JP2000044565A - Porphyrin derivative having iodomethyl substituent and amphipathic star-shaped oxazoline polymer having porphyrin at center - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound consisting of a porphyrin derivative having specific iodomethyl groups and useful for photocatalysts on photosyntheses, therapeutic agents for cancer agents on ray dynamic therapies, ray dynamic cancer diagnostic agents, MRI contrast media, X-ray contrast media, etc. SOLUTION: A compound of the formula [(n) is 1 or 2; M is two hydrogen atoms or a transition metal; the dotted line is not a bond or is a coordination bond, for example, tetra(p-iodomethylphenyl)porphyrin. The compound of the formula is obtained by mixing a benzaldehyde having an iodomethyl group with pyrrole in a molar ratio of 1: 1 in a polar solvent such as chloroform, adding a small amount of boron trifluoride.diethyl ether at room temperature to the mixture liquid, stirring the mixture at room temperature, simultaneously adding a small amount of triethylamine and chloranil, thermally refluxing the mixture, cooling the reaction mixture down to room temperature after the finish of the reaction, distilling away the solvent at reduced pressures to concentrate the reaction mixture, adding methylene chloride to the concentrated solution, filtering, recovering the solid contents, and subsequently recrystalizing the solid contents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to porphyrins having an iodomethyl group, to their use as polymerization initiators, and to star-shaped polymers centering on porphyrins. The porphyrins of the present invention include, for example, a porphyrin metal complex as a catalyst in an alkane / alkene oxidation reaction, a photocatalyst in photosynthesis, and photodynamic therapy (PDT).
Cancer therapeutics, photodynamic cancer diagnostics, MRI contrast agents,
It is useful as an X-ray contrast agent, an optical recording material in photochemical hole burning (PHB), and a material constituting an element in the field of optical / electronic devices.

[0002]

2. Description of the Related Art It is known that a porphyrin in which one porphyrin molecule is isolated in a three-dimensional structure of a single protein molecule having a molecular weight of about 40,000, such as cytochrome P-450 in nature, exhibits an oxidation catalytic function. Have been. on the other hand,
In the reaction center of photosynthetic bacteria in nature, a special pair of porphyrins is found in proteins having molecular weights of tens of thousands, and it is known that these porphyrins contribute to the photosynthetic reaction.

[0003] In the case of a low-molecular-weight porphyrin that has been unraveled from a large protein molecule, attempts have been made to introduce various substituents around the porphyrin skeleton in order to express its catalytic function and optical function. For example, in the Journal of American Chemical Society (J. Am. Chem. Soc.), Vol. 109, p. 2659 (1987), in the field of catalysis, to prevent the association of low-molecular porphyrin planes, It is disclosed to introduce bulky substituents. "Journal of
Organic Chemistry (J. Org. Chem.), Vol. 59, p. 7462 (1994) states that many porphyrins have been placed around the porphyrin skeleton in order to solubilize porphyrins in water in various medical applications. It is disclosed to introduce hydrophilic substituents (hydroxy, sugar, cation and anion). Further, Japanese Patent Application Laid-Open No. 2-45 discloses that, in the field of recording materials, a low molecular weight porphyrin is provided with a substituent capable of interacting with the high molecular weight matrix in order to monodisperse the low molecular weight porphyrin in a transparent high molecular weight matrix. It is known to be introduced.

[0004] It is known that the association of porphyrin molecules in a solution or in a solid prevents the porphyrin from exhibiting its catalytic / photofunctional function. For example, in the phototherapy of cancer in the medical field, it is known that simply introducing a hydrophilic substituent around the porphyrin skeleton does not solve the problem that porphyrin is most easily associated with an aqueous medium. ing. In addition, in the field of optical hole-banning recording materials, the low molecular porphyrin molecular design and the selection of the polymer matrix make it difficult to solve the compatibility deterioration between the two components, and porphyrin may condense in the transparent polymer matrix. It is a problem. That is, introduction of a low-molecular-weight substituent around the porphyrin skeleton could not effectively prevent the association of porphyrin molecules.

[0005] As a method for expressing the function of porphyrin at a single molecule level, "Angewande hemi (Angewa
ndte Chemie) International Edition (Int.
Ed. 37), p.1131 (1998) or "Chemical Communications (Chem. Commun.)", No. 2
277 (1997) "each discloses a method of incorporating a low-molecular-weight porphyrin into a micelle or an amphiphilic polymer solution. Also, Macromolecules, Vol. 29, p. 6505 (1996)
) "Discloses a method of binding porphyrin to a polymer side chain. However, these methods have a problem that the interaction between porphyrin residues depends on the type of the medium, and in order to prevent the interaction, the medium to be used must be limited to a specific medium.

In order to completely isolate one molecule of porphyrin, a porphyrin-centered branched polymer in which several polymer chains are bonded around one molecule of porphyrin is known. For example, "Journal of Chemical Society (J. Chem. Soc.) Chemical Communications (Chem. Commun.)", P. 391 (1988) discloses that an aluminum porphyrin complex is used as a polymerization initiator. A method for producing a porphyrin-centered star polymer in which another porphyrin derivative is used as a component of a monomer and an epoxy compound is polymerized on the monomer porphyrin is disclosed. However, in this method, aluminum porphyrin as a polymerization initiator cannot be introduced into the center of the star-shaped polymer, so that a separate porphyrin must be used as one component of the monomer. there were. "Journal of Chemical Society (J. Chem. Soc.) Chemical Communications (Chem. Commun.)"
On page 60 (1993), along with star-shaped branched polymers,
As a method for completely isolating porphyrin, a dendrimer polymer having a porphyrin center has been disclosed. However, there has been a problem that the synthesis of dendrimer porphyrin is multi-step and requires complicated isolation and purification steps.

[0007]

Fixing a porphyrin molecule having a photo / catalytic function at the center of a star-shaped polymer is equivalent to isolating one porphyrin molecule into a large cluster structure. As described above, it is expected that by isolating the porphyrin molecule, various functions of the porphyrin can be highly expressed. In addition, by selecting the peripheral polymer arm, the solubility or compatibility (amphiphilicity) of the porphyrin star polymer in another medium can be greatly improved, and in the case of a non-toxic polymer arm, Medical applications of porphyrins, for example,
It can be expected to be used as a phototherapy agent for cancer, particularly as a phototherapy agent for skin cancer. The porphyrin-centered star-shaped polymer opens up new possibilities for porphyrin-related oxidation catalysts, photocatalysts, phototherapeutic agents, optical recording materials, and multilayer film device materials.

An object of the present invention is to provide a porphyrin-centered star polymer.
An object of the present invention is to provide a porphyrin having a polymerization reaction initiating property, which is a raw material for producing such a porphyrin-centered star polymer.

[0009]

In order to solve the above-mentioned problems, the present invention provides (1) a compound represented by the following general formula (I):

[0010]

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(In the formula, n represents 1 or 2, M represents two hydrogen atoms or transition metals, and a dotted line represents no bond when M is a hydrogen atom, and a coordinate when M is a transition metal. The iodomethyl group represents the o of the phenyl ring.
It is bonded to any of the-, m- and p-positions. The present invention provides a porphyrin derivative having an iodomethyl group, which is represented by the following formula:

In order to solve the above-mentioned problems, the present invention provides (2) a compound represented by the following general formula (II):

[0013]

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(Wherein, R represents an alkyl or allyl group, p is an integer in the range of 3 to 500, and represents the number average degree of polymerization of the polyoxazoline arm. M represents two hydrogen atoms or a transition metal. And the dotted line represents no bond when M is a hydrogen atom, and represents a coordinate bond when M is a transition metal, and n represents 1 or 2. The n polyoxazoline arms have o-, and a porphyrin-centered amphiphilic star-shaped oxazoline polymer, which is bonded to any of the m- and p-positions.

In order to solve the above-mentioned problems, the present invention provides (3) a compound represented by the following general formula (III):

[0016]

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(Wherein R ₁ and R ₂ each independently represent an alkyl group or an allyl group, p and q each independently represent an integer in the range of 5-250, and Represents the number average degree of polymerization, the sum of which is 10
In the range of 500. M is two hydrogen atoms or transition metals, and the dotted line indicates no bond when M is a hydrogen atom, and indicates a coordinate bond when M is a transition metal. n is 1
Or 2 is represented. The n oxazoline block copolymer arms are attached at any of the o-, m- and p-positions of the phenyl ring. The present invention provides a porphyrin-centered amphiphilic star-shaped oxazoline polymer, which is represented by the following formula:

Further, the present invention provides (4) a compound represented by the following general formula (IV):

[0019]

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(Wherein, R ₁ and R ₂ are each independently an alkyl group or an allyl group, X is a numerical value from 0.1 to 0.9, and p is an integer from 3 to 500. And the number average degree of polymerization of the oxazoline copolymer arm.
Represents two hydrogen atoms or transition metals, and the dotted line represents no bond when M is a hydrogen atom, and represents a coordinate bond when M is a transition metal. n represents an integer of 1 to 3. n
Polyoxazoline copolymer arms have a phenyl ring o
It is bonded to any of the-, m- and p-positions. The present invention provides a porphyrin-centered amphiphilic star-shaped oxazoline polymer, which is represented by the following formula:

Furthermore, the present invention solves the above-mentioned problems by providing (5) a general formula (V)

[0022]

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Wherein p is an integer in the range of 3 to 500 and represents the number average degree of polymerization of the polyethyleneimine arm. N represents 1 or 2. The n polyethyleneimine arms have a phenyl ring. A porphyrin-centered polyoxazoline derivative, which is a star-shaped ethyleneimine polymer, which is bonded to any of the o-, m-, and p-positions.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The porphyrin derivative having an iodomethyl group represented by the general formula (I) of the present invention can be easily produced by a conventional method for obtaining a porphyrin derivative or a method analogous thereto. For example, a small amount of boron trifluoride / diethyl ether is added to a mixture of benzaldehyde having an iodomethyl group and pyrrole in a molar ratio of 1: 1 in a polar solvent such as chloroform, and the mixture is stirred at room temperature for 1 hour. Next, while stirring them, a small amount of triethylamine and chloranil are added at once, and the mixture is heated in an oil bath and refluxed for about 1 hour. After completion of the reaction, the reaction mixture is cooled to room temperature, and the solvent is distilled off under reduced pressure and concentrated. An appropriate amount of methylene chloride is added to the concentrate, and the mixture is filtered to collect a solid. The target porphyrin having an iodomethyl group represented by the general formula (I) is recrystallized from chloroform / methylene chloride in chloroform / methylene chloride or separated and purified using silica gel column chromatography using chloroform as a solvent. It can be obtained in 35-48% yield.

In this method, by using p-benzaldehyde as the benzaldehyde having an iodomethyl group, a porphyrin compound in which the i-methyl group is substituted at the p-position of the phenyl ring in the general formula (I) can be obtained. Further, for example, by using m-iodomethylbenzaldehyde or o-iodomethylbenzaldehyde as the benzaldehyde having an iodomethyl group, in the general formula (I), the iodomethyl group is located at the m-position or o-position of the phenyl ring, respectively. A substituted porphyrin compound can be obtained. Similarly, as a benzaldehyde having an iodomethyl group, 2,2
By using di (iodomethyl) benzaldehyde, 2,4-di (iodomethyl) benzaldehyde or 3,5-di (iodomethyl) benzaldehyde, in general formula (I), o
A porphyrin compound having an iodomethyl group substituted at each of the-and p-positions or two m-positions can be obtained.

The central metals of porphyrins are conventional transition metals, among which zinc, manganese, iron,
Cobalt is preferred, and zinc and manganese are particularly preferred.

For the porphyrin having such a central metal, for example, iodomethylporphyrin is dissolved in a polar solvent such as chloroform, and a methanol-saturated solution of a metal compound such as zinc acetate is added to the solution. The mixture is heated to reflux for about 3 hours. After completion of the reaction, the reaction solution is separated and purified by silica gel column chromatography to obtain a porphyrin metal complex into which a transition metal such as zinc has been introduced.

Among the porphyrin derivatives represented by the general formula (I) thus obtained, a porphyrin derivative having one iodomethyl group at the o-, m- or p-position of one phenyl group is preferable. Porphyrin derivatives having one iodomethyl group at the p-position of the phenyl group are particularly preferred. Further, among the porphyrin derivatives represented by the general formula (I), a porphyrin derivative in which one phenyl group is substituted with two iodomethyl groups is preferable to a porphyrin derivative in which one phenyl group is substituted with one iodomethyl group. Among porphyrin derivatives represented by the general formula (I) in which one phenyl group is substituted by two iodomethyl groups, a porphyrin derivative having an iodomethyl group at two m-positions of one phenyl group is particularly preferable.

The porphyrin-centered amphiphilic star-shaped oxazoline polymer represented by the general formula (II) of the present invention can be produced, for example, according to the following production method.

A porphyrin derivative having an iodomethyl group represented by the general formula (I) and a polar solvent are added to a flask under an atmosphere of an inert gas such as nitrogen or argon, and the porphyrin derivative is completely dissolved by sufficiently stirring.
The solution is added with, for example, 20-fold or more moles of the 2-oxazoline compound relative to 1 mole of the porphyrin derivative, and then heated in an oil bath, and the reaction is continued while stirring at a temperature of 40 ° C. or more for 10 hours or more. After completion of the reaction, the temperature of the reaction mixture is lowered to room temperature, an appropriate amount of a methanol solvent is added, and the mixture is concentrated under reduced pressure. A solution obtained by dissolving the concentrated polymer in methanol is poured into an ether solvent, the polymer is reprecipitated, and the polymer is recovered by suction filtration. The obtained polymer is placed in a desiccator in which a desiccant such as P ₂ O ₅ is placed, and suction dried with an aspirator for one hour or more. Further, by reducing the pressure with a vacuum pump and drying for 24 hours under vacuum, the porphyrin-centered amphiphilic star-shaped oxazoline polymer represented by the general formula (II) having a porphyrin color can be obtained in a yield of 90% or more ( The total value of the 2-oxazoline compound and the porphyrin derivative represented by the general formula (I) is defined as a theoretical value).

The central metal of the porphyrin is a conventional transition metal, of which zinc, manganese, iron and cobalt are preferred, and zinc and manganese are particularly preferred.

In order to obtain such a porphyrin-centered amphiphilic star-shaped oxazoline polymer having a central metal, a metal-complexed material is used as the porphyrin derivative having an iodomethyl group represented by the general formula (I). Good.

Among the porphyrin-centered amphiphilic star-shaped oxazoline polymers represented by the general formula (II) thus obtained, a polyoxazoline arm is provided at the o-, m- or p-position of one phenyl group. Those having one are preferred, and those having one polyoxazoline arm at the p-position of one phenyl group are particularly preferred. Also, among the porphyrin-centered amphiphilic star-shaped oxazoline polymers represented by the general formula (II), one polyphenyl group is substituted by one polyoxazoline arm, and two phenyl groups are substituted by one polyoxazoline arm. Those substituted with an oxazoline arm are preferred. Further, among porphyrin-centered amphiphilic star-shaped oxazoline polymers represented by the general formula (II) in which one phenyl group is substituted with two polyoxazoline arms, a polyphenylene group is located at two m-positions of one phenyl group. Those having an oxazoline arm are particularly preferred.

Examples of the 2-oxazoline compound used in this reaction include 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-α-methylvinyl-2-oxazoline and 2-propyl-2-oxazoline. 2-alkyl-2-oxazolines such as oxazoline; 2-
2-allyl-2-oxazolines such as phenyl-2-oxazoline and 2- (4-methylphenyl) -2-oxazoline; and the like. In this reaction, as the compound that can be used alone as in the case of the 2-oxazoline compound or that can be used in combination with the 2-oxazoline compound, for example, 5,
6-dihydro-2-methyl-1,3,4-oxazine,
1,3-oxazine compounds such as 5,6-dihydro-2-phenyl-1,3,4-oxazine; and the like.

In this reaction, the polar solvent used may be any ordinary polar organic solvent, and is preferably a solvent having a cyano group such as acetonitrile and cyanobenzene, and among them, phenylacetonitrile is particularly preferred.

The porphyrin derivative having an iodomethyl group represented by the general formula (I) and 2-oxazoline are used in an amount of 12 to 2 moles of the 2-oxazoline compound per mole of the porphyrin derivative having the iodomethyl group.
000 mol is preferable, and 60 to 120
A range of 0 is more preferable, and a range of 100 to 800 is particularly preferable. In order to obtain a high molecular weight polymer, it is sufficient to increase the above molar ratio, but a 2-oxazoline compound having a maximum of 400 equivalents per iodomethyl group in one molecule of the porphyrin derivative is used. You can also.

The polymerization reaction temperature may be 40 ° C., but it is desirable to set optimum temperature conditions depending on the reaction solvent used. For example, when using acetonitrile as the solvent,
The reaction temperature is preferably in the range of 60 to 80C. When phenylacetonitrile is used as the solvent, the reaction temperature is preferably in the range of 80 to 140C. When setting the reaction temperature, it is desirable to consider the boiling point of the 2-oxazoline compound.

The polymerization reaction time depends on the amount of the 2-oxazoline compound relative to the porphyrin derivative having an iodomethyl group represented by the general formula (I) and the reaction temperature. When the reaction temperature is high and the amount of the 2-oxazoline compound is small, a reaction time of about 10 hours is sufficient. In order to obtain a polymer having a large amount of 2-oxazoline compound and a high degree of polymerization, a long-time reaction is required.
Specifically, when the reaction temperature is 100 ° C., the reaction time is set to 24 hours, more preferably 48 hours, so that the average degree of polymerization (P) of one arm becomes 200. That is, the polymerization of all the 2-oxazoline compounds in a predetermined charge amount can be easily performed by appropriately extending the reaction time.

The resulting polymer is readily soluble in many polar organic solvents and also readily in water. Non-solvents in which the resulting polymer becomes insoluble include diethyl ether,
Ethers such as tetrahydrofuran. In purifying the obtained polymer, it is desirable to repeat the reprecipitation process a few times. A preferred good solvent in the reprecipitation process is methanol, and a preferred non-solvent is diethyl ether.

Although an iodine atom is bonded to the terminal structure of the produced polymer, the present invention is not limited to this, and may be a chlorine atom or a bromine atom. Furthermore,
The iodine atom can also be converted to another substituent by a chemical means according to the purpose.

The porphyrin-centered amphiphilic star-shaped oxazoline polymer represented by the general formula (III) of the present invention can be produced, for example, according to the following production method.

A porphyrin derivative having an iodomethyl group represented by the general formula (I) and a polar solvent are added to a flask under an atmosphere of an inert gas such as nitrogen or argon, and thoroughly stirred to completely dissolve the porphyrin. .
In this solution, for example, 2
0-fold mole or more of 2-oxazoline compound (hereinafter referred to as first
It is called a monomer. ), The mixture is heated in an oil bath, and the reaction is continued while stirring at a temperature of 40 ° C. or more for 10 hours or more. After confirming that 95% or more of the first monomer has been consumed by gas chromatography or ¹ H-NMR,
A 20-fold molar or more 2-oxazoline compound (hereinafter, referred to as a second monomer) is added, and the reaction is continued while stirring at the same temperature or a higher temperature for 10 hours or more. After completion of the reaction, the temperature of the reaction mixture is lowered to room temperature, an appropriate amount of a methanol solvent is added, and the mixture is concentrated under reduced pressure. A solution obtained by dissolving the concentrated polymer in methanol is poured into an ether solvent, the polymer is reprecipitated, and the polymer is recovered by suction filtration. The resulting polymer is placed in a desiccator in which a desiccant such as P ₂ O ₅ is placed, and suction dried with an aspirator for one hour or more. Further, by reducing the pressure with a vacuum pump and drying under vacuum for 24 hours, a porphyrin-centered amphiphilic star-shaped oxazoline polymer represented by the general formula (III) having a porphyrin color can be obtained in a yield of 90% or more ( The total value of the first monomer, the second monomer and the porphyrin derivative represented by the general formula (I) is defined as a theoretical value.)
Can be obtained at

The central metal of porphyrin is a conventional transition metal, of which zinc, manganese, iron and cobalt are preferred, and zinc and manganese are particularly preferred.

In order to obtain such a porphyrin-centered amphiphilic star-shaped oxazoline polymer having a central metal, a metal-complexed material is used as the porphyrin derivative having an iodomethyl group represented by the general formula (I). Good.

Among the porphyrin-centered amphiphilic star-shaped oxazoline polymers represented by the general formula (III) thus obtained, a block copolymer of oxazoline at the o-, m- or p-position of one phenyl group Those having one arm are preferred, and those having one oxazoline block copolymer arm at the p-position of one phenyl group are particularly preferred. Also, among the porphyrin-centered amphiphilic star-shaped oxazoline polymers represented by the general formula (III), one phenyl group is more substituted by one oxazoline block copolymer arm than one porphyrin derivative. Preferred are two oxazoline block copolymer arms substituted. Further, in the porphyrin-centered amphiphilic star-shaped oxazoline polymer represented by the general formula (III) in which one phenyl group is substituted by two block copolymer arms of oxazoline, two m-positions of one phenyl group are represented. Having an oxazoline block copolymer arm is particularly preferred.

In this reaction, the polar solvent to be used may be any of commonly used polar organic solvents, preferably a cyano group-containing solvent such as acetonitrile and cyanobenzene, and particularly preferably phenylacetonitrile.

The proportion of the porphyrin derivative having an iodomethyl group represented by the general formula (I) and the first monomer is in the range of 20 to 1000 mol per 1 mol of the porphyrin derivative having an iodomethyl group. Is more preferable, the range of 60 to 800 is more preferable, and the range of 100 to 200 is particularly preferable.
The input amount of the second monomer can also conform to the above ratio. In order to obtain a polymer having a high molecular weight, it is sufficient to increase the above molar ratio. However, a maximum of 400 combined with the first monomer and the second monomer is required for one iodomethyl group in one molecule of the porphyrin derivative. Equal amounts can be used.

The polymerization reaction temperature may be 40 ° C., but it is desirable to set optimum temperature conditions depending on the reaction solvent used. For example, when using acetonitrile as the solvent,
The reaction temperature is preferably in the range of 60 to 80C. When phenylacetonitrile is used as the solvent, the reaction temperature is preferably in the range of 80 to 140C. In setting the reaction temperature, it is desirable to also consider the boiling points of the first monomer and the second monomer used.

The polymerization reaction time can be set finely depending on the amount of the monomer and the reaction temperature with respect to the porphyrin derivative having an iodomethyl group represented by the general formula (I).
When the reaction temperature is high and the amount of the first monomer is small, the first
A reaction time of about 10 hours in the polymerization stage is sufficient. Thereafter, a second monomer may be added to set the polymerization time to the same aim. In order to obtain a polymer having a large amount of the whole monomer and a high degree of polymerization, a long-time reaction is required. Specifically, when the reaction temperature is 100 ° C., the average degree of polymerization (p + q) of one arm becomes 200,
The total reaction time of the first and second polymerization reactions is preferably 48 hours, more preferably 72 hours or more. That is, it is possible to easily carry out the polymerization of all the monomers of a predetermined charge amount by appropriately extending the reaction time.

The resulting polymer readily dissolves in many polar organic solvents and also in water. Non-solvents for the resulting polymer include ethers such as diethyl ether and tetrahydrofuran. In purifying the obtained polymer, it is desirable to repeat the reprecipitation process a few times. A preferred good solvent in the reprecipitation process is methanol, and a preferred non-solvent is diethyl ether.

The living polymerizability of oxazoline by an active halogen compound is well known. Accordingly, not only a diblock copolymer but also a ternary block copolymer can be easily produced for producing an oxazoline block copolymer using iodomethylporphyrin as an initiator. Therefore, the present method is not limited to the production of binary block copolymers, but can also be applied to the production of binary or more multi-block copolymers.

Although an iodine atom is bonded to the terminal structure of the formed block polymer, the terminal structure is not limited to this, and may be a chlorine atom or a bromine atom. Furthermore, it becomes possible to convert an iodine atom into another substituent, for example, a hydroxyl group, according to the purpose, by a chemical means.

As the first monomer and the second monomer, materials having different chemical structures from among the 2-oxazoline compounds exemplified above may be used.

The porphyrin-centered star-shaped oxazoline polymer of the present invention represented by the general formula (IV) can be produced, for example, according to the following production method.

A porphyrin having an iodomethyl group represented by the general formula (I) and a polar solvent are added to a flask under an atmosphere of an inert gas such as nitrogen or argon, and the porphyrin is completely dissolved by sufficiently stirring. After adding two kinds of 2-oxazoline compounds in an amount of, for example, 20 times or more mol of the porphyrin to this solution, the mixture is heated in an oil bath, and the reaction is continued while stirring at a temperature of 40 ° C. or more for 10 hours or more. . After completion of the reaction, the temperature of the reaction mixture is lowered to room temperature, an appropriate amount of a methanol solvent is added, and the mixture is concentrated under reduced pressure. A solution obtained by dissolving the concentrated polymer in methanol is poured into an ether solvent, the polymer is reprecipitated, and the polymer is recovered by suction filtration. The resulting polymer is placed in a desiccator over a desiccant such as P ₂ O ₅ ,
Suction dry for at least one hour with an aspirator. Further, by reducing the pressure with a vacuum pump and drying for 24 hours under vacuum, the porphyrin-centered star-shaped oxazoline polymer represented by the general formula (IV) having a porphyrin color is 90%
The above yield (the total value of the weights of the porphyrins of the 2-oxazoline compound and the initiator is defined as a theoretical value) can be obtained.

The central metal of the porphyrin is a conventional transition metal, of which zinc, manganese, iron and cobalt are preferred, and zinc and manganese are particularly preferred.

In order to obtain such a porphyrin-centered amphiphilic star-shaped oxazoline polymer having a central metal, a metal-complexed material is used as the porphyrin derivative having an iodomethyl group represented by the general formula (I). Good.

Among the porphyrin-centered amphiphilic star-shaped oxazoline polymers represented by the general formula (IV) thus obtained, a copolymer arm of oxazoline at the o-, m- or p-position of one phenyl group. Is preferable, and one having one oxazoline copolymer arm at the p-position of one phenyl group is particularly preferable. Further, among the porphyrin-centered amphiphilic star-shaped oxazoline polymers represented by the general formula (IV), two phenyl groups are more substituted by one phenyl group than one porphyrin derivative in which one oxazoline copolymer arm is substituted. Those in which the copolymer arm of oxazoline is substituted are preferred. Also, in the porphyrin-centered amphiphilic star-shaped oxazoline polymer represented by the general formula (IV) in which one phenyl group is substituted by two oxazoline copolymer arms, two m-positions of one phenyl group are present. Those having oxazoline copolymer arms are particularly preferred.

In this reaction, the polar solvent to be used may be any ordinary polar organic solvent, and is preferably a cyano group-containing solvent such as acetonitrile and cyanobenzene, and particularly preferably phenylacetonitrile.

The proportion of the porphyrin derivative having an iodomethyl group represented by the general formula (I) and two kinds of 2-oxazolines is such that the 2-oxazoline compound is from 12 to 2 moles per mole of the porphyrin derivative having an iodomethyl group. A ratio in the range of 2000 mol (A) is preferable, and a range in the range of 60 to 1200 is more preferable.
The range which becomes -800 is especially preferable. In order to obtain a high molecular weight polymer, it is sufficient to increase the above molar ratio, but a 2-oxazoline compound having a maximum of 400 equivalents per iodomethyl group in one molecule of the porphyrin derivative is used. You can also.

The composition of the resulting polymer is determined according to the composition of the two kinds of 2-oxazoline compounds. In the case of a mixed system of three kinds of 2-oxazoline compounds, a terpolymer can be easily obtained. . Therefore, the copolymer in the present production method is not limited to a binary copolymer, and can be applied to the production of a terpolymer.

The polymerization reaction temperature may be 40 ° C., but it is desirable to set optimum temperature conditions depending on the reaction solvent used. For example, when using acetonitrile as the solvent,
The reaction temperature is preferably 60 or 80 ° C. When phenylacetonitrile is used as the solvent, the reaction temperature is 80
It is desirable that the temperature is not less than 140 ° C and not more than 140 ° C. When setting the reaction temperature, it is desirable to consider the boiling points of the two types of 2-oxazoline compounds.

The polymerization reaction time can be finely set depending on the amounts of two kinds of 2-oxazoline compounds and the reaction temperature with respect to the porphyrin derivative having an iodomethyl group represented by the general formula (I). When the reaction temperature is high and the amount of the 2-oxazoline compound is small, a reaction time of about 10 hours is sufficient. In order to obtain a polymer having a large amount of 2-oxazoline compound and a high degree of polymerization, a long-time reaction is required. Specifically, the reaction temperature is 100 ° C.
In this case, the reaction time is set to 24 hours, more preferably 48 hours, so that the average degree of polymerization (P) of one arm becomes 200. In other words, two types of 2 with a predetermined charge amount
The polymerization of all the oxazoline compounds can be easily carried out by appropriately extending the reaction time.

The resulting polymer readily dissolves in many polar organic solvents and also in water. Non-solvents for the resulting polymer include ethers such as diethyl ether and tetrahydrofuran. In purifying the obtained polymer, it is desirable to repeat the reprecipitation process a few times. A preferred good solvent in the reprecipitation process is methanol, and a preferred non-solvent is diethyl ether.

Although an iodine atom is bonded to the terminal structure of such a produced block polymer, the terminal structure is not limited thereto, and may be a chlorine atom or a bromine atom. Furthermore, it becomes possible to convert an iodine atom into another substituent, for example, a hydroxyl group, according to the purpose, by a chemical means.

The porphyrin-centered star-shaped ethyleneimine polymer represented by the general formula (V) of the present invention can be produced, for example, according to the following production method.

A star-shaped polyoxazoline represented by the general formula (II) or (III) is dissolved in distilled water, and 3
0% aqueous sodium hydroxide solution was added, and the mixture was
After stirring at 00 ° C. for 3 hours or more, the temperature of the reaction solution is lowered to room temperature, and a porphyrin-colored purple solid precipitates. The solid is filtered off with suction, the solid is washed with cold water and washing is continued until the washings are neutral. After recrystallizing the solid in water or ethanol, the solid is dried under vacuum at 90 ° C. to obtain a compound of the formula (V) in a high yield of 90%.
A porphyrin-centered star-shaped ethyleneimine polymer represented by the following formula can be obtained.

The porphyrin-centered star-shaped ethyleneimine polymer represented by the general formula (V) of the present invention can be produced by another simple production method described below.

A star-shaped polyoxazoline represented by the general formula (II) or (III) is dissolved in distilled water, a concentrated hydrochloric acid solution is added thereto, and the mixture is refluxed for 5 hours or more. By this operation, the amide bond in the polymer chain represented by the general formula (II) or (III) is easily hydrolyzed, and in the star polymer represented by the general formula (V), a nitrogen atom is removed. A protonated hydrochloride derivative is obtained. The aqueous solution of the hydrochloride derivative is added to a 5% aqueous solution of sodium hydroxide and stirred at 60 ° C. for 20 minutes. By cooling the mixture to room temperature to precipitate a solid, a porphyrin-centered star-shaped ethyleneimine polymer represented by the general formula (V) can be obtained.

Among the porphyrin-centered star-shaped ethyleneimine polymers represented by the general formula (V) thus obtained, those having one polyethyleneimine arm at the p-position of one phenyl group are preferred. Further, among the porphyrin-centered star-shaped ethyleneimine polymers represented by the general formula (V), two polyethyleneimine arms per phenyl group are better than a porphyrin derivative in which one phenyl group is substituted by one polyethyleneimine arm. Are preferably substituted. Further, in the porphyrin-centered star-shaped ethyleneimine polymer represented by the general formula (V) in which one phenyl group is substituted by two polyethyleneimine arms, two m-m- groups at one position of one phenyl group are used.
Those having a polyethyleneimine arm at the position are particularly preferred.

[0071]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the scope of these Examples.

<Example 1> [Synthesis of tetra (p-iodomethylphenyl) porphyrin (abbreviation: TIMPP)] A 1000 ml eggplant-shaped flask equipped with a reflux condenser, a three-way cock and a gas bubbling tube was charged with p-iodine. 0.98 g of methylbenzaldehyde, 0.28 g of pyrrole and 400 ml of chloroform were added. This mixed solution was bubbled with argon gas for 10 minutes while stirring with a stirrer. Thereafter, a diethyl ether solution of 0.02 ml of boron tribromide was added, and the mixed solution was stirred at room temperature for 1 hour. Subsequently, 0.23 ml of triethylamine and 0.74 g of chloranil were added, and the mixture was refluxed for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and the reaction product was concentrated. An appropriate amount of methylene chloride is added to the concentrated solution, followed by filtration to collect an insoluble solid.The solid solution is converted into a chloroform solution, separated and purified using a silica column, and the eluate is evaporated using a rotary evaporator. After drying, 0.55 g of tetra (p-iodomethylphenyl) porphyrin (hereinafter abbreviated as TIMPP) was obtained. (Yield 47%)

The structure of TIMPP was identified by ¹ H-NMR (nuclear magnetic resonance spectrum), UV-Vis (ultraviolet-visible absorption spectrum), Mass (mass) analysis, and elemental analysis.

¹ H-NMR (300 MHz, CDCl
₃ , (CH ₃ ) ₄ Si internal standard) δ (ppm): −2.8 (s, 2 H), 4.7 (s,
8H), 7.7 to 7.8 (d, 8H), 8.1 to 8.
2 (d, 8H), 8.8 (s, 8H)

UV-Vis (in CHCl ₃ ) λmax (nm): 419.2, 515.3, 541.
5, 590.3, 648.8

FAB-Mass m / z: 1174, 1175

Elemental analysis: (measured value) C = 49.02%, H = 2.74%, N = 4.65% (calculated value) C = 49.09%, H = 2.92%, N = 4.77%

<Example 2> [Tetra (m, m'-diiodomethylphenyl) porphyrin (abbreviation: OIMPP)
Synthesis of tetra (m, m′-diene) in the same manner as in Example 1 except that in Example 1, 1.54 g of m, m-diiodomethylbenzaldehyde was used instead of p-iodomethylbenzaldehyde. 0.66 g of iodomethylphenyl) porphyrin (hereinafter abbreviated as OIMPP) was obtained. (38% yield)

The structure of OIMPP is represented by ¹ H-NMR, UV
-Identified by Vis, Mass analysis and elemental analysis.

¹ H-NMR (300 MHz, CDCl
₃ , (CH ₃ ) ₄ Si internal standard) δ (ppm): −2.8 (s, 2H), 4.9 (s, 1)
6H), 7.8-7.9 (t, 4H), 8.2-8.
3 (d, 8H), 8.8 (s, 8H)

UV-Vis (in CHCl ₃ ) λmax (nm): 419.4, 515.8, 542.
0, 591.1, 648.2

FAB-Mass m / z: 1734, 1735

Elemental analysis: (measured value) C = 35.89%, H = 2.38%, N = 3.51% (calculated value) C = 36.02%, H = 2.21%, N = 3.23%

<Example 3> [Zinc tetra (p-iodomethylphenyl) porphyrin (abbreviation: TIMPP-Z)
Synthesis of n)] In a 500 ml eggplant-shaped flask equipped with a reflux condenser, 200 mL of chloroform was added to the TIMP obtained in Example 1.
0.25 g of P was dissolved. While stirring the contents of the flask, 30 ml of a methanol saturated solution of zinc acetate was added, and the mixture was refluxed for 2 hours. After cooling the reaction mixture to room temperature, the reaction mixture is separated and purified by silica gel column chromatography using chloroform as an eluent, and zinc tetra (p-iodomethylphenyl) porphyrin (hereinafter referred to as TIMPP-ZnP). 0.23)
g was obtained. (86% yield)

<Example 4> [Star-shaped poly (methyloxazoline) using TIMPP as an initiator (abbreviation: TPMO-
Synthesis of P)] After replacing the inside of a 50 ml two-necked flask equipped with a three-way cock with argon gas, the TIMPP obtained in Example 1 was replaced.
0.0352 g and 8.0 ml of phenylacetonitrile were added, and the mixture was stirred at room temperature to completely dissolve TIMPP.
To this solution was added 3.4 ml of 2-methyl-2-oxazoline corresponding to 1280 times the molar amount of TIMPP (3.2 parts).
After 7 g) was added using a syringe, the mixture was reacted at 100 ° C. with stirring for 24 hours. After the temperature of the reaction mixture was lowered to room temperature, 10 ml of methanol was added to the reaction mixture, and the mixture was concentrated under reduced pressure. The residue is methanol 15ml
And the solution was poured into 100 ml of tetrahydrofuran to precipitate the polymer. After reprecipitating the polymer by the same method, the polymer obtained by suction filtration was put into a desiccator in which phosphorus pentoxide (P ₂ O ₅ ) was placed, and dried by suction with an aspirator for 1 hour. Further, the pressure is reduced by a vacuum pump, and the mixture is dried under vacuum for 24 hours.
Is abbreviated. ) 3.05 g were obtained. (Yield 92.3%)

The number average molecular weight of the polymer (TPMO-P) obtained in Example 4 measured by GPC (gel permeation chromatography) was 28,000, and the molecular weight distribution was 1.
56. From the ¹ H-NMR measurement results, the integral ratio between the ethylene proton in the polymer arm and the pyrrol ring proton of porphyrin at the polymer center was calculated, and the average degree of polymerization of each arm was 290.
Therefore, the number average molecular weight of the polymer (TPMO-P) obtained in Example 4 determined from ¹ H-NMR was estimated to be 99,900. It is a general feature of star polymers that the value of the number average molecular weight by ¹ H-NMR greatly exceeds the value of the number average molecular weight by GPC.

<Example 5> [Synthesis of star-shaped poly (methyloxazoline-b-phenyloxazoline) (abbreviation: TPMO-b-PO-P) using TIMPP as an initiator] A 50-ml capacity equipped with a three-way cock After replacing the inside of the two-necked flask with argon gas, the TIMPP obtained in Example 1 was obtained.
0.0352 g and 8.0 ml of phenylacetonitrile were added, and the mixture was stirred at room temperature to completely dissolve TIMPP.
To this solution, 1.06 ml of 2-methyl-2-oxazoline corresponding to 400 times the molar number of TIMPP (1.0
After 2 g) was added with a syringe, the mixture was reacted at 100 ° C. with stirring for 24 hours. At this point, 2-methyl-2-
The oxazoline conversion was 98%. After the temperature of the reaction solution was lowered to 60 ° C., 0.8% of 2-phenyl-2-oxazoline corresponding to 200 times the molar number of TIMPP was obtained.
After adding 83 g and 4.0 ml of phenylacetonitrile, the reaction was carried out again at 100 ° C. with stirring for 24 hours.
The temperature of the reaction mixture was lowered to room temperature, 10 ml of methanol was added, and the reaction mixture was concentrated under reduced pressure. The residue was dissolved in 15 ml of methanol and the solution was
The polymer was precipitated by pouring into 00 ml. In the same way,
The polymer was reprecipitated, and after suction filtration, the obtained polymer was treated with P
_The resultant was placed in a desiccator on which ₂ O ₅ was placed, and suction-dried with an aspirator for 1 hour. Further, the pressure was reduced by a vacuum pump, and the film was dried under vacuum for 24 hours to obtain a star-shaped poly (methyloxazoline-b-phenyloxazoline) (hereinafter referred to as TPMO-b).
Abbreviated as -PO-P. ) 1.88 g were obtained. (Yield 9
6.9%)

The block copolymer obtained in Example 5 (TPM
Ob-PO-P) had a number average molecular weight of 26,000 and a molecular weight distribution of 1.47 as measured by GPC.
Further, when the integral ratio between the ethylene proton in the polymer arm and the pyrrol ring proton of porphyrin at the polymer center was calculated by ¹ H-NMR, the average degree of polymerization of each arm was 142. Further, the molar composition ratio of methyl oxazoline residue to phenyl oxazoline residue measured by ¹ H-NMR was 68/32. Therefore, ¹ H
-The polymer obtained in Example 5 (TPMO-
The number average molecular weight of (b-PO-P) was estimated to be 60600.

Example 6 [Star-shaped poly (methyloxazoline-co-phenyloxazoline) using TIMPP zinc complex as initiator (abbreviation: TPMO-co-PO-P)
Synthesis of Zn)] After replacing the inside of a 50 ml two-necked flask equipped with a three-way cock with argon gas, the TIMPP obtained in Example 3 was obtained.
0.037 g of Zn, 8.0 ml of phenylacetonitrile
And stirred at room temperature to completely dissolve the TIMPP. 1.06 of 2-methyl-2-oxazoline corresponding to 400 times the molar number of TIMPP-Zn was added to this solution.
ml (1.02 g) and 0.883 g of 2-phenyl-2-oxazoline corresponding to a 200-fold molar number were added with a syringe, and the mixture was reacted at 100 ° C. with stirring for 24 hours. The temperature of the reaction mixture was lowered to room temperature, and methanol (10 ml) was added.
Was added, and the reaction mixture was concentrated under reduced pressure. The residue was dissolved in 15 ml of methanol and the solution was poured into 100 ml of tetrahydrofuran to precipitate the polymer. The polymer was reprecipitated by the same method, and after suction filtration, the obtained polymer was placed in a desiccator in which P ₂ O ₅ was placed, and suction-dried with an aspirator for 1 hour. Furthermore, the pressure is reduced by a vacuum pump,
After drying under vacuum for 24 hours, star-shaped poly (methyloxazoline-co-phenyloxazoline) (hereinafter referred to as TPMO
Abbreviated as -co-PO-PZn. ) 1.84 g were obtained. (Yield 94.8%)

The copolymer obtained in Example 6 (TPMO-co
-PO-PZn) had a number average molecular weight of 37000 and a molecular weight distribution of 1.61 measured by GPC. Further, when the integral ratio between the ethylene proton in the polymer arm and the pyrrol ring proton of porphyrin at the polymer center was calculated by ¹ H-NMR, the average degree of polymerization of each arm was 140. Further, the molar composition ratio of methyl oxazoline residue to phenyl oxazoline residue measured by ¹ H-NMR was 72/28. Therefore, ¹ H−
The copolymer obtained in Example 6 (TPMO-
The number average molecular weight of (co-PO-PZn) was estimated to be 58100.

<Example 7> [Star-shaped poly (2-ethyloxazoline) using OIMPP as an initiator (abbreviation: OPE
Synthesis of OP)] After replacing the inside of a 50 ml two-necked flask equipped with a three-way cock with argon gas, the OIMPP obtained in Example 2 was replaced with argon gas.
0.026 g and 8.0 ml of phenylacetonitrile were added, and the mixture was stirred at room temperature to completely dissolve TIMPP.
To this solution was added 1.24 ml of 2-methyl-2-oxazoline (1.1 times the molar number of OIMPP).
89 g) with a syringe, and then at 100 ° C. for 24 hours.
The reaction was performed while stirring for an hour. The temperature of the reaction mixture was lowered to room temperature, 10 ml of methanol was added, and the mixture was concentrated under reduced pressure. The residue was dissolved in 15 ml of methanol and the solution was poured into 100 ml of tetrahydrofuran to precipitate the polymer. The polymer was reprecipitated by the same method, and after suction filtration, the obtained polymer was placed in a desiccator in which P ₂ O ₅ was placed, and dried by suction with an aspirator for 1 hour. Further, the pressure is reduced by a vacuum pump and dried under vacuum for 24 hours to obtain a star-shaped poly (2-ethyloxazoline) (hereinafter, referred to as “poly (2-ethyloxazoline)”).
Abbreviated as OPEO-P. 1.18 g were obtained. (Yield 97%)

The number average molecular weight of the polymer (OPEO-P) obtained in Example 7 measured by GPC was 47000,
The molecular weight distribution was 1.42. In addition, when the integral ratio between the ethylene proton in the polymer arm and the pyrrol ring proton of porphyrin at the polymer center was calculated by ¹ H-NMR, the average degree of polymerization of each arm was 93. Therefore, the number average molecular weight of the polymer (OPEO-P) obtained in Example 7 determined from ¹ H-NMR was estimated to be 75500.

<Example 8> [Star-shaped poly (ethyleneimine) obtained by hydrolysis of TPMO-P (abbreviation: TPEI-
Synthesis of P)] Example 4 was placed in a 50-ml flask equipped with a reflux condenser.
1.0 g of TPMO-P obtained in the above, 10 ml of distilled water, concentrated hydrochloric acid 1
0 ml was added sequentially and stirred at room temperature to dissolve the polymer. The mixture was refluxed for 18 hours in an oil bath.
After the reaction, the aqueous hydrochloric acid solution was removed under reduced pressure to obtain a greenish solid. The solid was washed with methanol, dissolved in 10 ml of distilled water, and a 2% aqueous sodium hydroxide solution was added dropwise to the solution. While confirming that the aqueous solution changed from green to purple, a 2% aqueous sodium hydroxide solution was added dropwise until the pH of the aqueous solution reached 10, thereby precipitating the polymer.
The solid was filtered off with suction and washed with cold distilled water until the washings were neutral. Further, the solid was recrystallized in ethanol, and then dried under vacuum at 100 ° C. for 24 hours to obtain a star-shaped poly (ethyleneimine) (hereinafter referred to as TPEI).
Abbreviated as -P. ) 0.48 g was obtained. (94% yield)

Of the polymer (TPEI-P) obtained in Example 8
^When the integral ratio between the ethylene proton in the polymer arm and the pyrrol ring proton of porphyrin at the polymer center was calculated by ¹ H-NMR, the average degree of polymerization of each arm was 287. This basically coincided with the degree of polymerization of the polymer before hydrolysis. Therefore, ¹ H-NMR
The number average molecular weight of the polymer (TPEI-P) obtained in Example 8 was estimated to be 50,400.

<Evaluation> The porphyrin-centered amphiphilic star-shaped oxazoline polymer (TPMO-P) obtained in Example 4 was soluble in water and various organic solvents, and UV-Vis was measured for those solvent solutions. The maximum absorption wavelength measured was measured, and the results are shown in Table 1.

[0096]

[Table 1]

The porphyrin-centered amphiphilic star-shaped oxazoline polymer (TPMO-P) obtained in Example 4 showed very good solubility in water and many organic solvents. Usually, in the case of amphiphilic porphyrin, the maximum absorption wavelength strongly depends on the solvent, and is 5 to 6 times higher in water than in organic solvents.
It is known that the wavelength shifts to the shorter wavelength side as nm [Journal of Chemical Society (J. Chem. S.
oc. ) Faraday Tractions
ans. 93), p. 3945 (1997)]. However, in the porphyrin-centered amphiphilic star polymer of the present invention, the maximum absorption wavelength was almost the same regardless of the type of the solvent. This feature suggests that porphyrins are completely isolated in star-shaped polymer cages and that interactions between porphyrin skeletons are blocked by large polymer arms.

[0098]

According to the present invention, the porphyrin-centered amphiphilic star-shaped oxazoline polymer obtained from the porphyrin derivative having an iodomethyl group of the present invention has a porphyrin completely isolated in a star-shaped polymer cage and a porphyrin skeleton The blocking of the interaction is beneficial for the expression of the porphyrin's catalyst / photofunction, so that various applications as a photofunctional material, a photoelectric conversion device, and a drug for cancer treatment and diagnosis are expected.

Claims (15)

[Claims] 1. A compound of the general formula (I) (Wherein, n represents 1 or 2, M represents two hydrogen atoms or transition metals, and the dotted line represents no bond when M is a hydrogen atom, and a coordinate bond when M is a transition metal. The porphyrin derivative having an iodomethyl group, characterized in that the iodomethyl group is bonded to any of the o-, m- and p-positions of the phenyl ring. 2. The derivative represented by the general formula (I), wherein n is 1 and the iodomethyl group is
The porphyrin derivative having an iodomethyl group according to claim 1, which is bonded at a position. 3. The porphyrin derivative having an iodomethyl group according to claim 1, wherein in the derivative represented by the general formula (I), n is 2, and an iodomethyl group is bonded to two m-positions of a phenyl ring. 4. A compound of the general formula (II) (Wherein, R represents an alkyl or allyl group, and p is 3 to
An integer in the range of 500, representing the number average degree of polymerization of the polyoxazoline arm. M represents two hydrogen atoms or transition metals, and the dotted line represents no bond when M is a hydrogen atom, and represents a coordinate bond when M is a transition metal. n
Represents 1 or 2. The n polyoxazoline arms are attached to any of the o-, m- and p-positions of the phenyl ring. A porphyrin-centered amphiphilic star-shaped oxazoline polymer characterized by the following formula: 5. The porphyrin-centered amphiphilic star according to claim 4, wherein in the polymer represented by the general formula (II), n is 1 and the polyoxazoline arm is bonded to the p-position of the phenyl ring. Type oxazoline polymer. 6. The eight porphyrin centers according to claim 4, wherein in the polymer represented by the general formula (II), n is 2, and a polyoxazoline arm is bonded to two m-positions of a phenyl ring. Star oxazoline polymer. 7. A compound of the general formula (III) (Wherein, R ₁ and R ₂ each independently represent an alkyl group or an allyl group, and p and q each independently represent 5-250
And represents the number average degree of polymerization of the polyoxazoline segment, and the sum is in the range of 10 to 500. M is two hydrogen atoms or transition metals, and the dotted line indicates no bond when M is a hydrogen atom, and indicates a coordinate bond when M is a transition metal. n represents 1 or 2. The n oxazoline block copolymer arms are attached at any of the o-, m- and p-positions of the phenyl ring. A porphyrin-centered amphiphilic star-shaped oxazoline polymer characterized by the following formula: 8. The porphyrin center according to claim 7, wherein in the polymer represented by the general formula (III), n is 1, and the polyoxazoline block copolymer arm is bonded to the p-position of the phenyl ring. Amphiphilic star-shaped oxazoline polymer. 9. The porphyrin according to claim 7, wherein in the polymer represented by the general formula (III), n is 2, and the polyoxazoline block copolymer arm is bonded to two m-positions of a phenyl ring. Central amphiphilic star-shaped oxazoline polymer. 10. A compound of the general formula (IV) (Wherein, R ₁ and R ₂ are each independently an alkyl group or an allyl group, X is a numerical value from 0.1 to 0.9, and p
Is an integer in the range of 3 to 500 and represents the number average degree of polymerization of the arms of the oxazoline copolymer. M represents two hydrogen atoms or transition metals, and the dotted line represents no bond when M is a hydrogen atom, and represents a coordinate bond when M is a transition metal. n represents an integer of 1 to 3. The n polyoxazoline copolymer arms are attached to any of the o-, m- and p-positions of the phenyl ring. A porphyrin-centered amphiphilic star-shaped oxazoline polymer characterized by the following formula: 11. The porphyrin-centered parent according to claim 10, wherein in the polymer represented by the general formula (IV), n is 1, and the polyoxazoline copolymer arm is bonded to the p-position of the phenyl ring. Amphiphilic star oxazoline polymer. 12. The polymer represented by the general formula (IV), wherein n is 2, and a polyoxazoline copolymer arm is bonded to two m-positions of a phenyl ring.
A porphyrin-centered amphiphilic star-shaped oxazoline polymer according to the above. 13. A compound of the general formula (V) (In the formula, p is an integer in the range of 3 to 500 and represents the number average degree of polymerization of the polyethyleneimine arm. N is 1
Or 2 is represented. The arms of the n polyethyleneimines are linked to any of the o-, m- and p-positions of the phenyl ring. A star-shaped ethyleneimine polymer, which is a derivative of porphyrin-centered polyoxazoline represented by the following formula: 14. The porphyrin-centered polyoxazoline according to claim 13, wherein n is 1 in the polymer represented by the general formula (V) and the polyethyleneimine arm is bonded to the p-position of the phenyl ring. Star-shaped ethyleneimine polymer which is a derivative. 15. The porphyrin-centered polyoxazoline according to claim 13, wherein in the polymer represented by the general formula (V), n is 2, and a polyethyleneimine arm is bonded to two m-positions of a phenyl ring. Is a derivative of a star-shaped ethyleneimine polymer.