JP2001081091A - Porphyrin dimers using imidazolyl porphyrin metal complexes as monomers - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To provide a novel system capable of controlling allosterism
Providing a compound. SOLUTION: The following general formula (1): Embedded image ＭIn the formula, M represents Fe (II) or Co (II);
Represents the following imidazolyl group Im₁~ Im₆: Embedded image (Where R_Two, R_ThreeAnd R_FourIs independently a hydrogen atom or
Represents an alkyl group. ), And R₁Is the next
Substituted phenyl group (a): Embedded image (Where R_FiveIs a hydrogen atom, a halogen atom or an alkyl
R represents a group₆Is an alkyl group, an aryl group, an aryl
Represents a substituted alkyl group or a halogen-substituted alkyl group,
₇Is a hydrogen atom, a halogen atom, an alkyl group or -NH
CO-R₈And R ₈Represents an alkyl group, an aryl group,
Reel-substituted alkyl group or halogen-substituted alkyl group
You. ). Porphyrin dimer represented by｝
body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel porphyrin metal complex. More specifically, the present invention relates to a porphyrin dimer having an imidazolyl porphyrin metal complex as a monomer.

[0002]

2. Description of the Related Art A porphyrin metal complex is a complex in which a metal is inserted into the center of a cyclic tetrapyrrole in which four pyrrole nuclei are crosslinked by four methine groups. Of the porphyrin metal complexes, the porphyrin iron complex into which iron (II) is inserted as the central metal is called heme, which binds to a protein to form a heme protein. Many heme proteins are known to be involved in the adsorption / desorption reaction with oxygen molecules in vivo. Heme proteins can be classified into those having a Langmuir-type dissociation curve and those having a sigmoid-type dissociation curve of oxygen molecules according to the mode of binding to the oxygen molecules.
A typical example of the former heme protein showing a Langmuir-type dissociation curve is myoglobin, and a typical example of the latter heme protein showing a sigmoid-type dissociation curve is hemoglobin.

[0003] Heme proteins and porphyrin complexes that constitute them are important for respiratory physiology in vivo.
Various studies have been made.

For example, in 1975, Collmann et al. Synthesized a picket-fence porphyrin iron complex capable of Langmuir-type adsorption and desorption of molecular oxygen. Collmann et al. Also provide artificial myoglobin using a porphyrin oxygen molecular complex (J. Am. Chem. Soc., 105, 3038 (1983)). Also,
Have embedding a picket fence porphyrin iron complex in a liposome lipid membrane to provide artificial blood capable of Langmuir-type adsorption and desorption of oxygen molecules under physiological conditions (Che
m. Lett., 969 (1985)). Further, Traylor et al. (J. Am. C
hem. Soc., 104, 1391 (1982)), and a group of oxygen-adding enzymes, cytochrome P450.
The protein was modeled with porphyrin iron and manganese complexes, and some catalytic activity as artificial cytochrome P450 has been observed.

[0005] On the other hand, substances which bind to oxygen molecules in a sigmoid type and express allosterism control are known by natural allosteric enzymes such as hemoglobin, but are not so well known in other systems. Studies on the control of allosterism in systems other than the natural allosteric enzyme include, for example, the cooperative capture of metal ions by Rebek and Oyuya, and the cooperative capture of metal ions and neutral molecules by Reinhoult. In addition, although Tabushi et al. Are investigating the allosteric binding of gable porphyrin cobalt complex to oxygen molecules, they have not been successful.

[0006]

An object of the present invention is to provide a novel compound capable of controlling allosterism.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have attached an imidazolyl group to porphyrin and used two imidazolyl porphyrin metal complex molecules to form one imidazolyl. The present invention has been accomplished by coordinating the nitrogen atom of the imidazolyl group of the other imidazolyl porphyrin metal complex to the metal atom of the porphyrin metal complex, and achieving this by a dimerized porphyrin dimer. That is, the present invention provides the following general formula (1):

[0008]

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Wherein M represents Fe (II) or Co (II), and Im represents the following imidazolyl groups Im _{1 to} Im ₆ :

[0010]

Embedded image

(Wherein R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group), and R ₁ represents the following substituted phenyl group (a):

[0012]

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(Wherein R_FiveIs a hydrogen atom, a halogen atom
Or an alkyl group;₆Is an alkyl group, aryl
Group, aryl-substituted alkyl group or halogen-substituted alkyl
R represents a group₇Represents a hydrogen atom, a halogen atom, an alkyl
Group or -NHCO-R₈And R ₈Is an alkyl group,
Reel group, aryl-substituted alkyl group or halogen-substituted
Represents a alkyl group. ). Porf represented by｝
Providing a dimeric dimer.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the porphyrin dimer of the present invention will be described in detail.

In the above general formula (1), M is Fe
(II) or Co (II).

The imidazolyl group Im ₁ represented by Im
~ Im ₆ :

[0017]

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In the formula, R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group. In each formula, an arrow (↓) attached below N indicates that the metal (M) is coordinated through the nitrogen atom. Examples of the alkyl group represented by R ₂ , R ₃ and R ₄ include a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms,
Specific examples of these alkyl groups include methyl, isopropyl, and t-butyl.

In the above formula (1), the two imidazolyl groups represented by Im may be the same or different, but are preferably the same from the viewpoint of ease of production and the like.

A substituted phenyl group (a) represented by R ₁ :

[0021]

Embedded image

In the formula, R ₅ represents a hydrogen atom, a halogen atom or an alkyl group. If R ₅ is a halogen atom or an alkyl group, the substitution position of R ₅ is a substituted phenyl group (a) is with respect to the binding position of binding to porphyrin metal complex may be either m- position or p- position.

R_FiveExamples of halogen atoms represented by
Represents a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Contained, chlorine atoms are preferred in terms of production, stability, etc.
No. R _FiveIs an alkyl group, has 1 to 12 carbon atoms
Linear, branched or cyclic alkyl groups
Specific examples of isopropyl, t-butyl, neopentic
And cyclohexyl and adamantyl.

In the substituted phenyl group (a) of the general formula (1), R ₆ and R ₈ each independently represent an alkyl group, an aryl group, an aryl-substituted alkyl group or a halogen-substituted alkyl group. R ₆ and R ₈ are preferably a bulky hydrophobic group. This is because when R ₆ and R _{8 are} bulky hydrophobic groups, oxygen molecules bonded to the porphyrin dimer can be stabilized in particular. In particular, R ₆ = R ₈ is preferable from the viewpoint of synthesis.

When R ₆ and R ₈ are an alkyl group, the hydrophobic alkyl group includes a linear, branched or cyclic alkyl group having 3 to 20 carbon atoms. , Isopropyl, t-butyl, neopentyl, cyclohexyl, and adamantyl. When R ₆ and R ₈ are an aryl group, an aromatic ring having 6 to 20 carbon atoms and a condensed aromatic ring are included, and specific examples thereof include phenyl,
Includes naphthyl and pyrenyl. When R ₆ and R ₈ are an aryl-substituted alkyl group, it includes an aryl-substituted alkyl group having 7 to 20 carbon atoms, and specific examples include benzyl and triphenylmethyl. When R ₆ and R ₈ are a halogen-substituted alkyl group, the number of carbon atoms is 1
And halogen-substituted alkyl groups having from 1 to 20 halogen atoms, specifically, trichloromethyl and dichloromethyl.

In the substituted phenyl group (a) of the general formula (1), R ₇ represents a hydrogen atom, a halogen atom, an alkyl group or —NHCO—R ₈ . R ₇ is preferably a hydrogen atom from the viewpoint of production.

As shown in the general formula (1), the four pyrrole rings and the four methine groups of the porphyrin dimer of the present invention are arranged so as to be spread on the same plane. The imidazole ring of the imidazolyl group that substitutes for the porphyrin dimer is arranged to extend on a plane substantially perpendicular to the plane formed by the pyrrole ring and the methine group.
Similarly, the substituted phenyl ring substituted by the porphyrin dimer is arranged so as to extend on a plane substantially perpendicular to the plane formed by the pyrrole ring and the methine group.

In the general formula (1), the bond between the metal M and the nitrogen atom of the pyrrole nucleus is a coordinate bond. The bond between the central metal M and the nitrogen atom of the imidazolyl group is also a coordinate bond.

The method for synthesizing the porphyrin dimer represented by the general formula (1) of the present invention will be described below, but the method for synthesizing the porphyrin dimer of the present invention is not limited thereto.

In the porphyrin dimer of the present invention, M
When the metal represented by is iron (II),
It can be synthesized through step 6.

[0031]

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[0032]

Embedded image

<Step 1> Synthesis of Compound 4 Compound 2 (where R ₅ is as defined in general formula (1)) and Compound 3 (where Im is as defined in general formula (1)) ) Is dissolved in a solvent such as propionic acid or acetic acid, to which pyrrole (1) is added and reacted to synthesize porphyrin.

The amounts of compound 2, compound 3 and pyrrole (1) to be added can usually be set to 2: 1: 3 to 3: 1: 4.

The solvent can be used usually in an amount of 20 to 100 times the weight of pyrrole.

The reaction time can be usually set at 20 ° C. to reflux temperature.

The reaction time can usually be set to 30 to 60 minutes.

After the reaction, if necessary, the substance obtained is subjected to steps such as purification, and then subjected to the next step 2).

In the purification step, for example, after distilling off the solvent used in the above reaction, it is dissolved in a solvent such as chloroform or dichloromethane, filtered, and the obtained filtrate is concentrated.
It can be performed by silica gel column chromatography or the like.

<Step 2> Synthesis of Compound 5 The nitro group of Compound 4 obtained in Step 1 above is converted to an amino group. This reaction can be carried out by dissolving compound 4 in an acid such as hydrochloric acid and adding a compound capable of converting a nitro group to an amino group such as tin (II) chloride.

The amount of acid to be added is usually 5 to 5 parts by weight of the compound.
The amount can be set to 0 to 200 times.

The amount of the compound capable of converting a nitro group to an amino group can be usually set to 10 to 30 times.

The reaction temperature is usually room temperature (about 25 to 30).
C), and the reaction time can be set to 30 to 60 minutes.

After the reaction, the reaction is carried out with aqueous ammonia, aqueous sodium bicarbonate or the like.
The pH of the reaction solution is made weakly alkaline, preferably in the range of 8-9, and extracted with an organic solvent such as chloroform.

The organic layer can be subjected to washing (dilute aqueous ammonia, water, etc.), drying, concentration, etc., if necessary.

<Step 3> Purification of Compound 5C Compound 5 obtained in Step 2 is a mixture of isomers including the three (5A to 5C) rotamers shown in the above reaction step. Compound 5C having the desired configuration is purified from these mixtures.

Purification can be carried out by adsorbing compound 5C, which is the desired rotamer, on an adsorbent such as silica gel suspended in a nonpolar organic solvent such as benzene or toluene, and further by chromatography.

The adsorbent is usually used in an amount of 2 to the weight of the compound.
It can be used in an amount of 0 to 100 times.

The organic solvent can be used usually in an amount of 40 to 200 times.

The reaction is usually carried out under an inert gas atmosphere such as argon gas set at a temperature of 80 to 100 ° C.
It can be performed for 2 to 30 hours.

The obtained reaction solution can be further purified by filtering with a polar solvent such as a mixed solvent of chloroform / methanol, concentrating the filtrate, and subjecting it to thin-layer silica gel chromatography or the like.

<Step 4> Synthesis of Compound 6 The amino group of Compound 5C obtained in Step 3 is acylated. In this reaction, compound 5C is dissolved in a non-polar solvent such as chloroform, pyridine is added as a base, and an acyl halide: R ₆ C (＝ O) X (where R ₆ is a group represented by the general formula (1)) As specified, X represents a halogen atom such as chlorine or bromine.).

The amount of the solvent used can be set to 50 to 200 times.

The amount of the acyl halide can be set to 3 to 10 times.

The reaction can be carried out at room temperature, and is preferably carried out at a low temperature in order to prevent isomerization.

The reaction time can usually be set to 30 to 120 minutes.

The obtained reaction mixture can be subjected to steps such as concentration, washing (saturated sodium hydrogen carbonate solution, etc.), drying and the like, if necessary.

<Step 5> Synthesis of Compound 7 A metal atom is inserted into Compound 6 obtained in Step 4.

When the metal to be inserted is iron (II), iron compounds such as anhydrous iron (II) bromide and anhydrous iron (II) chloride can be used.

The addition amount of the iron compound can be set to 20 to 100 times.

The reaction can be carried out by dissolving in a solvent such as THF or acetic acid, adding a base such as 3,5-lutidine, and under an inert gas atmosphere such as nitrogen gas at a reflux temperature.

The reaction time can be usually set to 1 to 4 hours.

After the reaction, it can be subjected to concentration, washing (water etc.) and purification steps as required.

<Step 6> Synthesis of Compound 8 Compound 7 obtained in Step 5 is dimerized.

The dimerization is carried out by dissolving compound 7 in a solvent such as THF / benzene (1: 1) or benzene and reducing the compound such as sodium dithionite under an inert gas atmosphere such as nitrogen gas. It can be performed by adding an aqueous solution of the agent and stirring vigorously.

The amount of the solvent is usually 10 to the weight of the compound.
It can be used in an amount of 0 to 1000 times.

The reducing agent can be used usually in an amount of 20 to 200 times.

The stirring time can be set to 20 minutes to 60 minutes.

After stirring, the desired dimer can be extracted with an organic solvent such as benzene or toluene.

<Step 7> Synthesis of Compound 9 When the metal to be inserted is other than iron (II), the porphyrin dimer of the present invention was synthesized through the same steps as iron (II) up to the above step 4. Compound 6 can be synthesized by reacting a compound capable of inserting a desired metal into porphyrin.

When the metal to be inserted is cobalt (II),
As a compound capable of inserting a metal into porphyrin, cobalt (II) chloride and cobalt (II) acetate can be used.

The addition amount of the cobalt compound can be set to 5 to 20 times the weight of the compound. The reaction is
A solvent such as RHF, acetic acid, and methanol and 3,5-lutidine are added, and the reaction can be carried out at a reflux temperature under an inert gas atmosphere such as nitrogen gas. The reaction time is usually
It can be set to 30-60 minutes.

The porphyrin dimer of the present invention is a dimer composed of two porphyrin metal complex units. In the porphyrin metal complex unit constituting the porphyrin dimer of the present invention, an imidazolyl group which may be substituted is bonded to one of four positions at positions 5, 10, 15, and 20 of the porphyrin, and the remaining It has a structure in which a phenyl group substituted with a hydrophobic group is bonded to three positions.

The porphyrin dimer of the present invention comprises an imidazolyl group of one porphyrin metal complex unit and a metal of another porphyrin metal complex unit,
Form a dimer. The present inventors believe that the porphyrin dimer of the present invention can form a stable dimer by such two bonds between an imidazolyl group and a metal.

The porphyrin dimer of the present invention is
In three phenyl groups each having a substituted alkyl group in one porphyrin metal complex unit, the configuration of these alkyl groups is oriented outward in the opposite direction to the side of another porphyrin dimer unit. (Α position). The present inventors, in a porphyrin dimer having such a configuration, in particular,
It is believed that by making the alkyl group a hydrophobic group, oxygen molecules bonded to the metal represented by M in the general formula (1) can be stabilized. Further, when the porphyrin dimer iron (II) complex of the present invention is dimerized by a coordination bond, a deoxy form in which oxygen molecules are not adsorbed,
It is considered that the metal atom has a structure attracted to the imidazolyl group side from the porphyrin ring plane (crystal structure of a similar compound, J. Am. Chem. Soc. 1996, 118, 3980).
This corresponds to a T state in which oxygen molecule adsorption ability is low. When an oxygen molecule binds to one of the two iron (II) ions, the bound iron atom is attracted to the porphyrin plane, the porphyrin rings approach, and at the same time the iron atom to which the oxygen molecule is not bound is also a porphyrin. It is considered that a deoxy R state is generated near the surface, the affinity for oxygen molecules is increased, and it is thought that cooperative adsorption and desorption of oxygen molecules is performed.

By using the allosteric function of the porphyrin dimer of the present invention, the porphyrin dimer of the present invention is expected to be used as a component of artificial blood. In addition, since the porphyrin dimer of the present invention can activate cooperative molecular oxygen, it is also expected to be applied as a regioselective oxygenation reagent for higher alkanes and other hydrocarbons. In addition, the porphyrin dimer of the present invention has a gas-absorbing / desorbing force with molecules such as oxygen, nitric oxide and carbon monoxide, which rapidly changes when the amount of each molecule exceeds a specific value. Is also expected to be used as a highly sensitive sensor. Such a rapid change in the adsorption / desorption force that the porphyrin dimer of the present invention can exhibit is an advantageous effect that cannot be exhibited by a compound having a Langmuir-type adsorption / desorption function such as myoglobin.

[0077]

EXAMPLES The synthesis examples of the porphyrin dimer of the present invention are described below, but the porphyrin dimer of the present invention is not limited thereto.

1) Step 5,10,15-Tris (o-nitrophenyl) -20
Synthesis of imidazolyl porphyrin (4 ′) 2-nitrobenzaldehyde (2) (3.74 g, 2
4.8 mmol) and imidazole-2-carbaldehyde (3) (1.19 g, 12.4 mmol) were dissolved in 110 ml of propionic acid (hereinafter also referred to as “mL”), and pyrrole (1) (2.50 g) , 37.
2 mmol) was added. The reactor was immersed in a preheated oil bath, refluxed and stirred. After 40 minutes, propionic acid was distilled off, chloroform was added, and the mixture was filtered. The filtrate was concentrated and purified by silica gel column chromatography (developing solvent: CHCl ₃ / MeOH = 15/1). 713 mg of a purple solid were obtained.

MS (TOF) m / e 740 (M + 1), calculated value 740 (M + 1);
UV-visible absorption (CHCl ₃ ) λmax 423, 518, 555, 595, 654
nm; fluorescence intensity (CHCl ₃ ) λmax 658, 716 nm (λext 420 n
m).

2) Step 5,10,15-tris (o-aminophenyl) -20
Synthesis of imidazolyl porphyrin (5 ′) Compound 4 ′ (144 mg, 0.194 mmol) was treated with hydrochloric acid
Dissolved in 8 mL and excess tin (II) chloride dihydrate (642
mg, 2.85 mmol) and stirred at room temperature. 2
5 minutes later, ammonia water was added to make it slightly alkaline, and then C
HCl_ThreeAnd the organic layer was filtered. The filtrate is diluted
After washing with near water and water (× 2), anhydrous Na _TwoSO_FourDry
And concentrated. 70 mg (55.6%) of a purple solid are obtained
Was.

MS (TOF) m / e 650 (M + 1), calculated value 650 (M + 1);
UV-visible absorption (CHCl ₃ ) λmax 421, 515, 555, 586, 644
nm; fluorescence intensity (CHCl ₃ ) λmax 657, 718 nm (λext 420 n
m).

3) Step Synthesis of 5,10,15-tris (α, α, α-o-aminophenyl) -20-imidazolylporphyrin (5C ′) The isomer mixture 5 ′ (70 mg, 0.107 mmol),
2.52 g of silica gel was suspended in 6 mL of benzene, and bubbled with argon gas for several minutes. The reactor purged with argon gas was immersed in an oil bath at about 80 ° C. and stirred.
After 20 hours, the reaction solution was filtered with a mixed solvent of CHCl ₃ and MeOH, and the filtrate was concentrated. The component of Rf = 0.14 was purified by thin-layer silica gel chromatography (developing solvent: CHCl ₃ / acetone = 3/1) by silica gel column chromatography (developing solvent: CHCl ₃ / acetone = 3).
/ 1 / → 1/1) to obtain 11 mg (15.7%) of a purple solid.

MS (TOF) m / e 650 (M + 1), calculated value 650 (M + 1);
UV-visible absorption (CHCl ₃ ) λmax 421, 517, 555, 588, 647
nm; fluorescence intensity (CHCl ₃ ) λmax 657, 716 nm (λext 421 n
m).

4) Step 5,10,15-Tris (α, α, α-o-pivaloylaminophenyl) -20-imidazolylporphyrin (6 ′):

[0085]

Embedded image

Compound 5C ′ (11 mg, 0.016 mmol) was converted to CH
It was dissolved in 1 mL of Cl ₃ and 10 μL of pyridine was added. During the stirring, 10 μL of pivaloyl chloride was added, and the mixture was stirred at room temperature. After 2 hours, the reaction was concentrated, saturated aqueous NaHCO ₃ was added to CHCl _3, washed with water (× 2), anhydrous Na ₂
And dried over SO _4. After filtration and concentration, 31 mg of a purple solid was obtained.

The obtained solid was purified by silica gel column chromatography (developing solvent: CHCl ₃ / acetone = 10/1 → 9/1). Yield 7 mg (46.7%).

¹ H NMR (CDCl ₃ ) δ -2.69 (2H, s, NH), 0.0
3, 0.13 (18H, s; 9H, s; t-Bu), 7.15 (1H, s, NH), 7.2
7 (2H, s, Im), 7.47 (3H, q, benzene-c _1,2 ), 7.82 (5H,
q, benzene-a ₂ , b _1,2 ), 7.89 (1H, d, benzene-a ₁ ), 8.7
2 (3H, t, benzene-d _1,2 ), 8.81 (4H, s, pyrrole), 8.84
(2H, d, pyrrole), 9.06 (2H, s, pyrrole); MS (TOF) m / e
902 (M + 1), calculated value 902 (M + 1); UV-visible absorption (CHCl ₃ ) λm
ax 421, 514, 552, 588, 649 nm; fluorescence intensity (CHCl ₃ ) λma
x 655, 715 nm (λext 421 nm).

5) Step 5, Synthesis of 5,10,15-tris (α, α, α-o-pivaloylaminophenyl) -20-imidazolyliron (III) porphyrin (7 ′) Compound 6 ′ (15 mg, 0 .016 μmol) and excess anhydrous iron (II) bromide (244 mg, 1.13 mmol) were placed in a reactor in a glove box under a nitrogen atmosphere, and 2 mL of THF, about 5 mg of 3,5-lutidine were added in a laboratory.
(0.048 mmol), and the mixture was heated under reflux. After 3 hours, the solvent was distilled off, and the obtained brown solid was purified by alumina column chromatography (activity: 0, solvent: chloroform).

A 1% methanol solution of hydrobromic acid was added to the obtained fraction, stirred, extracted with chloroform, dried and concentrated to obtain a brown solid (4 mg, 0.003 mmol, 18.8).
%).

MS (TOF) m / e 955 (M +), calculated 955 (M +);
UV-visible absorption (CHCl ₃ ) λmax 415, 512 nm.

6) Step 5, Synthesis of 5,10,15-tris (α, α, α-o-pivaloylaminophenyl) -20-imidazolyliron (II) porphyrin dimer (8 ′) Nitrogen atmosphere probe box In the compound 7 ′ (4 mg,
0.003 mmol) in THF / benzene (1: 1) 2
Then, 3 mL of a 0.2 M aqueous sodium dithionite solution was added to the solution, and the mixture was vigorously stirred for 30 minutes. Benzene was added and the organic layer was extracted.

When the ultraviolet-visible absorption spectrum was measured, remarkable broadening of the sole band was confirmed as indicated by the solid line indicated by 8 'in FIG. The half-width was about twice that of the Soret band of picket fence porphyrin (broken line indicated by 10 in FIG. 1) which is a general artificial myoglobin model compound. This strongly suggests that compound 8 'has a dimer structure.

MS (TOF) m / e 956 (M + 1), calculated value 956 (M + 1);
UV-visible absorption (benzene) λmax 432, 558 nm.

7) Step 5,10,15-Tris (α, α, α-O-pivaloylaminophenyl) -20-imidazolylcobalt (II)
Synthesis of porphyrin dimer (9 ′) Compound 6 ′ (5 mg, 5.54 μm) under an argon atmosphere
ol) in 1 mL of THF and 3,5-lutidine 6
mg (55.4 μmol) was added. 1 mL of methanol
5mg of anhydrous cobalt chloride dissolved in water (38.5μmo
l) was added in excess and heated to reflux. After about 30 minutes, the reaction solution was concentrated, dissolved in chloroform, washed with water, extracted with an organic layer, dried over anhydrous sodium sulfate, and concentrated to obtain 5 mg of a purple solid. Crude yield 94.2%.

UV-visible absorption (chloroform) λmax: 43
9, 548 nm. MS (TOF) m / e 959 (M + 1) calcd 959 (M + 1).

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows porphyrin iron (II) imidazole 5
It is a graph which shows the ultraviolet-visible absorption spectrum of the compound 8 'which is a coordination complex, and the compound 10 shown in a figure.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shinichi Kugimiya 8916-5 Takayamacho, Ikoma, Nara Pref. Dormitory A-406 F-term (reference) 4C050 PA04 PA06 4C086 AA03 CB04 HA28 NA14 ZA52

Claims (6)

[Claims] (1) The following general formula (1):ＭIn the formula, M represents Fe (II) or Co (II);
Represents the following imidazolyl group Im₁~ Im₆:(Where R_Two, R_ThreeAnd R_FourIs independently a hydrogen atom or
Represents an alkyl group. ), And R₁Is the next
Substituted phenyl group (a):(Where R_FiveIs a hydrogen atom, a halogen atom or an alkyl
R represents a group₆Is an alkyl group, an aryl group, an aryl
Represents a substituted alkyl group or a halogen-substituted alkyl group,
₇Is a hydrogen atom, a halogen atom, an alkyl group or -NH
CO-R₈And R ₈Represents an alkyl group, an aryl group,
Reel-substituted alkyl group or halogen-substituted alkyl group
You. ). Porphyrin dimer represented by｝
body. 2. The porphyrin dimer according to claim 1, wherein in the general formula (1), R ₅ is a hydrogen atom. 3. In the general formula (1), R ₂ , R ₃ and R
3. The porphyrin dimer according to claim 1, wherein ₄ is a hydrogen atom. 4. In the general formula (1), R ₆ and R ₈ are
Each independently an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl-substituted alkyl group having 7 to 20 carbon atoms, or 1 to 20 carbon atoms
The porphyrin dimer according to any one of claims 1 to 3, which is a halogen-substituted alkyl group having 1 to 20 halogen atoms. 5. The porphyrin dimer according to claim ₁ , wherein in the general formula (1), the imidazolyl group represented by Im is Im ₁ . 6. The porphyrin dimer according to claim 5, wherein in the general formula (1), R ₆ is a t-butyl group.