CN111499667A - Method for synthesizing trivalent tetraarylferriporphyrin from pyrrole, aromatic aldehyde and ferrous salt - Google Patents
Method for synthesizing trivalent tetraarylferriporphyrin from pyrrole, aromatic aldehyde and ferrous salt Download PDFInfo
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- CN111499667A CN111499667A CN202010513469.0A CN202010513469A CN111499667A CN 111499667 A CN111499667 A CN 111499667A CN 202010513469 A CN202010513469 A CN 202010513469A CN 111499667 A CN111499667 A CN 111499667A
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- pyrrole
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 150000003934 aromatic aldehydes Chemical class 0.000 title claims abstract description 20
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000010992 reflux Methods 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 23
- -1 aryl aldehyde Chemical class 0.000 claims abstract description 21
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 15
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000000967 suction filtration Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 150000004032 porphyrins Chemical class 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Chemical group 0.000 claims description 4
- 229910052760 oxygen Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 abstract description 4
- 150000007524 organic acids Chemical class 0.000 abstract description 3
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 8
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- DXNNQSCFERUATE-UHFFFAOYSA-N 2-ethylpyrrole-2-carbaldehyde Chemical compound CCC1(C=CC=N1)C=O DXNNQSCFERUATE-UHFFFAOYSA-N 0.000 description 1
- SIXYIEWSUKAOEN-UHFFFAOYSA-N 3-aminobenzaldehyde Chemical compound NC1=CC=CC(C=O)=C1 SIXYIEWSUKAOEN-UHFFFAOYSA-N 0.000 description 1
- KSAVZSUPQGDMRC-UHFFFAOYSA-N 3-bromofuran-2-carbaldehyde Chemical compound BrC=1C=COC=1C=O KSAVZSUPQGDMRC-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- ZKTLLQZEGPAYNW-UHFFFAOYSA-N 5-chloronaphthalene-1-carbaldehyde Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1C=O ZKTLLQZEGPAYNW-UHFFFAOYSA-N 0.000 description 1
- XOFUWTYISOTGCT-UHFFFAOYSA-N 5-methoxyquinoline-2-carbaldehyde Chemical compound COc1cccc2nc(C=O)ccc12 XOFUWTYISOTGCT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- DCOVVYNGZMFMOA-UHFFFAOYSA-N formaldehyde;3-methylpyridine Chemical compound O=C.CC1=CC=CN=C1 DCOVVYNGZMFMOA-UHFFFAOYSA-N 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- ODVRHJKVXOGKEJ-UHFFFAOYSA-N iron 5,10,15,20-tetraphenyl-21,23-dihydroporphyrin Chemical compound [Fe].c1cc2nc1c(-c1ccccc1)c1ccc([nH]1)c(-c1ccccc1)c1ccc(n1)c(-c1ccccc1)c1ccc([nH]1)c2-c1ccccc1 ODVRHJKVXOGKEJ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing trivalent tetraaryl ferriporphyrin by pyrrole, aromatic aldehyde and ferrous salt. The reaction process is as follows: adding anhydrous aluminum trichloride, aryl aldehyde, pyrrole and ferrous salt into DMF in sequence under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuing heating for a certain time, stopping the reaction, cooling, standing at 273K for overnight, and performing suction filtration to obtain the ferroporphyrin. The method directly uses aromatic aldehyde, pyrrole and ferrous chloride as raw materials, does not need porphin or strong corrosive organic acid as a solvent, obtains high-purity tetraarylferriporphyrin at a high yield without adopting a complex separation means, and is easy to realize industrial production.
Description
Technical Field
The invention relates to a method for synthesizing trivalent tetraaryl ferriporphyrin by pyrrole, aromatic aldehyde and ferrous salt, in particular to a method for synthesizing tetraaryl ferriporphyrin in one step by taking aromatic aldehyde, pyrrole and ferrous chloride as raw materials and using anhydrous aluminum trichloride as a catalyst in a DMF solvent, belonging to the field of organic synthesis.
Background
Iron porphyrin is a substance widely present in the human and animal bodies, and iron porphyrin can be extracted from the blood of animals as heme. In the animal body, the main functions of iron porphyrin are oxygen carrying and oxygen activation. In industrial production and life, iron porphyrin is mainly used as a catalyst for chemical oxidation and electric and photo-oxidation. The iron porphyrin commonly used as a catalyst is a tetraaryliron porphyrin. The chemical synthesis method of the tetraarylporphyrin iron reported in the literature and the patent at present is generally based on the basic reaction of tetraarylporphyrin iron as a raw material with ferrous salt reported by Adler et al (J.Inorg.Nucl.chem.,1970,32, 2443). The chemical process comprises the following steps:
during the reaction, ferrous ions coordinate with tetraarylporphine to form a very unstable ferrous porphyrin intermediate, which then rapidly converts to a stable ferric porphyrin. Patent CN103880851B discloses a method for producing iron porphyrin on an industrial scale by a continuous process by reacting the above tetraarylporphine as a raw material with a ferrous salt. The biggest disadvantage of this reaction is that the raw material tetraarylporphine used for the synthesis of iron porphyrin is expensive. In addition, in the reaction process, the product ferric porphyrin is easy to form a byproduct, namely the biferroporphyrin through dimerization reaction, and the ferric porphyrin and the biferroporphyrin are mixed together and need to be separated to obtain pure ferric porphyrin.
From the existing literature, it is also found that the zinc porphyrin is synthesized in one step by taking aryl aldehyde, pyrrole and zinc salt as raw materials. Badger et al reported the one-step synthesis of zinc porphyrins starting from aryl aldehydes, pyrroles, zinc salts in an autoclave (Australian Jchem,1964,19, 1028).
However, this reaction condition cannot be used for preparing iron porphyrin, and in propionic acid solvent and under high temperature and high pressure, ferrous salt is rapidly converted into ferric salt, and ferric iron cannot form iron porphyrin.
In view of the fact that zinc porphyrin can be replaced by iron salt to obtain iron porphyrin (chemical science and technology, 2000, 8, 1; university of shenyang university of industry, 2010, 60; chemical research and application, 2012, 24, 154), patent CN1238355C discloses a reaction in which aryl aldehyde, pyrrole, and zinc salt are used as raw materials to obtain a mixture of zinc porphyrin and porphine without using an autoclave, and then the mixture of zinc porphyrin and porphine is reacted with ferrous chloride to synthesize iron porphyrin.
In the above process, the intermediate products of zinc porphyrin and porphine need to be obtained through a separation process, while the propionic acid solvent used in the first step is an organic acid, which has strong corrosivity, and in addition, if iron salt is directly added into the propionic acid system, iron porphyrin cannot be obtained.
Disclosure of Invention
Aiming at the defect that the prior art lacks a method for synthesizing iron porphyrin by aldehyde, pyrrole and ferric salt in one step and needs to synthesize the tetraaryl iron porphyrin from the oxidation metallization reaction of expensive tetraaryl porphine and ferrous salt or the metal replacement reaction of expensive tetraaryl zinc porphyrin and ferrous salt, the invention aims to provide a method for synthesizing the tetraaryl iron porphyrin by reacting aryl aldehyde, pyrrole and inorganic ferrous salt which are basic organic raw materials in one step and obtaining the high-purity tetraaryl iron porphyrin with high yield without adopting a complicated separation means, and the method is easy to realize industrial production.
The reaction raw materials selected for realizing the invention are simple organic raw materials of aromatic aldehyde, pyrrole and inorganic salt ferrous chloride, the reaction solvent is DMF, and the catalyst is aprotic inorganic acid anhydrous aluminum trichloride.
The chemical reactions on which the invention is based are as follows:
the aryl Ar can be a benzene ring or an aromatic heterocyclic ring such as pyridine, pyrrole, furan, naphthalene, quinoline and the like;
the substituent R on the aryl group Ar may be an alkyl substituent such as methyl, ethyl or propyl, or a halogen substituent such as chlorine, bromine or iodine, or an oxygen-containing substituent such as methoxy, ethoxy, hydroxy or carboxyl, or a nitrogen-containing substituent such as amino, dimethylamino or nitro.
The operation process for realizing the invention is as follows: adding DMF into a common reflux stirring reactor at room temperature, starting stirring, and sequentially adding anhydrous aluminum trichloride, aryl aldehyde, pyrrole and ferrous salt. And introducing nitrogen, heating, refluxing and reacting for 0.5 hour, removing the nitrogen, continuously heating for a certain time, and stopping the reaction. Cooling, standing overnight near 273K, and performing suction filtration to obtain the porphyrin iron purple crystal.
Aryl aldehydes, pyrroles, ferrous salts and anhydrous AlCl3The charging ratio (molar ratio) of (A) is as follows: 1-1.5: 1-1.5: 1-5:1-5, preferably in a ratio of 1:1:1.5: 1.5;
molar ratio of pyrrole to DMF 1: 500-: 1000, parts by weight;
the reaction time is 0.5 to 3 hours, preferably 1 hour.
The reaction requires the addition of all reactants at room temperature followed by heating to reflux. If the reactants are added after the reflux, or the ferrous salt is added after the reflux, the desired product cannot be obtained, or the product yield is reduced.
According to the technical scheme, condensation of aromatic aldehyde and pyrrole and metallization of a condensation product and ferrous ions occur simultaneously, so that the two-step reaction in the prior art for synthesizing the tetraaryl ferriporphyrin by taking the aromatic aldehyde and the pyrrole as raw materials is changed into one-step reaction, and meanwhile, the ferrous ions also play a role of a template in the condensation process of the aromatic aldehyde and the pyrrole so as to improve the condensation yield; aprotic acid anhydrous AlCl3The catalyst is used as an acid catalyst, can promote the condensation of aromatic aldehyde and pyrrole, can avoid the defect that ferrous ions are converted into ferric ions which cannot be subjected to a metallization reaction with porphin in a proton environment, and can ensure that ferrous salts are not converted into ferric ions before the reaction; AlCl3The provided acidic environment can also prevent the product of the tetraaryliron porphyrin from further reacting to form a bis-tetraarylporphyrin iron dimer by-product; use of DMF as solvent to dissolve anhydrous AlCl3Is favorable for exerting AlCl3The difference of DMF in the solubility to organic hydrocarbon substances and metal compounds leads the tetra-aryl ferriporphyrin to be crystallized and separated out at low temperature, and various intermediate impurities formed by condensation of aromatic aldehyde and pyrrole can not be separated out along with the product in the reaction process, thus leading the separation of the tetra-aryl ferriporphyrin to be simple.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) compared with the prior art for synthesizing the tetra-aryl ferriporphyrin by taking the porphin as a raw material, the raw materials of the aromatic aldehyde and the pyrrole used in the invention are more economical and easily obtained than the porphin, and the formation of a byproduct of the product, namely the tetra-aryl ferriporphyrin, which is further dimerized into the bisferriporphyrin can be effectively avoided, so that the product purity is improved, and the separation process is simplified;
2) compared with the prior art for synthesizing the tetraaryl ferriporphyrin by taking the aromatic aldehyde and the pyrrole as raw materials, the method only needs one-step reaction, does not need to use a special device, reduces the reaction steps, has the highest product yield reaching 57 percent under the optimal condition, can avoid the use of a large amount of corrosive organic acid, and has good environmental benefit.
3) The technical scheme of the invention has simple steps and strong operability, and meets the requirements of industrial production.
Examples
The following examples are intended to further illustrate the present invention without limiting the scope of the claims and, unless otherwise indicated, all starting materials in the examples are commercially available conventional materials.
The first embodiment is as follows:
adding 500m L DMF into a stirring reactor with a reflux condenser tube, sequentially adding 0.75 mol of anhydrous aluminum trichloride, 0.5 mol of benzaldehyde, 0.5 mol of pyrrole and 0.75 mol of ferrous chloride under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuously heating for 0.5 hour, stopping the reaction, cooling, standing overnight at 273K, and performing suction filtration to obtain tetraphenylporphyrin iron purple brown crystals with the yield of 57%.
Example two:
adding 1800m L DMF into a stirring reactor with a reflux condenser tube, sequentially adding 1 mol of anhydrous aluminum trichloride, 0.8 mol of 3-methylpyridine formaldehyde, 0.6 mol of pyrrole and 1.5 mol of ferrous chloride under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuously heating for 0.7 hour, cooling, standing overnight at 273K, and performing suction filtration to obtain a tetra (3-methylpyridine) porphyrin iron purple brown crystal with the yield of 50%.
Example three:
adding 2800m L DMF into a stirring reactor with a reflux condenser tube, adding 1.2 mol of anhydrous aluminum trichloride, 0.8 mol of 2-ethylpyrrolecarboxaldehyde, 0.7 mol of pyrrole and 2 mol of ferrous chloride in turn under stirring, introducing nitrogen, heating for reflux reaction for 0.5 h, removing the nitrogen, continuing heating for 1.5 h, cooling, standing overnight at 273K, and performing suction filtration to obtain a tetra (2-ethylpyrrole) porphyrin iron purple brown crystal with the yield of 32%.
Example four:
adding 1500m L DMF into a stirring reactor with a reflux condenser tube, sequentially adding 0.75 mol of anhydrous aluminum trichloride, 0.75 mol of 5-chloro-1-naphthaldehyde, 0.75 mol of pyrrole and 2 mol of ferrous chloride under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuously heating for 1.5 hours, cooling, standing overnight at 273K, and performing suction filtration to obtain tetra (5-chloro-1-naphthyridine) porphyrin iron purple crystals with the yield of 53%.
Example five:
adding 1000m L DMF into a stirring reactor with a reflux condenser tube, adding 1 mol of anhydrous aluminum trichloride, 0.6 mol of 3-bromofurfural, 0.5 mol of pyrrole and 1.8 mol of ferrous chloride in turn under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuing heating for 1.3 hours, cooling, standing overnight at 273K, and performing suction filtration to obtain tetra (3-bromofuran) porphyrin iron purple red crystal with the yield of 45%.
Example six:
adding 1500m L DMF into a stirring reactor with a reflux condenser tube, sequentially adding 0.5 mol of anhydrous aluminum trichloride, 0.7 mol of 5-methoxy-2-quinolinecarboxaldehyde, 0.5 mol of pyrrole and 1.2 mol of ferrous chloride under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuing heating for 2.5 hours, cooling, standing overnight at 273K, and performing suction filtration to obtain tetra (5-methoxy-2-quinoline) porphyrin iron purple crystals with the yield of 25%.
Example seven:
adding 2500m L DMF into a stirring reactor with a reflux condenser tube, sequentially adding 2 mol of anhydrous aluminum trichloride, 0.75 mol of 4-hydroxybenzaldehyde, 0.5 mol of pyrrole and 2 mol of ferrous chloride under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuing heating for 2 hours, cooling, standing overnight at 273K, and performing suction filtration to obtain a light green crystal of tetra (4-hydroxyphenyl) porphyrin iron with the yield of 30%.
Example eight:
adding 2000m L DMF into a stirring reactor with a reflux condenser tube, adding 2.5 mol of anhydrous aluminum trichloride, 0.5 mol of 3-aminobenzaldehyde, 0.5 mol of pyrrole and 1.5 mol of ferrous chloride in turn under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuing heating for 1.5 hours, cooling, standing overnight at 273K, and performing suction filtration to obtain a tetra (3-aminophenyl) porphyrin iron blue crystal with the yield of 18%.
Example nine:
adding 1800m L DMF into a stirring reactor with a reflux condenser tube, sequentially adding 2 mol of anhydrous aluminum trichloride, 0.6 mol of 4-carboxybenzaldehyde, 0.5 mol of pyrrole and 2.2 mol of ferrous chloride under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuously heating for 1 hour, cooling, standing overnight at 273K, and performing suction filtration to obtain a purple crystal of tetra (4-carboxyphenyl) porphyrin iron with the yield of 25%.
Example ten:
adding 1500m L DMF into a stirring reactor with a reflux condenser tube, sequentially adding 0.8 mol of anhydrous aluminum trichloride, 0.6 mol of 4-nitrobenzaldehyde, 0.5 mol of pyrrole and 2.5 mol of ferrous chloride under stirring, introducing nitrogen, heating for reflux reaction for 0.5 hour, removing the nitrogen, continuously heating for 0.3 hour, cooling, standing overnight at 273K, and performing suction filtration to obtain purple tetra (4-nitrophenyl) porphyrin iron crystals with the yield of 15%.
Claims (6)
1. A method for synthesizing trivalent tetraarylferriporphyrin from pyrrole, aromatic aldehyde and ferrous salt is characterized in that:
aromatic aldehyde, pyrrole and ferrous chloride are taken as raw materials, and anhydrous aluminum trichloride is taken as a catalyst in DMF solvent to synthesize the trivalent tetraaryl ferriporphyrin in one step. The reaction process is as follows: adding DMF into the reflux stirring reactor at room temperature, starting stirring, and sequentially adding anhydrous aluminum trichloride, aryl aldehyde, pyrrole and ferrous salt. And introducing nitrogen, heating, refluxing and reacting for 0.5 hour, removing the nitrogen, continuously heating for a certain time, and stopping the reaction. Cooling, standing overnight near 273K, and performing suction filtration to obtain the porphyrin iron crystal.
2. The method of claim 1, wherein the synthesis of the trivalent tetraarylferriporphyrin from pyrrole, aromatic aldehyde and ferrous salt is as follows: the synthesized product, namely the tetraarylferriporphyrin, has a structure shown in the scheme I:
the aryl Ar can be benzene ring and aromatic heterocyclic ring such as pyridine, pyrrole, furan, naphthalene, quinoline and the like;
the substituent R on the aryl group Ar may be an alkyl substituent such as methyl, ethyl or propyl, or a halogen substituent such as chlorine, bromine or iodine, or an oxygen-containing substituent such as methoxy, ethoxy, hydroxy or carboxyl, or a nitrogen-containing substituent such as amino, dimethylamino or nitro.
3. The method for synthesizing tetraaryl ferriporphyrin according to claim 1, characterized in that: the input ratio (molar ratio) of aryl aldehyde, pyrrole, ferrous salt and anhydrous AlCl3 is as follows: 1-1.5: 1-1.5: 1-5:1-5, preferably in a ratio of 1:1:1.5: 1.5.
4. The method for synthesizing trivalent tetraarylferriporphyrin from pyrrole, aromatic aldehyde and ferrous salt according to claim 1, wherein: the molar concentration of pyrrole in DMF is 1/500-1/5000, the preferred ratio is 1/1000.
5. The method of claim 1, wherein the synthesis of the trivalent tetraarylferriporphyrin from pyrrole, aromatic aldehyde and ferrous salt is as follows: the reaction time is 0.5 to 3 hours, preferably 1 hour.
6. The method of claim 1, wherein the synthesis of the trivalent tetraarylferriporphyrin from pyrrole, aromatic aldehyde and ferrous salt is as follows: the reaction was carried out under refluxing DMF.
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