JPH0446179A - Porphyrin derivative and production thereof - Google Patents

Abstract

NEW MATERIAL:Porphyrin derivative expressed by formula I [Q<1> to Q<4> are alkyl, expressed by formula II (R is alkyl or M is H, alkali metal or alkyl containable OH); at least a species of Q<1> to Q<4> is expressed by formula II]. EXAMPLE:Tetrakis(2-carbomethoxyheptadecylphenyl)porphyrin. USE:Used as a coloring matter of an auxiliary (photosensitizer) for generating color development or discoloration to coloring matter co-existing by photosensing action. PREPARATION:An aromatic-substituted alkanoic acid derivative having aldehyde group expressed by formula III is reacted with pyrrole to afford the aimed porphyrin derivative expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a porphyrin derivative and a method for producing the same.

[Conventional technology]

As a porphyrin derivative having an ionic functional group,
For example, JP-A-1-163740 discloses that at least one of the aromatic rings of tetraphenylporphyrin is -S○-H
Hole burning compounds having ionic functional groups such as COON a and COON a have been disclosed.

[Problem to be solved by the invention]

The porphyrin derivatives described in the above-mentioned publication do not have structural freedom because the anionic functional group is directly bonded to the aromatic ring, and also have poor compatibility with organic polymer compounds because they do not have lipophilic parts. .

The LB film forming ability was poor.

[Means to solve the problem]

The porphyrin derivative in the present invention has the following formula:
an alkyl group or a group represented by the formula (a) (where R is an alkyl group, M is an alkyl group which may have hydrogen, an alkali metal or a hydroxyl group) + Q', Q2 At least one of Q3 and Q4 is a group represented by general formula (a)].

- Specific examples of compounds represented by formula (I) include tetrakis(2-carbomethoxyheptadecylphenyl)
Porphyrin, tetrakis(2-carboethoxyheptadecylphenyl)porphyrin, tetrakis(2-carbomethoxynonenylphenyl)porphyrin, tetrakis(2-carbomethoxypentylphenyl)porphyrin, tetrakis(2-carboxyheptadecylphenyl)porphyrin, or tetrakis Sodium salt, tetrakis (
2-carboxynonenylphenyl phosphorus or its tetrasodium salt, tetrakis (2-carboxypentylphenyl) porphyrin or its tetrapotassium salt, monocarboxytetrakis (heptadecylphenyl) porphyrin, dicarboxytetrakis (heptadecylphenyl) porphyrin, monocarboxytetrakis (heptadecylphenyl) porphyrin Examples include lupoxytetraquinu(nonenylphenyl)porphyrin and tricarboxytetrakis(pentylphenyl)porphyrin.

The above-mentioned porphyrin derivative represented by formula (I) is -
An aromatic substituted alkanoic acid having an aldehyde group represented by the formula (n) (wherein R represents an alkyl group and M represents an alkyl group which may have hydrogen, an alkali metal, or a hydroxyl group) It can be produced by a method characterized by reacting a derivative with pyrrole.

Specific examples of the compound represented by general formula (n) include:

etc.

In the above reaction, when a compound in formula (■) in which M is hydrogen is used, a catalyst may not be used. - When M is an alkyl group in the formula (ff), use an alkanoic acid such as acetic acid or propionic acid, or an acid catalyst such as P-toluenesulfonic acid in an amount of 0.05 equivalent or more based on the compound represented by the general formula (■). It is preferable to use Also, -
When M in formula (n) is an alkali metal, it is preferable to use an acid catalyst as described above in an amount equal to or more than the amount of the compound represented by general formula (n). Toluene, xylene, benzene, etc. can be used as a reaction solvent, and the above-mentioned alkanoic acids may also be used as a solvent.

The reaction temperature may be below the reflux temperature, preferably above 100°C.

When a compound in general formula (II) in which M is hydrogen is used, decarboxylation is easy. Therefore - in formula (1), Ql, Q
In order to produce a porphyrin derivative in which 2, Q, and Q4 are represented by the general formula (a) and M is hydrogen [hereinafter referred to as tetrakis(carboxyalkylphenyl)porphyrin], - in formula (II), M is First, by reacting a compound that is an alkyl group with pyrrole, - formula (
In 1), Q8, Q2, Q3 and Q4 are general formula (a)
A compound represented by M is an alkyl group is prepared, and this is hydrolyzed in the presence of sodium hydroxide and potassium hydroxide to obtain tetrakis(carboxyalkylphenyl).
Preferably, a porphyrin salt is prepared and then treated with an acid, an ion exchange resin, a hydrous silica gel, or the like.

The aromatic group-substituted alkanoic acid derivative having an aldehyde group represented by the above-mentioned general formula (II) consists of the following formula (III) ＼ and is a cyclic acetal group which may have a substituent or a condensed ring, and A represents a divalent hydrocarbon group for constituting the cyclic acetal group, R represents an alkyl group, and M represents an alkyl group that may have hydrogen, an alkali metal, or a hydroxyl group) It can be produced by a method characterized by subjecting an aromatic substituted alkanoic acid compound to acid hydrolysis.

The acid hydrolysis is carried out at room temperature or below in an organic solvent such as acetone, methanol, ethanol, dioxane, tetrahydrofuran, or chloroform in the presence of an acid catalyst such as hydrochloric acid, nitric acid, sulfuric acid, trifluoroacetic acid, or trifluoromethanesulfonic acid, and water. It is preferable to carry out water in the reaction system with the general formula (I
The acid catalyst is preferably used in an amount of 1 mole or more per mole of the compound represented by I) so that the acid concentration in the reaction solution is j to 5N.

In the above formula (III), A is Shiri.

etc., and R is a methyl group, ethyl group, propyl group, butyl group, octyl group, hexadecyl group, etc., and those having 3 or more carbon atoms can be of any structural isomerism. M is Na if it is an alkal metal, Li
etc., and when it is an alkyl group, it is a methyl group, ethyl group, propyl group.

A butyl group, an octyl group, a hexadecyl group, etc. having 3 or more carbon atoms can have any structural isomerism, and an alkyl group having a hydroxyl group such as -C2H6○H, -+CH2→-OH etc. There may be.

general formula As a specific example of a compound represented by So, etc.

Said - formula Aromatic group-substituted al Canonic acid compound.

The general formula is the same as formula (III), and R2 are each independently an optionally substituted alkyl group or R1
and R2 together represent a divalent hydrocarbon group which may have a substituent or a condensed ring, and which together with ＼ C form a cyclic acetal group,
represents a halogen) can be produced by a method characterized by subjecting an aromatic haloacetal compound represented by the following formula to a thermal rearrangement/elimination reaction in the presence of water and a dehalogenation reagent.

In the above-mentioned formula (IV), when R1 and R2 are each independent alkyl group, a methyl group.

Ethyl group, propyl group, butyl group, octyl group.

Examples include hexadecyl group, and combinations of R1 and R2.

Also, X is chlorine.

bromine.

Iodine etc.

general formula As a specific example of a compound represented by Well then.

H, CCH. ＼　／ CH3CH□ etc.

In the reaction, water is preferably present in an amount equal to or more than the equivalent mole of the compound represented by the general formula (rV). Too little water will reduce the yield. Examples of de-)logen reagents include sodium salts of alkanoic acids such as acetic acid and propionic acid, metal salts of alkali metals or alkaline earth metals such as potassium salts and calcium salts, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, calcium carbonate, sodium methoxide, potassium methoxide, etc. Examples include alkoxides of alkali metals, silver salts such as silver nitrate, and silver carbonate. These dehalogenating reagents are preferably used in an amount equivalent to or more than the equivalent molar amount of the compound represented by the general formula (IV).

The above reaction is preferably carried out in the presence of an organic solvent,
Examples of the organic solvent include polar solvents such as dioxane, dimethylformamide, and dimethyl sulfoxide, aromatic solvents such as toluene, benzene, and xylene, and alcohol solvents such as methanol and ethanol. .

Ethanol and the like are preferred. The reaction temperature is preferably 70° C. or higher, and when the number of carbon atoms in R in general formula (IV) is large, it is preferable to carry out the reaction at a higher temperature.

Further, in the above reaction, the pH of the reaction system is adjusted to be 7 or more.

In the above reaction, in order to synthesize a compound (aromatic substituted alkanoate) in which M is an alkali metal in the general formula (I[r), an excess of a strong base such as an alkali metal hydroxide or alkoxide (especially , 2 mol or more per 1 mol of the compound represented by the general formula (mV)). When a strong base is used in an amount equal to or more than 2 moles relative to the compound represented by general formula (IV), general formula (III) is obtained.
A compound in which M is H (aromatic substituted alkanoic acid)
can be isolated. Furthermore, in the general formula (III), those in which M is an alkyl group (aromatic substituted alkanoic acid ester) are preferably synthesized using a weak base such as an alkali metal salt or an alkaline earth metal salt of an alkanoic acid.

In this case, when an aromatic haloacetal compound in which R1 and R2 are each independently an alkyl group in the general formula (rV) is used, an ester in which M is an alkyl group in the general formula (III) is produced; When using an aromatic haloacetal compound which forms a cyclic acetal group together with R1 and R2-〇\C in formula (IV),
A half ester in which M is an alkyl group having a hydroxyl group in the general formula (III) is produced. In the above cases, raising the reaction temperature makes it easier to produce aromatic substituted alkanoates, but whether the half esters or aromatic substituted alkanoic acids are more likely to be produced also depends on the solvent used. .

In the above reaction, the compound represented by the general formula (III) is
If more than one species is produced, it can be separated and purified as appropriate by column chromatography, etc.6 Compounds in which M is hydrogen in the general formula (m) can also be obtained by hydrolyzing the aromatic substituted alkanoate. I can do it. Hydrolysis is
Hydrochloric acid, sulfuric acid.

In the presence of acetic acid, propionic acid, and cation exchange resins.

Alcohol solvents such as methanol and ethanol.

It is preferable to carry out the reaction in a solvent such as ethyl acetate, chloroform, water, etc. at 0°C or lower. Furthermore, hydrolysis can also be carried out by column chromatography using hydrous silica gel as a column packing material or column chromatography using a cation exchange resin as a column packing material.

Among the compounds represented by the general formula (m), those in which M is an alkyl group can also be produced by esterifying the above aromatic substituted alkanoic acid with an alcohol such as methanol or ethanol. An ester in which M is a methyl group in general formula (I) can be synthesized by reacting the aromatic substituted alkanoic acid and diazomethane in a solvent such as ether or ethyl acetate at 0° C. or lower.

The aromatic/N-roacetal compound represented by the formula (IV) is an aromatic haloketone compound represented by the formula (V) / \ ○ is the same as the formula (III), and X represents a halogen. Partial alcohol or dihydric alcohol or dihydric phenol whose main chain has 2 to 4 carbon atoms and which may have a substituent or whose main chain carbon may be part of a carbon ring is used as an acidic catalyst. Alternatively, it can be produced by a method characterized by reacting in the presence of an acetalizing reagent.

Examples of the aromatic haloketone compound represented by the general formula (V) include the following.

Examples of the -hydric alcohol include methanol, ethanol, propatool, butanol, octatool, hexadecanol, etc., and any structural isomers of those having 3 or more carbon atoms can be used. As the dihydric alcohol or dihydric phenol.

HO-CH, -CH2-OH.

HO-CHyo-CH2-CH, -〇H9CH.

HO-CH, -C-CH, -OH.

CH.

etc.

Examples of the acid catalyst include methanesulfonic acid, para-toluenesulfonic acid, pyridine hydrochloride, paratoluenesulfonic acid pyridinium salt, acidic ion exchange resin, etc., which are used in a catalytic amount, and are represented by the formula (V). It is preferable to use 0.05 to 0.3 equivalents based on the aromatic haloketone compound. When using an acid catalyst, one reaction is performed using an alkane solvent such as hexane, an aromatic solvent such as benzene, toluene, or xylene, or chloroform. , halogenated solvents such as methylene chloride, ethereal solvents such as tetrahydrofuran and dioxane, and dimethylformamide.

Preferably, it is carried out in a polar solvent such as dimethyl sulfoxide. Further, the reaction is preferably carried out while removing water generated during heating from the reaction system, and a method for removing water includes azeotropic distillation with the solvent under reduced pressure if necessary.

The acetalizing reagent includes trimethylsilane chloride and the like, and is preferably used in an amount of 2 or more equivalents relative to the aromatic haloketone compound represented by formula (V). When using this acetalizing reagent, the reaction is preferably carried out in a halogenated solvent as described above at 0°C to room temperature. If the reaction temperature is too high, side reactions are likely to occur.

- The aromatic haloacetal compound represented by the formula (IV) can be converted into trimethylsilyl triflate using an aromatic haloketone represented by the formula (V) and the above-mentioned monohydric alcohol, dihydric alcohol, or dihydric phenol silyl ether as a catalyst. It can also be produced by reacting in the presence of. The reaction is preferably carried out at room temperature or lower (particularly at 0° C. or lower) in the presence of a halogenated solvent or an aromatic solvent.

The compound represented by formula (V) can be produced by a method characterized by reacting an aromatic ketone compound represented by formula (III) with a halogenating reagent. can.

Examples of the compound represented by the above-mentioned formula (Vl) include the following.

As the halogenating reagent, CQ2. Br2゜1,, PCQ,, PBr,, P I,, Pyridinium ha is used, and the 0 reaction which is preferably used in an equivalent or more amount with respect to the compound represented by formula (Vl) is the above-mentioned ether reaction. solvents, halogenated solvents.

It is preferable to carry out the reaction in a solvent such as an alkane solvent or an aromatic solvent, and the reaction temperature is preferably 0° C. to room temperature, but it may be better to heat the reaction.

- The compound represented by the formula (VI) is the same as the formula (■) ○ (III), where X represents a halogen] is reacted with Mg to synthesize a Grignard reagent. Reagent and general formula [However, in the formula,
R is the same as in general formula (III), R3 and R4 are each an optionally substituted alkyl group or alkoxy group, or a combination of R1 and R1 is a hydrocarbon group optionally having oxygen, and It can be produced by a method characterized by reacting a compound represented by the following formula (representing a group which forms a ring together with N).

The Grignard reagent is a compound represented by formula (■) and metal Mg in tetrahydrofuran.

In ethereal solvents such as dioxane and diethyl ether,
It can be obtained by carrying out the reaction while keeping the temperature below room temperature. Thereafter, the reaction solution and the compound represented by the general formula (■) are mixed and allowed to react preferably at room temperature or below, optionally with heating, to obtain the compound represented by the general formula (VI).

Examples of the compound represented by formula (■) include stearic acid morpholinamide, stearic acid dimethylamide, stearic acid diethylamide, stearic acid methoxymethylamide, stearin Examples include acid ethoxyethylamide, octanoic acid morpholinamide, butanoic acid dimethylamide, etc.

- The compound represented by formula (■) is - formula (IX) (where X represents a halogen) and the number of carbon atoms in the main chain is 2 to 2.
4 and which may have a substituent or whose main chain carbon may be part of a carbon ring. The reaction operation and reaction conditions are the same as those described above for the production of the compound represented by formula (rV).

- The porphyrin derivative represented by formula (1) is useful as a dye in itself, and is also useful as an auxiliary agent (photosensitizer) for causing color development or discoloration in coexisting dyes by photosensitizing action. It is.

In addition, in each of the one or more synthesis methods, after the reaction is completed, extraction is performed with a solvent such as chloroform or ethyl acetate.

The desired product can be purified by conventional methods such as recrystallization using hexane or the like, silica gel column chromatography, washing, drying, neutralization, desalting using an ion exchange resin, etc.

〔Example〕 Examples of the present invention will be shown below.

Synthesis Example 1 100ml Minus flask 10g of comobenzaldehyde, 6.75g of neopentyl glycol (1,2
20.4 m (1 (3 times equivalent)) of trimethylsilane chloride was taken and stirred at room temperature with a calcium chloride tube attached. After 7 hours, the reaction solution was cooled with ice water and 18 mQ of pyridine was added.
was added, followed by neutralization with an aqueous sodium hydrogen carbonate solution. This was extracted with methylene chloride, dried and concentrated under reduced pressure. The resulting residue was purified using silica gel column chromatography (developing solution: mixed solvent of hexane/ethyl acetate = 10/l), and then recrystallized from hexane. , 12.79 g (87%) of p-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl bromide was obtained as colorless needle-like crystals.

Synthesis Example 2 Methyl stearate Log in a 100mQ eggplant flask,
8.76 g (3 times equivalent) of morpholine was taken and heated and stirred at 160°C. After 244 hours, the reaction solution was extracted with ethyl acetate, washed with 0.6N hydrochloric acid, and washed with water.

The residue obtained by drying and concentration under reduced pressure was purified using silica gel column chromatography (developing solution: mixed solvent of hexane/acetone = 3/1) to obtain 10.7 g (91%) of stearic acid morpholinamide. .

Synthesis Example 3 0.92 g (3 times equivalent) of metallic magnesium was placed in a LoomΩ three-day flask equipped with a condenser, and heated and dried with a heat gun under reduced pressure with an oil rotary pump.

To this was added 20 mQ of anhydrous tetrahydrofuran, and 3.42 g (1.3 times equivalent) of p-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl bromide was prepared at room temperature.
A solution prepared by dissolving the above in 10 mQ of tetrahydrofuran was added and stirred. The mixture was kept at about 30° C. for 4 hours under stirring to synthesize a Grignard reagent. Then, a solution of 3.40 g of stearic acid morpholinamide dissolved in 20 ml of tetrahydrofuran was added, and the mixture was stirred while being kept at room temperature. After 12 hours, 2 ml of pyridine was added. This was neutralized with an aqueous sodium carbonate solution, extracted with chloroform, dried, and concentrated under reduced pressure. The resulting residue was purified using silica gel column chromatography (developing solution: hexane/ethyl acetate: 10/1 mixed solvent), and then Recrystallized from hexane and p-(5
,5-dimethyl-1,3dioxan-2-yl)phenylbutodecylketone (3.48 g (yield: 80%)) was obtained. The physical properties of this are as follows.

(1) Melting point near 2.2-73.2°C (2) “H-NMR spectrum (solvent CDCQ,) 0.
8 lppm (m, 3H) 0.88ppm (t, 3H) 0.9-1.4ppm (m, 288) 1-3ppm
(s, 3H) 1,4-1,8 (m, 2H) 2.94pp
a+ D, 2H) 3.3-3.9ppm (m, 4H) 5.43ppm (s, LH) 7.59ppm (d, 2H) 7.96ppm (d, 2H) [Please note that s in parentheses , d, t, m are respectively - double lines,
It means a doublet, triplet, and multiplet, and after these, the number of hydrogens determined from the areal intensity is shown.

The same applies below. ] (3) IR absorption spectrum (characteristic absorption) 1690c
m-1 (based on C=O) From the above, the compound obtained above has the following structural formula % Formula % p-(s,5-dimethyl-1
, 3-dioxan-2-yl) phenylbutodecyl ketone (3.47 g) and dioxane (16 mQ) were taken, and 2-61 g of pyridinium hydrodiene bromide perbromide was added.
(1.05 times equivalent) was added and stirred for 3 hours. The reaction solution was treated with sodium thiosulfate, extracted with ethyl acetate, dried, and concentrated under reduced pressure. The resulting residue was subjected to silica gel chromatography (
Developing solution: hexane/benzene = 1/1 mixed solvent) and purified with 4.2 g of p(5+5-dimethyl-1,3-dioxan-2-yl)phenyl(1-bromohebutodecyl)ketone (quantitative). ) was obtained. The physical properties of this are as follows.

(1) Melting point 58.2-59.3°C (2) H-NMR spectrum (solvent: cD
cu, ) 0.81 PPOI (s, 3 H) 0.8
spρm(t, 3H) 1.0-1.6ppn+ (m, 31H) 2.15
pp+m (m, 2H) 3.6-3.9 (m, 4B) 5, 11ppa+ (s, LH) 5.44ppm
(s, L H) 7.62 ppm (d, 2H) 8.00 ppm (d, 2H) (3) IR absorption spectrum (characteristic absorption) 1690a
o-" (based on C=O) From the above, the compound obtained above has the following structural formula % Formula % Synthesis Example 5 P (5,5-dimethyl-
1,3-dioxan-2-yl)phenyl(1-bromoheptodecyl)ketone 4.2g, neopentyl glycol 4.05g (5 times equivalent), p-toluenesulfonic acid 1
1.48 g (equal equivalent) of hydrate was added and dissolved using chloroform and toluene. This was subjected to a vacuum dehydration reaction at 60° C. for 10 hours using a vacuum concentrator. Concentrate the reaction solution under reduced pressure.

Silica gel column chromatography (developing solution: hexane/
5,5-
4.85 g of dimethyl-2-[p-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-2-(1-bromoheptodecyl)-1,3-dioxane (quantitative ) was obtained. The physical properties of this are as follows.

(1) Melting point: 49.3-53.5°C (2) 1H-NMR spectrum (solvent: CDC1,
) 0.54ppIIl (s, 3H) 0.82ppm (s, 3H) 0.8 8ppm (t, 3H) 0.1-
1.4ppa+ (m, 26H) 0.4-1.9ppm
(m, 4H) 3.4-3.5ppm (m, 4H) 3.68ppm (d, 2H) 3.80pp field (d, 2H) 3.95ppm (d, LH) 5.44ppm
(s, IH) 7.46pp layer (d, 2H) 7.57ppm (d, 2H) (3) IR absorption spectrum No absorption at 1690 m-1.

From the above, the compound obtained above is It is shown by the formula.

The following structural synthesis example 6 5,5-dimethyl-2-
[p-(5,5-dimethyl-↓, 3-dioxane-2-
yl)phenyl] -2-(1-bromoheptodecyl)
-1,3-dioxane 1.4g, sodium acetate 18.
4 g (100 times equivalent), mixed solvent 60 mR (dioxane/distilled water/ethanol = 1./l/2)
was added, and the mixture was heated and stirred at 180°C.

The reaction solution was extracted with ethyl acetate, dried, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (developing solution: mixed solvent of hexane/acetone/ethanol = 15/3/1) to obtain 2-[p- (5゜5-dimethyl-1,3-dioxan-2-yl)phenyl]stearic acid 626r
ng (yield 59%). The physical properties of this are as follows.

(1) Melting point: 69.7-71.3°C (2)'H-NMR spectrum (solvent CDCQ3) 0.
79ppm (s, 3H) 0.88ppm (t, 3H) 1, , 1-1.4ppm (m, but 1.28ppm
S to m.

31H (total)) 1.76ppn (m, LH) 2.0 lppm (m, LH) 3.52ppl (t, 1.H) 3.64ppH (d, 2H) 3.76ppm (d, 2H) 5 .37ppm (s, LH) 7゜31ρpIl (d, 2H) 7.46ppm (d, 2H) IR absorption spectrum (characteristic absorption) 1694■-” (based on C-〇H) From the above, the above The obtained compound is represented by the following structural formula.

Synthesis Example 7 2(p-(5,5-dimethyl-1,3-dioxane-2
-yl)phenyl]stearic acid 137mg 50mQ
It was weighed into an eggplant flask, dissolved in diethyl ether lomQ, and esterified using diazomethane. The residue obtained by concentrating the reaction solution under reduced pressure was purified by silica gel column chromatography (developing solution: hexane/ethyl acetate = 5/1 mixed solvent) to obtain 2Cp (5,5-dimethyl-1,3-dioxane). 137 mg (yield 99%) of methyl-2-yl)phenyl]stearate was obtained. The physical properties of this are as follows.

(1) Melting point: 37.4-39.3°C (2) "H-NMR spectrum (solvent CD Cn 3
) 0.80ppm (s, 3H) 0.88ppm (t, 3H) 1.1-1.4ppm (m, 288) 1.76ppm
(m, LH) 2, O4ppm (m, LH) 3.53ppm (t, IH) 3.61ppm (s, 3H) 3.64ppm (d, 2H) 3.77ppm (d, 2H) 5.38ppm (s , LH) 7, 30 ppm (d, 2l-()7.
46ppm (d, 2H) (3) IR absorption spectrum (characteristic absorption) 1738c
m-'' (based on C-0-CH) From the above, the compound obtained above is represented by the following structural formula.

Synthesis Example 8 Methyl 2-(p-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)stearate 137 mg
into a 50mQ eggplant flask, add 6mQ of methanol
and 2mα of 6N hydrochloric acid were added and stirred for 12 hours. The reaction solution was extracted with diethyl ether, concentrated under reduced pressure, and the resulting residue was subjected to silica gel column chromatography (developing solution: hexane/
The mixture was purified using a mixed solvent of acetone/methanol (15/3/1) to obtain 94 mg (yield: 83%) of methyl 2-(p-formylphenyl)stearate.

The gender is as follows.

(1) Melting point +42.7-43.3°C (2) LH-NMR spectrum (solvent CDC71,) 0
．． 88ppm (t, 3H) 1, ], -1,4ppm (m, 28H) 1.7-1.
9 ppm (m, LH) 2.0-2.2 ppm (
m, IH) 3.64. ppm (t, LH) 3.67 ppm (s, 3H) 7,48 ppm (d, 2H) 7.85
ppm (d, 2H) 10, OOppm (s, LH) (3) IR absorption spectrum As shown in FIG.

From the following, the compound obtained above is represented by the formula.

Following structure Example 1 Methyl 2-(p-formylphenyl)stearate 94
Transfer mg to a 50ml eggplant flask.

Toluene 6ml 1. Add 15.6 mg of pyrrole (equal mole) and 172 mg of propionic acid (10 times mole),
The mixture was heated under reflux at 150°C for 8 hours. After concentrating the reaction solution under reduced pressure,
The residue obtained by removing propionic acid by toluene azeotropy was purified by silica gel column chromatography (developing solution: mixed solvent of hexane/chloroform/acetone = 12/2/1) to obtain tetrakis (2-carbomethoxyheptase). Decylphenyl)porphyrin]-7 mg (yield 26%) was obtained. The physical properties of this are as follows.

(1) Properties: Amorphous solid (2) 1H-NMR spectrum (solvent CDCQ)
-2,82ppm (s, 2H) 0.85ppm (t, L2H) 1.0-1.6ppm (m, 112H) 1,9~2
, 3 ppm (m, 4H)2.3-2.
5ppm (m, 4H) 3.8-4.0ppm (m, 16H) 7.46pp
m (d, 8H) 8.15ppm (d, 8H) 9.83ppm (s, 8H) (3) IR spectrum as shown in Figure 2.

(4) Ultraviolet absorption spectrum As shown in Figure 3.

From the above, the compound obtained above is represented by the following structural formula.

H,C00C-C-(CH2J15'CH3 Example 2 Transfer 3 mg of tetrakis(2-carbomethoxyheptadecylphenyl)porphyrin IQ to a 50 ml eggplant flask, add 0.5 ml of 6N sodium hydroxide and 2.5 mQ of ethanol. The reaction mixture was heated and stirred at 90°C for 2 hours.The reaction solution was concentrated under reduced pressure, and the resulting oily residue containing the tetrasodium salt of tetrakis(2-carboxyheptadecylphenyl)porphyrin was subjected to hydrous silica gel column chromatography (developing solution: chloroform/ Acetone/methanol = 4/2/1 mixed solvent) and tetrakis (2
-carboxyheptadecylphenyl)porphyrin 10
．． 0 mg (quantitative) was obtained. The physical properties of this are as follows.

(1) Properties: Amorphous solid (2)'H-NMR spectrum (solvent CDCQ,)-2
,8ppm (broad S, 2H) 0.83pp
m (m, 12H) 1.0-1.8ppm (m, 112H)2, OOpp
m (s, 4H) 2.27 ppm (s, 4H) 3, 79 ppm (s, 4-H)
7.57 ppm (s, 8H) 8,04ppm (s, 8H) 8.70 ppm (s, 8H) Note that the absorption peak based on hydrogen of the carboxyl group was broadened and could not be seen.

(3) rR spectrum As shown in Figure 4.

(4) Ultraviolet absorption spectrum As shown in Figure 5.

From the above, the compound obtained above is represented by the following structural formula.

HOOCC-(CHzha,・CH.

An LB film was produced using the tetrakis(2-carboxyheptadecylphenyl)porphyrin obtained above. The pressure-area curve at this time is shown in FIG. 6, and the film formation curve of the LB film is shown in FIG.

Further, 0.08 mM of tetrakis(2-carboxyheptadecylphenyl)porphyrin, 0.05 mM of nickel (II) bis(dithiostilbene), and 6 mM of triethanolamine obtained above were dissolved in the acetonitrile-toluene mixed solvent. The ultraviolet absorption spectrum of the obtained solution was determined by irradiating the solution with light for 20 minutes using a xenon lamp (
Measurements were taken before and after the light wavelength (480-800 nm). The results are shown in FIG. In FIG. 8, curve 1 shows the ultraviolet absorption spectrum before light irradiation, and curve 2 shows the ultraviolet absorption spectrum after light irradiation. As is clear from this result, the above tetrakis(2-carboxyheptadecylphenyl)
It can be seen that porphyrin acts as a photosensitizer that causes discoloration of nickel (II) bis(dithiostilbene), a coexisting dye.

Synthesis Example 9 2-[p-(S, 5-dimethyl-1,3-dioxane-
572 mg of 2-yl)phenyl]stearic acid to 50 m
The mixture was weighed into a M round eggplant flask, dissolved in 12 mQ of acetone, added with 94 mQ of 6N salt, and stirred for 10 hours. Extract the reaction solution with chloroform.

The residue obtained by drying and concentration under reduced pressure was purified by silica gel column chromatography (developing solution: hexane/acetone = 2/1 mixed solvent) to obtain 346 mg of 2-(p-formylphenyl)stearic acid (yield 71%). ) was obtained. The physical properties of this are as follows.

(1) Melting point: 65.7-67.1°C (2) 'H-NMR spectrum (solvent CD(13)O1
88p pm (t t 3 H) 1.1-1.5pp
m (m, 24H) 1.80ppm (m, 2H) 2.09ρρIIl (m, 2H) 3-64ppm (t, 2H) 7.49ppm (d, 2H) 7.85ppm (d, 2H) 9. 99ppIIl(s, LH) (3) IR absorption spectrum as shown in FIG.

From the above, the compound obtained above is.

It is shown by the formula.

Following structure Example 3 2-(P-formylphenyl)stearic acid 149 mg
25.7 mg (equal moles) of pyrrole and 20 ml of propionic acid were added to the mixture, and the mixture was heated under reflux at 150° C. for 8 hours.

After concentrating the reaction solution under reduced pressure, propionic acid was removed by toluene azeotropy, and the resulting residue was subjected to column chromatography (adding and stirring the weight percent of water to the column filler Nijiri gel, developing solution: chloroform/ Acetone = 20
/1 mixed solvent) to obtain 17.6 mg of monocarboxytetrakis(heptadecylphenyl)porphyrin.
(yield: 5%). The physical properties of this are as follows.

(+) Properties: Amorphous (2)” H-NMR spectrum -2.77ppm (s, 2H) 0.86ppm (s, 12H) 1.0-2.8
ppm (m, 120H) 2-90ppm (t, 6
H) 3.94ppm (t, LH) 7.52ppm (d, 6H) 7,72ppm (d, 2H) 8.09ppm (d, 6H) 8.18ppm (d, 2H) 8.84ppm (d, 8H) (3) IR spectrum as shown in Figure 10.

(4) Ultraviolet absorption spectrum As shown in Figure 11.

From the above, the compound obtained above is It is shown by the formula.

(Solvent CDCl23) Following structure Monocarboxytetrakis(heptadecylphenyl)porphyrin obtained above 0,08 mM.

Nickel (If) bis(dithiostilbene) 0.05m
M, 6mM of triethanolamine was dissolved in an acetonitrile-toluene mixed solvent. The ultraviolet absorption spectrum of the obtained solution was measured before and after irradiating the solution with light for 20 minutes (light wavelength: 480 to 800 nm) using a xenon lamp. The results are shown in FIG. 12. In FIG. 12, curve 3 shows the ultraviolet absorption spectrum before light irradiation, and curve IllA4 shows the extra-violet absorption spectrum after light irradiation. As is clear from this result.

Nickel (II), which is a pigment in which the above monocarboxytetrakis(heptadecylphenyl)porphyrin coexists
[Effect of the Invention] The porphyrin derivative in claim 1 is a novel compound having photosensitizing ability and LB forming ability, and it is found that the porphyrin derivative acts as a photosensitizer that causes discoloration of bis(dithiostilbene). It can be easily produced by the method in Section 2.

[Brief explanation of drawings]

Figure 1 shows the IR spectrum of methyl 2-(P-formylphenyl) stearate obtained in Synthesis Example 8, and Figure 2 shows the IR spectrum of methyl 2-(P-formylphenyl) stearate obtained in Example 1. 3 is the ultraviolet absorption spectrum of the tetracarbomethoxyporphyrin, and FIG. 4 is the IR spectrum of the tetracarbomethoxyporphyrin obtained in Example 2.
2-carboxyheptadecylphenyl)porphyrin (
I of (hereinafter abbreviated as tetracarboxyporphyrin)
R spectrum, Figure 5 is the ultraviolet absorption spectrum of the tetracarboxyporphyrin, Figure 6 is the pressure-area curve of the tetracarboxyporphyrin, Figure 7 is the film formation curve of the LE film of the tetracarboxyporphyrin, and Figure 8 is the An ultraviolet absorption spectrum for investigating the function of the tetracarboxyporphyrin as a photosensitizing agent, FIG. 9 shows Synthesis Example 9.
Figure 10 shows the IR spectrum of 2-(p-formylphenyl)stearic acid obtained in Example 3.
11 is an ultraviolet absorption spectrum of the carboxyporphyrin, and FIG. 12 is an ultraviolet absorption spectrum for investigating the function of the carboxyporphyrin as a photosensitizer. [Explanation of symbols] 1.3... Ultraviolet absorption spectrum before light irradiation 2.4...
・Ultraviolet absorption spectrum after light irradiation Figure 3 Figure 5 Figure 7 Appropriate length (nm) Figure 8 f! 1s←i Constant curse Ij+-〆

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [However, in the formula, Q^1, Q^2, Q^3, and Q^4 are each independent. , an alkyl group or general formula (a) ▲ Numerical formula, chemical formula, table, etc. ▼ (a) (Here, R is an alkyl group, M is an alkyl group that may have hydrogen, an alkali metal, or a hydroxyl group. is a group represented by Q^1, Q^2, Q^3 and Q
At least one of ^4 is a group represented by general formula (a)]. 2. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (In the formula, R represents an alkyl group, and M represents hydrogen, an alkali metal, or an alkyl group that may have a hydroxyl group. 2. The method for producing a porphyrin derivative represented by the general formula (I) according to claim 1, characterized in that an aromatic substituted alkanoic acid derivative having an aldehyde group represented by the following group is reacted with pyrrole.