JPH04283580A - Fluorine-containing porphyrin - Google Patents

Abstract

PURPOSE:To obtain a new hydrophobia and nonionic fluorine-containing porphyrin, capable of solely forming a film, forming an excellent Langmuir- Blodgett(LB) film, useful as a functional thin-film material such as a sensor or a photoelectric converting material and having a specific substituent group at the 2-position of each phenyl group. CONSTITUTION:A tetra(o-substituted phenyl)porphyrin having, e.g. substituent groups R-CONH (R is 5-30C perfluoroether) at the 2-position of each phenyl group, e.g. a porphyrin expressed by formula I (R is formula II; the central atom may be FeII or ZnII other than COII). For example, the porphyrin expressed by formula I is obtained by regulating an acid halide, etc., of a perfluoroether dissolved in a solvent such as chloroform to <=5 deg.C, dropping the regulated acid halide into the tetra(o-aminophenyl)porphyrin dissolved in a solvent such as methanol at <=5 deg.C (a basic condensing agent such as pyridine may be added), increasing the temperature from a low temperature to ambient temperature, reacting both and isolating the resultant product. A metal is coordinated with porphyrin without containing the metal by reacting the aforementioned porphyrin with a metallic salt in a solvent such as water or methanol.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing porphyrin that is hydrophobic, nonionic, and capable of being formed into a single film. In particular, the present invention provides for example a good Langmuir-Blo
The present invention relates to fluorine-containing porphyrins that can form dgett films (hereinafter referred to as LB films) and can be used as functional thin film materials such as new types of separation membranes, sensors, and photoelectric conversion materials.

0002

[Prior Art] Porphyrins having an ionic group in their side chains are known as porphyrins that can form films independently [for example, Thin Solid Film].
ms, 99P. 33-40 (1983)]. but,
These known porphyrins have ionic groups in their side chains and are therefore hygroscopic. In such conventional porphyrins, the central metal is oxidized and degraded by oxygen in the presence of water.
Due to the loss of oxygen coordinating ability, when used as an oxygen separation membrane, the performance of separating oxygen from the atmosphere decreases, which is not preferable. Further, when used as an electronic material such as a photoelectric conversion material, the properties are undesirable because the properties change due to moisture absorption, and ions may adversely affect the properties of the device.

However, it has been conventionally believed that it is essential for LB membranes to have a strongly polar ionic group at the tip of a long hydrophobic chain; No porphyrin that can be formed into a membrane has been obtained.

0004

SUMMARY OF THE INVENTION An object of the present invention is to provide a new fluorine-containing porphyrin which is hydrophobic and nonionic and can be formed into a single film.

[0005]

[Means for Solving the Problems] As a result of extensive research to achieve the above object, the present inventors have developed a tetra(
It was discovered that o-substituted amidophenyl)porphyrin can be suitable for the purpose, and based on this finding, the present invention was completed.

That is, the present invention provides (1) a tetra(o-substituted phenyl) porphyrin. (2) Substituent R-CONH- (wherein R is a perfluoroether group having 5 to 30 carbon atoms, and all R's are in the same direction with respect to the porphyrin surface) at the 2-position of the phenyl group. α, α, α, α-tetra (o-
Substituted phenyl)porphyrin.

The porphyrin used in the present invention includes both metal-coordinated and metal-uncoordinated porphyrins. The metal coordinated to the porphyrin in the present invention is preferably a transition metal, with Co, Fe, Zn, and Cu being particularly preferred. Furthermore, the number of carbon atoms in the perfluoroether group in the present invention is 5.
to 30, preferably from 5 to 19, and more preferably from 5 to 11.

Specific examples of the perfluoroether group of the present invention include CF3 CF2 CF2 OCF(CF3)-F[C
F(CF3)CF2O]3 CF(CF3)-F
[CF(CF3)CF2O]5 CF(CF3)
-F[CF(CF3)CF2O]8 CF(CF3
)-CF3 CF(CF3)O[CF(CF3)
CF2 O]2 CF(CF3)- CF3 CF2 OCF2 CF2 OCF2 -CF
3 CF2 CF2 OCF2 CF2 CF2 OC
F2 CF2 − is mentioned.

[0009] Specific examples of the porphyrin of the present invention include compounds 1, 2, 3, 4, 5, and 6.

0010

[Chemical formula 1]

[0011]

[Case 2]

0012

[Chemical formula 3]

[0013]

[C4]

[0014]

[C5]

[0015]

[C6]

The porphyrins of the present invention are all new compounds; for example, tetra(o-aminophenyl)porphyrin (hereinafter referred to as AP) is reacted with an acid halide or ester of perfluoroether (hereinafter referred to as EX). It can be manufactured by For example, AP is J. Am. Chem. Soc. ,97(6
), P. 1427-1439 (1975) and the method described in "Porphyrin Chemistry" Kyoritsu Shuppan (1982). In addition, EX is, for example, a method of ring-opening polymerization of a fluorine-based epoxy compound [
For example, U.S. Pat. No. 3,250,807, 331
Specification No. 7484, Specification No. 3419610, No. 32
No. 50808, No. 3412148, Jo
urnal of Makromolecular
Science-Chemistry, A6 (6)
,P. 1027 (1972), Japanese Patent Publication No. 53-5360, Japanese Patent Application Laid-Open No. 63-265920, etc.).

According to the synthesis method described below, the porphyrin of the present invention reflecting the configuration of the amino group of the AP used can be obtained as the main product. That is, for example, if we use AP in which the amino groups are all in the same direction with respect to the porphyrin surface, the substituents of the generated porphyrin will also all be in the same direction with respect to the porphyrin surface,
If an AP containing an amino group that is not oriented in the same direction with respect to the porphyrin surface is used, the generated porphyrin will also contain a substituent that is not oriented in the same direction with respect to the porphyrin surface.

In the reaction between AP and EX, E is added to AP dissolved in a solvent (hereinafter referred to as solvent A) at a low temperature (usually below 5°C).
For X, the temperature of the reaction solution does not rise too much (for example, below 5°C)
Drip while being careful. In this case, EX is the solvent (
It will be referred to as solvent B hereafter. ) may be added dropwise after dilution. Also,
Addition of a basic condensing agent such as pyridine or trialkylamine accelerates the reaction.

Examples of the solvent A include alcohols such as methanol and ethanol, halogenated hydrocarbons such as chloroform and trichlorotrifluoroethane (Freon 113), aromatic hydrocarbons such as benzene and toluene, and mixtures thereof. is used. As the solvent B, halogenated hydrocarbons such as chloroform and trichlorotrifluoroethane are mainly used.

[0020] The reaction may be carried out at a low temperature throughout, or the temperature may be raised midway through and the reaction may be carried out at room temperature. In order to isolate the target compound from the reaction mixture thus obtained, the solvent is first removed by distillation under reduced pressure, and the residue is extracted with an organic solvent such as chloroform and filtered. For further purification, for example, this solution is concentrated and then separated using a column filled with silica gel or the like, or recrystallized.

[0021] The porphyrin of the present invention has, for example, an infrared absorption spectrum (IR) of C near 1240 cm-1.
Having strong absorption based on F and 1740 cm-
It can be identified by having an amide absorption near 1. Furthermore, in order to obtain a porphyrin metal complex (hereinafter referred to as MP) by coordinating a metal to a metal-free porphyrin (hereinafter referred to as H2P), H2P and a metal salt are reacted in a solvent.

Examples of the reaction solvent include water, alcohols such as methanol and ethanol, halogenated hydrocarbons such as chloroform, ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, N,N - Nitrogen-containing solvents such as dialkylformamides and mixtures thereof are used. The reaction temperature is not necessarily constant depending on the type of raw materials, the type of solvent, and other conditions, but is usually selected between about 50 and 70°C.

From the reaction mixture thus obtained,
To isolate the target compound, the solvent is first removed by distillation under reduced pressure, and the residue is extracted with an organic solvent such as chloroform and filtered. For further purification, for example, this solution is concentrated and then separated using a column packed with silica gel, basic alumina, etc., or recrystallized. The production of MP can be done by measuring the ultraviolet-visible spectrum, for example.
This can be confirmed by the fact that in MP, the number usually decreases to 1-2.

[0024] Commercially available general equipment can be used to form an LB film using the porphyrin of the present invention. In addition, LB
To form a membrane, it is preferable to use a porphyrin in which the substituents are all in the same direction with respect to the porphyrin face. First, the porphyrin of the present invention is dissolved in an organic solvent such as chloroform, and then it is dropped onto the liquid surface (usually on the water surface) in the tank of the device to develop it, and the solvent is evaporated. after that,
The porphyrin molecules on the liquid surface are compressed by a method such as moving a bar, and then at an appropriate angle (usually horizontal or vertical).
The substrate held in the tank is immersed in this bath and transferred onto the substrate. By repeatedly taking the substrate in and out of the tank, a porphyrin LB film can be accumulated on the substrate.

The porphyrin of the present invention is different from conventional porphyrins in that it has film-forming properties when used alone, but depending on the application or if necessary, it can be formed into a film together with other substances as in the conventional porphyrins. is also possible. As the substance to be used with the porphyrin of the present invention to form a film, materials commonly used for LB films can be used.

For example, amphiphiles such as long chain carboxylic acids such as arachidic acid and their salts, imidazole,
Examples include ligands such as pyridine and derivatives and substituted products thereof, dithiolene complexes, dyes such as viologen, and polymers such as polyamic acid salts. In addition, the substrate on which the film is formed is made of materials used in electronic materials such as copper and silicon, and porous films, especially porous films filled with solvent etc. in the case of LB films (the filler is removed as necessary when in use). ) Materials used for equal separation membranes are used.

[0027]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to the following Examples. Note that the following film forming operations were performed under dry nitrogen unless otherwise specified.

[0028]

[Reference Synthesis Example] 1 liter of acetic acid was refluxed, and 51.7 g (0.342 mol) of o-nitrobenzaldehyde was added and dissolved therein. Next, 25 ml of pyrrole (0.36 m
ol) was added dropwise. After 20 minutes of reaction under reflux, CHCl3
was added and allowed to cool. This was cooled with water and then with ice to precipitate crystals. The generated crystals are collected by suction filtration,
Washing with CHCl3 gave meso-tetra(o-nitrophenyl)porphyrin (hereinafter referred to as CP1). The yield after vacuum drying was 10.2 g (0.0128 mol, yield 15%).

[0029] Add 4.16 ml of this CP1 to 210 ml of concentrated hydrochloric acid.
g (5.23 mol) after dissolving, SnCl2 ・2H2
18.1 g of O was added and the temperature was rapidly raised to 65-75°C. After reacting at 65-75℃ for 25 minutes, 30% ammonia water 20
Neutralized with 0ml. Add CHCl3 to this solution and
Extracted into HCl3 layer. The CHCl3 layer was concentrated by evaporation, washed with aqueous ammonia, and then twice with water. Add this to anhydrous N
a2 After dehydration with SO4, CHCl3 was slowly concentrated using an evaporator to form crystals. The crystals were filtered and washed with methanol to obtain meso-tetra(o-aminophenyl)porphyrin (hereinafter referred to as CP2). The yield was 2.8 g (4.2 mmol/g, yield 80%). The NMR spectrum of the product is given in the literature [Journa
l of the American Che
mical Society, 97(6), P. 14
35 (1975)].

This CP2 is a mixture of rotamers due to rotation of the phenyl group (αααα-, αααβ-, α depending on which side of the porphyrin ring plane the amino group is present).
A mixture of four types of αββ-, αβαβ-forms). Therefore, all the amino groups are on the same side with respect to the porphyrin ring plane, a so-called αααα form (hereinafter referred to as CP3).
was separated.

[0031] 3.18 g of CP2 was dissolved in CHCl3 and charged into a silica gel column. First, it was developed with CHCl3. CHCl3 until the color of the effluent becomes light red.
After developing the column with CHCl3/ether=1
/1 until the coloring became very light. Thereafter, the αααα form was flushed out using acetone/ether=1/1. The fraction containing the αααα form was dried in an evaporator. Furthermore, this was dissolved in CHCl3, charged into a second silica gel column, and developed with benzene/ether=1/1 until the color of the effluent became very light. pure ααα
The α form was eluted with acetone/ether=1/1. The solvent was distilled off using an evaporator immersed in a water bath to obtain a solid. Yield 1.22g (yield 38.2%). Thin layer chromatography (silica gel, developed with benzene/ether = 1/1) showed a single spot.

[0032]

Example 1 A porphyrin having a perfluoropolyether chain in its side chain as shown in Chemical Formula 7 below was synthesized.

[0033]

[C7]

First, CP3 obtained in the reference synthesis example under ice cooling,
After dissolving 2g (3mmol) in 60ml of chloroform, 20ml of Freon 113 (trichlorotrifluoroethane)
1, and 3.6 ml (26 mmol) of triethylamine were added. Acid fluoride [F[CF(CF3)CF2O]3 CF(C
A solution was prepared by dissolving 12 g (18 mmol) of F3 ) COF in 40 ml of Freon 113 and adding 40 ml of chloroform, and this was added dropwise to the CP3 solution under ice cooling. After the completion of the dropwise addition, the reaction was carried out under ice cooling for 3 hours, and then at room temperature. The reaction was carried out while being monitored by infrared absorption spectroscopy (IR). After the reaction was completed, it was washed twice with 5% aqueous ammonia and twice with pure water. After drying over anhydrous sodium sulfate, a silica gel column (Wakogel C-200
Manufactured by Wako Pure Chemical Industries, Ltd. (Product name: CHCl3 filling)
and purified using chloroform as a developing solvent. The yield was 8.5 g (yield 90%). The introduction of perfluoroether chains into the product was carried out at 1240 cm by IR.
Having strong absorption based on F and 1740 cm-
This was confirmed by the fact that 1 had an amide absorption. Furthermore, it was confirmed by thin layer chromatography (silica gel, chloroform development) that the product was a monospot and did not contain any starting material.

[0035]

Example 2 A CoII-introduced porphyrin shown in Chemical Formula 8 below was synthesized.

[0036]

[Chemical formula 8]

First, 6 g of the porphyrin represented by chemical formula 7 obtained in Example 1 was dissolved in 300 ml of chloroform. To this, 9.3 g of cobalt acetate was dissolved in 60 ml of pure water and added. Add 0.24 ml of triethylamine to this system.
, add 300 ml of N,N-dimethylformamide, and add 6
The reaction was carried out at 3°C for 63 hours. The reaction was carried out while being monitored by ultraviolet-visible spectroscopy. After the reaction was completed, the solvent of the reaction solution was distilled off, chloroform was added, and the chloroform-soluble portion was filtered off.

Further, this chloroform solution was concentrated using an evaporator, and then applied to a silica gel column (Wakogel C-20).
0 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., filled with chloroform) and purified using chloroform as a developing solvent. The yield was 4.5 g (yield 70%). The introduction of Co into the product is based on the porphyrin of chemical formula 7644,58
This was confirmed by the disappearance of absorption at 7,546,512,418 nm and the appearance of new absorption at 529,412 nm.

[0039]

[Reference example] L of porphyrin of chemical formula 8 synthesized in Example 2
A B film was created. The chloroform solution of the porphyrin was developed on twice-distilled water, and after the chloroform was removed by evaporation,
When the relationship between the surface pressure and molecular occupied area (π-A curve) of the porphyrin was investigated at room temperature, it showed a good rise as shown in FIG. Next, this LB film was placed on the quartz plate 70 times (3 times as a Y-type film) by dipping the quartz plate vertically at room temperature.
5 times), it was accumulated as a Y-type film, and the cumulative ratio was 0.90, confirming that a good cumulative film was formed.

[0040]

Effects of the Invention: The fluorine-containing porphyrin of the present invention is hydrophobic and nonionic and can be formed into a single membrane, for example, forming a good Y-type LB membrane, so it can be used as a new type of separation membrane or sensor. It is useful as a functional thin film material such as photoelectric conversion material and recording material.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the surface pressure on the water surface and the molecular occupied area (π-A curve) of the LB film of the porphyrin shown by Chemical Formula 8, which is an example of the fluorine-containing porphyrin of the present invention.

Claims (2)

[Claims] [Claim 1] Substituent R-CON at the 2-position of the phenyl group
A tetra(o-substituted phenyl)porphyrin having H- (wherein R is a perfluoroether group having 5 to 30 carbon atoms). [Claim 2] Substituent R-CON at the 2-position of the phenyl group
α, α, α, α-tetra (o -substituted phenyl)porphyrin.