JP5823988B2 - Method for producing metal complex of compound having porphyrin type skeleton - Google Patents

Description

  The present invention relates to a method for producing a metal complex of a compound having a porphyrin type skeleton.

  A metal complex of porphyrin, which is one of compounds having a porphyrin-type skeleton, has various characteristics. For example, a metal complex of porphyrin has a π-conjugated system in the molecule, and π electrons move freely in the porphyrin molecule, thereby transmitting information and energy important for life activities. Further, the π-conjugated system has a certain spread, and the spread has a great influence on the absorption of ultraviolet light and visible light, and therefore has characteristic optical characteristics in the ultraviolet-visible region. Specifically, the porphyrin metal complex is derived from a heteropolyene structure (18π electron system) in the skeleton, and has a sharp absorption band called 400 nm to 500 nm called a Soray band and a 500 nm to 700 nm called Q band. Since the former is a forbidden transition while the latter is an allowable transition, there is a characteristic that there is a large difference in each molecular extinction coefficient. In addition, the Q band is split into four when porphyrin is used alone. However, when the complex is made into a complex, the symmetry increases and the number of splits is reduced. Furthermore, the absorption spectrum of the Soret band, the Q band, etc. is characterized in that it differs depending on the skeleton shape, external substituent, central metal, ligand, etc. of the porphyrin metal complex. Because of these diverse properties, porphyrin metal complexes are not only present in biological systems, but are frequently used as functional substances and are actively studied.

  For example, porphyrin metal complexes are used as analytical reagents based on the above-mentioned characteristic optical properties. In addition, chlorophyll metal complexes and porphyrin zinc complexes, which are compounds having a porphyrin-type skeleton, cause photoelectron transfer by absorbed light, and thus are being studied for application to solar cells. Moreover, many metal complexes of porphyrin are luminescent, and they have been studied as light emitting materials for organic EL. Among porphyrin metal complexes, those exhibiting stable redox properties have been utilized as catalysts for organic synthesis and the like. Furthermore, porphyrin metal complexes themselves become supramolecules due to interactions derived from the π-conjugated system. Porphyrin metal complexes also become supramolecules by complex formation with axial ligands. Since the metal complex of porphyrin strongly stacks to DNA, research as a sensitizer for phototherapy is also being conducted. Thus, since the metal complex of the compound having a porphyrin type skeleton has various characteristics, in recent years, it has been used in a wide range of fields such as functional materials such as solar cells and catalysts, pharmaceuticals such as sensitizers, and agricultural chemicals. Application is expected.

  Under such a background, various studies on methods for synthesizing metal complexes of compounds having a porphyrin-type skeleton have been conducted. It is said that a porphyrin metal complex can be synthesized by reacting porphyrin with metal acetate mainly in refluxed acetic acid or formic acid. For example, when porphyrin and copper acetate are reacted in refluxed acetic acid or formic acid, a porphyrin copper complex is formed, and when porphyrin and silver acetate are reacted, a porphyrin silver complex is formed, and porphyrin and gold chloride are combined. When reacted, a porphyrin gold complex is formed. When porphyrin and zinc acetate are reacted, a porphyrin zinc complex is formed. When porphyrin and manganese acetate are reacted, a porphyrin manganese complex is formed, and the porphyrin and iron acetate are reacted. It is said that a porphyrin iron complex is produced | generated, a porphyrin cobalt complex will be produced | generated when a porphyrin and cobalt acetate are made to react, and a porphyrin nickel complex will be produced | generated when a porphyrin and nickel acetate are made to react (nonpatent literature 1).

  Moreover, it is said that a metal complex of porphyrin can be synthesized by reacting porphyrin and mainly metal acetate in pyridine. For example, reacting porphyrin with cadmium acetate in pyridine produces a porphyrin cadmium complex, reacting porphyrin with mercury acetate produces a porphyrin mercury complex, and reacting porphyrin with thallium acetate produces a porphyrin thallium complex. When porphyrin and tin chloride are reacted, a porphyrin tin complex is formed. When porphyrin and lead acetate are reacted, a porphyrin lead complex is formed. When porphyrin magnesium acetate is reacted, a porphyrin magnesium complex is formed. (Non-Patent Document 2).

  Further, as a method for introducing a metal into a compound having a porphyrin-type skeleton, it is said that porphyrin dimethyl ester can be obtained by reacting porphyrin and mainly metal carbonyl in an organic solvent. For example, each porphyrin dimethyl ester is produced by reacting porphyrin with any one of chromium, cobalt, nickel, iron, carbonyl of vanadium, and diphenyltitanium in an organic solvent (non-patent document). Reference 3).

  Currently, as a method of synthesizing a metal complex of a compound having a porphyrin skeleton, there is a method of synthesizing a metal complex of porphyrin by dissolving them in a polar organic solvent in which both the compound having a porphyrin skeleton and a metal salt are dissolved. It has been proposed (Non-Patent Document 4). Specifically, by dissolving a compound having a porphyrin-type skeleton and a metal salt in a polar organic solvent such as N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetic acid and pyridine, and reacting them, It is said that a metal complex of a compound having a porphyrin skeleton can be synthesized. For example, tetraphenylporphyrin and any one selected from zinc, copper, magnesium, nickel, cobalt, iron, chromium, manganese, vanadium oxide, mercury, cadmium, lead, tin, magnesium, barium, calcium, palladium, and silver, It is said that when an acetate, a halide, a hydroxide or a carbonate is reacted in N, N-dimethylformamide (DMF), an equivalent tetraphenylporphyrin metal complex is formed (Non-patent Document 5).

  Furthermore, when tetraphenylporphyrin and copper chloride are reacted in dimethyl sulfoxide (DMSO) at 35 ° C. to 60 ° C., it has been proposed to form a tetraphenylporphyrin copper complex (Non-patent Document 6).

P. Rothemund and A.R.Menotti, “Porphryn Studies.V The Metal Complex Salts of α, β, γ, δ―Tetraphenylporphine”, J.Am.Chem.Soc., 70, 1808-1812 (1948). G.D.Dorough, J.R.Miller and F.M.Huennekens, “Spectra of the Metallo-derivatives of α, β, γ, δ-Tetraphenylporphine”, J.Am.Chem.Soc., 73, 4315-4320 (1951). M. Tsutsui, RAVelapoldi, K. Suzuki, F. Vohwinkel, M. Ichikawa and T. Koyano, “Unusual metalloporphyrins. IV. Novel methods for metal insertion into porphyrins”, J. Am. Chem. Soc., 91, 6262 -6266 (1969). A.D.Adler, F.R.Longo, J.D.Finarelli, J.Goldmacher, J.Assour and L.Korsakoff, “A Simplified Synthesis for meso-Tetraphenylporpjhin”, J.Org.Chem., 32, 476 (1967). A.D.Adler, F.R.Longo, F.Manpas and J.Kim, “On the preparation of metalloporphyrins”, J. Inorg. Nucl. Chem., 32, 2443-2445 (1970). R.F.Pasternack, G.C.Vogel, C.A.Skowronek, R.K.Harris and J.G.Miller, “Copper (II) Incorporation into Tetraphenylporphine in Dimethyl Sulfoxide”, J. Inorg.Chem., 20, 3763-3765 (1981).

  However, ordinary organic solvents have a problem that it is difficult to dissolve metal salts. In addition, the polar organic solvent can dissolve the metal salt, but is harmful, and depending on the type, there is a problem that handling is not easy, such as generating a bad odor. In addition, the polar organic solvent not only dissolves the compound and metal salt having a porphyrin-type skeleton that is a reaction raw material, but also dissolves the metal complex that is a product, so that it is difficult to separate the generated metal complex. There is a problem that there is. Furthermore, in the case of using a polar organic solvent, in order to separate the product from the polar solvent, a step of volatilizing the polar organic solvent having a high boiling point and a step of adding and reseparating a cosolvent are necessary. There is a problem that it is complicated.

  The present invention has been made in order to solve the above-mentioned problems, and the object thereof is not to use an organic solvent at the time of reaction, and after the reaction, the metal complex and water can be easily separated. It is an object of the present invention to provide a method for producing a metal complex of a compound having a porphyrin-type skeleton that has an extremely low environmental burden and is efficient in a small number of steps.

  As a result of intensive studies, the inventors have made a mixture of a metal salt and a compound having a porphyrin type skeleton in water at a high temperature and a high pressure, and dissolving the metal salt and the compound having a porphyrin type skeleton in high temperature and high pressure water. The inventors have found a technique for producing a metal complex of a compound having a porphyrin skeleton without using an organic solvent, and completed the present invention.

  The method for producing a metal complex of a compound having a porphyrin-type skeleton according to the present invention for solving the above-described problems is to react a compound having a porphyrin-type skeleton and a metal salt at a reaction temperature of 200 ° C. or higher and 450 ° C. or lower in water. It is characterized by.

  According to the present invention, the compound having a porphyrin-type skeleton and the metal salt are reacted in water at a reaction temperature of 200 ° C. or higher and 450 ° C. or lower, so that water is used without using a harmful and malodorous organic solvent. A metal complex of a compound having a porphyrin type skeleton can be produced. Moreover, since water is used as a solvent, the product metal complex can be easily separated from the water solvent. As a result, as in the case of using a polar organic solvent, in the solvent after the reaction, the compound and metal salt having a porphyrin type skeleton that is a reaction raw material, and the metal of the compound having a porphyrin type skeleton that is a product The problem that all of the complex is dissolved and separation becomes difficult can be avoided. Furthermore, when separating the metal complex and water, there is no need for a volatilization step or a co-solvent addition and re-separation step as in the case of using a high-boiling polar organic solvent. The separation process can be simplified. As described above, according to the production method of the present invention, a metal complex of a compound having a porphyrin skeleton can be efficiently produced by a method with a very small environmental load and with few steps.

  In a preferred embodiment of the method for producing a metal complex of a compound having a porphyrin skeleton according to the present invention for solving the above-mentioned problems, the compound having a porphyrin skeleton is tetraphenylporphyrin represented by the following formula (1). . In formula (1), Ph represents a phenyl group.

  According to this invention, since the compound having a porphyrin skeleton is tetraphenylporphyrin represented by the above formula (1), it can be easily applied widely to general compounds having a porphyrin skeleton.

  The method for producing a metal complex of a compound having a porphyrin-type skeleton according to the present invention for solving the above-mentioned problems is obtained by reacting a compound having a porphyrin-type skeleton and a metal salt in water at a reaction temperature of 200 ° C. or higher and 450 ° C. or lower. A reaction step of generating a metal complex of a compound having a porphyrin-type skeleton, and a separation step of lowering the reaction temperature to separate the water and the metal complex of the compound having a porphyrin-type skeleton. .

  According to the present invention, since the reaction step and the separation step described above are provided, a clean process using only water can be realized without using an organic solvent that generates harmful and offensive odors. Moreover, since water is used as a solvent, the product metal complex can be easily separated from the water solvent. As a result, as in the case of using a polar organic solvent, in the solvent after the reaction, the compound and metal salt having a porphyrin type skeleton that is a reaction raw material, and the metal of the compound having a porphyrin type skeleton that is a product The problem that all of the complex is dissolved and separation becomes difficult can be avoided. Furthermore, when separating the metal complex from water, there is no need for a volatilization step or co-solvent addition and re-separation step as in the case of using a high-boiling polar organic solvent. The process can be simplified. As described above, according to the production method of the present invention, a metal complex of a compound having a porphyrin skeleton can be efficiently produced by a method with a very small environmental load and with few steps.

  In a preferred embodiment of the method for producing a metal complex of a compound having a porphyrin-type skeleton according to the present invention for solving the above problems, the compound having a porphyrin-type skeleton is tetraphenylporphyrin represented by the following formula (1). The metal complex of the compound having a porphyrin type skeleton is a tetraphenylporphyrin metal complex represented by the following formula (2). In formula (1), Ph represents a phenyl group. In formula (2), Ph represents a phenyl group, and M represents a metal.

  According to this invention, the compound having a porphyrin type skeleton is tetraphenylporphyrin represented by the above formula (1), and the metal complex thereof is a tetraphenylporphyrin metal complex represented by the above formula (2). It becomes easy to apply widely to general compounds having a porphyrin type skeleton.

  In a preferred embodiment of the method for producing a metal complex of a compound having a porphyrin type skeleton according to the present invention for solving the above-mentioned problems, the metal salt is a sulfate.

  According to the present invention, since sulfate is used as the metal salt, the metal species are likely to exist in a cation state. As a result, the metal salt easily reacts with the compound having a porphyrin skeleton, and the metal complex can be stably produced at a high yield. In addition, a metal complex of a compound having a porphyrin skeleton can be manufactured using an inexpensive metal salt.

  According to the method for producing a metal complex of a compound having a porphyrin skeleton according to the present invention, the metal complex and water can be easily separated after the reaction without using an organic solvent. As a result, a metal complex of a compound having a porphyrin-type skeleton can be efficiently produced by a method with a very low environmental load and with few steps.

  Specifically, the phenomenon that both a compound having a porphyrin-type skeleton and a metal salt are dissolved in water only at a predetermined reaction temperature is used. As a result, it is possible to produce a metal complex of a compound having a porphyrin-type skeleton in which the produced metal complex and water can be easily separated without using a harmful organic solvent.

It is a figure which shows the metal introduction | transduction reaction to the compound which has a porphyrin type frame | skeleton. It is thin film chromatography which shows the influence of the temperature with respect to reaction with tetraphenylporphyrin and copper sulfate aqueous solution. It is a graph which shows the temperature dependence of reaction with tetraphenylporphyrin and copper sulfate aqueous solution. It is a graph which shows the temperature dependence of reaction with tetraphenylporphyrin and nickel sulfate aqueous solution. It is a graph which shows the temperature dependence of reaction with tetraphenylporphyrin and cobalt sulfate aqueous solution. It is a graph which shows the relationship between the yield of tetraphenylporphyrin copper complex, and reaction time. It is a graph which shows the effect of an anion. It is a graph which shows metal seed | species dependence. It is a graph which shows porphyrin species dependence.

  Hereinafter, the manufacturing method of the metal complex of the compound which has a porphyrin type skeleton concerning the present invention is explained concretely, referring to drawings. The present invention is not limited to the following embodiments and experimental examples.

[Method for producing metal complex]
The method for producing a metal complex of a compound having a porphyrin type skeleton according to the present invention (hereinafter also simply referred to as “metal complex”) is preferably a compound having a porphyrin type skeleton and a metal salt in water at 200 ° C. or higher and 450 ° C. or lower, preferably Is a reaction at a reaction temperature of 300 ° C. or higher and 400 ° C. or lower.

(Compound having porphyrin skeleton)
A porphyrin-type skeleton is a skeleton structure such as porphyrin, and a compound having a porphyrin-type skeleton is a compound having such a skeleton structure. Specifically, the compound having a porphyrin type skeleton includes a compound having a structure represented by the following formula (3) and the following formula (4). In formula (3), Z ^ia and Z ^ib represent a hydrogen atom, a halogen atom or a monovalent organic group, R ^{1 to} R ⁴ represent a hydrogen atom, a halogen atom or a monovalent organic group, and i is 1 Represents an integer of ~ 4. In formula (4), Z ^ia and Z ^ib represent a hydrogen atom, a halogen atom or a monovalent organic group, and i represents an integer of 1 to 4.

As Z ^ia and Z ^ib (wherein i represents an integer of 1 to 4) in the above formula (3) and the above formula (4), a hydrogen atom; a hydroxyl group; and an optionally substituted one having 1 to 10 carbon atoms, Alkyl group, alkoxy group, mercapto group (alkylthio group), acyl group and carboxyl group; ester of carboxyl group and alcohol having 1 to 10 carbon atoms; formyl group; carbamoyl group; halogen atoms such as fluorine, chlorine, bromine and iodine An amino group and a nitro group which may be substituted with an alkyl group having 1 to 10 carbon atoms; These may further have a substituent. Z ^ia and Z ^ib may be bonded to each other to form a ring. ^Examples of the ring formed as a structure of Z ^ia —CH═CH—Z ^ib include a benzene ring, a naphthalene ring and an anthracene ring. Aromatic hydrocarbons such as pyridine ring, quinoline ring, furan ring and thiophene ring; non-aromatic cyclic hydrocarbons such as cyclohexene; Moreover, as monovalent organic group of R < ¹ > -R < ⁴ >, the alkyl group, aryl group, alkoxy group, mercapto group, carboxyl group, and carboxyl group which may be substituted, and C1-C10 alcohol Examples include esters.

  The compound having a porphyrin type skeleton is particularly preferably one or two selected from tetraphenylporphyrin and tetra-t-butyltetraazaporphyrin represented by the following formula (1). In formula (1), Ph represents a phenyl group.

The compound having a porphyrin-type skeleton is contained in water described later in a range corresponding to 5 × 10 ⁻⁴ mol / L to 1 mol / L, preferably 5 × 10 ⁻³ mol / L to ¹ × 10 ^−1. included in a range corresponding to a mol / L, more preferably, it comprises in the range corresponding to ^{1 × 10 -2 mol / L~5 ×} 10 -2 mol / L.

(Metal salt)
The metal salt is not particularly limited as long as it is a reaction raw material for reacting with a compound having a porphyrin-type skeleton to form a metal complex, but it may literally be a metal salt or other metal and halogen atoms, etc. It may be a salt (metal complex salt) of an atom bonded to an atom or a metal complex. Examples of metal salts and metal complex salts include sulfates, nitrates, chlorides, acetates, carbonates, bicarbonates, dihydrogen phosphates, hydroxides, and citrates.

  Examples of the metal salt, metal complex salt and metal constituting the metal complex include alkali metals such as Li, Na and K; alkaline earth metals such as Mg, Ca and Ba; transition metals such as Fe, Ni, Cu and Au And the like. Examples of the metal complex salt in which the metal and other atoms are bonded include those in which the metal is bonded to a halogen atom or the like.

  As a metal complex, the porphyrin metal complex which has the above-mentioned metal can be mentioned. The porphyrin metal complex is insoluble in water at room temperature, but in the present invention, high-temperature and high-pressure water is used as a solvent, so the porphyrin metal complex is soluble in water. As a result, the porphyrin metal complex can be used as a reaction raw material for generating the metal complex. As such a porphyrin metal complex, a porphyrin metal complex in which one porphyrin ring coordinates one or two or more metal atoms, two or more porphyrin rings have one or two or more metal atoms A porphyrin metal complex in which three or more of these are bonded together and a porphyrin metal complex in which three or more of these are bonded to form a long chain can be exemplified, but the invention is not limited thereto.

Metal salt, preferably selected Cu, Ni, Co, V = O, Fe, Mn, Mg, Cr, Zn, from ^{Fe-B 1, Al-B} 2, Ti = O, and ^Si-B 3 B ⁴ 1 type or 2 types or more selected, More preferably, 1 type or 2 types or more chosen from Cu, Ni, Co, and V = O is included. Note that “=” in “Ti═O” and “V═O” represents a double bond, and “−” in “Fe—B ¹ ”, “Al—B ² ”, and “Si—B ³ B ⁴ ”. "Represents a single bond. B ¹ , B ² , B ^3, and B ⁴ represent any one monovalent group selected from a halogen atom, an alkyl group, and an alkoxy group.

  Since the metal salt dissolves well in water, which will be described later, inexpensive metal salts such as sulfates, chlorides and hydroxides can be used without using expensive acetates. Among the above metal salts, sulfate is preferable in terms of increasing the yield of the product. Specifically, it is preferable that it is 1 type, or 2 or more types chosen from copper sulfate, nickel sulfate, cobalt sulfate, and vanadyl sulfate.

The metal salt is contained in water described later in the range of 1 × 10 ⁻³ mol / L to 5 mol / L, preferably in the range of 1 × 10 ⁻² mol / L to 5 × 10 ⁻¹ mol / L. More preferably, it is contained in the range of 5 × 10 ⁻² mol / L to ¹ × 10 ⁻¹ mol / L.

(water)
Water acts as a solvent. In the present invention, since no organic solvent is used, a method for producing a clean metal complex with an extremely low environmental load can be obtained. In addition, since water dissolves the above-described metal salts well, metal complexes can be formed using inexpensive metal salts such as sulfates, chlorides and hydroxides without using expensive metal salts such as acetates. Can be manufactured. In addition, since the metal complex to be produced is insoluble in water below the predetermined reaction temperature, after the metal complex is produced, for example, the metal complex can be easily separated from water simply by bringing the temperature of the water to room temperature. It is possible to simplify the manufacturing process and make it economical. Furthermore, since the metal complex can be easily separated from water, the metal complex can be recovered in a high yield, and industrial production can be expected. Thus, by using water as a solvent, it can be set as the manufacturing method which can use an inexpensive metal salt with little environmental burden, and can isolate | separate and collect | recover a metal complex easily.

  Water dissolves inorganic salts such as metal salts well. However, room temperature water has a high dielectric constant, and therefore hardly dissolves nonpolar organic substances. Therefore, the temperature of the water is set to 250 ° C. or more and 400 ° C. or less, and the pressure is further increased. Such high-temperature and high-pressure water has a dielectric constant as low as that of a polar organic solvent, and dissolves inorganic salts as well as inorganic salts. In particular, near the critical temperature of water (374.1 ° C.), water dissolves organic substances well enough to form a homogeneous phase with various organic substances. As described above, high-temperature and high-pressure water has a feature that it becomes a reaction solvent capable of dissolving both inorganic substances and organic substances.

  For example, when a dissolution experiment in which tetraphenylporphyrin (hereinafter sometimes abbreviated as “TPP”), which is a compound having a porphyrin type skeleton, is dissolved in water, a liquid phase (aqueous phase) is obtained at 250 ° C. (3.4 MPa). And dissolved in a liquid phase (aqueous phase) at 300 ° C. (7.8 MPa). As the temperature rises and the density of water in the gas phase approaches the density of water in the liquid phase, TPP dissolves in the water in the gas phase. When the vapor phase and the liquid phase become uniform at 375 ° C. (21.3 MPa), TPP is completely dissolved in water. Thus, high-temperature high-pressure water is expected as a new reaction field because it dissolves a compound having a porphyrin-type skeleton.

  The mechanism by which high-temperature high-pressure water dissolves a compound having a porphyrin skeleton is considered as follows. As the water temperature increases, the dielectric constant of the water decreases. Along with this, the polarity of water decreases and approaches nonpolarity. From this, as the temperature of the water rises, the high-temperature and high-pressure water will dissolve the organic matter, and will dissolve TPP well.

  The method for producing a metal complex of a compound having a porphyrin-type skeleton according to the present invention includes a compound having a porphyrin-type skeleton by reacting a compound having a porphyrin-type skeleton and a metal salt in water at a reaction temperature of 200 ° C. to 450 ° C. A reaction step of generating a metal complex, and a separation step of lowering the reaction temperature to separate water and the metal complex of the compound having a porphyrin-type skeleton. By providing such a reaction step and a separation step, a method for producing a metal complex of a compound having a clean porphyrin-type skeleton that is extremely simple, inexpensive, has a low environmental impact, and is industrially easy to employ. Can be provided.

(Reaction process)
The reaction step is a step of producing a metal complex of a compound having a porphyrin type skeleton by reacting a compound having a porphyrin type skeleton and a metal salt in water at a reaction temperature of 200 ° C. or higher and 450 ° C. or lower. In the reaction step, a compound having a porphyrin-type skeleton is dissolved in water and reacted with a metal salt at a high temperature of 200 ° C. to 450 ° C. and a high pressure state of 1.0 MPa to 50.0 MPa. When the reaction temperature is less than 200 ° C., the reaction rate is low, and thus the efficiency is deteriorated. When the reaction temperature exceeds 450 ° C., side reactions other than the metal complex that is the target product are likely to proceed. The reaction temperature is preferably 300 ° C. or higher and 400 ° C. or lower, more preferably 350 ° C. or higher and 380 ° C. or lower. The compound having a porphyrin-type skeleton, metal salt and water used in the reaction step are as described above.

  In the reaction step, for example, an aqueous metal salt solution and a compound having a porphyrin skeleton are introduced into a sealed reaction vessel (for example, a high-temperature high-pressure vessel capable of applying temperature and pressure), and the high-pressure vessel is placed in a sand bath. It is possible to carry out the process at a predetermined temperature and pressure. The reaction time is from 10 minutes to 120 minutes, preferably from 30 minutes to 60 minutes. By setting the reaction time within the above range, the metal complex can be reliably produced. In addition, reaction time here means the time which passed since the reaction container inside became a high temperature / high pressure state.

  FIG. 1 is a diagram showing a metal complex formation reaction when tetraphenylporphyrin (TPP) is used as a compound having a porphyrin-type skeleton. As shown in FIG. 1, TPP and a metal salt are reacted in water at a temperature of 300 ° C. or higher and 400 ° C. or lower under high pressure. By bringing the mixture of the metal salt and the compound having a porphyrin-type skeleton into a high-temperature and high-pressure state in water, the metal salt and the compound having a porphyrin-type skeleton can be dissolved in the high-temperature and high-pressure water without using an organic solvent. A metal complex of a compound having a porphyrin type skeleton can be produced.

  Prior to the reaction step, necessary pre-steps such as a step of preparing a compound having a porphyrin-type skeleton and a metal salt can be appropriately added. In the reaction step, an appropriate amount of components necessary for producing a metal complex of a compound having a porphyrin type skeleton may be contained in water as long as it is within the scope of the present invention.

(Separation process)
The separation step is a step of separating water and the metal complex by lowering the reaction temperature after the above-described reaction step. Since the metal complex of the compound having a porphyrin type skeleton is insoluble in water at a temperature lower than the predetermined reaction temperature described above, the metal complex becomes a solid product by lowering the reaction temperature after the reaction step. Precipitate. As a result, the metal complex and water can be easily separated. When the reaction temperature is lowered to room temperature, the metal complex and water can be separated and the subsequent operation is facilitated. Room temperature refers to the temperature at which the liquid phase is formed at approximately 100 ° C. or lower. Separation of water and the metal complex can be performed, for example, by putting the reaction vessel after the reaction into a water bath and cooling it. Thereafter, the water after the reaction is filtered to separate the solid product, and the metal complex contained in the solid product can be recovered.

  In addition, when there exists a compound which has an unreacted porphyrin type skeleton in the water after making it react, the compound which has an unreacted porphyrin type skeleton is also contained in the solid product. In this case, the metal complex contained in the solid product and the compound having an unreacted porphyrin-type skeleton can be separated by column chromatography or the like. In this way, the metal complex contained in the solid product can be recovered. Moreover, when there exists an unreacted metal salt in the water after making it react, the unreacted metal salt is also contained in this water. In this case, water can also be referred to as an aqueous metal salt solution containing an unreacted metal salt.

  In addition, you may add another process after a isolation | separation process as needed. As such a process, for example, a nonpolar organic solvent such as chloroform is added to the reaction vessel after the reaction, the metal complex is extracted into the organic phase, and the organic phase is volatilized and concentrated, or column chromatography is performed. And a step of separating a metal complex from a compound having an unreacted porphyrin-type skeleton and a by-product.

[Metal complex]
Examples of the metal complex produced by the method for producing a metal complex of a compound having a porphyrin skeleton according to the present invention include a tetraphenylporphyrin metal complex, a phthalocyanine metal complex, and a tetraazaporphyrin metal complex. The obtained metal complex can be qualitatively analyzed by an ultraviolet-visible spectrophotometer, a mass spectrometer, or the like.

  As described above, the method for producing a porphyrin metal complex according to the present invention can produce a metal complex of a compound having a porphyrin-type skeleton using water without using an organic solvent that generates harmful and offensive odors. it can. Moreover, since water is used as a solvent, the product metal complex can be easily separated from the water solvent. As a result, the separation process can be simplified. As described above, according to the production method of the present invention, a metal complex of a compound having a porphyrin skeleton can be efficiently produced by a method with a very small environmental load and with few steps.

  EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.

(Dissolution observation)
The solubility of tetraphenylporphyrin (TPP) in water was confirmed using a visualization cell having an internal volume of 10 cm ³ . Specifically, the visualization cell containing TPP and water is 50 ° C. (0.1 MPa), 150 ° C. (0.3 MPa), 200 ° C. (1.3 MPa), 250 ° C. (3.4 MPa), 300 ° C. (7.8 MPa), 325 ° C. (11.2 MPa), 350 ° C. (16.0 MPa) and 375 ° C. (21.3 MPa) were set to the respective conditions, and whether or not TPP was dissolved in water was observed. . As a result, it was slightly dissolved in the liquid phase (water) at 250 ° C. (3.4 MPa) and dissolved in the liquid phase (water phase) at 300 ° C. (7.8 MPa). As the temperature increased, TPP dissolved in water in the gas phase. When the gas phase and the liquid phase became uniform at 375 ° C. (21.3 MPa), TPP was completely dissolved in water.

(Experimental Example 1-1)
Using a 50 mL volumetric flask, 1.208 g of copper sulfate as a metal salt was dissolved in 50 mL of distilled water to prepare a 0.1 mol / L CuSO ₄ aqueous solution. Next, 0.02 g (3.3 × 10 ⁻⁵ mol) of tetraphenylporphyrin (TPP) as a compound having a porphyrin type skeleton in a batch reactor (made of stainless steel) having an internal volume of 6 cm ³ as a reaction vessel, An aqueous copper sulfate solution (3.0 g) and reaction vessel corrosion prevention were charged with 0.032 g of sodium carbonate equivalent to copper sulfate, and the reaction vessel was purged with argon and sealed. Next, the reaction vessel was put into a sand bath set at 350 ° C. The reaction temperature reached the reaction temperature in about 4 minutes.

  After making it react for 60 minutes after throwing in, the reaction container was thrown into the water bath and quenched. The reaction vessel was washed with chloroform, and the aqueous phase and the chloroform phase in the reaction vessel were all collected in a screw tube bottle, transferred to a separating funnel, and the aqueous phase and the chloroform phase were separated. Subsequently, the chloroform phase was washed with distilled water and saturated brine. Next, the chloroform phase was passed through sodium sulfate to remove water, and then the chloroform was removed with a rotary evaporator. The obtained solid content was separated by column chromatography using silica gel 60N (manufactured by Kanto Chemical Co., Inc.) as a filler and a 1: 1 solution of chloroform-hexane as a developing solvent to obtain a TPP copper complex solution. When performing column chromatography, thin layer chromatography was appropriately used to confirm whether the TPP copper complex was separated. Thereafter, the developing solvent was further flowed to recover the unreacted TPP solution and by-products.

  These samples were dried and weighed. In addition, the solid product obtained by drying was dissolved again in chloroform as needed at the time of analysis. For the analysis, a visible light absorption spectrum was measured with an ultraviolet-visible spectrophotometer (V-560, manufactured by JASCO Corporation), and further, a matrix-assisted laser desorption ionization method-time-of-flight mass spectrometer (autoflex TOF / TOF, BRUKER) Qualitative analysis was conducted by measuring the mass spectrum.

(Experimental example 1-2)
A TPP copper complex was produced in the same manner as in Experimental Example 1-1 except that the reaction temperature was changed to 150 ° C, 200 ° C, 250 ° C, 300 ° C, and 400 ° C, respectively. The development of thin layer chromatography at each reaction temperature is shown in FIG. 2, and a graph showing the effect of reaction temperature on the yield of TPP copper complex is shown in FIG. In FIG. 3, the rhombus plot represents the yield (mol%) of the TPP copper complex, and the square plot represents the yield (mol%) of TPP.

  As shown in FIG. 2, when the reaction temperature was 150 ° C., the TPP copper complex line was thin and the TPP line was dark, indicating that the reaction hardly proceeded. When the reaction temperature was 200 ° C., the TPP metal complex line was darker than 150 ° C., and when the reaction temperature was increased to 250 ° C. and 300 ° C., the TPP copper complex line became dark. Further, when the reaction temperature was increased to 350 ° C. and 400 ° C., the TPP copper complex line remained dark and the TPP line became thinner. Therefore, it was found that the reaction proceeded efficiently with increasing temperature.

  The pressure in the reaction vessel at each reaction temperature is specifically 0.5 MPa at 150 ° C., 1.6 MPa at 200 ° C., 4.0 MPa at 250 ° C., and 8.6 MPa at 300 ° C. Yes, it was 16.5 MPa at 350 ° C., 27.1 MPa at 380 ° C., and 37.2 MPa at 400 ° C.

  As shown in FIG. 3, the temperature dependence of the reaction between TPP and an aqueous copper sulfate solution was examined. The yield of the TPP copper complex was 8 mol% at 150 ° C, 8 mol% at 200 ° C, 18 mol% at 250 ° C, 32 mol% at 300 ° C, 80 mol% at 350 ° C, and 91 mol% at 400 ° C. From these results, the reaction rapidly progressed around 350 ° C., which was consistent with the dissolution observation result shown in FIG. The yield of the TPP copper complex was 90 mol% or more.

(Experimental Example 1-3)
A TPP copper complex was produced in the same manner as in Experimental Example 1-1 except that the reaction time was changed to 10 minutes, 20 minutes, 30 minutes, and 120 minutes, respectively. The graph showing the yield of the metal complex in each reaction time is shown in FIG. As shown in FIG. 6, the yield of the TPP metal complex is 27 mol% when the reaction time is 10 minutes, 41 mol% for 20 minutes, 42 mol% for 30 minutes, 80 mol% for 60 minutes, and In the case of 120 minutes, it was 66 mol%.

(Experimental example 2-1)
As the metal salt, instead of _{CuSO 4, CoSO 4, NiSO 4} , VOSO 4, Co (NO 3) 2, Ni (NO 3) 2, Cu (NO 3) 2, CoCl 2, NiCl 2 and CuCl _2, respectively A TPP metal complex was produced in the same manner as in Experimental Example 1-1 except that it was used. 7 and 8 show the yields of TPP metal complex, unreacted TPP, by-products and the like when each metal salt is used. FIG. 7 is a graph showing the effect of the anion of the metal salt, and FIG. 8 is a graph showing the effect of the metal species. As shown in FIG. 7 and FIG. 8, when CoSO ₄ is used as the metal salt, the yield of the TPP metal complex is 67 mol%, the yield of unreacted TPP is 27 mol%, and the by-products and unrecovered The yield of the product was 6 mol%. When NiSO ₄ was used as the metal salt, the yield of TPP metal complex was 43 mol%, the yield of unreacted TPP was 53 mol%, and the yield of by-products and unrecovered products was 4 mol%. .

As shown in FIGS. 7 and 8, the yield of TPP metal complex when CuSO ₄ is used as the metal salt is 80 mol%, and the yield of unreacted TPP is 11 mol%. The yield of the recovered product was 8 mol%. The yield of the TPP metal complex when Co (NO ₃ ) ₂ is used as the metal salt is 37 mol%, the yield of unreacted TPP is 20 mol%, as shown in FIG. The yield of unrecovered material was 43 mol%.

As shown in FIG. 7, when Ni (NO ₃ ) ₂ is used as the metal salt, the yield of the TPP metal complex is 27 mol%, the yield of unreacted TPP is 60 mol%, and the by-products and The yield of unrecovered material was 13 mol%. When Cu (NO ₃ ) ₂ is used as the metal salt, the yield of TPP metal complex is 18 mol%, the yield of unreacted TPP is 40 mol%, and the yields of by-products and unrecovered products are It was 42 mol%.

As shown in FIG. 7, when CoCl ₂ is used as the metal salt, the yield of the TPP metal complex is 64 mol%, the yield of unreacted TPP is 25 mol%, and the yield of by-products and unrecovered products is reduced. The rate was 11 mol%. When NiCl ₂ was used as the metal salt, the yield of TPP metal complex was 63 mol%, the yield of unreacted TPP was 32 mol%, and the yield of by-products and unrecovered products was 6 mol%. It was.

As shown in FIG. 7, the yield of the TPP metal complex when CuCl ₂ is used as the metal salt is 72 mol%, and the yield of unreacted TPP is 16 mol%. The yield was 12 mol%. The yield of TPP metal complex when VOSO ₄ is used as the metal salt is 43 mol%, the yield of unreacted TPP is 48 mol%, as shown in FIG. The yield was 9 mol%.

(Experimental example 2-2)
Of the metal salts described in Experimental Example 2-1, NiSO ₄ was used, and the reaction temperature was changed to 150 ° C., 200 ° C., 250 ° C., 300 ° C., and 400 ° C., respectively, as in Experimental Example 2-1, A TPP nickel complex was prepared. The results are shown in FIG. FIG. 4 is a graph showing the temperature dependence of the reaction between TPP and aqueous nickel sulfate solution. In the figure, the rhombus plot represents the yield (mol%) of the TPP nickel complex, and the square plot represents the yield (mol%) of TPP. The yield of the TPP nickel complex was 4 mol% at 200 ° C, 21 mol% at 250 ° C, 27 mol% at 300 ° C, 43 mol% at 350 ° C, and 50 mol% at 400 ° C. In addition, the TPP nickel complex was not obtained at 150 degreeC. From these results, the reaction rapidly progressed around 350 ° C., which was consistent with the dissolution observation result shown in FIG. 2 as in Experimental Example 1-2.

(Experimental Example 2-3)
In the same manner as in Experimental Example 2-1, except that CoSO ₄ was used among the metal salts described in Experimental Example 2-1, and the reaction temperature was changed to 150 ° C, 200 ° C, 250 ° C, 300 ° C, and 400 ° C, respectively. A TPP cobalt complex was prepared. The results are shown in FIG. FIG. 5 is a graph showing the temperature dependence of the reaction between TPP and an aqueous cobalt sulfate solution. In the figure, the rhombus plot represents the yield (mol%) of the TPP cobalt complex, and the square plot represents the yield (mol%) of TPP. The yield of TPP cobalt complex was 4 mol% at 200 ° C, 18 mol% at 250 ° C, 39 mol% at 300 ° C, 67 mol% at 350 ° C, and 82 mol% at 400 ° C. In addition, the TPP cobalt complex was not obtained at 150 degreeC. From these results, the reaction rapidly progressed around 350 ° C., which was consistent with the dissolution observation result shown in FIG. 2 as in Experimental Example 1-2.

(Experimental example 3-1)
A compound having a porphyrin type skeleton is 2,3,7,8,12,13,17,18-octaethylporphyrin represented by the following formula (5), tetrathienylporphyrin represented by the following formula (6), And a reaction temperature of 350 ° C. in the same manner as in Experimental Example 1-1, except that it was changed to 5,10,15,20-tetrakis (2,4,6-trimethylphenyl) porphyrin represented by the following formula (7). And the porphyrin metal complex was manufactured on the conditions for 60 minutes of reaction time. The yields of porphyrin metal complex, unreacted porphyrin, and by-products in each case are shown in FIG. FIG. 9 is a graph showing porphyrin species dependency. As shown in FIG. 9, when 2,3,7,8,12,13,17,18-octaethylporphyrin was used, the yield of the porphyrin metal complex was 60 mol%, and the remaining 40% was not recovered. Product and by-product. When tetrathienylporphyrin was used, the yield of porphyrin metal complex was 43 mol%, the yield of unreacted porphyrin was 10 mol%, and the remaining 47 mol% was unrecovered and by-products. When 5,10,15,20-tetrakis (2,4,6-trimethylphenyl) porphyrin is used, the yield of the porphyrin metal complex is 44 mol%, and the yield of unreacted porphyrin is 54 mol%. The remaining 2 mol% was unrecovered and by-products.

(Experimental example 3-2)
A porphyrin metal complex is produced under the conditions of a reaction temperature of 350 ° C. and a reaction time of 60 minutes, as in Experimental Example 1-1, except that the compound having a porphyrin-type skeleton is changed to a benzoporphyrin represented by the following formula (8). did. The analysis was qualitative by collecting the contents and drying them, and evaluating the presence or absence of peaks with a matrix-assisted laser desorption ionization method-time-of-flight mass spectrometer. As a result, peaks were confirmed at 511.388 m / z and 571.304 m / z, and formation of unreacted benzoporphyrin and benzoporphyrin copper complex was confirmed. Moreover, the peak of the by-product was confirmed at 451.312 m / z or the like.

(Experimental example 3-3)
A compound having a porphyrin type skeleton, and a phthalocyanine represented by the following formula (9), a metal salt CuSO _4, except that the one of NiSO ₄ and CoSO _4, like the Experimental Example 1-1, the reaction temperature A phthalocyanine metal complex was produced under the conditions of 350 ° C. and a reaction time of 60 minutes. The analysis was qualitatively performed by washing the contents, collecting them, drying them to obtain the collected substances, and evaluating the presence or absence of peaks with a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer. The results are shown in Table 1 below. As shown in Table 1, when CuSO ₄ was used as the metal salt, peaks were confirmed at 514.270 m / z and 575.199 m / z, and when NiSO ₄ was used, 514.311 m / z and 570 A peak was confirmed at .233 m / z, and when CoSO ₄ was used, peaks were confirmed at 514.282 m / z and 571.205 m / z. In either case, unreacted phthalocyanine and phthalocyanine metal complex were formed. It was confirmed.

(Experimental example 3-4)
A compound having a porphyrin type skeleton, except that the 2,3-naphthalocyanine represented by the following formula (10) and then change the metal salt CuSO _4, NiSO ₄ and CoSO ₄ same manner as in Experimental Example 1-1 In addition, a naphthalocyanine metal complex was produced under the conditions of a reaction temperature of 350 ° C. and a reaction time of 60 minutes. The analysis was qualitatively performed by evaluating the presence or absence of a peak with a matrix-assisted laser desorption / ionization method-time-of-flight mass spectrometer after the contents were washed and recovered and dried to obtain a recovered product. The results are shown in Table 1 below. As shown in Table 1, when CuSO ₄ was used as the metal salt, peaks were confirmed at 714.303 m / z and 775.239 m / z, and unreacted 2,3-naphthalocyanine and 2,3-naphtha were observed. Formation of phthalocyanine metal complex was confirmed. When NiSO ₄ was used as the metal salt, peaks were confirmed at 714.336 m / z and 770.277 m / z, and formation of unreacted 2,3-naphthalocyanine and 2,3-naphthalocyanine metal complex was confirmed. In addition, a by-product peak was confirmed at 737.342 m / z and the like. When CoSO ₄ was used as the metal salt, peaks were confirmed at 714.419 m / z and 771.378 m / z, and formation of unreacted 2,3-naphthalocyanine and 2,3-naphthalocyanine metal complex was confirmed. In addition, the formation of by-products was confirmed at 737.460 m / z and the like.

  As described above, a metal complex of a compound having a porphyrin skeleton can be produced using water as a solvent without using any harmful organic solvent. In addition, separation and recovery of the metal complex after the reaction is extremely easy. Specifically, by appropriately setting the reaction temperature, it is possible to synthesize a metal complex of a compound having a porphyrin-type skeleton in a high yield without using a polar organic solvent that generates harmful and offensive odors. Since water is used, inexpensive and safe metal salts (sulfates, chlorides, hydroxides, etc.) can be used. In particular, it has been confirmed that the reaction temperature is 400 ° C. and the yield of the TPP copper complex is 90% or more. In addition, since the metal complex produced is insoluble in water below the predetermined reaction temperature, water and the metal complex can be easily separated and the metal complex can be easily recovered by lowering the temperature after the reaction. Can do.

Claims (2)

A compound having a porphyrin type skeleton represented by the following formula (3) or formula (4) and a metal salt are reacted in water at a reaction temperature of 200 ° C. or higher and 450 ° C. or lower and a pressure of 1.0 MPa or higher and 50.0 MPa or lower . A method for producing a metal complex of a compound having a porphyrin skeleton,

(In Formula (3) and Formula (4), Z ^ia and Z ^ib are each independently a hydrogen atom; an alkyl group, an alkoxy group, a mercapto group, an acyl group having 1 to 10 carbon atoms; a carboxyl group and a carbon number. esters of 1 to 10 alcohol; formyl group; a carbamoyl group, a halogen atom, or a two-Toro group, Z ^ia and Z ^ib is an aromatic hydrocarbon ring bonded to each other, heterocyclic or non-aromatic cyclic A hydrocarbon may be formed, i represents an integer of ^{1 to 4.} R ^{1 to} R ⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a mercapto group, or a carboxyl group. An ester of a group and an alcohol having 1 to 10 carbon atoms, or a thienyl group.)   The method for producing a metal complex of a compound having a porphyrin-type skeleton according to claim 1, wherein the metal salt is a sulfate.

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