CN102993206B - Method for synthesising tetraphenylporphyrin metal complex via one-step process - Google Patents
Method for synthesising tetraphenylporphyrin metal complex via one-step process Download PDFInfo
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- CN102993206B CN102993206B CN201210552262.XA CN201210552262A CN102993206B CN 102993206 B CN102993206 B CN 102993206B CN 201210552262 A CN201210552262 A CN 201210552262A CN 102993206 B CN102993206 B CN 102993206B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention discloses a method for synthesising a tetraphenylporphyrin metal complex via a one-step process, comprising the following steps of: (1) dissolving metal acetate in DMF (dimethyl formamide), wherein the ratio of the metal acetate to DMF is 1 g: (8 to 16 ml); (2) adding a solvent, namely, propionic acid, in a reaction container, then sequentially adding benzaldehyde, the DMF solution dissolved with the metal acetate, and a pyrrole solution diluted by propionic acid, and refluxing for 30-120 minutes at a temperature ranging from 120 to 150 DEG C, wherein the molar ratio of benzaldehyde to pyrrole to the metal acetate is 1: 1: (0.25 to 2.5), and the volume ratio of the solvent, namely, propionic acid, to DMF is 1: 1 to 1: 1.5; and (3) after the reaction is concluded, cooling, removing the solvent, and separating to obtain the product. The process has the characteristics of being low in the cost of the used raw materials, moderate in reaction conditions, simple to operate, less in pollution and environment-friendly, changes the previous method of synthesising metalloporphyrin via a two-step process, saves time, and can be used for preparing more tetraphenylporphyrin metal complexes, thus providing more possibility for the applications of various metalloporphyrin dyes to dye-sensitized solar cells.
Description
Technical field
The invention belongs to synthetic chemistry field, be specifically related to a kind of synthetic method of tetraphenylporphyrin metal complexes.
Background technology
Porphyrin is a kind of important organic compound, is used to synthesize various agricultural chemicals, medicine, high-grade dyestuff and various functional materials.It is the main large ring conjugated structure having flexibility concurrently that porphyrins has rigidity, and have certain aromaticity, good stability, spectral response is wide, thus has been widely used.Metal porphyrins plays an important role in medical science, biology, catalysis, material etc., causes the broad interest of people, and there is huge application potential.Tetraphenylporphyrin metal complexes is the intermediate of porphyrin solar cell sensitizing agent, can be used to the porphyrin dye sensitizing agent synthesizing more structures, thus provides more possibility for it is applied in dye sensitization solar battery.
The structure of tetraphenylporphyrin metal complexes is as follows:
Adler(J.Am.Chem.Soc., 1964,84 (15): 3145-3149) a kind of synthetic method of tetraphenylporphyrin metal complexes is reported, the first step is reacted with pyrroles and phenyl aldehyde and is first generated tetraphenylporphyrin under the condition of solvent made by propionic acid, and second step generates metal tetraphenylporphyrin with reacting metal salt again under the condition of chloroform give solvent.This method productive rate is very low, and the first step only has about 15%, and second step is about 80%, and two-step reaction overall yield only has about 12%; And the method reaction process is complicated, the reaction times is longer, not easy to operate.
Summary of the invention
The object of the invention is for overcoming above-mentioned the deficiencies in the prior art, a kind of method of one-step synthesis method tetraphenylporphyrin metal complexes is provided, make the method for two step synthetic metals porphyrins become one-step synthesis, save the time, improve productive rate, be easier to operation.
For achieving the above object, the present invention adopts following technical proposals:
A method for one-step synthesis method tetraphenylporphyrin metal complexes, comprises the following steps:
(1) metal acetate salt is dissolved in DMF(N, dinethylformamide) in, metal acetate salt: DMF=1g:8 ~ 16ml;
(2) first will add solvent propionic acid in reaction vessel, then add phenyl aldehyde sequentially successively, be dissolved with the DMF solution of metal acetate salt and the chromium solution with propionic acid dilution, at 120-150 DEG C of scope internal reflux 30-120min; Wherein the mol ratio of phenyl aldehyde, pyrroles and metal acetate salt is 1:1:0.25 ~ 2.5, and the volume ratio of solvent propionic acid and DMF is 1:1 ~ 1:1.5;
(3), after reaction terminates, cooling, except desolventizing, carries out laminate separation with silicagel column, obtains product.
The volume ratio of described propionic acid and pyrroles for diluting pyrroles is: 3:1 ~ 10:1.
Described metal acetate salt is zinc acetate, neutralized verdigris or nickel acetate.
Step except desolventizing in described step (3) is: be poured into water by cooled reaction solution, carries out suction filtration again, get filter residue after producing precipitation.
The step that described step (3) la m is separated is: the material after desolventizing is dissolved in chloroform after vacuum-drying, employing silica gel is stationary phase, chloroform is that eluent carries out dry method and crosses post, collects the purplish red colour band of the second layer, concentrated, drying, obtains purplish red pressed powder and is product.
Further comprising the steps of before step (2) reaction: reflux pyrroles at 115 DEG C, obtains colourless solution, keep in Dark Place.
The concrete steps of described step (2) are: in reaction vessel, add solvent propionic acid, then phenyl aldehyde is added, stir, reflux at 120-150 DEG C, after temperature-stable, be dissolved with the DMF solution of metal acetate salt with constant pressure funnel instillation, more slowly add with glue head dropper the propionic acid solution being dissolved with pyrroles, after reactant all adds, reaction 30-120min.
Described reflux temperature is 140 DEG C.
The described reaction times is 90min.
Reaction formula of the present invention is:
Wherein M can be the metallic elements such as zinc, copper, nickel.
In the present invention, (1) is original solvent propionic acid because metal acetate salt is insoluble to, and is dissolved in by metal-salt in the DMF solution close with propionic acid boiling point.(2) time due to the DMF solution being dissolved with metal-salt is added propionic acid, being added to a certain amount of rear metal-salt can separate out, and finds that the proportional range of propionic acid and DMF is more suitable when being approximately 1:1 ~ 1:1.5 after experiment.(3) in reaction process, the sequencing that various reactant adds is followed successively by phenyl aldehyde, is dissolved with the DMF solution of metal-salt, the chromium solution of propionic acid dilution, such addition sequence can prevent pyrroles and phenyl aldehyde from synthesizing other forms of polymer effectively, reduces the production loss of target product.(4) due to black solid, in chloroform, dissolve required solvent more, be unsuitable for wet method and cross post, therefore the present invention uses dry method upper prop, more effectively can reduce the loss of product.
Metal-salt is dissolved in after in DMF and directly adds reaction system by the present invention in the process of preparation, and single step reaction directly obtains tetraphenylporphyrin metal complexes.This technique has (1) and uses cheaper starting materials to be easy to get, and can reduce costs, material toxicity is little, less to human injury; (2) reaction conditions gentle, simple to operate, save time; (3) pollution is produced little, friendly to environment.The present invention changes the method in the past using two step synthetic metals porphyrins, saves the time, can prepare more tetraphenylporphyrin metal complexes, thus provides more possibility in various metalloporphyrin application to dye sensitization solar battery.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic resonance figure of the Tetraploid rice of synthesis in embodiment 1.
Fig. 2 is the local spectrogram of the Tetraploid rice of synthesis in embodiment 1.
Embodiment
Below by specific examples, the present invention will be further elaborated, should be noted that following explanation is only to explain the present invention, not limiting its content.
Embodiment 1:
The first step: because pyrroles is placed on easily oxidized in atmosphere for a long time, therefore the pyrroles that first refluxes at 115 DEG C, obtain colourless solution, keep in Dark Place, the pyrroles measuring 0.68ml pours in the propionic acid of 3.5ml, shakes up, with to be used.
Second step: take 2.9g zinc acetate, is dissolved in the DMF solution of 35ml, stirs and makes it dissolve completely, and be poured in constant pressure funnel, with to be used.
3rd step: the propionic acid adding 35ml in the three-necked flask of 100ml, the phenyl aldehyde of 1ml, stir, reflux at 140 DEG C, after temperature-stable, be dissolved with the solution 35ml of the DMF of 2.9g zinc acetate with constant pressure funnel instillation, more slowly add with glue head dropper the propionic acid solution being dissolved with 0.65ml pyrroles, after reactant all adds, reaction 90min.
4th step: after reaction terminates, cooling, pours into product in about 500ml water, occurs a large amount of black solid, suction filtration, by filter residue vacuum-drying.
5th step: product is dissolved in chloroform, then adds silica gel, adopting dry method to cross post, is stationary phase with silica gel, and chloroform, as eluent, collects the purplish red colour band of the second layer, concentrated, dry, obtains violet solid powder 0.36g, productive rate 25%.
Embodiment 2:
Identical with embodiment 1, but the zinc acetate in second step changes neutralized verdigris into, and propionic acid is 1:1.2 with the volume ratio of the DMF solution being dissolved with neutralized verdigris, every gram of neutralized verdigris is dissolved in 15mlDMF solution, is obtained by reacting violet solid powder 0.22g, and productive rate is 15%.
Embodiment 3:
Identical with embodiment 1, but the zinc acetate in second step changes nickel acetate into, and propionic acid is 1:1.5 with the volume ratio of solution of the DMF being dissolved with nickel acetate, every gram of nickel acetate is dissolved in 16mlDMF solution, is obtained by reacting violet solid powder 0.18g, and productive rate is 12%.
Attention: neutralized verdigris and the nickel acetate solubleness in DMF is not very large, by metal-salt grind into powder, will be beneficial to dissolving.
Claims (4)
1. a method for one-step synthesis method tetraphenylporphyrin metal complexes, is characterized in that, comprises the following steps:
(1) metal acetate salt is dissolved in DMF, metal acetate salt: DMF=1g:8 ~ 16ml;
(2) first will add solvent propionic acid in reaction vessel, then add phenyl aldehyde sequentially successively, be dissolved with the DMF solution of metal acetate salt and the chromium solution with propionic acid dilution, at 120-150 DEG C of scope internal reflux 30-120min; Wherein the mol ratio of phenyl aldehyde, pyrroles and metal acetate salt is 1:1:0.25 ~ 2.5, and the volume ratio of solvent propionic acid and DMF is 1:1 ~ 1:1.5;
(3), after reaction terminates, cooling, except desolventizing, carries out chromatographic separation with silicagel column, obtains product;
In described step (3), the step of chromatographic separation is: the material after desolventizing is dissolved in chloroform after vacuum-drying, employing silica gel is stationary phase, chloroform is that eluent carries out dry method and crosses post, collects the purplish red colour band of the second layer, concentrated, drying, obtains purplish red pressed powder and is product;
Further comprising the steps of before step (2) reaction: at 115 DEG C, to distill pyrroles, obtain colourless solution, keep in Dark Place;
The volume ratio of described propionic acid and pyrroles for diluting pyrroles is: 3:1 ~ 10:1.
2. method according to claim 1, is characterized in that, described metal acetate salt is zinc acetate, neutralized verdigris, nickel acetate.
3. method according to claim 1, is characterized in that, the step except desolventizing in described step (3) is: be poured into water by cooled reaction solution, carries out suction filtration again, get filter residue after producing precipitation.
4. method according to claim 1, it is characterized in that, the concrete steps of described step (2) are: in reaction vessel, add solvent propionic acid, then add phenyl aldehyde, stir, reflux at 120-150 DEG C, after temperature-stable, be dissolved with the DMF solution of metal acetate salt with constant pressure funnel instillation, more slowly add with glue head dropper the propionic acid solution being dissolved with pyrroles, after reactant all adds, reaction 30-120min.
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| CN111606913A (en) * | 2020-06-08 | 2020-09-01 | 沅江华龙催化科技有限公司 | Synthesis method of tetraaryl nickel porphyrin catalyzed by anhydrous aluminum trichloride |
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| CN114887077A (en) * | 2022-02-15 | 2022-08-12 | 浙江大学 | Preparation method of organic metal nano material with mitochondrion targeting capability |
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