CN109824679A - A kind of preparation method of substituted aryl porphyrin - Google Patents
A kind of preparation method of substituted aryl porphyrin Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of substituted aryl porphyrin, comprising the following steps: a) aromatic aldehyde shown in formula (1) is dissolved in reaction dissolvent, obtains lysate；B) pyrrolo- is added dropwise under the conditions of oxygen-containing gas, in Xiang Suoshu lysate to be reacted, substituted aryl porphyrin shown in formula (2) is formed.Formula (1) aromatic aldehyde is first dissolved in reaction dissolvent by the present invention, again under the conditions of oxygen-containing gas, another reaction raw materials-pyrroles is added dropwise, two kinds of reaction raw materials come into full contact with and react, substituted aryl porphyrin shown in production (2), gained substituted aryl porphyrin are 3,5- substituted aryl porphyrin or 3,4,5- substituted aryl porphyrins.Preparation method of the invention can be improved the yield of substituted aryl porphyrin, reduce wastage of material；Meanwhile this method is simple and easy, synthesizes and aoxidizes while carrying out, can directly obtain 3,5- substituted aryl porphyrin, and produce target product in a short time, shortens manufacturing cycle, reduce energy consumption.
Description
Technical field
The present invention relates to technical field of organic synthesis, in particular to a kind of preparation method of substituted aryl porphyrin.
Background technique
Porphyrin is the conjugation ring molecule using the porphines with planar structure as basic structure, be important color developing agent and
Luminescent material, and the raw material of synthesis metalloporphyrin.Therefore, the synthesis of porphyrin and the exploitation of new varieties are of great significance.
The method for synthesizing porphyrin comparative maturity mainly includes Rothemund method (J.Am.Chem.Soc., 1936,58:625)
With Adler method (J.Am.Chem.Soc., 1964,86:3145)；The reaction time is long for the former, is only used for synthesis tetraphenylporphyrin；
Compared with the former, the latter has many advantages, such as that easy to operate, synthetic yield is high；But above two method reaction yield is below
20%, and contain 5%~10% impurity (i.e. dihydro tetraphenylporphyrin).In order to improve product purity, researcher is to Adler
Method has carried out a large amount of improvement: a kind of method is to purify the product containing impurity by the method that column chromatographs；It is another
Scheme is that the product containing impurity is dissolved in such as toluene, dimethylbenzene, in methylene chloride organic solvent, weak oxide is then added
Dihydro tetraphenylporphyrin is oxidized to tetraphenylporphyrin by agent such as 2,3,5,6-tetrachlorophenylhydrazine, 2,3-5,6- dicyano benzoquinone etc..With
Upper two kinds of purification schemes require a large amount of organic solvents, and complicated for operation, process is more, high production cost, are not suitable for further industry
Metaplasia produces.
By be added weak oxidant scheme inspiration, occur successively in recent years by air or oxygen aoxidize method come
Porphyrin compound is prepared, if the patent application of Publication No. CN101550140A and CN102952143A are using Adler method as base
Plinth is disclosed using pyrroles, aromatic aldehyde and air as raw material, and high yield synthesizes the batch process of tetaraary porphyrin.Above-mentioned conjunction
It is related to completing synthesis and oxidation process in two different reactors respectively at method, it is complicated for operation, further relate to the secondary of product
Dissolution, solvent usage is big, high production cost.Publication No. CN103880852A and CN105085536A also disclose with pyrroles,
Aromatic aldehyde and air are the method for Material synthesis porphyrin, and pyrroles is completed at the same time in the same reactor and aromatic aldehyde is polycondensed into
Air oxidation two reactions of chlorin and chlorin, but will appear the continued emissions of fixed gas in reaction process, instead
It answers solvent, unreacted pyrroles and aromatic aldehyde that can be taken away by reaction gas, causes to also create environmental pollution while increased costs.
Above-mentioned the mostly of preparation method preparation are 2,3,4- substituted aryl porphyrins, and from the above, it can be seen that, preparation process is typically more multiple
It is miscellaneous or more not environmentally, higher cost.
Currently, researcher also researches and develops the porphyrin and preparation method thereof of new construction in continuous exploration, it has been investigated that, 3,5- take
It can be reacted with diethyl aluminum chloride for aryl-porphyrin, prepare metalloporphyrin aluminum chloride catalyst, carbon dioxide can be catalyzed
Coupling reaction or copolyreaction occurs with epoxides.It is well known that carbon dioxide is a kind of greenhouse gases, scientists from all over the world are
The development and utilization for very paying close attention to carbon dioxide, is fixed into high molecular material and has become the project being widely noticed.As one
Kind is capable of the catalyst of efficient catalytic carbon dioxide and epoxides copolymerization, and efficiently synthesizing for 3,5- substituted aryl porphyrins has weight
The realistic meaning wanted.The prior art mainly adopts propionic acid methods to prepare 3,5- substituted aryl porphyrin, is being returned using pyrroles and aromatic aldehyde
The control reaction time synthesized at 20 hours or more in stream propionic acid, and product yield made from this method is not good enough, 45% hereinafter, separately
Outside, generated time is longer, usually needs 20 hours or so, energy consumption is larger, integrates, and preparation cost is higher, is unfavorable for scale
Change production application.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation methods of substituted aryl porphyrin.It is provided by the invention
Preparation method can be improved the yield of 3,5- substituted aryl porphyrin product, and can be completed in a short time preparation, can drop significantly
Low energy consumption, and advantageously reduce production cost.
The present invention provides a kind of preparation methods of substituted aryl porphyrin, comprising the following steps:
A) aromatic aldehyde shown in formula (1) is dissolved in reaction dissolvent, obtains lysate；
B) pyrrolo- is added dropwise under the conditions of oxygen-containing gas, in Xiang Suoshu lysate to be reacted, is formed and is replaced shown in formula (2)
Aryl-porphyrin；
In the formula (1) and formula (2), R1And R3Be each independently selected from alkyl, alkoxy, hydroxyl, halogen atom, amino or
Nitro；R2Selected from hydrogen atom, alkyl, alkoxy, hydroxyl, halogen atom, amino or nitro.
Preferably, in the step b), the air pressure of oxygen-containing gas is 0.1~1.5MPa；The oxygen content of oxygen-containing gas is
80%~99%.
Preferably, the molar ratio of the pyrroles and aromatic aldehyde shown in formula (1) is 1: (1~1.5).
Preferably, in the step b), dropwise addition carries out at 120~150 DEG C of temperature；
The temperature of the reaction is 120~150 DEG C.
Preferably, the step b) includes:
Under the conditions of oxygen-containing gas, pyrroles is added dropwise in Xiang Suoshu lysate, is added dropwise in 0.1~0.5h, it is subsequent
0.1~1.5h of continuous reaction, forms and replaces porphyrin shown in formula (2).
Preferably, in the step a), the temperature of dissolution is 25~150 DEG C.
Preferably, in the step a), reaction dissolvent is the mixed liquor of acetic acid, acetic acid and propionic acid or is acetic acid and hexamethylene
Mixed liquor.
Preferably, in the step a), concentration of the aromatic aldehyde in reaction dissolvent shown in formula (1) is 50~350mmol/L.
Preferably, the step b) includes:
B1 pyrrolo- is added dropwise) under the conditions of oxygen-containing gas, in Xiang Suoshu lysate to be reacted, reactant is obtained；
B2) by after reaction system cooling, the reactant is filtered, washed and dried, obtain replacing shown in formula (2)
Aryl-porphyrin.
Preferably, the oxygen content of the oxygen-containing gas is 90%~99%.
The present invention provides a kind of preparation methods of substituted aryl porphyrin, comprising the following steps: a) by fragrance shown in formula (1)
Aldehyde is dissolved in reaction dissolvent, obtains lysate；B) pyrrolo- is added dropwise under the conditions of oxygen-containing gas, in Xiang Suoshu lysate to carry out
Reaction, forms substituted aryl porphyrin shown in formula (2).
Aromatic aldehyde shown in reaction raw materials-formula (1) is first dissolved in reaction dissolvent by the present invention, then in oxygen-containing gas condition
Under, another reaction raw materials-pyrroles is added dropwise, two kinds of reaction raw materials come into full contact with and react, substituted aryl shown in production (2)
Porphyrin, gained substituted aryl porphyrin are 3,5- substituted aryl porphyrin or 3,4,5- substituted aryl porphyrins.Preparation method of the invention
It can be improved the yield of substituted aryl porphyrin, reduce wastage of material；In addition, of the invention, preparation method is simple, synthesis and
It aoxidizes while carrying out, 3,5- substituted aryl porphyrin can be directly obtained, and produce substituted aryl Porphyrin Products in a short time,
Manufacturing cycle is substantially reduced, energy consumption is reduced, is integrated, production cost can be substantially reduced.
Test result shows 3,5- substituted aryl porphyrin or 3 made from preparation method of the invention, 4,5- substituted aryl porphins
The yield of quinoline has been obviously improved product yield 50% or more compared with the prior art；Its synthesis can be complete within 2 hours
At being obviously shortened manufacturing cycle compared with the prior art.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the nuclear magnetic spectrogram of 1 products therefrom of embodiment.
Specific embodiment
The present invention provides a kind of preparation methods of substituted aryl porphyrin, comprising the following steps:
A) aromatic aldehyde shown in formula (1) is dissolved in reaction dissolvent, obtains lysate；
B) pyrrolo- is added dropwise under the conditions of oxygen-containing gas, in Xiang Suoshu lysate to be reacted, is formed and is replaced shown in formula (2)
Aryl-porphyrin；
In the formula (1) and formula (2), R1And R3Be each independently selected from alkyl, alkoxy, hydroxyl, halogen atom, amino or
Nitro；R2Selected from hydrogen atom, alkyl, alkoxy, hydroxyl, halogen atom, amino or nitro.
Aromatic aldehyde shown in reaction raw materials-formula (1) is first dissolved in reaction dissolvent by the present invention, then in oxygen-containing gas condition
Under, another reaction raw materials-pyrroles is added dropwise, two kinds of reaction raw materials come into full contact with and react, substituted aryl shown in production (2)
Porphyrin, gained substituted aryl porphyrin are 3,5- substituted aryl porphyrin or 3,4,5- substituted aryl porphyrins.Preparation method of the invention
It can be improved the yield of substituted aryl porphyrin, reduce wastage of material；In addition, of the invention, preparation method is simple, synthesis and
It aoxidizes while carrying out, 3,5- substituted aryl porphyrin can be directly obtained, and produce substituted aryl Porphyrin Products in a short time,
Manufacturing cycle is substantially reduced, energy consumption is reduced, is integrated, production cost can be substantially reduced.
According to the present invention, first aromatic aldehyde shown in formula (1) is dissolved in reaction dissolvent, obtains lysate.
In the present invention, the aromatic aldehyde of use has structure shown in formula (1):
Wherein, R1And R3It is each independently selected from alkyl, alkoxy, hydroxyl, halogen atom, amino or nitro；The alkyl is excellent
It is selected as the alkyl of C1~C4.R2Selected from hydrogen atom, alkyl, alkoxy, hydroxyl, halogen atom, amino or nitro；The alkyl is preferred
For the alkyl of C1~C4.The present invention is not particularly limited the source of the aromatic aldehyde, for general commercially available product or according to this field
Preparation method known to technical staff obtains.
In the present invention, the reaction dissolvent is preferably the mixed liquor of acetic acid, acetic acid and propionic acid or for acetic acid and hexamethylene
Mixed liquor；More preferably acetic acid.Solvent can not only be used for using above-mentioned reaction dissolvent, the catalyst of reaction is alternatively arranged as, after promotion
The progress of continuous synthetic reaction.In the present invention, when the reaction dissolvent is the mixed liquor of acetic acid and propionic acid, the volume of acetic acid and propionic acid
Than being preferably 2: (0~1).When the reaction dissolvent is the mixed liquor of acetic acid and hexamethylene, the volume ratio of acetic acid and hexamethylene is excellent
It is selected as 2: (0~1).
In the present invention, concentration of the aromatic aldehyde in reaction dissolvent shown in the formula (1) is preferably 50~350mmol/L, more
Preferably 200~300mmol/L.
In the present invention, when aromatic aldehyde shown in formula (1) to be dissolved in reaction dissolvent, the mode of dissolution does not have special limit
System, can sufficiently dissolve raw material, such as can promote dissolution by stirring.In the present invention, the temperature of the dissolution is preferably
25~150 DEG C, more preferably 80~100 DEG C.
According to the present invention, after obtaining lysate, pyrrolo- is added dropwise under the conditions of oxygen-containing gas, in Xiang Suoshu lysate and carries out
Reaction, forms substituted aryl porphyrin shown in formula (2).
In the present invention, subsequent mixing and reaction process are carried out under the conditions of oxygen-containing gas, it, can under the conditions of oxygen-containing gas
Intermediate product chlorin is oxidized to substituted aryl porphyrin, directly obtains substituted aryl Porphyrin Products.It is described to contain in the present invention
The air pressure of carrier of oxygen is preferably 0.1~1.5MPa, and subsequent reactions are carried out under above-mentioned air pressure conditions, advantageously reduces oxygen damage
It loses, and then chlorin is promoted to be converted to porphyrin, improve porphyrin yield, and equipment requirement can also be reduced, guarantee safe operation
Property.
Wherein, the oxygen content of the oxygen-containing gas is preferably 80%~99%, and more preferably 90%~99%.The present invention
In, the ratio of the oxygen content refers to volume ratio, i.e. the oxygen volume ratio that accounts for oxygen-containing gas total amount.The present invention is to the oxygen-containing gas
Composition be not particularly limited, meet above-mentioned oxygen content, such as the gaseous mixture of air, oxygen and other gases.
In the present invention, when introducing pyrroles's raw material into the lysate, introduced by the way of dropwise addition.By the way that pyrrole is added dropwise
The mode coughed up makes aromatic aldehyde in system be constantly in excessive state, and pyrroles can be made to come into full contact with aromatic aldehyde, thus favorably
In the conversion of pyrroles, pyrroles can be made more to be polycondensed into porphyrin ring with aromatic aldehyde, rather than generate two polypyrroles, and then advantageous
The generation of the substituted aryl porphyrin shown in formula (2), and improve yield.
In the present invention, the pyrroles and the molar ratio of aromatic aldehyde shown in formula (1) are preferably 1: (1~1.5).
In the present invention, when being added dropwise pyrroles into lysate, preferably it is added dropwise in 0.1~0.5h.After completion of dropwise addition,
0.1~1.5h of reaction is preferably continued to, that is, forms substituted aryl porphyrin shown in formula (2).Compared with the prior art, the present invention is small 2
When it is interior mixing and reaction can be completed, substantially reduce manufacturing cycle, reduce energy consumption, improve production efficiency.
In the present invention, the dropwise addition is preferably carried out at 120~150 DEG C of temperature；Specifically, lysate can be risen in advance
120~150 DEG C, pyrroles is then added dropwise thereto.In the present invention, in the reaction process, temperature is preferably 120~150 DEG C.
In the present invention, after the reaction, it is also preferable to include: after reaction system cooling, gained reactant was carried out
Filter, washing and drying, and then obtain substituted aryl porphyrin shown in formula (2).In the present invention, it is preferably cooled to 20~35 DEG C.Institute
After stating cooling, the recycling of oxygen-containing gas is preferably also carried out.After cooling, comprising remaining oxygen-containing gas and cooling anti-in reaction system
Object is answered, can first be recycled oxygen-containing gas；Specifically, oxygen-containing gas can be delivered to air accumulator by pumping, it is oxygen-containing in air accumulator
Gas can be reused for synthetic reaction after compression, recycle oxygen-containing gas.
After gas phase is recycled, then reactant is post-processed, in the present invention, filtration treatment is first carried out, by solid reaction
Object and remaining reaction dissolvent etc. separate；Separating obtained filtrate can recycle reaction dissolvent by simple process, utilize again, Bu Huiying
Ring the yield and purity of porphyrin.The present invention is not particularly limited the processing mode of filtrate, according to known to those skilled in the art
The mode of recycling design carry out, such as can by way of distillation recycling design.
After filtering, obtained solid reactant is washed.In the present invention, the washing preferably includes organic solvent and washes
It washs and is washed with hot water.The type of the organic solvent is not particularly limited, and is well known to those skilled in the art for washing
Solvent is save the cost and improves safety, and the organic solvent preferably includes one or more of methanol and ethyl alcohol.
The usage amount of the organic solvent is preferably the 30%~50% of the reaction dissolvent.After above-mentioned organic solvent washing, carry out
Hot water washing；The temperature of the hot water is preferably 60~90 DEG C.
After the washing, preferably also it is dried.The present invention is not particularly limited the temperature of the drying, can incite somebody to action
Remaining washing reagent removal on solid product, specific drying temperature can be 50~80 DEG C.
In the present invention, above-mentioned preparation process carries out preferably in pressure reactor, and closing carries out porphin in pressure reactor
Quinoline synthesis, can reduce oxygen loss, improve oxygen content in reaction system, and being more advantageous to chlorin, (prior art mesoporphyrin is received
Rate is low mainly due to generating chlorin) it is converted to porphyrin, improve porphyrin yield；And during the preparation process without any gas
Body discharge, is also convenient for collecting unreacted residual gas after the completion of reaction, reduces exhaust process and take organic solvent out of, reduces
Environmental pollution.Specifically, first aromatic aldehyde shown in formula (1) can be dissolved in the voltage-resistant reactor equipped with reaction dissolvent, heat up
It is passed through to target temperature, then by oxygen-containing gas from reactor bottom, and controls the air pressure of oxygen-containing gas, pyrrolo- is then added dropwise again
It is reacted, forms substituted aryl porphyrin shown in formula (2).Then it cools down, oxygen-containing gas pump is delivered to air accumulator, then by institute
It obtains reactant to be filtered, washed and dried, obtains substituted aryl porphyrin shown in formula (2).
The present invention provides a kind of preparation methods of substituted aryl porphyrin, first that aromatic aldehyde shown in reaction raw materials-formula (1) is molten
Another reaction raw materials-pyrroles is added dropwise in reaction dissolvent, then under the conditions of oxygen-containing gas in solution, and two kinds of reaction raw materials come into full contact with
And react, substituted aryl porphyrin shown in production (2), gained substituted aryl porphyrin be 3,5- substituted aryl porphyrin or 3,4,
5- substituted aryl porphyrin.Preparation method of the invention can be improved the yield of substituted aryl porphyrin, reduce wastage of material；In addition,
Of the invention preparation method is simple, synthesis and oxidation while carrying out, and can directly obtain 3,5- substituted aryl porphyrin or 3, and 4,
5- substituted aryl porphyrin, and substituted aryl Porphyrin Products are produced in a short time, manufacturing cycle is substantially reduced, is reduced
Energy consumption integrates, and can substantially reduce production cost.
Test result shows 3,5- substituted aryl porphyrin or 3 made from preparation method of the invention, 4,5- substituted aryl porphins
The yield of quinoline has been obviously improved product yield 50% or more compared with the prior art；Its synthesis is completed within 2 hours, phase
Than being obviously shortened manufacturing cycle in the prior art.
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Embodiment 1
3,5- dimethoxy benzaldehyde 126g is dissolved in the 3L voltage-resistant reactor equipped with 2.5L acetic acid solution, by temperature
It is raised to 130 DEG C；Oxygen-containing gas (oxygen content 85%) is passed through reactor from reactor bottom, pressure is controlled in 1.5MPa；
42mL pyrroles is added drop-wise in reactor in 0.5h, after reacting 1.5h, is cooled to 30 DEG C of stopping reactions；It will be oxygenous after cooling
Body is discharged into air accumulator, and filter cake is obtained by filtration to reactant obtained in reactor, washs filter cake with 1.0L methanol, then uses
0.4L hot water washs filter cake, obtains 77.6g product after dry.It is stand-by that filtering gained filtrate can recycle acetic acid by air-distillation.
Nuclear magnetic spectrogram detection is carried out to products therefrom, as a result as shown in FIG. 1, FIG. 1 is the nuclear-magnetism of 1 products therefrom of embodiment spectrums
Figure.As shown in Figure 1, products therefrom is formula (1) structure, wherein R1And R3For-OCH3, R2For H.
According to the material quantity of investment and products therefrom amount, and following formula is combined to calculate product yield: synthesis yield=reality virtue
Base replaces quality/pyrroles of porphyrin to be fully converted to the quality that aryl replaces porphyrin.The results show that product yield is 60.0%.
By column chromatography for separation method test product purity, the results show that products therefrom purity is 99.7%.
Embodiment 2
3,5- dimethylbenzaldehyde 82g is dissolved in the 3L voltage-resistant reactor equipped with 2.5L acetic acid solution, by temperature liter
To 130 DEG C；Oxygen-containing gas (oxygen content 99%) is passed through reactor from reactor bottom, pressure is controlled in 0.5MPa；?
42mL pyrroles is added drop-wise in reactor in 0.2h, after reacting 1.5h, is cooled to 30 DEG C of stopping reactions；By oxygen-containing gas after cooling
It is discharged into air accumulator, and filter cake is obtained by filtration to reactant obtained in reactor, filter cake is washed with 1.0L methanol, then uses
0.4L hot water washs filter cake, obtains 55.1g product after dry.It is stand-by that filtering gained filtrate can recycle acetic acid by air-distillation.
Product is characterized according to the detection method of embodiment 1, the results show that products therefrom is formula (1) structure,
In, R1And R3For-CH3, R2For H.
Product yield and purity are tested according to the test method of embodiment 1, the results show that product yield is 50.0%, it is pure
Degree is 99.6%.
Embodiment 3
3,4,5-Trimethoxybenzaldehyde 119g is dissolved in the 3L voltage-resistant reactor equipped with 2.5L acetic acid solution, it will be warm
Degree is raised to 150 DEG C；Oxygen-containing gas (oxygen content 80%) is passed through reactor from reactor bottom, pressure control is existed
0.5MPa；42mL pyrroles is added drop-wise in reactor in 0.5h, after reacting 1.4h, is cooled to 20 DEG C of stopping reactions；After cooling
Oxygen-containing gas is discharged into air accumulator, and filter cake is obtained by filtration to reactant obtained in reactor, washs filter with 1.0L methanol
Then cake washs filter cake with 0.4L hot water, obtains 77.0g product after dry.Filtering gained filtrate can be recycled by air-distillation
Acetic acid is stand-by.
Product is characterized according to the detection method of embodiment 1, the results show that products therefrom is formula (1) structure,
In, R1、R2And R3For-OCH3。
Product yield and purity are tested according to the test method of embodiment 1, the results show that product yield is 53.0%, it is pure
Degree is 99.4%.
Embodiment 4
3,5- 4-dihydroxy benzaldehyde 125g is dissolved in the 3L voltage-resistant reactor equipped with 2.5L acetic acid solution, by temperature liter
To 130 DEG C；Oxygen-containing gas (oxygen content 90%) is passed through reactor from reactor bottom, pressure is controlled in 1.0MPa；?
42mL pyrroles is added drop-wise in reactor in 0.3h, after reacting 1.2h, is cooled to 30 DEG C of stopping reactions；By oxygen-containing gas after cooling
It is discharged into air accumulator, and filter cake is obtained by filtration to reactant obtained in reactor, filter cake is washed with 1.0L methanol, then uses
0.4L hot water washs filter cake, obtains 67.2g product after dry.It is stand-by that filtering gained filtrate can recycle acetic acid by air-distillation.
Product is characterized according to the detection method of embodiment 1, the results show that products therefrom is formula (1) structure,
In, R1And R3For-OH, R2For H.
Product yield and purity are tested according to the test method of embodiment 1, the results show that product yield is 60%, purity
It is 99.6%.
Embodiment 5
3,5- dibromo benzaldehyde 160g is dissolved in the 3L voltage-resistant reactor equipped with 2.5L acetic acid solution, temperature is raised to
130℃；Oxygen-containing gas (oxygen content 85%) is passed through reactor from reactor bottom, pressure is controlled in 1.5MPa；?
42mL pyrroles is added drop-wise in reactor in 0.5h, after reacting 1.5h, is cooled to 30 DEG C of stopping reactions；By oxygen-containing gas after cooling
It is discharged into air accumulator, and filter cake is obtained by filtration to reactant obtained in reactor, filter cake is washed with 1.0L methanol, then uses
0.4L hot water washs filter cake, obtains 95g product after dry.It is stand-by that filtering gained filtrate can recycle acetic acid by air-distillation.
Product is characterized according to the detection method of embodiment 1, the results show that products therefrom is formula (1) structure,
In, R1And R3For-Br, R2For H.
Product yield and purity are tested according to the test method of embodiment 1, the results show that product yield is 50.3%, it is pure
Degree is 99.1%.
Embodiment 6
3,5- diaminobenzene formaldehyde 91g is dissolved in the 3L voltage-resistant reactor equipped with 2.5L acetic acid solution, by temperature liter
To 130 DEG C；Oxygen-containing gas (oxygen content 99%) is passed through reactor from reactor bottom, pressure is controlled in 0.8MPa；?
42mL pyrroles is added drop-wise in reactor in 0.3h, after reacting 1.5h, is cooled to 30 DEG C of stopping reactions；By oxygen-containing gas after cooling
It is discharged into air accumulator, and filter cake is obtained by filtration to reactant obtained in reactor, filter cake is washed with 1.0L methanol, then uses
0.4L hot water washs filter cake, obtains 63.5g product after dry.It is stand-by that filtering gained filtrate can recycle acetic acid by air-distillation.
Product is characterized according to the detection method of embodiment 1, the results show that products therefrom is formula (1) structure,
In, R1And R3For-NH2, R2For H.
Product yield and purity are tested according to the test method of embodiment 1, the results show that product yield is 57.0%, it is pure
Degree is 99.7%.
Embodiment 7
3,4,5- trinitrobenzen formaldehyde 210g are dissolved in the 3L voltage-resistant reactor equipped with 2.5L acetic acid solution, by temperature
It is raised to 150 DEG C；Oxygen-containing gas (oxygen content 93%) is passed through reactor from reactor bottom, pressure is controlled in 0.5MPa；
42mL pyrroles is added drop-wise in reactor in 0.5h, after reacting 1.4h, is cooled to 20 DEG C of stopping reactions；It will be oxygenous after cooling
Body is discharged into air accumulator, and filter cake is obtained by filtration to reactant obtained in reactor, washs filter cake with 1.0L methanol, then uses
0.4L hot water washs filter cake, obtains 107.7g product after dry.It is stand-by that filtering gained filtrate can recycle acetic acid by air-distillation.
Product is characterized according to the detection method of embodiment 1, the results show that products therefrom is formula (1) structure,
In, R1、R2And R3For-NO2。
Product yield and purity are tested according to the test method of embodiment 1, the results show that product yield is 61.6%, it is pure
Degree is 99.5%.
By Examples 1 to 7 it is found that compared with the prior art (yield is 45% hereinafter, synthesis cycle was up to for ten a few houres),
Preparation method of the invention can be improved the yield of substituted aryl porphyrin, reduce wastage of material；In addition, preparation method of the invention
It is simple and easy, it synthesis and oxidation while carrying out, can directly obtain 3,5- substituted aryl porphyrin or 3,4,5- substituted aryl porphyrins, and
Substituted aryl Porphyrin Products are produced in a short time, are substantially reduced manufacturing cycle, are reduced energy consumption.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention, including best mode, and but also this field is appointed
What technical staff can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.
It should be pointed out that for those skilled in the art, it without departing from the principle of the present invention, can also be right
Some improvement and modification can also be carried out by the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.This hair
The range of bright patent protection is defined by the claims, and may include those skilled in the art it is conceivable that other implementations
Example.If these other embodiments, which have, is similar to the structural element of claim character express, or if they include with
Equivalent structural elements of the character express of claim without essence difference, are wanted then these other embodiments should also be included in right
In the range of asking.
Claims (10)
1. a kind of preparation method of substituted aryl porphyrin, which comprises the following steps:
A) aromatic aldehyde shown in formula (1) is dissolved in reaction dissolvent, obtains lysate；
B) pyrrolo- is added dropwise under the conditions of oxygen-containing gas, in Xiang Suoshu lysate to be reacted, substituted aryl shown in formula (2) is formed
Porphyrin；
In the formula (1) and formula (2), R1And R3It is each independently selected from alkyl, alkoxy, hydroxyl, halogen atom, amino or nitro；
R2Selected from hydrogen atom, alkyl, alkoxy, hydroxyl, halogen atom, amino or nitro.
2. preparation method according to claim 1, which is characterized in that in the step b), the air pressure of oxygen-containing gas is 0.1
~1.5MPa；The oxygen content of oxygen-containing gas is 80%~99%.
3. preparation method according to claim 1, which is characterized in that mole of the pyrroles and aromatic aldehyde shown in formula (1)
Than being 1: (1~1.5).
4. preparation method according to claim 1, which is characterized in that in the step b), be added dropwise in temperature 120~150
It is carried out at DEG C；
The temperature of the reaction is 120~150 DEG C.
5. preparation method according to claim 1 or 4, which is characterized in that the step b) includes:
Under the conditions of oxygen-containing gas, pyrroles is added dropwise in Xiang Suoshu lysate, is added dropwise in 0.1~0.5h, continues later anti-
0.1~1.5h is answered, is formed and replaces porphyrin shown in formula (2).
6. preparation method according to claim 1, which is characterized in that in the step a), the temperature of dissolution is 25~150
℃。
7. preparation method according to claim 1, which is characterized in that in the step a), reaction dissolvent is acetic acid, acetic acid
With the mixed liquor of propionic acid or be the mixed liquor of acetic acid and hexamethylene.
8. preparation method according to claim 1, which is characterized in that in the step a), aromatic aldehyde shown in formula (1) is anti-
Answering the concentration in solvent is 50~350mmol/L.
9. preparation method according to claim 1, which is characterized in that the step b) includes:
B1 pyrrolo- is added dropwise) under the conditions of oxygen-containing gas, in Xiang Suoshu lysate to be reacted, reactant is obtained；
B2) by after reaction system cooling, the reactant is filtered, washed and dried, substituted aryl shown in formula (2) is obtained
Porphyrin.
10. preparation method according to claim 1 or 2, which is characterized in that the oxygen content of the oxygen-containing gas be 90%~
99%.
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