JPH0959280A - Catalyst for synthesizing porphyrin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for synthesizing porphyrin, having a high yield of porphyrin, repeatedly usable. SOLUTION: This catalyst for synthesizing porphyrin comprises a porous body having a great number of pores. The pores have pore diameters showing the maximum peak in the pore diameter distribution curve in the region of 1-10nm and >=60% of the pores have diameters in the region of the pore diameter showing the maximum peak in the pore diameter distribution curve ±40%. The porous body is an Si oxide and prefetably consists of a crystalline three- dimensional structure. Aluminum is preferably introduced into the porous body.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for synthesizing porphyrin.

[0002]

2. Description of the Related Art Porphyrin is a generic term for derivatives in which methyl, ethyl, vinyl, allyl, phenyl and other groups are introduced at positions 1 to 8 (and α to δ) of the porphine nucleus shown in "Chemical Formula 1". To do. Porphyrins play important roles in the body such as oxygen transport, oxidation reaction, and electron transfer. Porphyrins also act effectively as catalysts for epoxidation of double bonds, hydrogenation of aromatic or fatty acid compounds and reduction of ketones. Photochemical hole burning (PHB) has been confirmed at low temperatures, and its application to the electronics field such as optical recording materials is also drawing attention.

[0003]

Embedded image

Further, porphyrin is a packing material for high performance liquid chromatography (JP-A-4-148860),
It is used as a conductor for an electrocatalyst (JP-A-2-291602), a deodorant filter (JP-A-1-288318), an oxygen concentration detection reagent (JP-A-57-46154), and the like.

The above porphyrins have hitherto been synthesized using, for example, a homogeneous catalyst such as boron trifluoride (BF ₃ .OEt ₂ ) and trifluoroacetic acid, and a solid catalyst such as acid-treated montmorillonite. However, since a homogeneous catalyst exerts a catalytic action in a state of being dissolved in a solvent, separation operation after the reaction takes time.

On the other hand, since the solid catalyst does not dissolve in the solvent, separation after the reaction is easy. In addition, when an oxidizing agent such as p-chloranil is added, the presence of the solid catalyst causes the oxidizing agent to adhere to the surface of the solid catalyst, so that the treatment for separating the oxidizing agent after the reaction is easy. In addition, acid-treated montmorillonite is a good catalyst for porphyrin because it has mesopores that can serve as a synthesis site for porphyrin.

[0007]

However, the mesopores of the acid-treated montmorillonite have a so-called card house structure in which the edges and surfaces of the silicate layer of montmorillonite are randomly contacted. Therefore, the pore size of mesopores is not necessarily constant and has a certain degree of distribution.

Since porphyrin has a cyclic molecular structure, its yield is highest in mesopores having a pore size suitable for the molecular size. Therefore, when acid-treated montmorillonite with a certain distribution of pore size is used as described above, the amount of by-products other than the target product porphyrin, for example, chain molecules, increases, and porphyrin There is a problem that the yield cannot be increased sufficiently.

In view of such conventional problems, the present invention aims to provide a porphyrin synthesis catalyst having a high porphyrin yield.

[0010]

The present invention relates to a catalyst for synthesizing porphyrin, which is composed of a porous body having a large number of pores, wherein the pores show the maximum peak in the pore size distribution curve. The pore diameter is in the range of 1 to 10 nm, and 60% or more of the pores have a diameter within the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve. And a catalyst for porphyrin synthesis.

Porphyrins are porphine nuclei 1 to 8 (and α to δ) shown in "Chemical Formula 1" above.
At the position of methyl, ethyl, vinyl, allyl, phenyl,
It is a general term for derivatives in which other groups are introduced.
As the porous body constituting the above-mentioned synthesis catalyst, one made of a metal oxide is preferable. That is, the porous body made of a metal oxide is, for example, a porous body made of a metal oxide or a composite metal oxide made of two or more different metals. The above-mentioned porous body may be one in which a different metal or metal oxide is carried or coated on the surface of a porous body made of a metal oxide.

Examples of the above-mentioned porous body include complex metal oxides such as silica-alumina, silica-titania, silica-magnesia, silica-zirconia, silica-lanthanum, silica-barium oxide, and silica-strontium oxide, or , Alumina, silica, titania, and metal oxides such as tungsten oxide. These have a solid acidity suitable for porphyrin synthesis reaction.

The pores have a pore diameter (hereinafter referred to as a central pore diameter) showing the maximum peak in the pore diameter distribution curve within a range of 1 to 10 nm, and 60 pores.
% Or more has a diameter within a range of ± 40% of the central pore diameter. The reason is shown below.

That is, porphyrin has a cyclic molecular structure and is most easily produced in pores having a pore size suitable for the molecular diameter. Therefore, it is preferable that the pore diameter of the porous body is close to the molecular diameter of porphyrin and the pore distribution is as narrow as possible. In addition, porphyrin molecules exist in various sizes depending on the type of the substituent. Therefore, a sufficient porphyrin yield can be obtained by appropriately selecting the central pore diameter and the diameter of the pores within the above range according to the desired size of porphyrin. If the amount exceeds the above range, the amount of by-products different from porphyrin, for example, a linear molecule, increases, and the porphyrin yield decreases.

The central pore diameter of the pores is the diameter of the pore having the maximum peak in the pore diameter distribution curve.
Here, the above-mentioned pore diameter distribution curve is a curve in which a value (dV / dD) obtained by differentiating the pore volume (V) with the pore diameter (D) is plotted against the pore diameter (D) (Fig. 4).

The pore size distribution curve is prepared, for example, by the gas adsorption method shown below. The most commonly used gas in this method is nitrogen. First, nitrogen gas is introduced into the catalyst at liquid nitrogen temperature (-196 ° C), and the adsorption amount is determined by the constant volume method or the gravimetric method. The adsorption isotherm is created by gradually increasing the pressure of the introduced nitrogen gas and plotting the adsorption amount of the nitrogen gas with respect to each pressure (Fig. 3).
reference). From this adsorption isotherm, Cranston-In
The pore size distribution curve is obtained by using a calculation method such as the Clay method or the Pollimore-Heal method.

The above 60% or more of the pores means that the ratio of the surface area of the pores within the range of ± 40% of the central pore diameter to the total surface area of the catalyst for synthesis is 60% or more. To calculate this ratio, a curve obtained by plotting the integrated value of the specific surface area of the catalyst for synthesis with respect to the pore diameter against the pore diameter is used. This curve is Cra from the adsorption isotherm of nitrogen.
It can be created using the nston-Inclay method or the like.

When there are two or more maximum peaks in the pore size distribution curve, at least one of them is selected.
It suffices that the pore diameters showing the two maximum peaks exist in the range of 1 to 10 nm. In addition, when there are two or more maximum peaks in the range of 1 to 10 nm, among these maximum peaks,
It suffices that there is at least one maximum peak satisfying the condition that 60% or more of the pores have a diameter within the range of ± 40% of the maximum peak pore diameter.

Next, the action of the above-mentioned catalyst for porphyrin synthesis will be described. The catalyst for porphyrin synthesis is
A porous body having the above-mentioned pore characteristics. Therefore, when porphyrin is synthesized in the presence of the synthesis catalyst,
The porphyrin yield is improved. The reason is considered as follows.

Porphyrin is a typical macrocyclic heterocyclic compound. For example, a meso-substituted porphyrin, a type of porphyrin, is formed by direct polymerization cyclization of an aldehyde and pyrrole. Aldehyde and pyrrole
Alternately polymerize to form an intermediate incorporating four of each.
If the intramolecular ring closure reaction occurs here, porphyrinogen, which is a precursor of porphyrin, is produced. However, in general, the process of forming a chain copolymer is more advantageous than the ring closure, and the probability of forming a cyclic porphyrin is low.

However, it is considered that by carrying out these reaction processes in a uniform space close to the molecular diameter of porphyrin, the formation of chain polymer is suppressed and the ring closure process becomes advantageous. The meso-substituted porphyrin has a molecular diameter of about 2 nm, but depending on the size of the substituent, it may be 1.5 to 1
It can be 0 nm. Therefore, it is considered that the yield of porphyrin was improved by using the above-mentioned catalyst for synthesis having uniform pores corresponding to the molecular diameter of the desired product, porphyrin.

Further, since the above-mentioned synthesis catalyst is a solid catalyst, separation after the reaction is easy. When an oxidizing agent such as p-chloranil is added to the synthesis catalyst, the oxidizing agent adheres to the surface of the synthesis catalyst, so that the treatment for separating the oxidizing agent after the reaction is easy.

Next, with respect to the above-mentioned porphyrin synthesis catalyst, a more preferable constitution of the invention will be described. The porous body forming the synthesis catalyst of the present invention is preferably made of a thermally stable metal oxide. This synthesis catalyst is stable and does not collapse its pore structure even at a high temperature of about 500 ° C. required for the regeneration treatment of the synthesis catalyst.
Therefore, the above-mentioned synthesis catalyst can be repeatedly used by performing a regeneration treatment after the porphyrin formation reaction.

On the other hand, the acid-treated montmorillonite has a problem that it cannot be used repeatedly. That is, after one reaction, the porphyrin produced was recovered and then calcined at a temperature of about 500 ° C. for the purpose of removing by-products and oxidants attached to the catalyst, the structure of the acid-treated montmorillonite collapsed, and It does not act as a catalyst during the second reaction. Therefore, the acid-treated montmorillonite is consumed in a single reaction, and must be replaced anew for each reaction, which increases the cost of porphyrin synthesis.

The porous body made of the above metal oxide is an oxide of Si and is preferably composed of a crystalline three-dimensional structure. The reason is that Si is particularly thermally stable, and furthermore, since the porous body is a crystal having a three-dimensional skeleton structure, the pores formed inside the crystal have an extremely stable structure. is there. Therefore, it withstands the regeneration process accompanied by heat treatment and can be used repeatedly.

Further, it is preferable that aluminum (Al) is further introduced into the porous body made of the above metal oxide. The reason is that by introducing Al into SiO ₂ , solid acidity is developed. This is 4
It is considered that the substitution of trivalent Al with trivalent Al causes excess and deficiency of charges. Also, Al
This is because the introduced solid acid effectively acts as an acid catalyst required in the porphyrin synthesis reaction, and the porphyrin yield increases.

Next, as a method of synthesizing porphyrin using the above-mentioned synthesis catalyst, for example, aldehyde and pyrrole are subjected to a polymerization cyclization reaction in the presence of the above-mentioned synthesis catalyst, and then oxidized by adding an oxidizing agent. Then, there is a method of synthesizing a porphyrin having a cyclic porphine nucleus (see FIG. 9).
In this method, the reaction between aldehyde and pyrrole is
Perform in a solvent such as methylene chloride.

The reaction temperature is preferably 0 to 40 ° C. At temperatures below 0 ° C, the reaction rate is slow,
It may take a long time to complete the reaction. If the temperature exceeds 40 ° C, a side reaction may occur and the porphyrin yield may be reduced. The reaction time is preferably 10 minutes to 3 hours.

It is preferable that the above synthesis catalyst is sufficiently dried before being added to the reaction solution. This is because if the water adheres to the synthesis catalyst, the solid acidity may not be sufficiently expressed. Completion of the synthesis reaction of porphyrin can be confirmed using thin layer chromatography (hereinafter referred to as “TLC”) and gas chromatography (hereinafter referred to as “GC”) that the raw material aldehyde and pyrrole have disappeared. it can.

After the reaction, an oxidizing agent (for example, p-chloranil) is added, and the mixture is heated to reflux at a temperature of 20 to 70 ° C. The heating time is preferably 30 minutes to 2 hours. Then, the reaction solution is filtered to remove the above-mentioned synthesis catalyst. The filtrate is concentrated to give porphyrin. Porphyrin may be purified and crystallized.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiment 1 A porphyrin synthesis catalyst according to an embodiment of the present invention will be illustrated and described. The above-mentioned catalyst for porphyrin synthesis is a porous body having a large number of pores, and its composition is SiO ₂ . Hereinafter, a method for producing a catalyst for porphyrin synthesis will be described.

First, powdered sodium silicate (SiO ₂ / Na
₂ O = 2.00, manufactured by Nippon Kagaku Kogyo Co., Ltd.) was fired at 700 ° C. in air for 6 hours. 50 g of the calcined powdered sodium silicate was crushed to a particle size of 1 mm or less, dispersed in 500 ml of water, and stirred at room temperature for 3 hours. Then, the solid content was filtered off using a Buchner funnel to synthesize kanemite (NaHSi ₂ O ₅ .3H ₂ O), which is one of the layered silicates.

Next, the kanemite was not dried but dispersed in each of 5 kinds of aqueous solutions of alkyltrimethylammonium [C _n H _{2n + 1} N ⁺ (CH ₃ ) ₃ ] having different alkyl chain lengths in a wet state. It was The above-mentioned five kinds of alkyltrimethylammonium aqueous solutions are 0.1 mol of alkyltrimethylammonium chloride (n = 14, 16) or alkyltrimethylammonium bromide (n =
8, 10, 12) was dissolved in 1000 ml of water. Only n = 8 octyltrimethylammonium bromide was dissolved in 1000 ml of water in an amount of 0.5 mol.

Next, this dispersion was placed in a flask having a volume of 2000 ml. First, the mixture was heated in a water bath at 70 ° C. for 3 hours while stirring with a stirring motor. Then 2
An aqueous solution of N hydrochloric acid was added dropwise to slowly adjust the pH to 8.5. Then, the mixture was further heated at 70 ° C. for 3 hours with stirring.

Then, the dispersion was cooled to room temperature and the solid product was filtered off. It was washed with 1000 ml of ion-exchanged water 5 times in total, and then dried. 550 these powders
The mixture was calcined in air at 6 ° C for 6 hours to obtain 5 kinds of porous materials, that is, catalysts for porphyrin synthesis. These synthesis catalysts are
In order from the shorter alkyl chain length (n = 8, 10, 12, 14, 16), FSM-13, 20, 23, 24, 28
And

Embodiment 2 The porphyrin synthesis catalyst in this embodiment is a porous body having a large number of pores, and its composition is SiO ₂ . Hereinafter, a method for producing this synthesis catalyst will be described. First, 0.1 mol of hexadecyltrimethylammonium chloride is dissolved in 1000 ml of water, and then mesitylene (1,3,5-trimethylbenzene) is added thereto.
0.05, 0.1, 0.2 mol, respectively,
Three types of solutions were prepared. In addition, wet kanemite was prepared from calcined powdered sodium silicate by the same method as in Example 1.

50 g of wet kanemite was dispersed in each of the above three kinds of solutions. 2000 of these dispersions
The mixture was placed in a flask having a capacity of ml and heated in a water bath at 70 ° C. for 3 hours while stirring with a stirring motor. Then, a 2N hydrochloric acid aqueous solution was added dropwise to slowly adjust the pH to 8.5. Then, it heated at 70 degreeC, stirring for 3 hours.

Then, the dispersion was cooled to room temperature and the solid product was filtered off. It was washed with 1000 ml of ion-exchanged water 5 times in total, and then dried. By firing these powders in air at 550 ° C for 6 hours, three types of porous materials,
That is, a catalyst for porphyrin synthesis was obtained. These synthesis catalysts were used in the order of FSM-32,
6, 47.

Embodiment 3 In this example, a catalyst for porphyrin synthesis was prepared.
The crystal structure was observed. The catalyst for porphyrin synthesis is the FSM-1 produced in the first and second embodiments.
3, 20, 23, 24, 28, 32, 36, 47 were used. The powder X-ray diffraction patterns of these are shown in FIG.

From the figure, FSM-23, 24, 28, 3
As for No. 2, 3 to 4 diffraction peaks indexed to a hexagonal structure were observed in the range where the diffraction angle was 10 ° or less. On the other hand, for FSM-13, 20, 36, 10
One to two diffraction peaks were observed in the range of ° or less. Further, regarding FSM-47, no clear peak was observed in the range of 1 ° or more. From these, it is understood that many porphyrin synthesis catalysts have a regular structure.

Next, the crystal structure of FSM-28 is shown in the transmission electron micrograph (magnification: 1.4 million times) of FIG. From this photograph, it can be seen that the cells have a honeycomb structure in which pores having a diameter of about 3 nm are regularly arranged.

Embodiment 4 In this example, the pore size distribution of the porphyrin synthesis catalyst was measured. The catalysts for porphyrin synthesis are FSM-13, 20, 23, 24 produced in Embodiments 1 and 2,
28, 32, 36 and 47 were used.

A method for measuring the pore size distribution of the above-mentioned synthesis catalyst will be described. First, a nitrogen adsorption isotherm was created by the following device and method. The device is an absolute pressure type transducer (Baratron 1 manufactured by Nippon MKS Co., Ltd.).
27AA) and a control valve (248A manufactured by Nippon MKS Co., Ltd.) were used for the measurement by the constant volume method. About 50 mg of sample was weighed into a sample tube and vacuum degassed at 150 ° C. for 2 hours. The degree of vacuum after 2 hours was 10 ⁻³ torr. Then, the nitrogen adsorption measurement was performed while immersing the sample tube in liquid nitrogen. The obtained nitrogen adsorption isotherm is shown in FIG.

From this nitrogen adsorption isotherm, Cranston
FIG. 4 shows the pore size distribution curve calculated by the Inclay method.
It was shown to. The central pore diameter obtained from the peak position of this pore diameter distribution curve is shown in Table 1. The central pore diameter is 1.3 nm for FSM-13 and 2.0 for FSM-20.
nm, FSM-23 is 2.3 nm, FSM-24 is 2.
4 nm, FSM-28 is 2.8 nm, FSM-32 is 3.2 nm, FSM-36 is 3.6 nm, FSM-47.
Was found to be 4.7 nm and changed in the range of 1.3 nm to 4.7 nm.

Next, the integral curve of the specific surface area of the catalyst for synthesis with respect to the pore diameter was calculated by the Cranston-Inclay method. The ratio of the specific surface area within the range of ± 40% of the central pore diameter to the total surface area was determined. This was defined as ± 40% porosity. The ± 40% porosity is shown in Table 1 along with the total surface area of the synthesis catalyst. As a result, the ratio was 66% at the lowest and 93% at the highest.

[0046]

[Table 1]

Embodiment 5 The porphyrin synthesizing catalyst of this example is obtained by introducing Al into a porous body made of a metal oxide. The composition of the synthesis catalyst is SiO ₂ —Al ₂ O ₃ . The manufacturing method will be described below.

Among the synthesis catalysts of Embodiments 1 and 2, those having an alkyl chain length of n = 10,16 (FSM-20,2
8), and 0.1 mol of mesitylene added (FS
According to the production method of M-36), three kinds of powdery organic composites were prepared. However, the final firing at 550 ° C is not performed.

The three kinds of organic composite powders containing the organic substance are respectively hydrated aluminum chloride (AlCl
₃ · 6H ₂ O) was dispersed in an aqueous solution having dissolved therein. The amount of water that dissolves aluminum chloride was set so that the organic complex was sufficiently immersed. The hydrous aluminum chloride at this time was added so that 4% by weight of Al ₂ O ₃ was finally introduced into the organic composite. That is, the addition amount of hydrous aluminum chloride is the weight of SiO ₂ (W <Si
For O ₂ >), the weight of Al ₂ O ₃ (W <Al ₂ O ₃ >) calculated by the following equation (1) is converted to aluminum (Al) to have the same mole of hydrous aluminum chloride. The ratio of SiO _{2 in} the organic composite was obtained from the weight residual ratio after firing the organic composite at 700 ° C.

W <Al ₂ O ₃ > ÷ (W <SiO ₂ > + W <Al ₂ O ₃ >) = 0.04 (1)

A dispersion of this organic composite in an aqueous solution of aluminum chloride was stirred with a magnetic stirrer at room temperature for 5 hours. After that, by heating up to about 100 ° C., water was evaporated and completely dried. The obtained powder was calcined in air at 700 ° C. for 6 hours. Thus, including Al ₂ O ₃ 4 wt%, SiO ₂ ─Al ₂ O ₃
Three types of porous materials having different compositions, that is, catalysts for synthesizing porphyrin were obtained. A porous body containing Al produced by using alkyltrimethylammonium having an alkyl chain length of n = 10 and 16 was designated as Al-FSM-20, 28. Also,
A porous body containing Al produced by adding 0.1 mol of mesitylene was designated as Al-FSM-34.

The powder X-ray diffraction patterns were almost the same as those of the porous body (FDM-20, 16, 36) of SiO ₂ composition produced under the same conditions without adding Al.

Embodiment 6 In this example, the pore characteristics of the porphyrin synthesis catalyst were evaluated. As a synthesis catalyst, Embodiment 5 is used.
The Al-FSM-20, 28, 34 manufactured in 1. was used.

In the evaluation, the nitrogen adsorption isotherms of these synthesis catalysts were obtained by the same method as in Embodiment 4, and the pore size distribution curve and the synthesis catalysts of the catalysts for synthesis were determined from the nitrogen adsorption isotherm by using the Cranston-Inclay method. An integral curve of the specific surface area to the pore diameter was obtained. In addition, this integral curve is
With the pore diameter of 30 nm as a reference, the specific surface area was integrated and plotted while decreasing the pore diameter from there. 5 to 7 are graphs showing the characteristics of the specific surface area and pores of Al-FSM-20, 28, and 34. The upper part of FIGS. 5 to 7 shows the integral curves of their specific surface areas, and the lower part shows their pore size distribution curves.

From these figures, the diameter of each central pore is determined from the pore diameter distribution curve, and is ± 40% of the diameter of the central pore.
The pore range was calculated, and the range is shown in Table 2 as a ± 40% pore range. Further, the ratio of the specific surface area of the synthetic catalyst in the range of ± 40% of the central pore diameter to the total surface area of the synthetic catalyst is determined from the above-mentioned integral surface area curve,
The results are shown in Table 2 as ± 40% porosity.

From the table, the central pore diameter of the synthesis catalyst of the present invention is 2.0 nm for Al-FSM-20 and Al-FS.
M-28 is 2.8 nm, Al-FSM-34 is 3.4 n
It can be seen that 65 to 89% of the pores were present in the range of m and ± 40% of the central pore diameter.

On the other hand, as a synthetic catalyst of Comparative Example, acid-treated montmorillonite K.10 (manufactured by Aldrich)
The pore characteristics of were determined in the same manner as above. The results are shown in FIG. 8 and Table 2 as in the above. From the results, in Comparative Example, only 55% of the pores were present in the range of ± 40% of the central pore diameter.

[0058]

[Table 2]

Embodiment 7 In this example, mesotetraphenylporphyrin (hereinafter referred to as T), which is a kind of porphyrin, was used with a catalyst for synthesis.
Also called PP. ) Will be described.

First, 1.0 g of the above-mentioned synthesis catalyst (Al-FSM-28) having a composition of SiO ₂ --Al ₂ O _{3 was} weighed and put in a 200 ml eggplant-shaped flask and kept at 120 ° C., 0.
After drying at 5 mmHg or less for 3 hours, argon replacement was performed. Next, in an argon atmosphere, CH ₂ C
95 ml of 1 ₂ (which was dehydrated by adding molecular sieve 4A) was added.

Next, benzaldehyde (C ₆ H ₅ CH
After adding 5 ml of a CH ₂ Cl ₂ solution of O, 1 mmol), 1 mmol of pyrrole was added with a syringe, and the mixture was stirred at room temperature. After confirming the completion of the reaction by TLC and GC, 0.75 mmol of p-chloranil was added, and the mixture was gently heated to reflux using an oil bath at 45 to 50 ° C. After 1 hour, Al-FSM-28 was removed by suction filtration through Celite.

After the filtrate was concentrated, it was supported on 0.2 g of Florisil (florisil), and roughly purified by a short column (100 g of alumina, activity II to III). The obtained crude porphyrin was again subjected to a short column (alumina 100 g, activity I).
I-III) and the TPP was isolated.

The isolated TPP crystal was heated at 80 ° C. for 0.5 m.
After drying under mHg for 6 hours, measure the crystal weight and
The P yield was determined. Also, instead of Al-FSM-28 described above, Al-FSM-20 or Al-FSM-34 was used and the above reaction was carried out under the same conditions.

On the other hand, as the synthesis catalyst of the comparative example, an acid-treated montmorillonite K.10 (manufactured by Aldrich Co.) which is a solid acid catalyst, and BF ₃ .OEt ₂ (0) which is a homogeneous catalyst instead of the solid acid catalyst. .1 mmol, 10
^-3 M), and CF ₃ CO ₂ H (0.5 mmol, 5 × 1
The above reaction was carried out under the same conditions using a CH ₂ Cl ₂ solution of 0 ⁻³ M). For acid-treated montmorillonite K.10, the reaction after addition of p-chloranil was carried out for 2 hours,
The other synthesis catalysts were run for 1 hour. Table 3 shows the results.

As is known from the table, the synthesis catalyst (Al-FSM-2) of the present invention having a central pore diameter of 2.8 nm.
8) showed the highest TPP yield among the solid acid catalysts.

[0066]

[Table 3]

Embodiment 8 In this example, an aromatic aldehyde of the general formula shown in FIG. 9 is reacted with pyrrole in the presence of a catalyst for synthesis in place of benzaldehyde, and mesotetraarylporphyrin (hereinafter referred to as TAP). Was synthesized. The above-mentioned aromatic aldehydes are 2-methylbenzaldehyde, 4-methylbenzaldehyde, and 2-methoxybenzaldehyde, which are compounds, respectively. X in the general formula of the aromatic aldehyde in FIG. 9 is shown in Table 4.

As the synthesis catalyst, Al-FSM-28 which is the synthesis catalyst of Example 7 was used. On the other hand, as for the synthesis catalyst of Comparative Example, a solid acid catalyst acid treated montmorillonite K · 10 (Aldrich), as well as homogeneous catalysts in place of the solid acid catalyst BF ₃ · OEt ₂ and CF ₃ CO ₂ H Was used to carry out the same reaction. What is the TAP yield when TAP was synthesized using the above-mentioned catalyst for synthesis. The results are shown in Table 4.

As a result, Al-FSM-2 according to the present invention
In No. 8, the TAP yields of all aromatic aldehydes were higher than those of the acid-treated montmorillonite K.10 of Comparative Example. Further, Al-FSM-28 is a homogeneous catalyst BF ₃ · O for 4-methylbenzaldehyde and 2-methoxybenzaldehyde (compound).
The TAP yields of Et ₂ and CF ₃ CO ₂ H were also exceeded.

[0070]

[Table 4]

Embodiment 9 In this example, after completion of the TPP synthesis reaction, the removed synthesis catalyst was regenerated by calcining in air at 500 ° C. for 3 hours,
The same synthetic reaction was performed again. As the synthesis catalyst, Al-FSM-28 according to the present invention and the acid-treated montmorillonite K.10 of Comparative Example were used. The change in the TPP yield was plotted when the regeneration treatment was performed 5 times in total with the same catalyst. The results are shown in Fig. 10. From the figure, the acid-treated montmorillonite K.10 had a TPP yield of 0 after one regeneration treatment, whereas the catalyst for synthesis of the present invention showed no TPP yield even after five regeneration treatments. No decrease in TPP yield was observed.

As described above, according to the porphyrin synthesis catalyst of the present invention, a porphyrin having a cyclic porphine nucleus can be synthesized in high yield. Furthermore, porphyrins having a porphine nucleus can be obtained in high yield regardless of the type.

[0073]

Industrial Applicability According to the present invention, it is possible to provide a porphyrin synthesis catalyst which has a high yield of porphyrin and can be repeatedly used.

[Brief description of drawings]

FIG. 1 is a catalyst for porphyrin synthesis in Example 3 of FSM-13, 20, 23, 24, 28, 3;
The characteristic view which shows the powder X-ray-diffraction pattern of 2,36,47.

FIG. 2 is a transmission electron micrograph showing a crystal structure of FSM-28 which is a catalyst for porphyrin synthesis in Embodiment 3.

FIG. 3 shows FSM-13, 20, 23, 24, 28, 3 which is a catalyst for porphyrin synthesis in Embodiment 4.
The characteristic diagram which shows the nitrogen adsorption isotherm of 2,36,47.

FIG. 4 shows FSM-13, 20, 23, 24, 28, 3 which is a catalyst for porphyrin synthesis in Embodiment 4.
The characteristic view which shows the pore diameter distribution curve of 2,36,47.

FIG. 5 is a characteristic diagram showing an integral curve (upper part) and a pore size distribution curve (lower part) of a specific surface area of Al-FSM-20 which is a catalyst for porphyrin synthesis in Embodiment 6.

FIG. 6 is a characteristic diagram showing an integral curve (upper part) and a pore size distribution curve (lower part) of a specific surface area of Al-FSM-28 which is a catalyst for porphyrin synthesis in Embodiment 6.

FIG. 7 is a characteristic diagram showing an integral curve (upper part) and a pore size distribution curve (lower part) of the specific surface area of Al-FSM-34 which is the catalyst for porphyrin synthesis in Embodiment 6.

FIG. 8 is a characteristic diagram showing an integral curve (upper part) and a pore size distribution curve (lower part) of the specific surface area of the acid-treated montmorillonite K · 10 which is the catalyst for synthesizing porphyrin of Comparative Example in Embodiment 6.

FIG. 9 is an explanatory diagram showing a reaction formula for synthesizing TAP (mesotetraarylporphyrin) by reacting an aromatic aldehyde and pyrrole in the presence of a synthesis catalyst in Embodiment 8.

FIG. 10 shows an Al- according to the present invention in Embodiment 9;
FSM-28 and acid-treated montmorillonite K of Comparative Example
The characteristic view which shows the change of the TPP yield when 10 is reused.

Front page continued (72) Inventor Shinji Inagaki Aichi Prefecture Nagakute-cho, Aichi-gun, Nagacho, Yokocho 1 41 of Toyota Central Research Institute Co., Ltd. (72) Inventor Kisho Fukushima Aichi-gun, Nagakute-cho, Nagakage, Yokomichi 41 Address 1 Toyota Central Research Institute Co., Ltd. (72) Inventor Atsushi Onaka 3-51-2 Kojima-cho, Chofu-shi, Tokyo (72) Inventor Tomotaka Shinoda 183 Shinchi, Kuwana-shi, Mie (72) Izumi Izumi Yuryu 4-907 Hara, Tenshiro-ku, Nagoya-shi, Aichi (72) Inventor Hiroshi Sato 2-10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Co., Ltd.

Claims (4)

[Claims] 1. A catalyst for synthesizing porphyrin, which comprises a porous body having a large number of pores,
The pores have pore diameters in which the maximum peak in the pore diameter distribution curve is in the range of 1 to 10 nm, and 60% or more of the pores have fine peaks in the pore diameter distribution curve. A catalyst for the synthesis of porphyrins, which has a diameter within the range of ± 40% of the pore diameter. 2. The catalyst for synthesizing porphyrin according to claim 1, wherein the porous body is made of a metal oxide. 3. The catalyst for synthesizing porphyrin according to claim 2, wherein the porous body made of the metal oxide is an oxide of Si and is composed of a crystalline three-dimensional structure. 4. The method according to claim 1, wherein
A catalyst for porphyrin synthesis, wherein aluminum is further introduced into the porous body.