JP2001342190A - New tetrapyrrolyl-substituted porphyrin and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new porphyrin derivative useful for detecting a protein and as a precursor for porphyrin or its photosensitive coloring matter (functional) derivative useful for a photodynamic therapy using photoexcitation energy and to provide a method for producing the same. SOLUTION: This metal or metal-free tetrapyrrolyl-substituted porphyrin compound substituted hith pyrrol groups at the whole meso positions is represented by formula 1 [Pyr1, Pyr2, Pyr3 and Pyr4 are wholly pyrrol groups of formula 2 (R1 is H or a 1-3C hydrocarbon group; R2 is H, formyl or a group of formula 4) or formula 3 (R1 and R2 are as shown above), may be a mixture of the two kinds of pyrrol groups or are each a group selected from formula 2 and formula 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel porphyrin derivative and a method for producing the same.
The present invention relates to a novel tetrapyrrolyl-substituted porphyrin and a method for producing the same. Since the compound of the present invention has a reactive functional group, it is possible to obtain a polymer that can be used as a molecular wire with a large number of porphyrin skeletons. Holding
The aldehyde group binds to the amino group of the protein by reductive amination, so that this reaction can be used for protein detection and photodynamic therapy using photoexcitation energy such as porphyrin or its photosensitive dye (functional) derivative. Provides useful precursors.

[0002]

2. Description of the Related Art Porphyrin compounds exist in nature as active centers such as chlorophyll for photosynthesis, hemoglobin as an oxygen carrier, and cytochrome P-450 for activating molecular oxygen to metabolize substances.
Each plays an important function. Therefore, for many years, metal porphyrin complexes have been studied in various ways to elucidate the functions of these enzyme systems. Due to the diversity of synthesis and transformation, many meso-substituted tetraarylporphyrins have been synthesized, and these have been studied for model substances of biological processes, catalysts, functional dyes, contrast agents, anticancer agents, antiviral agents, etc. Used in the field. Among the meso-aryl-substituted compounds, heterocyclic aromatics such as pyridyl or imidazolyl have many potential uses to provide the building blocks for the formation of (self) organized assemblies of metal coordinating supramolecules. There is interest.

In addition, porphine derivatives have been used as therapeutic materials for photodynamic therapy for many years, and some clinical cases have been reported. In this case, there is a drawback in that it is very slow in terms of solubility until it is taken into the body as described above, and it takes a long time for the treatment and burdens the patient. When the porphine derivative is water-soluble, an extremely excellent therapeutic effect can be expected. Furthermore, although metal complexes of porphyrin derivatives have been variously studied as organic synthesis reaction catalysts (selective oxidizing agents and reducing agents), the application range may be dramatically expanded due to improved solubility. In order to improve the solubility, it is necessary to devise a method such as introducing a group having a group that improves water solubility, such as an alkyl group, a sulfonic acid group, a carboxyl group, and an amino group, into the porphyrin. Thus, it is clear that the provision of basic porphyrins that can be molecularly designed for many of these uses will make a significant technical contribution.

[0004]

On the other hand, porphyrins having a pyrrolyl substituent have not been well reported, though they are important from the viewpoint of the possibility of application as a porphyrin skeleton and a molecular wire.
The object of the present invention is to have a pyrrolyl substituent at the meso position,
An object of the present invention is to provide a porphyrin containing eight pyrrolyl units in a molecule and to provide a method for producing the porphyrin. The present inventors have made it possible to cause both formyl groups to be incorporated into the porphyrin macrocycle by reacting 1: 1 condensation of 2,4-diformylpyrrole and pyrrole using an acid catalyst. , Two types of mixed N
Compound A corresponding to a porphyrin having (a compound in which only the α-position of pyrrole binds via a methine bond and a compound in which the α- and β-positions of pyrrole bind via a methine bond) Or B

[0005]

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[0006] The synthesis experiments of A and B were carried out with the expectation that the compound could be obtained. However, contrary to expectations,
The product isolated in the synthesis experiment was not the porphyrins having the two kinds of mixed N, but the meso-tetrapyrrolyl porphyrins (TPyrPs) in which all of the meso positions of the porphyrin ring were substituted with a pyrrole group. Equation 1
It has been found that compounds having only one formyl group, which is a compound represented by the formula, are reacted.

[0007]

A first aspect of the present invention is a metal or metal-free tetrapyrrolyl-substituted porphyrin compound represented by the formula 1 in which all meso positions are substituted with a pyrrole group.

[0008]

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[In the formula 1, Pyr1, Pyr2, Pyr
3, and Pyr4 may be all pyrrole groups of the formula 2 or 3, or a mixture of the two types of pyrrole, and are groups selected from the groups of the formula 2 or 3. Where Equation 2 is

[0010]

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(In the formula 2, R ¹ is H or a hydrocarbon group having 1 to 3 carbon atoms, and R ² is H, formyl or formula 4.)

[0012]

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(In the formula 3, R ¹ and R ² are the same as the formula 2)

[0014]

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A second aspect of the present invention is to provide a pyrrole represented by the formula (5):

[0016]

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Diformylpyrrole compound represented by the formula (6)

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(Wherein R in the formula 6 is H or a hydrocarbon group having 1 to 3 carbon atoms) to give a compound of the formula 7 to give a compound of the formula 7 with a transition metal compound or an acid catalyst and This is a method for producing a metal or metal-free tetrapyrrolyl-substituted porphyrin compound of the above formula 1 by treating in the presence of pyrrole.

[0019]

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[In the formula 7, Pyr′1, Pyr′2, Py
r′3 and Pyr′4 may be all formyl-substituted pyrrole groups of the formula 8 or 9 or a mixture of the above two types of pyrrole; Is a group selected from Where Equation 8 is

[0021]

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(In the formula 8, R ¹ is H or a hydrocarbon group having 1 to 3 carbon atoms.)

[0023]

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(In the formula 9, R ¹ is the same as the formula 8.)

Preferably, the method is for producing the tetrapyrrolyl-substituted porphyrin compounds, wherein an acid is present in a reaction system for obtaining the metal-free compound of the formula 1. More preferably, the metal-free compound of the formula 1 is prepared. The method for producing the tetrapyrrolyl-substituted porphyrin compounds, wherein the reaction for obtaining the compound is performed in pyrrole in the presence of trifluoroacetic acid.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. A. The novel porphyrins of the present invention are characterized by using the pyrrole of the formula 5 and the diformyl-substituted pyrrole of the formula 6. Examples of the acid used in the reaction include trifluoroacetic acid (TFA), boron trifluoride, and boron trifluoride etherate (BF ₃ OE) used in the production of porphyrins.
t ₂ ), montmorillonite contacted with a mineral acid, and the like. In addition, the acids can be used as an acid to be present in pyrrole when producing the metal-free porphyrin of Formula 1 above.

[0027]

EXAMPLES Example 1 2,4-Diformylpyrrole derivative tetrapyrrolporphyrin compounds (α, β mixed formyltetrapyrrolylporphyrin compounds) (2-H, 3-H + 4-H, 5- H) A mixture of pyrrole (134 mg, 2 mmol) and 2,4-diformylpyrrole (246 mg, 2 mmol) was dissolved in acetic acid (100 mL), and
Stirred at 0 ° C. for 40 minutes. The solvent was subjected to silica gel (Wakogel C-300) column chromatography as 3% methanol -CH ₂ Cl ₂ solution and the residue after removal of. R ₁
The values were determined by means of a 10% methanol-CH ₂ Cl ₂ solution by means of Merck-type thin-layer chromatography (Merck-Type 60 TLC).

Physical Properties of Each Compound 1. 2-H: αβββ Formyltetrapyrrolylporphyrin Compound R ₁ = 0.62; ¹ HNMR (DMSO-d ₆ , 500 MHz, 50 ° C.): δ (ppm) 13.02
(s, 1H, pyrrole-NH), 12.85 (s, 3H, pyrrole-NH), 10.11 (s, 1
H, β-CHO), 9.89 (s, 3H, α-CHO), 9.15 (s, 2H, βH) 8.21 (s, 1
H, pyrrole-αH), 8.08 (d, J = 7.0 Hz, 3H, pyrrole-αH), 7.9
1 (d, J = 6.0Hz, 3H, pyrrole-βH), 7.39 (s, 1H, pyrrole-β
H), -2.68 (s, 2H, inner-NH); UV / vis (DMF): λmax (nm) 42
1,520,559,654; MALDI-TOF; M / Z = 683.4 (M ⁺⁺ 1). MALDI-TOF = Matrix-assited Laser Desorption Ionizati
on-Time of Flight 2.3-H: αβαβ and 4-H: ααββ formyltetrapyrrolylporphyrin compounds (two isomers are inseparable) R ₁ = 0.58; ¹ HNMR (DMF-d ₇ , 500MHz, 20 ℃): δ (ppm) 12.83
(br, 2H, pyrrole-NH), 12.81 (s, 2H, pyrrole-NH), 9.99 (s, 2
H, β-CHO), 9.76 (s, 2H, α-CHO), 9.04 (br, 4H, βH) 8.91 (b
r, 4H, βH), 8.15 (s, 2H, pyrrole-αH), 8.04 (s, 2H, pyrrole
-αH), 7.81 (s, 2H, pyrrole-βH),-2.83 or -2.85 (s, 2H, i
nner-NH) 3.5-H: α, α, α, β formyl tetrapyrrolylporphyrin compound R ₁ = 0.55; ¹ H NMR (DMSO-d ₆ , 500 MHz, 27 ° C.): δ (ppm) 13.14
(s, 3H, pyrrole-NH), 13.00 (s, 1H, pyrrole-NH), 10.10 (s, 3
H, β-CHO), 9.89 (s, 1H, α-CHO), 9.20 (br, 2H, βH) 9.07 (m,
6H, βH), 8.34 (s, 3H, pyrrole-αH), 8.27 (s, 1H, pyrrole-
αH), 8.11 (s, 1H, pyrrole-βH),-2.79 (br, 2H, inner-NH)

Example 2 Production of N-methyl-2,4-diformylpyrrole derivative tetrapyrrolylporphyrin compounds (2-Me, 3-Me, + 4-Me). Manufactured in the same manner as in Example 1. For silica gel column chromatography, a 1% methanol-CH ₂ Cl ₂ solution was used. Physical properties of obtained compound 1. 2-Me: αβββ form N-methyl-2,4-diformyl-tetrapyrrolylporphyrin compound R ₁ = 0.78; ¹ HNMR (CDCl ₃ , 500 MHz, 27 ° C.): δ (ppm) 10.13
(s, 1H, β-CHO), 9.93 (d, J = 3.5 Hz, α-CHO), 9.13 (m, 6H, β
H), 8.84 (s, 2H, βH), 7.80 (m, pyrrole-αH), 7.69 (d, J = 5.5
Hz, 3H, pyrrole-βH), 7.50 (s, 1H, pyrrole-βH), 4.37 (s, 9
_{H, CH 3), 3.42 (} s, 3H, CH 3), - 2.67 (s, 2H, inner-NH); UV / vis
(DMF): λmax (nm) 421,520,559,654; FABMS; m / z (% intensity)
= 783.4 (100, M ⁺ ). 2.3-Me: αβαβ and 4-Me: ααββ form N-methyl-2,4-
Diformyl-tetrapyrrolylporphyrin compound R ₁ = 0.71; ¹ H NMR (CDCl ₃ , 500 MHz, 27 ° C.): δ (ppm) 10.15
(m, 2H, β-CHO), 9.96 (s, 2H, α-CHO), 9.17 (m, 4H, βH), 8.8
9 (s, 4H, βH), 7.83 (s, 4H, pyrrole-αH), 7.71 (S, 2H, pyrro
le-βH), 4.39 (s , 6H, CH 3), 3.43 (m, 6H, CH 3), - 2.66 or -
2.71 (br, 2H, inner-NH)

Example 3 N-isopropyl-, 4-diformylpyrrole derivative tetrapyrrolylporphyrin compounds (1- ⁱ Pr, 2- ⁱ Pr, 3- ⁱ Pr, + 4- ⁱ
Production of Pr). A. Preparation of 1- ⁱ Pr 2.4-Diformyl-1-isopropylpyrrole (165 mg, 1.0 mm
ol) and an equivalent amount of pyrrole in CHCl ₃ (100 mL).
Boron trifluoride etherate (BF ₃ OEt ₂ : 12.6μL, 0.10m
mol) and stir at room temperature for 1 hour. Then DD
Q (2,3-dichloro-5,6-dicyano-1,4-benzoquinone)
(170 mg, 0.75 mmol) and stirred at room temperature for 1 hour.
The purple product was separated by silica gel column chromatography (Wakogel C-200, as a 1% methanol / CH ₂ Cl ₂ solution), and methanol / CH
Recrystallization from ₂ Cl ₂ gives 1- ⁱ Pr as a purple solid. Yield 20%. 1- ⁱ Pr: Physical properties of ββββ form Melting point,> 300 ° C; ¹ HNMR (CDCl ₃ , 500 MHz, 27 ° C): δ (ppm)
9.94 (d, J = 2.0 Hz, 4H, CHO), 9.13 (s, 8H, β-H), 8.00 (s, 4H,
pyrrolyl-αH), 7.86 (d, J = 2.0 Hz, 4H, pyrrolyl-βH) 5.84
(sept, J = 6.5 Hz, 4H, CH ₃ ), 1.8 (d, J = 6.5 Hz, 24H, CH ₃ ),-2.
60 (s, 2H, inner- NH); 13 CNMR (CDCl 3, 125.65MHz, -50 ℃):
δ (ppm) 180.50 (CHO), 155.07,138.13,133.89 (βC), 131.4
1 (pyrrole-αC), 131.24 (pyrrole-βC), 130.48,127.66
(βC), 125.82, 112.76, 49.68 (CH), 23.87 (CH3); IR (KBr): 1
662.82 cm ^-1 (v (C = O)); UV / vis (CHCl ₃ ): λmax (nm) (ε × 1
0 ^-4 ) 428.5 (57), 526.0 (1.4), 568.5 (2.0), 662.0 (0.87)
(Spectrum: FIG. 1); FABMS: m / z (% intensity) = 850.6 (86,
^{M +), 851.7 (100,} M + +1); HRMS (FAB): C 52 H 5 1N8O4 [M ⁺ +1]:
Calc 851.4033; found 851.4139; Component _{Analysis: C 52 H 50 N 8 0} 4 H
₂ : Calculated: C, 71.87; H, 6.03; N, 12.89. Found: C, 72.26; H,
6.00; N, 12.50. Protonated 1- ⁱ Pr: UV / vis (1% TFA-CH ₂ C
l ₂ ): Top view 2 (a) and side view 2 (b) of the compound λmax [nm] 454.0, 709.0

B. Production of 2- ⁱ Pr, 3- ⁱ Pr, + 4- ⁱ Pr 2.4-Diformyl-1-isopropylpyrrole (165 mg, 1.0 mm
ol) and SnCl ₂ (379 mg, 1.0 mmol) in acetic acid (10 ml), add pyrrole (67 mg, 1 mmol) and stir at room temperature for 1 hour. DDQ (340.5 mg, 1.5 mmol) is added and stirred for 30 minutes. After removing the solvent, flash silica gel column chromatography (Merck Type 60; 1% methanol / CH ₂ Cl ₂ )
To separate the three components. The second fraction was recrystallized from methanol / CH ₂ Cl ₂ to give a purple 2- ⁱ Pr solid.
From the third fraction a mixture of 3- ⁱ Pr and 4- ⁱ Pr (1: 1) was obtained. 2- ⁱ Pr: physical properties of αβββ form ¹ HNMR (CDCl ₃ , 500 MHz, 27 ° C.): δ (ppm) 10.17 (s, 1H, βCH
O), 9.94 (d, J = 1.0 Hz, 1H, α-CHO), 9.93 (d, J = 1.0 Hz, 2H,
α-CHO), 9.13 (m, 6H, β-H), 8.88 (d, J = 4.5 Hz, 2H, β-H),
8.00 (s, 1H, pyrrolyl-αH), 7.98 (s, 2H, pyrrolyl-αH), 7.
97 (d, J = 2.0 Hz, 1H, pyrrolyl-αH), 7.86 (d, J = 2.0 Hz, 1H,
pyrrolyl-βH), 7.84 (d, J = 2.0 Hz, 2H, pyrrolyl-βH), 7.4
9 (d, J = 2.0 Hz, 1H, pyrrolyl-βH), 5.82 (sept, J = 6.5 Hz, 3
H, CH), 3.99 (sept, J = 6.5 Hz, 1H, CH), 1.80 (d, J = 6.5 Hz, 6
H, CH ₃ ), 1.79 (d, J = 6.5 Hz, 12H, CH ₃ ), 1.27 (d, J = 6.5 Hz, 6
_{H, CH 3), - 2.59} (s, 2H, inner-NH); UV / vis (CHCl 3): λmax [n
m) 428.5, 525.0, 565.5), 658.0.

Physical properties of the 3- ⁱ Pr: αβαβ and 4- ⁱ Pr: ααββ forms (the two isomers cannot be separated) ¹ H NMR (CDCl ₃ , 500 MHz, 27 ° C.): δ (ppm) 10.17 or 10.16
(s, 2H, β-CHO), 9.93 or 9.92 (d, J = 2.0 Hz, 2H, α-CHO),
9.14 (m, 4H, β-H), 8.89 (m, 4H, βH), 7.97 (m, 4H, pyrrolyl-
αH), 7.97 (m, 4H, pyrrolyl-αH), 7.84 or 7.82 (d, J = 2.0
Hz, 2H, pyrrolyl-βH), 7.50 or 7.47 (d, J = 2.0 Hz, 2H, pyr
rolyl-βH), 5.81 (m, 2H, CH), 3.95 (m, 2H, CH), 1.77 (m, 12H,
CH ₃ ), 1.25 (m, 12H, CH ₃ ),-2.62 or -2.68 (br, 2H, inner-N
H)

Example 4 N-isopropyl-tetrapyrrolylporphyrin dipyrrome
Tan derivatives 1-ⁱTo a solution of Pr (17 mg, 0.02 mmol) in pyrrole (2 mL) was added
Add fluoroacetic acid (TFA, 6.2 μL 0.08 mmol) and add
Stir for 30 minutes. A small amount of triethylamine (Et_ThreeN)
In addition, the pyrrole is removed by distillation. Blue-green generation
The product is silica gel column chromatography (Wakogel C-
200). result of analysis¹ NNMR (2% Et_ThreeN / CDCl_Three, 500 MHz, room temperature): δ (ppm) 9.14 (br,
8H, dipyrrometane-pyrrole-NH), 8.53 (s, 8H, βH), 7.54
(s, 4H, meso-pyrrole-αH), 6.90 (s, 4H, meso-pyrrole-β
H), 6.78 (d, J = 2.0 Hz, 8H, dipyrrometane-pyrrole-αH),
6.24 (s, 8H, dipyrrometane-pyrrole-βH), 5.89 (s, 4H, dip
yrrometane-meso-H), 4.64 (sept, J = 6.5 Hz, 4H, isopropyl
-CH), 1.53 (d, J = 6.5Hz, 24H, isopropyl-CH_Three),-2.42 (br, 2
H, inner-NH); UV / vis (CHCl_Three): λmax (nm) 438.5,539.5,5
88.0,680.0); MALDI-TOF-MS: m / z = 1315.8 (M ⁺+1).
Protonated form: UV / vis (CH_TwoCl_Three): λmax (nm) 454.5,767.
Five

Example 5 N-isopropyl-formyl-tetrapyrrolylporphyrin
Ni complex 1-iPr (315mg, 0.37mmol) in toluene solution
Acetylacetone (190mg, 0.74mmol) was added and the reflux temperature
For 0.75 hours. Solvent is basic alumina column
Through to remove excess nickel salts and evaporate
Remove more solvent. Methanol / CH_TwoCl_ThreeRecrystallized from
A red solid compound was obtained in a yield of 94%. Product analysis results¹ NNMR (CDCl_Three, 500 MHz, 27 ° C): δ (ppm) 9.86 (d, J = 1.0 H
z, 4H, CHO), 8.99 (s, 8H, β-H), 7.73 (s, 4H, pyrrole-αH),
7.69 (d, J = 1.0 Hz, 4H, pyrrole-βH), 6.96 (dd, 4H, pyrroly
l-H), 4.53 (sept, J-2.0 Hz, 4H, CH), 1.69 (d, J = 6.5 Hz, 24
H, CH_Three); UV / vis (CH_TwoCl _Three): λmax (nm) 429.0,538.0; FABM
S: m / z (% strength) = 906.4 (93, M⁺), 907.4 (100, M⁺+1).

Example 6 N-isopropyl-tetrapyrrolylporphyrin Ni complex TFA was added to a pyrrole solution of compound 7 (235 mg, 0.26 mmol).
(19.9 μL, 0.26) and stirred at room temperature for 3 hours. A small amount of Et3N is added and the pyrrole is removed by distillation. The purple product is separated by flash silica gel chromatography (Merck Type 60). Recrystallization from methanol / CH ₂ Cl ₃ yielded a purple solid compound in 46 yield.
%. Analysis result of product ¹ NNMR (CDCl ₃ , 500 MHz, room temperature): δ (ppm) 9.08 (d, J = 3.0 H
z, 8H, β-H), 7.31 (dd, 4H, pyrrole-αH), 7.12 (dd, 4H, pyrr
ole-αH), 6.96 (dd, 4H, pyrrole-βH), 4.53 (sept, J = 6.5 H
z, 4H, CH), 1.69 (d, J-6.5 Hz, 24H, CH 3); UV / vis (CH 2 Cl 3):
λmax [nm] 433.5, 544.0; 588.5 (spectrum, FIG. 3); F
ABMS: m / z (% intensity) = 794.4 (100, M ⁺ ).

It should be noted that the porphyrins may be Z in addition to Ni.
n, Mg, Ca, Sr, Ba, Sc, Y, La, Ce,
Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, E
r, Tm, Yb, Lu, Ti, Zr, Hf, V, Nb,
Ta, Th, U, Cr, Mo, W, Mn, Tc, Re,
Fe, Ru, Os, Co, Rh, Ir, Pd, Pt, C
u, Ab, Au, Cd, Hg, Al, Ga, In, T
Of course, it can be replaced with 1, Si, Ge, Sn, Pb, As, Sb, Bi or the like.

[0037]

As described above, the porphyrins are used as they are, and the reactive group of the porphyrin, N
An excellent effect is obtained that it can be used for synthesizing many useful compounds by utilizing the coordination characteristics of atoms with a transition metal.

[Brief description of the drawings]

FIG. 1 shows the spectrum of form 1- ⁱ Pr: ββββ of Example 3.

FIG. 2 is a top view (a) and a side view (b) of the 1- ⁱ Pr: ββββ form of Example 3.

FIG. 3 is a spectrum of the N-isopropyl-tetrapyrrolylporphyrin Ni complex of Example 6.

Claims (4)

[Claims] 1. A metal or metal-free tetrapyrrolyl-substituted porphyrin compound represented by the formula 1, wherein all meso positions are substituted with a pyrrole group. Embedded image [In the formula 1, Pyr1, Pyr2, Pyr3, and Pyr
The group 4 may be a pyrrole group of the formula 2 or 3 or a mixture of the two types of pyrrole, and is a group selected from the group of the formula 2 or 3. However, Equation 2 is (In the formula 2, R ¹ is H or a hydrocarbon group having 1 to 3 carbon atoms, and R ² is H, formyl or formula 4.) (In the formula 3, R ¹ and R ² are the same as the formula 2.) 2. Pyrrole represented by the formula (5): Diformylpyrrole compound represented by Formula 6 (Wherein R in the formula 6 is H or a hydrocarbon group having 1 to 3 carbon atoms) to obtain a compound of the formula 7, wherein the compound of the formula 7 is a transition metal compound or the presence of an acid catalyst and pyrrole. A method for producing a metal or metal-free tetrapyrrolyl-substituted porphyrin compound of the above formula 1 by treating under the following conditions. Embedded image [In Formula 7, Pyr′1, Pyr′2, Pyr′3, and Pyr′4 are all formyl-substituted pyrrole groups of Formula 8 or Formula 9, or a mixture of the two types of pyrrole. Which is a group selected from the groups of the formulas 8 and 9. Where Equation 8 is (In the formula 8, R ¹ is H or a hydrocarbon group having 1 to 3 carbon atoms.) (In the formula 9, R ¹ is the same as the formula 8)] 3. The method for producing tetrapyrrolyl-substituted porphyrin compounds according to claim 2, wherein an acid is present in a reaction system for obtaining the metal-free compound of the formula 1. 4. The method for producing tetrapyrrolyl-substituted porphyrin compounds according to claim 3, wherein the reaction for obtaining the metal-free compound of the formula 1 is carried out in pyrrole in the presence of trifluoroacetic acid.