JP3127467B2 - Tetraphenylporphyrin derivative and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a tetraphenylporphyrin derivative and a method for producing the same.

[Conventional technology]

Numerous studies have been made on porphyrin compounds, particularly tetraphenyl porphyrin compounds, due to their thermal stability and photocatalytic properties. Particularly, its usefulness as a photooxidation-reduction reaction catalyst is known, and attempts to utilize a porphyrin compound as a sensitizer in a photoinduced electron transfer reaction system have been actively conducted from the viewpoint of a photosynthesis model compound. In the photosynthesis system, the technique of arranging porphyrin compounds as thin films is particularly interesting because the porphyrin compounds are arranged in the membrane of plant cells, and among them, the Langmuir-Brozeit membrane (LB membrane) has a structure close to the actual arrangement of plant systems Of particular interest is the ability to experimentally fabricate membranes by controlled means. Porphyrin compounds
In order to produce an LB film, it is common to provide a porphyrin compound with a hydrophobic group such as a long-chain alkyl for imparting a hydrophobic interaction. However, it is known that the porphyrin compound easily associates with a dimer or the like in a solution or a solid. For example, in the 196th Annual Meeting of the American Chemical Society, Inorganic Chemistry, Lecture No. 201 (1988), it was reported that a Langmuir brodiet film was produced using tetra (4-octadecyloxyphenyl) polyfilin. It is estimated from the molecular occupation area of the film that the porphyrin molecule has a structure in which the porphyrin rings face each other and the porphyrin rings are arranged perpendicularly or obliquely to the water surface (substrate).

On the other hand, it is also known that porphyrin molecules are horizontal in the LB film. For example, Andre Balow (Andre Balow)
rraud) et al. Thin Solid Films
Films, Vol. 99, p. 33 (1988), reports on the LB film of long-chain alkyltetrapyridinium porphyrins and shows that the porphyrin ring is horizontal. In this case, it is considered that the charged pyridinium group strongly interacts with the water used for the subphase, but the charge of the pyridinium group is mainly due to the nitrogen atom at the base of the long chain alkyl group, which is a hydrophobic group, and the LB film It is considered that the inside faces toward the hydrophobic group side (above the subphase).

[Problems to be solved by the invention]

The present invention relates to a tetraphenylpolyphenylene derivative different from the above-mentioned tetra (4-octadecyloxyphenyl) polyfilin and a long-chain alkyltetrapyridinium polyfilin, wherein a hydrophobic group and a hydrophilic group are clearly separated. And a method for producing the same, which can form an LB film having a structure as described above.
It is intended to provide a method for producing an LB film using the porphyrin derivative.

[Means for solving the problem]

The tetraphenylporphyrin derivative of the present invention has the general formula (I) (Wherein, M represents two hydrogens, and R ¹ , R ² , R ³ and R ⁴ each independently represent an alkoxy group) or a salt thereof.

In the general formula (I), when M is a metal, the metal may be a group Ib, IIa, IIb, IIIa, IVa, Ia
There are metals of Vb group, Vb group, VIb group, VIIb group, VIII group, for example, Cu, Zn, Mg, Al, Ge, Ti, Sn, Pb, Cr, Mo, Mn, Fe, Co , Ni, I
n, Pt, Pd, etc.

As the metal halide when the M is a metal _{halide, AlCl, GeCl 2, SiCl 2} , FeCl, there is SnCl _2, InCl _2, etc., Ti is the M is as the metal oxide when the metal oxides
O, VO, etc., and when M is a metal hydroxide, the metal hydroxide may be Al (OH), Si (OH) ₂ , Ge (OH) ₂ , Sn (OH).
There are ₂ etc.

In the general formula (I), the porphyrin derivative in which M is two hydrogens is represented by the general formula (II) (Wherein, R represents an alkoxy group) and a benzaldehyde derivative represented by the following formula: As the above-mentioned benzaldehyde derivative, a compound containing 25 mol% or more of a compound represented by the general formula (II) wherein R is an alkyl group having 8 or more carbon atoms is preferable. It is particularly preferred to use By using such a benzaldehyde derivative, a long-chain alkyl group can be easily introduced into the tetraphenylpolyphenylene derivative represented by the general formula (I), so that the LB film-forming ability of the derivative is enhanced. Can be.

In the above reaction, an alkanoic acid such as acetic acid and propionic acid, and an acid catalyst such as p-toluenesulfonic acid are represented by the general formula (II)
Is preferably used in an amount of 0.05 equivalent or more based on the benzaldehyde derivative represented by The reaction solvent is toluene,
Xylene, benzene and the like can be used, and the above alkanoic acid may be used as a solvent. The reaction temperature may be lower than the reflux temperature, preferably higher than 100 ° C.

By performing the above reaction in the presence of a metal salt, a porphyrin derivative in which M is a metal, a metal halide or a metal oxide in general formula (I) can be produced. The metal salt will be described later.

The benzaldehyde derivative represented by the general formula (II) can be produced by the following reaction.

General formula (III) Can be obtained by reacting a compound represented by the formula with an alkyl halide.

The reaction is preferably carried out in the presence of a basic compound such as sodium hydroxide, potassium hydroxide, sodium hydride and sodium amide in an organic solvent at a temperature in the range of room temperature to 100 ° C. In the reaction, it is preferable to use 1 equivalent or more of an alkyl halide relative to 1 equivalent of the compound represented by the general formula (III).
It is preferably at least 2 mol per 1 mol of the compound represented by I). The compound represented by the general formula (III) includes 5-
Formylsalicylic acid, 4-formylsalicylic acid, 3
-Formyl-5-hydroxy-benzoic acid, and the like.
There are similar chlorides such as ethyl iodide, octyl iodide, lauryl iodide, iodooctadecane, ethyl bromide, octyl bromide, lauryl bromide and octadecyl bromide. Examples of the organic solvent include alcohols such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, and ethanol. After completion of the reaction, the reaction solution can be purified by pouring it into water, collecting the crystals precipitated by neutralization, and recrystallizing the crystals from an alcohol such as ethanol.

In the general formula (I), M is a metal, a metal halide,
The tetraphenylporphyrin derivative which is a metal oxide or metal hydroxide can be produced by reacting a metal salt with a tetraphenylporphyrin derivative in which M is two hydrogens in the general formula (I). it can. Examples of the metal salt include metal halides, nitrates, sulfates, and acetates. As a reaction solvent, a hydrocarbon solvent such as toluene, xylene, benzene, quinoline, and pyrroline can be used, and the reaction is preferably performed in the presence of an acid. Examples of the acid include alkanoic acid such as propionic acid and acetic acid, and paratoluenesulfonic acid, and the alkanoic acid may be used as a reaction solvent. The reaction temperature is preferably around the reflux temperature of the solvent.
In addition, SiCl ₄ , SiBr ₄ , Si
There are I ₄ , GeCl ₄ , GeBr ₄ , SnCl ₄ , SnI ₂ , FeCl ₃ , InCl _{3 and the} like. When these are used, a tetraphenylporphyrin derivative, which is a metal halide described above, can be obtained. By hydrolyzing this under heating, it is possible to obtain tetraphenylporphyrin in which M is a metal hydroxide. In addition, CuCl ₂ , NiCl ₂ , PdCl ₂ ,
ZnCl ₂ or the like can be used, and in this case, a tetraphenylporphyrin derivative where M is a metal is obtained. Further, as the halides of the above metals, VCl ₃ , T
iCl ₄ or the like can be used to obtain a tetraphenylporphyrin derivative in which the above M is a metal halide, which is easily hydrolyzed and the above M is an oxide of a metal such as tetraphenylporphyrin. It becomes a porphyrin derivative. Other metal salts can be used in the same manner to obtain a tetraphenylporphyrin derivative wherein M is a metal, a metal oxide, or a metal hydroxide. The metal salt may be present during the reaction between the benzaldehyde derivative and pyrrole.

Examples of the salt of the compound represented by the general formula (I) include an alkali metal salt such as a sodium salt and a potassium salt, an alkaline earth metal salt such as a calcium salt, a trimethylamine addition salt, a triethylamine addition salt, and a tributylamine addition salt. Tertiary amine addition salts, tetramethylammonium salts,
Quaternary ammonium salts such as tetraethylammonium salt and tetrabutylammonium salt;
And hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide, trialkylamines such as trimethylamine, triethylamine and tributylamine, and tetramethyl It can be produced by reacting quaternary ammonium chloride such as ammonium chloride, tetraethylammonium chloride and tetrabutylammonium chloride in a solvent such as the above-mentioned organic solvent, water and alcohol. In this reaction,
An alkali metal hydroxide, an alkaline earth metal hydroxide, a trialkylamine, a quaternary ammonium chloride or the like is used in an amount of 4 equivalents or more per 1 equivalent of the carboxyl group of the compound represented by the general formula (I). Is preferred.

In the above, the product of each step can be purified by silica gel column chromatography, recrystallization and the like.

The tetraphenylporphyrin derivative in the present invention has, as a structure, four phenylene groups around a porphyrin ring, and a hydrophilic carboxyl group or a salt thereof is bonded to each phenylene group. Has a hydrophobic alkyl group bonded thereto.
That is, since the hydrophilic group and the hydrophobic group are easily positioned above and below the porphyrin ring plane, the LB film forming ability is excellent. In particular, when at least one of the alkyl groups is a long-chain alkyl group, the LB film-forming ability is particularly excellent.
The tetraphenylporphyrin derivative represented by the general formula (I) has a photosensitizing function, and can be subjected to an electron transfer reaction in combination with a functional substance capable of performing a redox reaction.

In the present invention, the LB film can be manufactured by the following method. That is, the method is characterized in that a tetraphenylporphyrin derivative represented by the general formula (I) can be developed on a subphase and transferred onto a substrate while controlling the surface pressure. In this method, a hydrophobic functional substance, a polar functional substance, and an LB film forming aid can be used simultaneously.

The compound to be developed on the subphase is dissolved in an organic solvent which is easily evaporated, and is dropped on the subphase and developed. After the organic solvent evaporates, the developed molecules are agglomerated (compressed) by a movable barrier, a single-molecule agglomerated film is formed on the subphase, and this is copied onto a substrate to form an LB film. Is done.

In the above LB production method, a hydrophobic functional substance and / or a polar functional substance can be further incorporated into the LB film.
As a first method, a polar functional material and / or a hydrophobic functional material and, if necessary, an LB film forming aid are spread on a subphase together with the tetraphenylporphyrin derivative, and the LB film is formed by the above-described method. Is formed. As a second method, particularly when the polar functional substance is a salt of a functional anion and a counter ion thereof, a reaction is performed in advance with the tetraphenylporphyrin derivative and the polar functional substance (ion exchange) to newly form the polar functional substance. There is a method in which a salt is isolated and purified, the newly generated salt, and if necessary, a hydrophobic functional substance and an LB film forming aid are spread on a subphase, and an LB film is produced by the above-described method. As a third method, in the case where the polar functional substance is dissolved in the subphase, the polar functional substance is dissolved in the subphase in advance, and the hydrophobic functional substance and the LB film are formed as necessary together with the tetraphenylporphyrin derivative. There is a method in which an auxiliary agent is developed on a subphase and an LB film is produced by the method described above. In this method, when the polar functional substance is the same as that in the second method, the substance and the tetraphenyl are used. By performing an ion exchange reaction between the porphyrin derivatives on the subphase, the polar functional substance can be incorporated into the LB film. Similarly, in the first method, a similar ion exchange reaction may be performed on the subphase.

In the above method, the substance to be developed on the subphase is used by being mixed and dissolved in an organic solvent or separately.

The mixing ratio of the tetraphenylporphyrin derivative and the other functional substance is arbitrary, and can be selected according to the purpose.

The organic solvent to be used only needs to dissolve the materials to be used in common, and a mixed solvent may be used.

As the solvent to be used, those which are insoluble in water and evaporate easily are particularly preferable. Examples are chloroform, methylene chloride,
Trichloroethane, tricrene, benzene, toluene,
Xylene, hexane, pentane, heptane, octane,
Chlorobenzene, ethyl acetate, methyl acetate, propyl acetate and the like can be mentioned. Depending on the material used, a polar solvent may be partially added to increase the solubility. Examples include ethanol, methanol, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, acetone, tetrahydrofuran, and the like, but should be kept to a minimum.

Normally, water is used as the subphase, but pH adjusted water,
Organic solvents such as ion-containing water, ethylene glycol, glycerin and the like can sometimes be used. The subphase temperature is generally around room temperature, but cooling water is often used.

Known manufacturing means can be applied as it is as the LB film manufacturing means. These usually include a developing water tank, a fixed barrier, a moving barrier, a means for detecting and controlling surface pressure, and a substrate lifting device, and have a function of transferring a monomolecular film formed on a subphase to a substrate at a predetermined surface pressure. There is no particular limitation as long as it is the same. Examples of such devices include LB film manufacturing equipment manufactured by Kyowa Interface Science Co., Ltd., LB film balance manufactured by Lauda, LB film manufacturing equipment manufactured by Joyce Label, and LB film manufacturing equipment manufactured by San-S Measurement Inc. It can be used as it is. Optimum conditions for film formation and the like should be set depending on the materials used, and are not limited in the present invention.

As a method of lifting the substrate, a vertical immersion method and a horizontal deposition method are known, and are selected according to the properties of the material.
Any substrate can be used as long as it is clean and smooth, and it is selected according to the purpose. As the substrate, a glass substrate such as quartz glass, borosilicate glass, pyrex glass, or soda glass, a crystal substrate such as silicon or CaF ₂ , an aluminum substrate, a plastic substrate, an indium tin oxide (ITO) substrate, or the like is used.

In the method of manufacturing an LB film according to the present invention, it is possible to form the LB film in a normal environment, but it is preferable to perform the film formation in an atmosphere substituted with an inert gas. This makes it possible to stably form a film of a material that is unstable with respect to air. Examples of the inert gas include a nitrogen gas, an argon gas, and a helium gas. By passing these gases through the LB film manufacturing apparatus, an inert gas atmosphere can be obtained. Prior to this, it is more preferable that the subphase is also ventilated to replace the dissolved elements in the subphase with an inert gas.

The LB film forming aid is used when a material that does not form a stable LB film by itself is used. Examples of the LB film forming aid that can be used in this case include fatty acids having long-chain aliphatic groups such as stearic acid, arachidic acid, and palmitic acid, and long-chain aliphatic acids such as stearic amide, arachidic amide, and palmitic amide. Long chain alkanes such as acid amide compounds having a group, such as octadecane, nonadecane, eicosane, docosane, and hexadecane. Long-chain alkyl alcohols such as eicosanol and octadecanol; long-chain fatty acid esters such as methyl stearate, methyl arachidate and metal palmitate; aromatic hydrocarbons such as biphenyl, terphenyl and bisphenol A; sodium lauryl phosphate And sodium long-chain alkyl sulfonates. The type and amount of these LB film forming aids are determined in consideration of the charge state, molecular occupation area, and arrangement state of a material containing ions capable of forming an LB film in the presence of the LB film formation aid. Typically 0.1 to the quaternary ammonium salt.
It is preferable to use 1 equivalent to 10 equivalents, and it is desirable to keep the equivalent to the minimum that an LB film can be formed.

As the functional substance, a substance having polarity (particularly a substance having charge) and / or a substance having hydrophobicity are appropriately selected and used. Such functional materials include transition metal complexes, for example, cobalt bis (dithiomaleonitrile) complex, manganese bis (dithiomaleonitrile) complex, iron bis (dithiomaleonitrile) complex, copper bis (dithiomaleonitrile) complex , Nickel (bisdithiomaleonitrile) complex, platinum (bisdithiomaleonitrile)
Complex, palladium (bisdithiomaleonitrile) complex,
Nickel bis (toluene-3,4-dithiolate) complex,
Nickel bis (octadecylbenzene-3,4-dithiolate) complex, platinum bis (toluene-3,4-dithiolate) complex, copper bis (toluene-3,4-dithiolate) complex, nickel bis (benzene-4-dithiomethylamino-1) complex , 2-dithiolate) complex, nickel bis (benzene-4-dioctadecylamino-1,2-dithiolate) complex, nickel bis (benzene-3,4,5,6-tetrabromo-1,2-dithiolate) complex, nickel bis (1 , 2-Dithionaphthalene) complex, platinum bis (1,2-dithionaphthalene) complex, nickel bis (dithiostyribene) complex, platinum bis (dithiostyribene) complex, palladium bis (dithiostyribene) complex, nickel bis (p-chlorodithiostyribene) Complex, nickel bis (p-methoxydithiostyriben) complex, nickel bis (p -Octadecyloxydithiostyriben) complex, nickel bis (p-dimethylaminodithiostyribene) complex, nickel bis (p
-Dioctadecylaminodithiostyriben) complex, nickel bis (1,2-phenylene diimine) complex, platinum bis (1,2-phenylene diimine) complex, parachium bis (1,2-phenylene diimine) complex , Nickelvis (4
-Chloro-1,2-phenylenedimine) complex, nickel bis (3,4-dichloro-1,2-phenylenedimine) complex, nickel bis (4-alkyl-1,2-phenylenedimine) complex, Nickel bis (diiminomaleonitrile) complex, platinum bis (diiminomaleonitrile) complex,
Palladium bis (diiminomaleonitrile) complex, nickel bis [bis (trifluoromethyl) ethylene-1,2
-Dithiate] complex, platinum bis [bis (trifluoromethyl) ethylene-1,2-dithiate] complex, palladium bis [bis (trifluoromethyl) ethylene-1,2-dithiate] complex, nickel bis (dimercaptoisotrithione) Complexes, platinum bis (dimercaptoisotrithione) complex, palladium bis (dimercaptoisotrithione) complex, iron bis (dimercaptoisotrithione) complex and the like. These can exist in various oxidation states, but it is desirable in consideration of the stability of the compound to select them in consideration of the first redox reaction.

〔Example〕

 Next, examples of the present invention will be described.

Synthesis Example 1 (Synthesis of 3-carboxy-4-octadecyloxybenzaldehyde) 8.3 g of 5-formylsalicylic acid and 50 ml of N, N-dimethylformamide were placed in a reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping device. And dissolved. Next, 4.0 g of sodium hydroxide was added, and the temperature was raised to 70 ° C. Here, 19.0 g of iodooctadecane was added, and the mixture was added at 70 ° C. for 4 hours and then at 90 ° C.
Allowed to react for hours. Thereafter, the reaction solution is poured into a large amount of water,
The mixture was neutralized by adding dilute hydrochloric acid, and the precipitated crystals were collected by filtration and recrystallized from ethanol to obtain 10.6 g (yield 51%) of 3-carboxy-4-octadecyloxybenzaldehyde.

Example 1 [Synthesis of tetrakis (3-carboxy-4-octadecyloxyphenyl) porphine] 2.09 g of 3-carboxy-4-octadecyloxybenzaldehyde, 0.34 g of distilled and purified pyrrole, and 30 of propionic acid
ml was placed in a reaction flask and heated under reflux for 6 hours. The reaction mixture was distilled under reduced pressure to remove propionic acid, and an oily residue was obtained. The residue was subjected to silica gel column chromatography using chloroform as a developing solution, and a red-purple effluent was collected. After concentrating this, it was recrystallized with a mixed solvent of acetone-ethanol to obtain 0.44 g (yield 19%) of tetrakis (3-carboxy-4-octadecyloxyphenyl) porphine as purple crystals.

The structural formula of tetrakis (3-carboxy-4-octadecyloxyphenyl) porphine is It is.

The NMR spectrum of the compound obtained above is shown in FIG. In FIG. 1, the single peak at 11.2 ppm is the proton of the carboxyl group, the single peak at 8.9 ppm is the pyrrole proton of the polyphenylene ring, the multiple peaks at 8.77 ppm, 8.3 ppm and 7.4 ppm are the benzene ring protons and the triple peak at 4.4 ppm. Is the methylene group proton adjacent to the oxygen of the octadecyloxy group, the triple peak of 1.7 ppm is the methylene group proton adjacent to the methylene group, and the peak ranging from 1.3 to 1.1 is the other methylene group proton of the octadecyloxy group, 0.8 ppm. The triple peak was due to the terminal methyl group proton of the octadecyloxy group and the single peak at -2.8 ppm was due to the amine proton of the pyrrole group in the porphyrin ring, and was confirmed to be the desired product.

In FIG. 1, the amine proton of pyrrole is shielded at an extremely high magnetic field, indicating the formation of a porphyrin ring and clearly showing that this is a metal-free porphyrin.

The peak at 7.25 ppm was chloroform (solvent) and 1.5 peaks.
The peak at 5 ppm is based on water in the crystal, and the peak at 0 ppm is based on tetramethylsilane (standard substance).

Example 2 [Synthesis of zinc complex of tetrakis (3-carboxy-4-octadecyloxyphenyl) porphyrin] 100 mg of tetrakis (3-carboxy-4-octadecyloxyphenyl) porphyrin, 0.8 g of zinc acetate and glacial acetic acid
The mixture was placed in a 30 ml shaped flask and reacted at 120 ° C. under reflux for 8 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was washed with water to remove excess zinc acetate. Thereafter, the residue was dissolved in chloroform, purified by silica gel chromatography using chloroform as a developing solution, and a red-purple effluent was collected. 80 mg (76% yield) of a tetrakis (3-carboxy-4-octadecyloxyphenyl) porphyrin zinc complex as a purple oily substance was obtained.

Its structural formula is It is.

FIG. 2 shows the NMR spectrum of the compound obtained above. FIG. 2 shows almost the same peaks as FIG. 1, but the remarkable difference is that the protons shielded at the high magnetic field (−2.8 ppm) shown in FIG. It clearly indicates that it has been generated. This product showed a single spot with an Rf value of 0.8 by silica gel thin layer chromatography (developing solution: chloroform / methanol = 3/1; volume ratio), and showed red-orange fluorescence when irradiated with ultraviolet light (365 nm).

Example 3 (Preparation of LB film) Tetrakis (3-carboxy-4) obtained in Example 2
-Octadecyloxyphenyl) porphyrin zinc complex was dissolved in acetone. This solution was developed at 15 ° C. as a subphase using purified water purified by a quartz two-stage distillation column using a hetero LB film manufacturing apparatus manufactured by San-S Keisoku Co., Ltd.
The area (molecule occupied area) curve was measured. This result is the third
Shown in the figure.

〔The invention's effect〕

The tetraphenylporphyrin derivative according to claim 1 is novel, has excellent LB film forming ability, and can be easily produced by the method according to claim 2.

[Brief description of the drawings]

FIG. 1 shows the NM of tetrakis (3-carboxy-4-octadecyloxyphenyl) porphyrin obtained in Example 1.
R spectrum, FIG. 2 is an NMR spectrum of the tetrakis (3-carboxy-4-octadecyloxyphenyl) porphine zinc complex obtained in Example 3, and FIG.
2 shows a surface pressure-area curve measured in the above.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazumasa Takeuchi 48, Wadai, Tsukuba, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Tsukuba Development Laboratory Co., Ltd. (72) Tachiko Obata 48th Wadai, Tsukuba, Ibaraki Hitachi, Ltd. Inside Tsukuba Development Laboratory Co., Ltd. (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 487/22 CAPLUS (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the general formula (I) (Wherein, M represents two hydrogens, and R ¹ , R ² , R ³ and R ⁴ each independently represent an alkoxy group) or a tetraphenyl polyphenylene comprising a salt thereof Derivatives. 2. A compound of the general formula (II) The method for producing a tetraphenylporphyrin derivative according to claim 1, wherein the benzaldehyde derivative represented by the formula (wherein, R represents an alkoxy group) is reacted with pyrrole.