JP4465289B2 - Tetraazaporphyrin compounds - Google Patents

Description

  The present invention relates to a novel tetraazaporphyrin compound having excellent solubility, a clear blue color and excellent light resistance, which is used in electrophotographic toners and inkjet inks.

In recent years, there has been a demand for a dye having excellent solubility and a clear blue color and excellent light resistance for use in full-color electrophotographic toners and ink jet recording inks.
Metal phthalocyanine compounds are used in various applications as blue pigments. For example, in Japanese Patent Application Laid-Open No. 3-195833, a metal phthalocyanine sulfonic acid amide compound is used for ink jet recording ink, but since the maximum absorption wavelength of the metal phthalocyanine sulfonic acid amide compound is around 670 nm, a clear blue color is I can't get it.
JP-A-2-276866 discloses a tetraazaporphine compound as a dye for an optical recording medium, which is a compound having a central metal different from that of the compound of the present invention. However, when this compound is used in an inkjet ink or the like, the maximum absorption wavelength is around 650 nm and cannot be said to be a clear blue color.
Therefore, there is a strong demand for an organic solvent-soluble colorant having a strong absorption particularly near 600 nm.
Recently, a colorant having a high solubility in a polar organic solvent, such as methyl lactate or ethyl lactate, which is excellent in work environment and safety, has been particularly demanded as a colorant for a polymer material.
Japanese Patent Laid-Open No. 3-195833 JP-A-2-276866

  An object of the present invention is to provide an organic solvent-soluble tetraazaporphine compound having a clear blue color, excellent light resistance, and strong absorption near 600 nm. That is, more specifically, it is to provide a tetraazaporphine compound having high solubility in an organic solvent or resin that can be used for a highly transparent toner, a clear blue inkjet ink, or the like. Another object is to provide a dye that can be used as a colorant for a polymer material and has high solubility in polar organic solvents such as methyl lactate and ethyl lactate.

The present inventors have intensively studied to solve the above-described problems. As a result, the tetraazaporphine compound having a specific structure has a strong absorption near 600 nm, has a clear blue color, has excellent light resistance, and has high solubility in organic solvents and resins, thereby solving the above problems. It came to.
That is, the present invention provides the following general formula (1)

（式（１）中Ａ^１、 Ａ^２、 Ａ^３及びＡ^４で表される環は、それぞれ独立に

(In formula (1), the rings represented by A ¹ , A ² , A ³ and A ⁴ are each independently

を表し、Ａ^１、 Ａ^２、 Ａ^３及びＡ^４の少なくとも１つは、

And at least one of A ¹ , A ² , A ³ and A ⁴ is

である。Ｒ^１、Ｒ^２は独立に、水素原子または置換もしくは非置換のアルキル基を表し、ｍは１〜８の整数を表し、ｎは１〜４の整数を表す。ただしＲ^１とＲ^２が同時に水素原子であることはない。）
で表されるテトラアザポルフィリン化合物を提供するものである。

It is. R ¹ and R ² independently represent a hydrogen atom or a substituted or unsubstituted alkyl group, m represents an integer of 1 to 8, and n represents an integer of 1 to 4. However, R ¹ and R ² are not hydrogen atoms at the same time. )
The tetraazaporphyrin compound represented by these is provided.

Detailed description of the invention

In the tetraazaporphyrin compound of the general formula (1) of the present invention, R ¹ and R ² are preferably an unsubstituted alkyl group, preferably a C 1-12 alkyl group, a methyl group, an ethyl group, Examples thereof include linear or branched alkyl groups such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-dodecyl group, etc. A linear or branched alkyl group having a number of 4 to 12 is preferred.

R ¹ and R ² are each a substituted alkyl group, preferably an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond, and especially having 2 to 4 carbon atoms containing an oxygen atom. ~ 12 linear, branched and cyclic alkyl groups are preferred. Examples include methoxymethyl group, ethoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-butoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl. Group, butoxyethoxyethyl group, methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, acetylmethyl group, acetylethyl group, propionylmethyl group, propionylethyl group, tetrahydrofurfuryloxymethyl group, 2, 2-dimethyl-1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonyl Ethyl, propoxycarbonylethyl, butoxycarbonylethyl, pentoxycarbonylbutyl, 1- (butoxymethyl) ethyl, 1- (methoxymethyl) propyl, 1- (ethoxymethyl) propyl, 1- (butoxy Methyl) propyl group, 1- (2-methoxy-ethoxy-methyl) propyl group, 1- (2-ethoxy-ethoxy-methyl) propyl group, 1- (2-methoxy-2-ethoxy-2-ethoxymethyl) ethyl Group, 1- (2-ethoxy-2-ethoxy-2-ethoxymethyl) ethyl group, 1- (2-butoxy-2-ethoxy-2-ethoxymethyl) ethyl group, 1- (2-methoxy-2-ethoxy) -2-ethoxymethyl) propyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxymethyl) propyl group, 1- (2 Propoxy-2-ethoxy-2-ethoxymethyl) propyl group, 1- (2-butoxy-2-ethoxy-2-ethoxymethyl) propyl group, 1- (2-methoxy-2-ethoxy-2-ethoxymethyl) butyl A group, 1- (2-ethoxy-2-ethoxy-2-ethoxymethyl) butyl group, 1- (2-propoxy-2-ethoxy-2-ethoxymethyl) butyl group,

1- (2-methoxy-2-ethoxy-2-ethoxymethyl) pentyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxymethyl) pentyl group, 1- (2-methoxy-2-ethoxy-2) -Ethoxy-2-ethoxymethyl) ethyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxy-2-ethoxymethyl) ethyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2) -Ethoxymethyl) propyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxy-2-ethoxymethyl) propyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2-ethoxymethyl) Butyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2-ethoxyethyl) ethyl group, 1- (2-ethoxy-2-ethoxy-2-ethoxy-2-ethoxye) L) ethyl group, 1- (2-methoxy-2-ethoxy-2-ethoxy-2-ethoxyethyl) propyl group, 1,1-di (methoxymethyl) methyl group, 1,1-di (ethoxymethyl) methyl Group, 1,1-di (propoxymethyl) methyl group, 1,1-di (butoxymethyl) methyl group, 1,1-di (2-methoxy-ethoxymethyl) methyl group, 1,1-di (2- Examples include ethoxy-ethoxymethyl) methyl group, 1,1-di (2-propoxy-ethoxymethyl) methyl group, and 1,1-di (2-butoxy-ethoxymethyl) methyl group.
Among these, it is particularly preferable that at least one of R ¹ and R ² is the following formula (2).

（式（２）中、 Ｒ^３、Ｒ^４はそれぞれ独立に、水素原子；非置換アルキル基；酸素原子をエーテル結合、カルボニル結合、および／またはエステル結合の形で含むアルキル基；アルキルカルボニル基；またはアルコキシカルボニル基を示す。ただしＲ^３、Ｒ^４のうち少なくとも一方は、酸素原子をエーテル結合、カルボニル結合、および／またはエステル結合の形で含むアルキル基；アルキルカルボニル基；またはアルコキシカルボニル基である。）

(In the formula (2), R ³ and R ⁴ each independently represent a hydrogen atom; an unsubstituted alkyl group; an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond; an alkylcarbonyl group; Or an alkoxycarbonyl group, wherein at least one of R ³ and R ⁴ is an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond; an alkylcarbonyl group; or an alkoxycarbonyl group .)

In the formula (2), as R ³ and R ⁴ are unsubstituted alkyl groups, alkyl groups having 1 to 8 carbon atoms are preferable, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. Group, pentyl group, hexyl group and octyl group.
R ³ and R ⁴ are preferably an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond, preferably an alkyl group having 2 to 10 carbon atoms containing 1 to 4 oxygen atoms. . Examples include methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethoxymethyl, ethoxyethoxymethyl, propoxyethoxymethyl, butoxyethoxymethyl, methoxyethoxyethoxymethyl, ethoxyethoxyethoxymethyl. Group, propoxyethoxyethoxymethyl group, butoxyethoxyethoxyethoxymethyl group, methoxyethoxyethoxyethoxymethyl group, ethoxyethoxyethoxyethoxymethyl group, propoxyethoxyethoxyethoxymethyl group, butoxyethoxyethoxyethoxymethyl group, acetylmethyl group, propionylmethyl group, Tetrahydrofurfuryloxymethyl group, 2,2-dimethyl-1,3-dioxolane-4-methoxymethyl group, 2- (1,3-dioxolane) Ethoxymethyl group, 2- (1,3-dioxane) ethoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, butoxycarbonylmethyl group, and pentoxycarbonyl methyl group.

As R ^3, R ⁴ is an alkylcarbonyl group or an alkoxycarbonyl group are those preferably having a total carbon number of 2-10. Examples include an acetyl group, a propionyl group, a propylcarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, and a pentoxycarbonyl group.

As the tetraazaporphyrin compound represented by the general formula (1) of the present invention, R ¹ and R ² are each independently a hydrogen atom (however, R ¹ and R ² are not simultaneously hydrogen atoms); Preferred is a substituted alkyl group; or a substituted alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond.

R ¹ and R ² are each independently a hydrogen atom (however, R ¹ and R ² are not simultaneously hydrogen atoms); an unsubstituted alkyl group having 1 to 12 carbon atoms; or an oxygen atom connected to an ether bond, carbonyl Particularly preferred is a substituted alkyl group having 2 to 12 carbon atoms containing 1 to 4 in the form of a bond and / or an ester bond, and among them, at least one of R ¹ and R ² is an oxygen bond with an ether bond, a carbonyl What is a C2-C12 substituted alkyl group containing 1 to 4 bonds and / or ester bonds is preferred because of its high solubility in polar organic solvents.
In particular, at least one of R ¹ and R ² is represented by the following general formula (2)

（式（２）中、 Ｒ^３、Ｒ^４はそれぞれ独立に、水素原子；非置換アルキル基；酸素原子をエーテル結合、カルボニル結合、および／またはエステル結合の形で含むアルキル基；アルキルカルボニル基；またはアルコキシカルボニル基を示す。ただしＲ^３、Ｒ^４のうち少なくとも一方は、酸素原子をエーテル結合、カルボニル結合、および／またはエステル結合の形で含むアルキル基；アルキルカルボニル基；またはアルコキシカルボニル基である。）
で表される置換アルキル基であるテトラアザポルフィリン化合物が特に好ましい。
一般式（１）のテトラアザポルフィリン化合物におけるｍは１〜８個の整数であるが、１〜６個が好ましく、吸光度の高さから、１〜４個が特に好ましい。
またｎは１〜４の整数であるが、２〜３が好ましく，２が特に好ましい。
本発明のテトラアザポルフィリン化合物は、一般式（１）で表され、 Ａ^１、 Ａ^２、 Ａ^３及びＡ^４で表わされる環は、

で表わされる芳香環であり、その縮環方向及びそこに結合する置換基の置換位置により多数の異性体が存在する。具体的には、環の基本骨格として下記式（３）〜（７）の５種類の構造があり、さらにピリジン環の縮合方向の違いで、Ｎの位置が異なる位置異性体が存在する。更に臭素等の置換基の置換位置が異なる異性体がまたそれぞれに存在する。

(In the formula (2), R ³ and R ⁴ each independently represent a hydrogen atom; an unsubstituted alkyl group; an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond; an alkylcarbonyl group; Or an alkoxycarbonyl group, wherein at least one of R ³ and R ⁴ is an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond; an alkylcarbonyl group; or an alkoxycarbonyl group .)
A tetraazaporphyrin compound which is a substituted alkyl group represented by the formula is particularly preferred.
M in the tetraazaporphyrin compound of the general formula (1) is an integer of 1 to 8, preferably 1 to 6, and particularly preferably 1 to 4 in terms of absorbance.
N is an integer of 1 to 4, preferably 2 to 3, and particularly preferably 2.
The tetraazaporphyrin compound of the present invention is represented by the general formula (1), and the rings represented by A ¹ , A ² , A ³ and A ⁴ are:

There are many isomers depending on the direction of the condensed ring and the substitution position of the substituent bonded thereto. Specifically, there are five types of structures of the following formulas (3) to (7) as the basic skeleton of the ring, and there are positional isomers with different N positions depending on the condensation direction of the pyridine ring. Furthermore, isomers having different substitution positions of substituents such as bromine also exist.

本発明のテトラアザポルフィリン化合物は、これら多数の異性体の一部又は、すべてを含むものである。

The tetraazaporphyrin compound of the present invention contains some or all of these many isomers.

  Specific examples of the tetraazaporphyrin compound represented by the general formula (1) of the present invention are shown in Table-1. These specific examples do not limit the scope of the compounds of the present invention.

(Method for producing tetraazaporphyrin compound)
The manufacturing method of the tetraazaporphyrin compound represented by the said General formula (1) of this invention is demonstrated below.
The outline of a typical manufacturing method is as follows.
(1) Basics of bromo-substituted tetraazaporphyrin compounds by reacting a mixture appropriately selected from the group of phthalic acid, bromo-substituted phthalic acid, pyridine-2,3-dicarboxylic acid and bromo-substituted pyridine-2,3-dicarboxylic acid The skeleton is manufactured.
(2) This is then chlorosulfonylated.
(3) The desired product is obtained by reacting the resulting chlorosulfonylated bromo-substituted tetraazaporphyrin with an amine and amidating.
As another synthetic method, a mixture of phthalic acid and pyridine-2,3-dicarboxylic acid is reacted to synthesize a tetraazaporphyrin compound, chlorsulfonylated, amidated and then brominated, or a tetraazaporphyrin compound Can also be obtained by brominating, followed by chlorosulfonylation and amidation.

Next, the production method will be described in more detail.
(1) Bromo-substituted tetraazaporphyrin ring forming step As a method of forming a tetraazaporphyrin ring, phthalic acid, bromo-substituted phthalic acid, pyridine-2, 3-dicarboxylic acid and bromo-substituted pyridine-2,3-dicarboxylic acid A mixture appropriately selected from the group and copper powder, copper oxide or copper salt, in the presence of ammonia gas, ammonium compound or urea, and ammonium molybdate as a catalyst without solvent or tetralin, 1-chloro It is obtained by heating to 120 to 300 ° C. in a solvent such as naphthalene, nitrobenzene, trichlorobenzene, DMI.

A mixture selected from the group of phthalic acid (A), bromo-substituted phthalic acid (B), pyridine-2, 3-dicarboxylic acid (C) and bromo-substituted pyridine-2, 3-dicarboxylic acid (D) in the above ring-forming reaction The molar ratio of (A) + (B) :( C) + (D) is 3.5: 0.5 to 0: 4, preferably 3: 1 to 0.5: 3.5, More preferably, the ratio is 3: 1 to 1: 3, and (A) + (C) :( B) + (D) is 3.5: 0.5 to 0: 4, preferably 3: 1 to 0.3. 5: 3.5, more preferably 3: 1 to 1: 3. Further, in place of phthalic acid, bromo-substituted phthalic acid, pyridine-2, 3-dicarboxylic acid, bromo-substituted pyridine-2, 3-dicarboxylic acid, dicyano compounds and acid anhydrides thereof can be used.
Specific examples of the bromo-substituted phthalic acid include 3-bromophthalic acid, 4-bromophthalic acid, 3, 4, 5, 6-tetrabromophthalic acid and the like. Specific examples of bromo-substituted pyridine-2,3-dicarboxylic acid include 5-bromopyridine-2,3-dicarboxylic acid, 6-bromopyridine-2,3-dicarboxylic acid and the like.

(2) Chlorosulfonylation step The bromo-substituted tetraazaporphyrin compound obtained in the step (1) above is added little by little so as to maintain 20 ° C or less in 5 to 20 times weight of chlorosulfonic acid. After stirring at the same temperature for 1 hour, the mixture is reacted at 155 to 160 ° C. for 4 hours. The solution is cooled to 80 ° C., and 2 to 5 times the weight of thionyl chloride of the tetraazaporphyrin compound is added dropwise over 1 to 2 hours while maintaining at 70 to 80 ° C. After stirring at the same temperature for 2 to 10 hours, the mixture is cooled to 15 to 20 ° C. and stirred at the same temperature for 12 hours. After discharging this reaction solution little by little into ice water having a weight of 50 to 200 times the amount of chlorosulfonic acid used, the precipitate was filtered and washed with ice water until neutral, and sulfonyl chloride of a bromo-substituted tetraazaporphyrin compound. Get the body.
The reaction conditions described above are mainly conditions for obtaining tetrasulfonyl chloride, but when mono-, di- or tri-substituted sulfonyl chlorides are to be obtained, it is possible to make the reaction conditions in chlorosulfonic acid milder. . That is, it is achieved by lowering the reaction temperature or shortening the reaction time.

(3) Sulfonamidation step The bromo-substituted tetraazaporphyrin sulfonyl chloride obtained above is suspended in ice water,
Following formula (8):
NHR ¹ R ² (8)
(Wherein R ¹ and R ² are the same as those in formula (1))
The organic amine compound represented by the formula (2 to 8 times molar ratio of the bromo-substituted tetraazaporphyrin compound) is dropped so as to keep the temperature at 15 ° C. or lower. After dropping, the mixture is stirred at 20 to 30 ° C. for 15 to 24 hours, filtered, washed with water, and dried to obtain the desired bromo-substituted tetraazaporphyrin compound of the formula (1).

The product thus obtained is often a mixture of a plurality of isomers as described above, but even a mixture can achieve the object of the present invention and is within the scope of the present invention.
This mixture can be purified by a conventional purification method such as recrystallization with an organic solvent such as ethyl acetate, acetone, methanol or the like, if necessary, to obtain a single compound. You can also.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Example 1] Synthesis of tetraazaporphyrin compound specific example -28 29.6 g of phthalic anhydride, 22.2 g of 4-bromophthalic anhydride, 16.7 g of pyridine-2,3-dicarboxylic acid, 144 g of urea, first chloride 9.9 g of copper and 1.6 g of ammonium molybdate were suspended in 400 mL of 1-chloronaphthalene and stirred at 190 ° C. to 220 ° C. for 5 hours. The reaction mixture was poured into 250 mL of methanol, filtered, washed with methanol, water, and acetone in this order, and then dried to obtain 31.3 g of a blue bromo-substituted tetraazaporphyrin compound.

  13.1 g of this bromo-substituted tetraazaporphyrin compound was charged into 100 g of chlorosulfonic acid at 20 ° C. or less over 30 minutes. Next, the temperature was raised to 70 to 80 ° C., stirred at the same temperature for 1 hour, heated to 140 to 145 ° C. over 2 hours, reacted at the same temperature for 4 hours, and then cooled to 80 ° C. Further, 30 g of thionyl chloride was added dropwise over 1 hour while maintaining the temperature at 70 to 80 ° C., followed by stirring at 70 to 80 ° C. for 4 hours. It cooled to 15-20 degreeC and stirred at the same temperature for 12 hours. After the reaction solution was discharged little by little in 1000 g of ice water, the precipitate was separated by filtration and washed with ice water until neutral, to obtain a sulfonyl chloride of a hydrated paste-like bromo-substituted tetraazaporphyrin compound. This was immediately poured into 400 g of ice water, and after 30 minutes of dispersion and stirring at 10 ° C. or lower, 30 g of 2-amino-1 (2-ethoxyethoxy) butane was added dropwise. Next, the temperature was raised to 20 to 30 ° C., and after stirring for 18 hours at the same temperature, the product was separated by filtration, dispersed and filtered with 200 g of water twice, and then dried at 60 ° C. for 16 hours. 18 g of blue powder was obtained. Further, recrystallization with ethyl acetate gave 10 g of blue crystals.

As a result of X-ray fluorescence analysis, this blue crystal has an average sulfonamide group of 1.9 per molecule due to the strength ratio of copper and sulfonamide group sulfur atom and bromine as the central metal of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of bromine atoms was 1.2.
A pigment resin solution of 0.3 g of this blue crystal, 0.5 g of an acrylic resin (Delpet 80N: manufactured by Asahi Kasei Co., Ltd.) and 9.5 g of ethyl lactate is prepared, and applied to a glass plate by a spin coat method, and then heated to 60 ° C And dried for 1 hour, and then the transmission spectrum was measured. This transmission spectrum is shown in FIG.
5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 1.5 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has two sulfonamide groups per molecule, depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. FD-MS analysis result: m / z 1100.2. As a result, it was confirmed that the compound was mainly composed of the compound of specific example-28 in which one pyridine ring was introduced.

[Example 2] Synthesis of tetraazaporphyrin compound specific example -29 14.8 g of phthalic anhydride, 45.4 g of 4-bromophthalic anhydride, 16.7 g of pyridine-2,3-dicarboxylic acid, 144 g of urea, first chloride 9.9 g of copper and 1.6 g of ammonium molybdate were suspended in 400 mL of 1,3-dimethyl-2-imidazolidinone and stirred at 190 ° C. to 220 ° C. for 5 hours. The post-process similar to Example 1 was performed, and 41.1g of bromo substituted tetraazaporphyrin compounds were obtained. Chlorosulfonated, amidated and post-treated in the same manner as in Example 1 to obtain 15.5 g of blue crystals.
As a result of fluorescent X-ray analysis, this blue crystal has an average sulfonamide group of 2.1 per molecule depending on the strength ratio of the copper atom of the bromo-substituted tetraazaporphyrin skeleton and the sulfur atom and bromine of the sulfonamide group. It was confirmed that the number of bromine atoms was 2.2. The transmission spectrum of the blue crystal was measured in the same manner as in Example 1. This transmission spectrum is shown in FIG.
5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 1.0 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has two sulfonamide groups per molecule, depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. The number of atoms was confirmed to be 2, and the result of FD-MS analysis: from m / z 1178.1, it was confirmed that the compound was composed mainly of the compound of Example 29 in which one pyridine ring was introduced. .

[Example 3] Synthesis of tetraazaporphyrin compound specific example-30 4-bromophthalic anhydride 68.1 g, pyridine-2,3-dicarboxylic acid 16.7 g, urea 144 g, cuprous chloride 9.9 g, molybdic acid 1.6 g of ammonium was suspended in 400 mL of 1,3-dimethyl-2-imidazolidinone and stirred at 190 ° C. to 220 ° C. for 5 hours. The post-process similar to Example 1 was performed, and 25 g of bromo substituted tetraazaporphyrin compounds were obtained. Chlorosulfonated, amidated and post-treated in the same manner as in Example 1 to obtain 9.9 g of blue crystals.
As a result of X-ray fluorescence analysis, this blue crystal has an average sulfonamide group of 1.9 per molecule due to the strength ratio of copper and sulfonamide group sulfur atom and bromine as the central metal of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of bromine atoms was 3.1. The transmission spectrum of the blue crystal was measured in the same manner as in Example 1. This transmission spectrum is shown in FIG.
5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 3.0 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has two sulfonamide groups per molecule, depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of atoms was 3, and as a result of FD-MS analysis, it was confirmed that the compound was composed mainly of the compound of Specific Example 30 in which one pyridine ring was introduced from m / z 1256.0. .

[Example 4] Synthesis of tetraazaporphyrin compound specific example-7 Example 1 except that 25 g of 3-butoxypropylamine was used instead of 30 g of 2-amino-1 (2-ethoxyethoxy) butane in Example 1. 1 was obtained in the same manner as 1 to obtain 13 g of blue crystals.
As a result of X-ray fluorescence analysis, this blue crystal has an average sulfonamide group of 1.9 per molecule due to the strength ratio of copper and sulfonamide group sulfur atom and bromine as the central metal of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of bromine atoms was 1.1. The transmission spectrum of the blue crystal was measured in the same manner as in Example 1.
5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 3.0 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has two sulfonamide groups per molecule, depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. As a result of FD-MS analysis: m / z 1040.1, it was confirmed that the compound was composed mainly of the compound of Specific Example 7 in which one pyridine ring was introduced. .

[Example 5] Synthesis of tetraazaporphyrin compound specific example-16 Example 1 except that 40 g of 2-ethylhexylamine was used instead of 30 g of 2-amino-1 (2-ethoxyethoxy) butane in Example 1. And 11 g of blue crystals were obtained.
As a result of fluorescent X-ray analysis, this blue crystal has 2.2 average sulfonamide groups per molecule depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of bromine atoms was 1.2. The transmission spectrum of the blue crystal was measured in the same manner as in Example 1.
5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 1.0 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has two sulfonamide groups per molecule, depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. The number of atoms was confirmed to be one, and the result of FD-MS analysis: from m / z 1036.2, it was confirmed that the compound was composed mainly of the compound of Example 16 in which one pyridine ring was introduced. .

[Example 6] Synthesis of tetraazaporphyrin compound specific example -65 14.8 g of phthalic anhydride, 22.7 g of 4-bromophthalic anhydride, 33.4 g of pyridine-2,3-dicarboxylic acid, 144 g of urea, first chloride 9.9 g of copper and 1.6 g of ammonium molybdate were suspended in 400 mL of 1-chloronaphthalene and stirred at 190 ° C. to 220 ° C. for 5 hours. The post-process similar to Example 1 was performed, and 28 g of bromo substituted tetraazaporphyrin compounds were obtained. In the same manner as in Example 1, chlorosulfonation, amidation and post-treatment were performed to obtain 6.8 g of blue crystals.
As a result of X-ray fluorescence analysis, this blue crystal has an average sulfonamide group of 1.8 per molecule depending on the intensity ratio of copper and sulfonamide group sulfur atom and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of bromine atoms was 0.9. The transmission spectrum of the blue crystal was measured in the same manner as in Example 1.
5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 1.0 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has two sulfonamide groups per molecule, depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of atoms was one, and as a result of FD-MS analysis: from m / z 1179.1, it was confirmed that the compound was composed mainly of the compound of specific example-65 in which two pyridine rings were introduced. .

[Example 7] Synthesis of tetraazaporphyrin compound specific example-33 In Example 1, instead of 30 g of 2-amino-1 (2-ethoxyethoxy) butane, 20 g of L-valine methyl hydrochloride and 15 g of triethylamine were used. Was carried out in the same manner as in Example 1 to obtain 6.7 g of blue crystals. As a result of X-ray fluorescence analysis, this blue crystal has an average sulfonamide group of 1.9 per molecule due to the strength ratio of copper and sulfonamide group sulfur atom and bromine as the central metal of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of bromine atoms was 1.2. The transmission spectrum of the blue crystal was measured in the same manner as in Example 1.
5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 0.5 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has two sulfonamide groups per molecule, depending on the strength ratio of copper and sulfonamide group sulfur atoms and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of atoms was one, and as a result of FD-MS analysis: from m / z 1040.1, it was confirmed that the compound was composed mainly of the compound of Example 33 in which one pyridine ring was introduced. .

[Example 8] Synthesis of tetraazaporphyrin compound example-101 4-bromophthalic anhydride 22.7 g, pyridine-2,3-dicarboxylic acid 50.1 g, urea 144 g, cuprous chloride 9.9 g, molybdic acid 1.6 g of ammonium was suspended in 400 mL of 1-chloronaphthalene and stirred at 190 ° C. to 220 ° C. for 5 hours. The post-process similar to Example 1 was performed, and 15 g of bromo substituted tetraazaporphyrin compounds were obtained. In the same manner as in Example 1, chlorosulfonation (reaction temperature: 125 to 130 ° C.), amidation and post-treatment were performed to obtain 4.5 g of blue crystals.
As a result of fluorescent X-ray analysis, this blue crystal has an average sulfonamide group of 1.2 per molecule depending on the strength ratio of copper and sulfonamide group sulfur atom and bromine, which are the central metals of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of bromine atoms was 1.1. The transmission spectrum of the blue crystal was measured in the same manner as in Example 1.
3.5 g of this blue crystal was separated and purified by silica gel column chromatography with a mixed solution of ethyl acetate / methanol to obtain 0.8 g of purified blue powder. As a result of X-ray fluorescence analysis, this purified blue powder has one sulfonamide group per molecule and bromine depending on the strength ratio of copper and sulfonamide group sulfur atom and bromine as the central metal of the bromo-substituted tetraazaporphyrin skeleton. It was confirmed that the number of atoms was one, and as a result of FD-MS analysis: from m / z 879.1, it was confirmed that the compound was composed mainly of the compound of Example 101 in which three pyridine rings were introduced. .

[Comparative Example 1] 12 g of copper phthalocyanine (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged into 120 g of chlorosulfonic acid at 20 ° C. or less over 30 minutes. Next, the temperature was raised to 70 to 80 ° C., stirred at the same temperature for 1 hour, heated to 130 to 135 ° C. over 2 hours, reacted at the same temperature for 4 hours, and then cooled to 80 ° C. Further, 20 g of thionyl chloride was added dropwise over 1 hour while maintaining the temperature at 70 to 80 ° C., followed by stirring at 70 to 80 ° C. for 4 hours. It cooled to 15-20 degreeC and stirred at the same temperature for 12 hours.
The reaction solution was discharged into 1000 g of ice water little by little, and then the precipitate was separated by filtration and washed with ice water until neutrality to obtain a hydrated phthalocyanine sulfonyl chloride. This was immediately poured into 400 g of ice water, and after 30 minutes of dispersion and stirring at 10 ° C. or less, 20 g of 3-butoxypropylamine was added dropwise. Next, the temperature was raised to 20 to 30 ° C. and stirred at the same temperature for 18 hours. The product was separated by filtration, dispersed in 200 g of water and filtered twice, and then dried at 60 ° C. for 15 hours. As a result, 15 g of blue powder was obtained. Further, recrystallization from ethyl acetate gave 6.4 g of blue crystals. From the fluorescent X-ray analysis, the average sulfonamide group per molecule was 3.8 depending on the intensity ratio of copper, which is the central metal of the phthalocyanine skeleton, to the sulfur atom of the sulfonamide group.
The transmission spectrum of the blue crystal was measured in the same manner as in Example 1. This transmission spectrum is shown in FIG.
The transmission spectrum of the tetraazaporphyrin compound of the present invention has a strong absorption around 600 nm and a clear blue color, whereas the transmission spectrum of this comparative compound shows an absorption around 680 nm and has a greenish blue color. Met.

本発明のテトラアザポルフィリン化合物は、非常に耐光性に優れていた。 [Light resistance test]
After irradiating a xenon lamp with 50,000 lux for 20 hours (equivalent to 1 million lux · h) to each glass substrate prepared during transmission spectrum measurement in each example and comparative example, chromaticity meter MCPD-1000 (Otsuka Electronics) The change in chromaticity in the pattern image before and after irradiation, that is, the ΔEab value was measured. The obtained color difference ΔEab value was evaluated based on the following criteria as an index indicating the degree of light resistance. A smaller ΔEab value indicates better light resistance.
○: ΔEab value is less than 2 Δ: ΔEab value is 2 or more and less than 5 ×: ΔEab value is 5 or more

The tetraazaporphyrin compound of the present invention was very excellent in light resistance.

[Industrial applicability]
The tetraazaporphyrin compound of the present invention has a clear blue color, excellent light resistance, strong absorption near 600 nm, and high solubility in organic solvents and resins. Therefore, a highly transparent toner and a clear blue inkjet ink, Suitable for coloring polymer materials.

2 is a transmission spectrum of a blue crystal obtained in Example 1. 3 is a transmission spectrum of a blue crystal obtained in Example 2. 3 is a transmission spectrum of a blue crystal obtained in Example 3. 2 is a transmission spectrum of the crystal obtained in Comparative Example 1.

Claims (5)

A tetraazaporphyrin compound represented by the following general formula (1).

(In formula (1), the rings represented by A ¹ , A ² , A ³ and A ⁴ are each independently

And at least one of A ¹ , A ² , A ³ and A ⁴ is

It is. R ¹ and R ² are each independently a hydrogen atom (provided that R ¹ and R ² are not hydrogen atoms at the same time); an unsubstituted alkyl group; or an oxygen atom with an ether bond, a carbonyl bond, and / or an ester bond And m represents an integer of 1 to 8, and n represents an integer of 1 to 4. However, R ¹ and R ² are not hydrogen atoms at the same time. R ¹ and R ² are each independently a hydrogen atom (wherein R ¹ and R ² are not hydrogen atoms at the same time); an unsubstituted alkyl group having 1 to 12 carbon atoms; or an oxygen atom with an ether bond or a carbonyl bond and / or an ester bond 1-4 including substituted alkyl group having 2 to 12 carbon atoms in the form of, m is tetraazaporphyrin compound of claim 1 which is an integer from 1 to 4. 3. The tetraaza according to claim ¹ , wherein at least one of R ¹ and R ² is a substituted alkyl group having 2 to 12 carbon atoms containing 1 to 4 oxygen atoms in the form of an ether bond, a carbonyl bond and / or an ester bond. Porphyrin compound. At least one of R ¹ and R ² is represented by the following general formula (2)

(In the formula (2), R ³ and R ⁴ each independently represent a hydrogen atom; an unsubstituted alkyl group; an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond; an alkylcarbonyl group; Or an alkoxycarbonyl group, wherein at least one of R ³ and R ⁴ is an alkyl group containing an oxygen atom in the form of an ether bond, a carbonyl bond, and / or an ester bond; an alkylcarbonyl group; or an alkoxycarbonyl group .)
The tetraazaporphyrin compound of Claim 3 which is a substituted alkyl group represented by these. R ³ and R ⁴ each independently represents a hydrogen atom; an unsubstituted alkyl group having 1 to 8 carbon atoms; an oxygen atom having 1 to 4 carbon atoms in the form of an ether bond, a carbonyl bond, and / or an ester bond; A substituted alkyl group having 10 carbon atoms; an alkylcarbonyl group having 2 to 10 carbon atoms; or an alkoxycarbonyl group having 2 to 10 carbon atoms, and at least one of R ³ and R ⁴ has an oxygen atom as an ether bond, a carbonyl bond, and 5. The tetraazaporphyrin compound according to claim 4 , which is an alkyl group contained in the form of an ester bond; an alkylcarbonyl group; or an alkoxycarbonyl group.

Images