mixture of aryl porphines and zinc aryl-porphyrin is synthetic;
Mol ratio by 1: 1～3: 1～5 in the organic solvent that refluxes drops into pyrroles, aromatic aldehyde and zinc salt, and pyrroles's concentration is 10 in the reaction system
-4～1mol/L, the reaction times is 0.5-3 hour; Reactant obtains the mixture of aryl porphines and zinc aryl-porphyrin through cooling, separation;
(2) metalloporphyrin is synthetic: above-mentioned aryl porphines and the zinc aryl-porphyrin mixture ratio according to 0.1～5% (weight) is dissolved in the organic solvent, add metal-salt, the molar ratio of aryl porphines and zinc aryl-porphyrin mixture and metal-salt is 1～10, reaction solution backflow 0.5-5 hour; Product is the metal aryl-porphyrin;
More than the building-up reactions of the second single metal porphyrin under at alkaline condition, carry out, promptly with the pH value of basic cpd conditioned reaction liquid greater than 7, product is μ-oxygen bimetal aryl-porphyrin.
Reactant obtains finished product through cooling, separation.
In production practice, also can replace aryl porphines and zinc aryl-porphyrin mixture to prepare μ-oxygen bimetal aryl-porphyrin with aryl porphines or zinc aryl-porphyrin separately.
The zinc salt that the present invention uses should be soluble zinc salt, for example ZnCl
2, Zn (OAc)
2, ZnBr
2
The organic solvent that the present invention uses is identical with the organic solvent that existing synthetic method is used, and for example, can be propionic acid, acetate, benzene,toluene,xylene, methylene dichloride, trichloromethane, DMF, DMSO or their mixture.
The metal-salt that metal-salt that the present invention uses and existing synthetic method are used is indistinction also, can be Co (acac)
2, Cu (OAc)
2, NiCl
2, Zn (OAc)
2, Zn (OAc)
2, FeCl
24H
2O, MnCl
24H
2O or CrCl
26H
2O.
The basic cpd and the prior art of the pH value of the conditioned reaction liquid that the present invention uses do not have assorted petty difference yet, can be pyridines, triethylamine, NaOCH
3, NaOC
2H
5, NaOH, Na
2CO
3Or NaHCO
3
Synthetic method with existing metal aryl-porphyrin compares, and the present invention can make the synthetic yield of metal aryl-porphyrin improve 10～15%, reaches 20～40%; The present invention's μ-oxygen bimetal aryl-porphyrin synthetic method can make two step processes of existing synthetic method become a one-step process, and the synthesis yield of μ-oxygen bimetal aryl-porphyrin can improve 30～40%, and productive rate can reach 90～95%; The synthetic cost of metal aryl-porphyrin and μ-oxygen bimetal aryl-porphyrin can significantly reduce thus.
Embodiment
The invention will be further described by the following examples.
Embodiment 1: with 5g compound 1, R
1=OCH
3, R
2=R
3=H and 4g pyrroles, 5g ZnCl
2, adding in the 100ml propionic acid, reaction stirred is 0.5 hour under refluxing, and cooling, separation obtain mixture 2.Gained mixture 2 is dissolved in the dimethylbenzene of backflow, adds 1g Co (acac)
2, reacted 2 hours, obtain compound 3 (M=Co, R
1=OCH
3, R
2=R
3=H).The transformation efficiency of compound 1 is 30%, and the transformation efficiency of mixture 2 is 95%.
Embodiment 2: with 5g compound 1, R
1=OH, R
2=R
3=CH
3And 4g pyrroles, 5g ZnCl
2, adding in the 120ml acetic acid, reaction stirred is 1 hour under refluxing, and cooling, separation obtain mixture 2.Gained mixture 2 is dissolved among the trichloromethane/DMF of backflow, adds 1g Cu (OAc)
2, reacted 2 hours, obtain compound 3 (M=Cu, R
1=OCH
3, R
2=R
3=H).The transformation efficiency of compound 1 is 35%, and the transformation efficiency of mixture 2 is 94%.
Embodiment 3: with 5g compound 1, R
1=N (CH
3)
2, R
2=Cl, R
3=CH
3And 4g pyrroles, 5gZn (OAc)
2, adding in the 120ml acetic acid, reaction stirred is 1 hour under refluxing, and cooling, separation obtain mixture 2.Gained mixture 2 is dissolved among the trichloromethane/DMF of backflow, adds 1g NiCl
2, reacted 1.5 hours, obtain compound 3 (M=Ni, R
1=N (CH
3)
2, R
2=Cl, R
3=H).The transformation efficiency of compound 1 is 32%, and the transformation efficiency of mixture 2 is 90%.
Embodiment 4: with 5g compound 1, R
1=F, R
2=NO
2R
3=CH
3And 4g pyrroles, 5gZn (OAc)
2, adding in the 120ml acetic acid, reaction stirred is 1 hour under refluxing, and cooling, separation obtain mixture 2.Gained mixture 2 is dissolved among the DMF of backflow, adds 1g Ru
3(CO)
12, reacted 3 hours, obtain compound 3 (M=Ru, R
1=F, R
2=NO
2, R
3=CH
3).The transformation efficiency of compound 1 is 30%, and the transformation efficiency of mixture 2 is 92%.
Embodiment 5: with 5g compound 1, R
1=CH (CH
3)
2, R
2=H, R
3=Br and 4g pyrroles, 5gZnBr
2, adding in the 80ml Mono Chloro Acetic Acid, reaction stirred is 0.5 hour under refluxing, and cooling, separation obtain mixture 2.Gained mixture 2 is dissolved among the DMSO of backflow, adds 1g FeCl
24H
2O reacted 1 hour, obtained compound 3 (M=Fe, R
1=CH (CH
3)
2, R
2=H, R
3=Br).The transformation efficiency of compound 1 is 38%, and the transformation efficiency of mixture 2 is 95%.
Embodiment 6:
With 1g mixture 2, R
1=CH
3, R
2=Cl, R
3=H and 0.3g FeCl
24H
2O adds in the 35ml dimethylbenzene, adds NaHCO under refluxing
3Control pH=8, reaction stirred 1 hour gets μ-oxygen bimetal aryl-porphyrin (M
1=M
2=Fe, R
1=CH
3, R
2=Cl, R
3=H).The synthesis yield of μ-oxygen bimetal aryl-porphyrin is 90%.
Embodiment 7: with 1g mixture 2, R
1=COOH, R
2=H, R
3=Cl and 0.3g FeCl
24H
2O adds among 35ml methylene dichloride/DMF, adds pyridine control pH=9 under refluxing, and reaction stirred 1 hour gets compound 4 (M
1=M
2=Fe, R
1=COOH, R
2=H, R
3=Cl).The synthesis yield of μ-oxygen bimetal aryl-porphyrin is 95%.
Embodiment 8: with 1g mixture 2, R
1=OH, R
2=Br, R
3=H, and 0.3gMnCl
24H
2O adds among the 35ml DSMO, adds NaOH control pH=10 under refluxing, and reaction stirred 2 hours gets compound 4 (M
1=M
2=Mn, R
1=OH, R
2=Br, R
3=H).The synthesis yield of μ-oxygen bimetal aryl-porphyrin is 93%.
Embodiment 9: with 1g aryl porphines, R
1=NH
2, R
2=F, R
3=H and 0.3g MnCl
25H
2O adds in the 35ml benzene, adds triethylamine control pH=10 under refluxing, and reaction stirred 3 hours gets compound 4 (M
1=M
2=Mn, R
1=NH
2, R
2=F, R
3=H).The synthesis yield of μ-oxygen bimetal aryl-porphyrin is 91%.
Embodiment 10: with 1g zinc aryl-porphyrin, R
1=NO
2, R
2=H, R
3=CH
3And 0.3g CrCl
26H
2O adds in the 35ml methylene dichloride, adds NaOCH under refluxing
3Control pH=13, reaction stirred 0.5 hour gets compound 4 (M
1=M
2=Cr, R
1=NO
2, R
2=H, R
3=CH
3).The synthesis yield of μ-oxygen bimetal aryl-porphyrin is 93%.
Claims (8)
1. the synthetic method of a metalloporphyrin is characterized in that comprising the steps:
(1) aryl porphines and zinc aryl-porphyrin mixture is synthetic:
Mol ratio by 1: 1～3: 1～5 in organic solvent drops into pyrroles, aromatic aldehyde and soluble zinc salt, and pyrroles's concentration is 10 in the reaction system
-4～1mol/L, reflux also stirred 0.5-3 hour; Reactant obtains the mixture of aryl porphines and zinc aryl-porphyrin through cooling, separation;
(2) metalloporphyrin is synthetic: above-mentioned aryl porphines and the zinc aryl-porphyrin mixture ratio according to 0.1～5% weight is dissolved in the organic solvent, add soluble transition metal salt, the mol ratio of aryl porphines and zinc aryl-porphyrin mixture and metal-salt is 1～10, reaction solution reflux 0.5-5 hour; Reactant obtains finished product through cooling, separation.
2. synthetic method according to claim 1, the building-up reactions that it is characterized in that the second single metal porphyrin are as carrying out under neutrality or acidic conditions, and product is the metal aryl-porphyrin.
3. synthetic method according to claim 1 is characterized in that the building-up reactions of the second single metal porphyrin is carried out under at alkaline condition, the pH value of promptly using basic cpd conditioned reaction liquid is greater than 7, and product is μ-oxygen bimetal aryl-porphyrin.
4. synthetic method according to claim 3 is characterized in that and can replace aryl porphines and zinc aryl-porphyrin mixture to prepare μ-oxygen bimetal aryl-porphyrin with aryl porphines or zinc aryl-porphyrin separately.
5. synthetic method according to claim 1 is characterized in that, described soluble zinc salt is ZnCl
2, ZnBr
2, or Zn (OAc)
2
6. synthetic method according to claim 1 is characterized in that, described organic solvent can be propionic acid, acetate, benzene,toluene,xylene, methylene dichloride, trichloromethane, DMF, DMSO or their mixture.
7. synthetic method according to claim 1 is characterized in that, what described soluble transition metal salt can be in the following salt is a kind of: Co (acac)
2, Cu (OAc)
2, NiCl
2, Zn (OAc)
2, Zn (OAc)
2, FeCl
2, MnCl
2, CrCl
3
8. according to claim 3 or 4 described synthetic methods, it is characterized in that described basic cpd can be a pyridine, triethylamine, NaOCH
3, NaOC
2H
5, Na
2CO
3Or NaHCO
3
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| CN 200310110537 CN1238355C (en) | 2003-11-21 | 2003-11-21 | Metalloporphyrin synthesizing method |
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|---|---|---|---|
| CN 200310110537 CN1238355C (en) | 2003-11-21 | 2003-11-21 | Metalloporphyrin synthesizing method |
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| CN1238355C true CN1238355C (en) | 2006-01-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167704A (en) * | 2011-03-20 | 2011-08-31 | 扬州大学 | Water-soluble porphyrin gold (III) anticancer compounds and preparation method thereof |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2914302A1 (en) * | 2007-03-30 | 2008-10-03 | Sanofi Pasteur Sa | PROCESS FOR PREPARING PORPHYRIN DERIVATIVES, SUCH AS PROTOPORPHYRIN (IX) AND INTERMEDIATE SYNTHESIS |
| CN102382116B (en) * | 2011-08-31 | 2013-10-16 | 沅江华龙催化科技有限公司 | Synthesis technology and equipment of tetraaryl cobalt porphyrin |
| CN102408430B (en) * | 2011-09-07 | 2013-11-06 | 沅江华龙催化科技有限公司 | Synthetic process and special equipment for substituted bis [tetraphenylporphinatoiron] |
| CN102391269B (en) * | 2011-09-22 | 2015-03-18 | 西北师范大学 | Zinc protoporphyrin containing heterocyclic ring as well as synthesis and applications of zinc protoporphyrin containing heterocyclic ring and metal complex of zinc protoporphyrin containing heterocyclic ring |
| CN102391270A (en) * | 2011-10-17 | 2012-03-28 | 华东理工大学 | Preparation method for tetra-(o-pivaloyl amino phenyl) zinc protoporphyrin isomer compound |
| CN103880851B (en) * | 2014-03-11 | 2016-03-02 | 沅江华龙催化科技有限公司 | The continuous production processes of four metal arylide porphyrins |
| CN103880852B (en) * | 2014-03-11 | 2016-02-24 | 沅江华龙催化科技有限公司 | The continuous production processes of four aryl porphines |
| CN105646505B (en) * | 2016-01-15 | 2018-08-28 | 唐江涛 | A kind of continuous preparation method of mu-oxo tetraphenyl bimetallic porphyrin |
| CN112939992B (en) * | 2021-02-19 | 2022-08-12 | 中国人民解放军军事科学院防化研究院 | Synthesis method of tetra (4-aminophenyl) porphyrin metal complex |
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2003
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102167704A (en) * | 2011-03-20 | 2011-08-31 | 扬州大学 | Water-soluble porphyrin gold (III) anticancer compounds and preparation method thereof |
| CN102167704B (en) * | 2011-03-20 | 2014-05-14 | 扬州大学 | Water-soluble porphyrin gold (III) anticancer compounds and preparation method thereof |
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| CN1544435A (en) | 2004-11-10 |
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