JPWO2020045200A1 - Alkylene compound, quinophthalone compound and quinophthalone mixture - Google Patents

Abstract

［式（１）中、Ｘ^１及びＸ^２は各々独立に水素原子又はハロゲン原子を示し、Ｚは炭素数１〜３のアルキレン基を示す。］An alkylene compound represented by the following formula (1).
[Chemical 1]

[In the formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

Description

The present invention relates to a method for producing an alkylene compound and a quinophthalone compound, a quinophthalone compound and a quinophthalone mixture.

Currently, coloring compositions are used in various fields, and specific applications of coloring compositions include printing inks, paints, colorants for resins, colorants for fibers, and color materials for IT information recording (color filters). , Toner, inkjet) and the like. The dye used in the coloring composition is required to have color characteristics (coloring power, sharpness), resistance (weather resistance, light resistance, heat resistance, solvent resistance) and the like. Dyes are mainly classified into pigments and dyes. Pigments, unlike dyes that develop color in the molecular state, develop color in the particle state (aggregates of primary particles). Therefore, in general, pigments are superior to dyes in resistance, but inferior in coloring power and saturation (sharpness).

Against this background, pigments with high coloring power and high saturation are required, and organic pigments, which are considered to be superior in terms of coloring power, are attracting particular attention. For example, Patent Document 1 discloses a coloring composition containing a predetermined quinophthalone compound.

Japanese Unexamined Patent Publication No. 2012-247587

However, the conventional coloring composition containing a quinophthalone compound is not always excellent in coloring power, and is by no means sufficient for use in applications requiring high color reproducibility such as a color filter. Since the quinophthalone compound is obtained by the condensation reaction of the quinaldine (2-methylquinolin) compound and the phthalic anhydride, it is important to develop a new quinalzine compound in order to find the quinophthalone compound having excellent coloring power. Become.

Therefore, an object of the present invention is to provide a novel quinaldine compound for producing a quinophthalone compound having excellent coloring power as a pigment. Another object of the present invention is to provide a method for producing a quinophthalone compound having excellent coloring power as a pigment. Another object of the present invention is to provide a novel quinophthalone compound and a quinophthalone mixture containing the quinophthalone compound.

［式（１）中、Ｘ^１及びＸ^２は各々独立に水素原子又はハロゲン原子を示し、Ｚは炭素数１〜３のアルキレン基を示す。］One aspect of the present invention is an alkylene compound represented by the formula (1).

[In the formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

The Z may be a methylene group.

［式（１）中、Ｘ^１及びＸ^２は各々独立に水素原子又はハロゲン原子を示し、Ｚは炭素数１〜３のアルキレン基を示す。］

［式（２）中、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は各々独立に水素原子又はハロゲン原子を示す。］

［式（３）中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は各々独立に水素原子又はハロゲン原子を示し、Ｚは炭素数１〜３のアルキレン基を示す。］

［式（４）中、Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４、Ｘ^５及びＸ^６は各々独立に水素原子又はハロゲン原子を示し、Ｚは炭素数１〜３のアルキレン基を示す。］Another aspect of the present invention is the first quinophthalone compound represented by the formula (3) by condensing the alkylene compound represented by the formula (1) and the acid anhydride represented by the formula (2). A method for producing a quinophthalone compound, which comprises a step of obtaining at least one selected from the group from the second quinophthalone compound represented by the formula (4).

[In the formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

[In formula (2), X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom. ]

[In formula (3), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

[In formula (4), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

In one aspect, the step may be a step of condensing the alkylene compound and the acid anhydride in the presence of an acid catalyst.

Yet another aspect of the present invention is the quinophthalone compound represented by the formula (4).

Yet another aspect of the present invention is a quinophthalone mixture containing a first quinophthalone compound represented by the formula (3) and a second quinophthalone compound represented by the formula (4).

According to the present invention, a novel quinaldine compound for producing a quinophthalone compound having excellent coloring power as a pigment is provided. Further, according to the present invention, there is provided a method for producing a quinophthalone compound having excellent coloring power as a pigment. Further, according to the present invention, a novel quinophthalone compound and a quinophthalone mixture containing the quinophthalone compound are provided.

Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.

(Alkylene compound)
The alkylene compound according to this embodiment is a compound represented by the following formula (1).

In formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms.

The halogen atom in the formula (1) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom.

Specific examples of the alkylene group having 1 to 3 carbon atoms in the formula (1) include a methylene group, an ethylene group (1,1-ethanediyl group or 1,2-ethanediyl group), and a propylene group (1,1-). Propanediyl group, 2,2-propanediyl group, 1,2-propanediyl group or 1,3-propanediyl group) is preferable, methylene group, 1,1-ethanediyl group, 1,1-propanediyl group, 2 , 2-Propanediyl group is more preferable, and methylene group is more preferable.

Hereinafter, one aspect of the method for producing the above-mentioned alkylene compound will be described, but the production method is not limited thereto.

The alkylene compound according to the present embodiment can be obtained, for example, by a method including the following steps I, II and III. Incidentally, the formula (1-i) and the formula (1-ii) a plurality of ^{X 1} and between the plurality of ^{X 2} each other in may be the same or different.

<Step I>
First, J. According to the method described in Heterocyclic, Chem, 30, 17 (1993) or the like, 2-3 equivalents of crotonaldehyde are added to 1 equivalent of bisanilins, and the mixture is reacted in a strong acid in the presence of an oxidizing agent, and the following formula (1) -I) Synthesize the compound.

In formula (1-i), X ¹ , X ² and Z are as described above.

Here, examples of the strong acid include hydrochloric acid, sulfuric acid, nitric acid and the like. Examples of the oxidizing agent include sodium iodide, p-chloranil, nitrobenzene and the like.

With respect to step I, the reaction temperature may be 80 ° C. to 100 ° C., preferably 90 ° C. to 100 ° C., and the reaction time may be 1 hour to 6 hours, preferably 3 hours to 6 hours.

<Step II>
Further, the compound of the formula (1-ii) can be obtained by reacting the obtained compound of the formula (1-i) with nitric acid or fuming nitric acid in the presence of concentrated sulfuric acid.

In formula (1-ii), X ¹ , X ² and Z are as described above.

With respect to Step II, the reaction temperature may be −20 ° C. to 70 ° C., preferably 0 ° C. to 50 ° C., and the reaction time may be 1 hour to 4 hours, preferably 1 hour to 3 hours.

<Step III>
Further, by reducing the obtained compound of the formula (1-ii) to convert the nitro group (-NO ₂ ) into the amino group (-NH ₂ ), the alkylene compound represented by the above formula (1) can be obtained. Obtainable.

In the step (III), for example, the alkylene compound represented by the formula (1) can be obtained by reducing the compound of the formula (1-ii) with reduced iron. At this time, the amount of reduced iron may be 6 to 8 equivalents with respect to 1 equivalent of the compound of the formula (1-ii), and the reaction temperature is 60 ° C to 80 ° C, preferably 70 ° C to 80 ° C. The reaction time may be 1 hour to 3 hours, preferably 2 hours to 3 hours.

Further, in the step (III), the compound of the formula (1-ii) is reduced by using a metal catalyst such as palladium-carbon (Pd-C), platinum-carbon (Pt-C), Raney nickel or the like to carry out the reduction treatment. The alkylene compound represented by (1) can also be obtained. At this time, the amount of the metal catalyst may be, for example, 0.4% by mass to 5% by mass of the compound of the formula (1-ii) as the metal amount, and the reaction temperature may be, for example, 30 ° C. to 100 ° C. Well, the reaction time may be, for example, 1 hour to 10 hours. As the hydrogen source for the reaction, hydrogen gas, hydrazine, ammonium formate and the like can be used.

(Manufacturing method of quinophthalone compound)
The method for producing a quinophthalone compound according to the present embodiment is represented by the following formula (3) by condensing an alkylene compound represented by the following formula (1) and an acid anhydride represented by the following formula (2). The present invention comprises a step of obtaining at least one selected from the group from the first quinophthalone compound and the second quinophthalone compound represented by the following formula (4) (hereinafter, referred to as step IV). Incidentally, equations (3) and (4) a plurality of X ³ together, a plurality of X ⁴ each other, a plurality of X ⁵ and between the plurality of X ⁶ each other in may the same as or different from each other.

In formula (1), X ¹ , X ² and Z are as described above.

In formula (2), X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom. The halogen atom in the formula (2) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and more preferably a chlorine atom.

In the acid anhydride represented by the formula (2), at least one of X ³ , X ⁴ , X ⁵ and X ⁶ is preferably a halogen atom, and more preferably two or more are halogen atoms. .. Further, it is preferable that at least one of X ⁴ and X ⁵ is a halogen atom, more preferably X ⁴ and X ⁵ are each a halogen atom. By introducing a halogen atom into X ³ , X ⁴ , X ⁵ or X ⁶ , the dispersibility and durability of the quinophthalone compound produced using the above-mentioned anhydride are further improved, and the above-mentioned effect becomes more remarkable. Tends to be obtained.

Examples of the acid anhydride represented by the formula (2) include phthalic anhydride and halogen-substituted phthalic anhydride, and specific examples of the halogen-substituted phthalic anhydride include tetrafluorophthalic anhydride and tetra. Examples thereof include chlorophthalic anhydride, tetrabromophthalic anhydride, 4,5-dichlorophthalic anhydride, 4-chlorophthalic anhydride, 4,5-dibromophthalic anhydride and the like.

As the acid anhydride represented by the formula (2), one kind may be used alone, or two or more kinds may be combined. By using an acid anhydride represented by the formula (2) two or more, to obtain a plurality of X ³ together, a plurality of X ⁴ each other, a plurality of X ⁵ and between the plurality of X ⁶ each other different said quinophthalone compound be able to.

In formulas (3) and (4), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom. The halogen atom in the formula (3) and the formula (4) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and is a chlorine atom. Is more preferable.

In the quinophthalone compounds represented by the formulas (3) and (4), at least one of X ³ , X ⁴ , X ⁵ and X ⁶ is preferably a halogen atom, and two or more are halogen atoms. Is more preferable. Further, it is preferable that at least one of X ⁴ and X ⁵ is a halogen atom, more preferably X ⁴ and X ⁵ are each a halogen atom. By introducing a halogen atom into X ¹ , X ² , X ³ , X ⁴ , X ⁵ or X ⁶ , the dispersibility and durability of the quinophthalone compound are further improved, and the above-mentioned effects can be obtained more remarkably. Tend.

The structure of the formula (3) includes tautomers having the following formulas (3-i) and formula (3-ii), and the quinophthalone compound has any of these structures. You may. Further, the structure of the formula (4) also has a plurality of tautomers, and the quinophthalone compound may have any of these structures.

In formula (3-i) and formula (3-ii), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ and Z are as described above.

Specific examples of the quinophthalone compound are given below, but the quinophthalone compound is not limited thereto.

The quinophthalone compound exhibits selective absorption and permeation by dimerizing the heterocyclic skeleton centered on the quinoline ring. In addition, the quinophthalone compound dimerizes the heterocyclic skeleton using an alkylene group as a linking group as a spacer, whereby the conjugation is cleaved and excessive redness is suppressed. Further, the dispersibility of the quinophthalone compound is improved by introducing an imide structure. From these facts, according to the above-mentioned quinophthalone compound, a pigment having excellent brightness and coloring power can be obtained. Specifically, for example, the yellow pigment composed of the above quinophthalone compound has better brightness than the commonly used yellow pigment (CI Pigment Yellow 150) at present, and is superior to this. Has coloring power.

In step IV, for example, by the method described in JP2013-61622A, 3 to 6 equivalents of the acid anhydride represented by the formula (2) with respect to 1 equivalent of the alkylene compound represented by the formula (1). May be a step of condensing the alkylene compound represented by the formula (1) and the acid anhydride represented by the formula (2) by reacting the compound in the presence of an acid catalyst.

The reaction temperature of the condensation may be 180 ° C. to 250 ° C., preferably 200 ° C. to 250 ° C. The reaction time for condensation may be 1 hour to 8 hours, preferably 3 hours to 8 hours.

Examples of the acid catalyst include Bronsted acids such as benzoic acid, p-toluenesulfonic acid, zinc chloride and iron chloride, or Lewis acids.

Step IV may be a step of obtaining a first quinophthalone compound represented by the formula (3) or a second quinophthalone compound represented by the formula (4), and the first quinophthalone compound and the second quinophthalone compound may be obtained. May be a step of obtaining a mixture of (quinophthalone mixture).

The quinophthalone compound (or quinophthalone mixture) obtained by the production method according to the present embodiment has excellent coloring power as a pigment. The pigmentation of the quinophthalone compound may be carried out by a known and commonly used method.

The pigment (yellow pigment) composed of the quinophthalone compound may be refined by, for example, a salt milling treatment or the like. Further, the yellow pigment may be surface-treated by a method such as rosin treatment, surfactant treatment, solvent treatment, or resin treatment.

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δｐｐｍ：２．８１（ｓ，６Ｈ），４．２４（ｓ，２Ｈ），７．３４（ｄ，Ｊ＝８．０Ｈｚ，２Ｈ），７．４９（ｓ，２Ｈ），７．６７（ｓ，２Ｈ），７．９９（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ）
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３）δｐｐｍ：２５．８，４１．１，１２３．２，１２６．２，１２７．８，１３０．９，１３３．１，１３６．３，１３７．６，１４３．１，１６０．０
ＦＴ−ＩＲ ｃｍ^−１：３０５４，３０３０，２９１５，１６０３，１４８７，１２０６
ＦＤ−ＭＳ：３６６Ｍ＋(Example A-1)
5.00 g (56.1 mmol) of 4,4'-methylenebis (2-chloroaniline), 27.6 g (112 mmol) of p-chloranil, 150 ml of water, 150 ml of concentrated hydrochloric acid, and 100 ml of n-butanol were added to the flask. The mixture was stirred at ° C. for 30 minutes. To this mixture was added dropwise 11.8 g (168 mmol) of crotonaldehyde dissolved in 12 ml of n-butanol, and the mixture was further stirred for 1 hour. The temperature was lowered to 80 ° C., 15.3 g (112 mmol) of zinc chloride was added little by little, 200 ml of THF was added, and the mixture was stirred for 1 hour while maintaining 80 ° C. After allowing to cool to room temperature, the ocher powder was recovered by vacuum filtration. The obtained ocher powder was washed with 200 ml of THF, and the ocher powder was recovered by vacuum filtration again. Further, the obtained ocher powder was transferred to a flask, 200 ml of water and 40 ml of 28% aqueous ammonia were added, and the mixture was stirred at room temperature for 2 hours. The powder was recovered by vacuum filtration to obtain 20.3 g of a crude product. The obtained crude product was dissolved in toluene, the insoluble material was removed by filtration, and then recrystallized to obtain 12.6 g of intermediate (i). (Yield: 61%)

^{1 1} H-NMR (CDCl ₃ ) δppm: 2.81 (s, 6H), 4.24 (s, 2H), 7.34 (d, J = 8.0Hz, 2H), 7.49 (s, 2H) ), 7.67 (s, 2H), 7.99 (d, J = 8.8Hz, 2H)
¹³ C-NMR (CDCl ₃ ) δppm: 25.8, 41.1, 123.2, 126.2, 127.8, 130.9, 133.1, 136.3, 137.6, 143.1, 160.0
FT-IR cm ^-1 : 3054, 3030, 2915, 1603, 1487, 1206
FD-MS: 366M +

^１Ｈ−ＮＭＲ（ＣＤＣｌ_３）δｐｐｍ：２．８６（ｓ，６Ｈ），４．２７（ｓ，２Ｈ），７．５６（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），７．６２（ｓ，２Ｈ），８．０８（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ）
^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３）δｐｐｍ：２５．７，３２．４，１１９．９，１２５．６，１２７．５，１３０．１，１３１．１，１３７．３，１４３．１，１４５．９，１６２．２
ＦＴ−ＩＲ ｃｍ^−１：１６０４，１５３０，１４８７，１３６２
ＬＣ−ＭＳ：４５７［ＭＨ］＋Next, 4.15 g (11.3 mmol) of intermediate (i) and 7.55 mL of concentrated sulfuric acid were added to the flask, and the mixture was stirred at 45 ° C. for 20 minutes. Then, 1.62 mL of fuming nitric acid was added dropwise, the temperature was maintained, and stirring was continued for 1 hour. After allowing to cool, 250 mL of ice water was slowly poured into the system. Further, the pH was adjusted to 8 to 9 using a 10 wt% sodium hydroxide aqueous solution. The precipitated powder was collected by vacuum filtration and washed with 200 mL of distilled water and 100 mL of ethanol to obtain 4.86 g (10.6 mmol) of the intermediate (ii) (yield: 94%).

^{1 1} H-NMR (CDCl ₃ ) δppm: 2.86 (s, 6H), 4.27 (s, 2H), 7.56 (d, J = 8.8Hz, 2H), 7.62 (s, 2H) ), 8.08 (d, J = 8.8Hz, 2H)
¹³ C-NMR (CDCl ₃ ) δppm: 25.7, 32.4, 119.9, 125.6, 127.5, 130.1, 131.1, 137.3, 143.1, 145.9, 162.2
FT-IR cm ^-1 : 1604, 1530, 1487, 1362
LC-MS: 457 [MH] +

7.36 g (132 mmol) of reduced iron and 125 ml of acetic acid were added to the flask and heated to 60 ° C. with stirring. Next, 7.36 g (16.1 mmol) of the intermediate (ii) was added in several portions, and the mixture was stirred at 60 to 70 ° C. for 1 hour. After cooling the reaction solution to 35 ° C. or lower, it was poured into 500 ml of ice water and adjusted to pH 9 with 20% NaOH water. The resulting precipitate was filtered and washed with water. The obtained solid is air-dried at 70 ° C., added to 200 ml of N, N-dimethylformamide (DMF), stirred at 30 ° C. for 2 hours, and the insoluble material is filtered off to remove the obtained filtrate with 1.2 L of water. And stirred at room temperature for 40 minutes. The resulting precipitate was filtered, washed with water, and air-dried at 70 ° C. to obtain 5.52 g (13.9 mmol) of the target alkylene compound. (Yield 86%)
^{1 1} H-NMR (CDCl ₃ ) δppm: 2.65 (s, 6H), 3.97 (s, 2H), 5.91 (s, 4H), 7.32 (s, 2H), 7.37 ( d, J = 8.8Hz, 2H), 8.58 (d, J = 8.8Hz, 2H)
¹³ C-NMR (CDCl ₃ ) δppm: 24.8, 31.3, 116.2, 117.1, 117.4, 120.4, 131.3, 131.7, 141.5, 142.6 158.3
FT-IR cm ^-1 : 3476, 3373, 1627, 1605, 1409, 1359, 1250
LC-MS: 397 [MH] +
The results of the analysis showed that the obtained compound had the structure of formula (1-1).

^１Ｈ−ＮＭＲ（ＤＭＳＯ-ｄ６）δｐｐｍ：２．７０（ｓ，６Ｈ），４．４２（ｓ，２Ｈ），７．５８（ｄ，Ｊ=８．８Ｈｚ，２Ｈ），７．６３（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．０９（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．１３（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ）
^１３Ｃ−ＮＭＲ（ＤＭＳＯ−ｄ６）δｐｐｍ：２４．５，３２．０，１１７．７，１２４．８，１２７．５，１２９．８，１３０．５，１３１.９，１４５．８，１４６．２，１６０．７
ＦＴ−ＩＲ（ＫＢｒ ｄｉｓｋ）ｃｍ^−１：３０４８，１６０２，１５２０，１４９４，１３６３
ＬＣ−ＭＳ：３８９［ＭＨ］＋(Example A-2)
6. 6'-methylenediquinalgin obtained by the method described in the literature (Polymer, volume39, No. 20 (1998), p4949) while charging 55.0 g of concentrated sulfuric acid in a flask and stirring under ice-cooling. 00 g (23.5 mmol) was added. 6.1 g of 60% nitric acid was added dropwise while maintaining 10 ° C. or lower, and stirring was continued at 10 ° C. to 20 ° C. for 1 hour. The reaction solution was poured into 150 ml of ice water, and the pH was adjusted to 3 with a 20 wt% sodium hydroxide aqueous solution. The precipitated powder was collected by vacuum filtration and washed with water to neutrality. The obtained solid was air-dried at 70 ° C., and then the crude product was washed and filtered with 100 ml of hot ethyl acetate and then 60 ml of hot toluene to obtain 6.52 g (16.8 mmol) of the intermediate (iii). (Yield: 72%)

^{1 1} H-NMR (DMSO-d6) δppm: 2.70 (s, 6H), 4.42 (s, 2H), 7.58 (d, J = 8.8Hz, 2H), 7.63 (d, J = 8.8Hz, 2H), 8.09 (d, J = 8.8Hz, 2H), 8.13 (d, J = 8.8Hz, 2H)
¹³ C-NMR (DMSO-d6) δppm: 24.5, 32.0, 117.7, 124.8, 127.5, 129.8, 130.5, 131.9, 145.8, 146.2 , 160.7
FT-IR (KBr disk) cm ^-1 : 3048, 1602, 1520, 1494, 1363
LC-MS: 389 [MH] +

5.30 g of reduced iron and 135 ml of acetic acid were placed in a flask and heated to 50 ° C. with stirring. Next, 4.50 g (11.6 mmol) of the intermediate (iii) was added so as to keep the temperature below 70 ° C. After completion of the addition, stirring was continued at 60 ° C. for 1 hr, the reaction solution was cooled to 35 ° C. or lower, poured into 500 ml of ice water, and adjusted to pH 9 with 20% NaOH water. The resulting precipitate was filtered under reduced pressure over Celite. The solid was collected, air-dried at 70 ° C., added to a mixed solvent of 100 ml of dimethyl sulfoxide (DMSO) and 100 ml of N, N-dimethylformamide (DMF), and stirred at 90 ° C. for 1 hr. The mixture was filtered under reduced pressure over Celite to remove insoluble material, and the obtained filtrate was added to 1 L of water with stirring. The produced precipitate was collected by vacuum filtration, washed with water, and then air-dried at 70 ° C. to obtain 3.80 g (11.6 mmol) of the target alkylene compound. (Yield 100%)
^{1 1} H-NMR (DMSO-d6) δppm: 2.57 (s, 6H), 3.95 (s, 2H), 5.66 (s, 4H), 7.06 (d, J = 8.2Hz, 2H), 7.16 (d, J = 8.2Hz, 2H), 7.23 (d, J = 8.2Hz, 2H), 8.49 (d, J = 8.2Hz, 2H)
¹³ C-NMR (DMSO-d6) δppm: 24.6, 32.1, 115.8, 116.2, 119.5, 130.9, 131.8, 141.5, 147.4, 157.0
FT-IR (KBr disk) cm ^-1 : 3464, 3363, 3315, 3192, 1640, 1591, 1573, 1415, 1365, 801
LC-MS: 329 [MH] +
The results of the analysis showed that the obtained compound had the structure of formula (1-2).

(Example A-3)
Under a nitrogen atmosphere, 10.0 g (25.8 mmol) of the intermediate (iii), 10% Pd-C 1.00 g, 50 ml of ethanol, and 100 ml of tetrahydrofuran (THF) were added to the flask and stirred at room temperature. Then, 12.9 g (257 mmol) of hydrazine monohydrate dissolved in a mixed solution of 20 ml of ethanol and 40 ml of THF was added dropwise. After completion of the dropping, the mixture was stirred at 60 to 65 ° C. for 3 hr. 140 ml of N-methylpyrrolidone (NMP) was added to the reaction mixture to dissolve the precipitate, and then the filtrate obtained by removing Pd-C by filtration was poured into 1800 g of 10% NaCl water and stirred at room temperature for 1 hr. The produced precipitate was collected by vacuum filtration, washed with water, and then air-dried at 70 ° C. to obtain 8.40 g (25.6 mmol) of the target alkylene compound. (Yield 99%)
The results of ¹ H-NMR, ¹³ C-NMR, FT-IR, and LC-MS were in agreement with Example A-2. That is, the result of the analysis showed that the obtained compound had the structure of the formula (1-2).

(Example B-1)
14.1 g (116 mmol) of benzoic acid was weighed in a flask under a nitrogen atmosphere and melted at 140 ° C. To this, 1.44 g (3.62 mmol) of the alkylene compound obtained in Example (A-1) and 5.53 g (19.3 mmol) of tetrachlorphthalic anhydride were added, and the mixture was stirred at 220 ° C. for 4 hours. After allowing to cool, 300 mL of acetone was added to the reaction solution, and the mixture was stirred for 1 hour, and then 4.41 g (3.00 mmol) of quinophthalone compound B-1 as a yellow powder was obtained by vacuum filtration (yield: 83%).
FT-IR cm ^-1 : 3449, 1727, 1622, 1536, 1410, 1363, 1308, 1192, 1112, 737
FD-MS: 1467M +
The results of the analysis showed that the obtained compound had a structure of formula (3-1-i).

(Example B-2)
In a nitrogen atmosphere, 135 g (1.11 mol) of benzoic acid was weighed in a flask and melted at 140 ° C. To this, 3.80 g (11.6 mmol) of the alkylene compound obtained in Example A-2, 18.0 g (62.9 mmol) of tetrachlorphthalic anhydride, and 0.490 g (3.60 mmol) of anhydrous zinc chloride were added. , 220 ° C. for 6 hours. The reaction mixture was cooled to 120 ° C., 300 mL of chlorobenzene was added, the mixture was stirred for 1 hour, and the mixture was filtered under reduced pressure. The obtained solid was washed successively with chlorobenzene, acetone and methanol to obtain 10.5 g (7.5 mmol) of quinophthalone compound B-2 as a yellow powder. (Yield: 65%)
FT-IR cm- ¹ : 1788, 1729, 1688, 1638, 1607, 1537, 1420, 1310, 732
FD-MS: 1400M +
The results of the analysis showed that the obtained compound had the structure of formula (3-2-i).

(Example C-1)
Under a nitrogen atmosphere, 58.0 g (475 mmol) of benzoic acid was weighed in a flask and melted at 140 ° C. To this, 2.00 g (5.03 mmol) of the alkylene compound obtained in Example (A-1) and 5.04 g (17.6 mmol) of tetrachlorphthalic anhydride were added, and the mixture was stirred at 220 ° C. for 4 hours. After allowing to cool, 500 mL of acetone was added to the reaction solution, and after stirring for 1 hour, 6.00 g of quinophthalone compound C-1 as a yellow powder was obtained by vacuum filtration.
As a result of MALDI-MS, it was found that the obtained C-1 was a mixture of the compound of the above formula (3-1-i) and the compound of the above formula (4-1-i).

(Example C-2)
Under a nitrogen atmosphere, 58.0 g (475 mmol) of benzoic acid was weighed in a flask and melted at 140 ° C. To this, 2.00 g (6.09 mmol) of the alkylene compound obtained in Example A-2, 6.09 g (21.3 mmol) of tetrachlorphthalic anhydride, and 0.205 g (1.50 mmol) of anhydrous zinc chloride were added. , 220 ° C. for 6 hours. The reaction mixture was cooled to 120 ° C., 500 mL of chlorobenzene was added, the mixture was stirred for 1 hour, and the mixture was filtered under reduced pressure. The obtained solid was washed successively with chlorobenzene, acetone and methanol to obtain 7.00 g of quinophthalone compound C-2 as a yellow powder.
As a result of MALDI-MS, it was found that the obtained C-2 was a mixture of the compound of the above formula (3-2-i) and the compound of the above formula (4-2-i).

(Pigmentation example 1)
0.500 parts by mass of the quinophthalone compound represented by the formula (3-1-i) obtained in Example B-1 was ground together with 1.50 parts by mass of sodium chloride and 0.750 parts by mass of diethylene glycol. Then, this mixture was poured into 600 parts by mass of warm water and stirred for 1 hour. The water-insoluble matter was separated by filtration, washed well with warm water, and then air-dried at 90 ° C. for pigmentation to obtain a quinophthalone pigment. The average aspect ratio of the obtained pigment particles was less than 3.00, and the average primary particle diameter was 100 nm or less.

(Pigmentation example 2)
Instead of the quinophthalone compound represented by the formula (3-1-i) obtained in Example B-1, the quinophthalone compound represented by the formula (3-2-i) obtained in Example B-2 Pigmentation was carried out in the same manner as in Pigmenting Example 1 except that the above was used to obtain a quinophthalone pigment. The average aspect ratio of the obtained pigment particles was less than 3.00, and the average primary particle diameter was 100 nm or less.

(Example D-1)
0.660 parts by mass of the quinophthalone pigment obtained in Pigmenting Example 1 was placed in a glass bottle, and 0.040 parts by mass of a sulfonic acid derivative (5) synthesized by the method described in JP2013-54200A, propylene glycol monomethyl ether. Add 12.60 parts by mass of acetate, 1.400 parts by mass of BYK LPN-21116 (manufactured by Big Chemie Co., Ltd.), 22.0 parts by mass of 0.3-0.4 mmφ seple beads, and use a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 2 It was dispersed for half an hour to obtain a pigment dispersion. It is shown that the sulfonic acid group in the formula (5) is substituted with any of the hydrogen atoms on the quinoline ring.

Next, 4.00 parts by mass of the pigment dispersion, 0.600 parts by mass of acrylic resin solution Unidic (registered trademark) ZL-295 (manufactured by DIC Corporation), and 0.220 parts by mass of propylene glycol monomethyl ether acetate were placed in a glass bottle. A composition for yellow toning was prepared by shaking.

(Example D-2)
A composition for yellow toning was obtained in the same manner as in Example D-1 except that the quinophthalone pigment obtained in Pigmentization Example 2 was used instead of the quinophthalone pigment obtained in Pigmentization Example 1.

(Comparative Example d-1)
C. I. Pigment Yellow 150 (manufactured by Sanyo Dye Co., Ltd.) 1.14 parts by mass in a poly bottle, propylene glycol monomethyl ether acetate 12.0 parts by mass, BYK LPN-21116 (manufactured by Big Chemie Co., Ltd.) 2.84 parts by mass, 0. 38.0 parts by mass of 3-0.4 mmφ Sepul beads was added and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 4 hours to obtain a pigment dispersion. Further, 2.00 parts by mass of the obtained pigment dispersion, 0.490 parts by mass of acrylic resin solution Unidic (registered brand name) ZL-295 (manufactured by DIC Corporation), and 0.110 parts by mass of propylene glycol monomethyl ether acetate were added. A composition for yellow toning was prepared by putting it in a glass bottle and shaking it.

(Manufacturing Example 1)
C. I. Pigment Green 59 (manufactured by DIC Corporation) 2.48 parts by mass in a glass bottle, propylene glycol monomethyl ether acetate 10.9 parts by mass, BYK LPN-6919 (manufactured by Big Chemie Co., Ltd.) 1.24 parts by mass, acrylic resin solution Uni Dick (registered trademark) ZL-295 (manufactured by DIC Corporation) 1.86 parts by mass, 0.3-0.4 mmφ Sepul beads were added and dispersed with a paint shaker (manufactured by Toyo Seiki Co., Ltd.) for 2 hours to obtain a pigment dispersion. Obtained. Further, 4.00 parts by mass of the obtained pigment dispersion, 0.980 parts by mass of acrylic resin solution Unidic (registered trademark) ZL-295 (manufactured by DIC Corporation), and 0.220 parts by mass of propylene glycol monomethyl ether acetate are placed in a glass bottle. A composition for green toning was prepared by putting it in a container and shaking it.

(Example E-1)
The yellow toning composition obtained in Example D-1 and the green toning composition obtained in Production Example 1 are mixed at a ratio of 39:61 to obtain a green toning composition. It was.

(Example E-2)
The yellow toning composition obtained in Example D-2 and the green toning composition obtained in Production Example 1 are mixed at a ratio of 40:60 to obtain a green toning composition. It was.

(Comparative Example e-1)
The yellow toning composition obtained in Comparative Example d-1 and the green toning composition obtained in Production Example 1 are mixed at a ratio of 66:34 to obtain a green toning composition. It was.

The characteristics of the color filter formed from the green toning compositions obtained in Example E-1 and Example E-2 and Comparative Example e-1 were measured by the following methods. The results are shown in Table 1.

<Color filter characteristic test>
The green toning compositions obtained in Examples and Comparative Examples were each applied on a glass substrate by a spin coater, dried, heated at 230 ° C. for 1 hour, and predetermined when a C light source was used. An evaluation sample showing green chromaticity was obtained. The chromaticity of the evaluation sample is a value obtained by a spectrophotometer (U3900 / 3900H type manufactured by Hitachi High-Tech Science Corporation), and the green chromaticity is used in Japanese Patent Application Laid-Open No. 2015-191208 (0). .224,0.669) was used. The brightness Y of the obtained evaluation sample was measured by a spectrophotometer (U3900 / 3900H type manufactured by Hitachi High-Tech Science Corporation). Further, with respect to the obtained evaluation sample, the thickness of the colored film formed on the glass substrate was measured by a film thickness meter (VS1330 scanning white interference microscope manufactured by Hitachi High-Tech Science Corporation). It can be said that the thinner the film thickness, the higher the coloring power. The results are shown in Table 1.

The quinaldine compound according to the present invention is useful as a raw material compound for producing a quinophthalone compound having excellent coloring power as a pigment.

Claims (6)

An alkylene compound represented by the following formula (1).

[In the formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ] The alkylene compound according to claim 1, wherein Z is a methylene group. The alkylene compound represented by the following formula (1) and the acid anhydride represented by the following formula (2) are condensed to form the first quinophthalone compound represented by the following formula (3) and the following formula (4). A method for producing a quinophthalone compound, comprising a step of obtaining at least one selected from the group from the second quinophthalone compound represented by.

[In the formula (1), X ¹ and X ² each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

[In formula (2), X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom. ]

[In formula (3), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

[In formula (4), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ] The production method according to claim 3, wherein the alkylene compound and the acid anhydride are condensed in the presence of an acid catalyst. A quinophthalone compound represented by the following formula (4).

[In formula (4), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ] A quinophthalone mixture containing a first quinophthalone compound represented by the following formula (3) and a second quinophthalone compound represented by the following formula (4).

[In formula (3), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]

[In formula (4), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ each independently represent a hydrogen atom or a halogen atom, and Z represents an alkylene group having 1 to 3 carbon atoms. ]