JP2012122006A - Compound for dyestuff - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having high molecular absorptivity and a high spectroscopic concentration.SOLUTION: The compound is represented by formula (I), wherein Xdenotes -CO-O-; and Ldenotes an alkanediyl group; Rdenotes an aliphatic hydrocarbon group; Rdenotes a cyano group or the like; Rdenotes a methyl group or the like; Rto Rdenote a hydrogen atom, an amido group or the like; and Adenotes a sodium cation or the like.

Description

  The present invention relates to compounds useful as dyes.

  Conventionally, a dye of a metal complex salt compound has been used for color display using reflected light or transmitted light in various fields (for example, fiber materials, liquid crystal display devices, etc.). Examples of such a dye include C.I. represented by the following formula, which is a dye of a chromium complex having an azo compound as a ligand. I. Solvent Yellow 21 is widely known.

Industrial Dies Chemistry, Properties, Applications, WILEY-VCH, 2003.

  Conventionally known compounds described above have a small molar extinction coefficient and are not sufficiently satisfactory in terms of spectral concentration.

The present invention provides the following [1] to [6].
[1] A compound represented by the formula (I).

［式（Ｉ）中、Ｘ^１は、−ＣＯ−Ｏ−を表す。
Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。
Ｒ^１は、炭素数１〜８のアルキル基を置換基として有していてもよい炭素数３〜１２の１価の脂環式炭化水素基を表す。
Ｒ²は、水素原子、シアノ基、又はカルバモイル基を表す。
Ｒ^３は、炭素数１〜４のアルキル基又はトリフルオロメチル基を表す。
Ｒ^４〜Ｒ^７は、互いに独立に、水素原子、炭素数１〜９のアルキル基、炭素数６〜１０の１価の芳香族炭化水素基、炭素数１〜８のアルコキシ基、ヒドロキシ基、ニトロ基、シアノ基、又は−ＮＲ^１１Ｒ^１２を表し、該アルキル基、該アルコキシ基及び該芳香族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−又は−ＣＯ−で置き換わっていてもよい。Ｒ^４及びＲ^５、Ｒ^５及びＲ^６並びにＲ^６及びＲ^７は、互いに結合してベンゼン環の炭素を含んだ６〜７員環を形成してもよい。
Ｒ^１１及びＲ^１２は、互いに独立に、水素原子、炭素数１〜８の１価の脂肪族炭化水素基、炭素数２〜８のアシル基又はテトラヒドロフルフリル基を表す。Ｒ^１１及びＲ^１２は、互いに結合して窒素原子を含んだ環を形成してもよい。
Ａ^＋は、ヒドロン、ナトリウムカチオン、カリウムカチオン又は炭素数１〜４のテトラアルキルアンモニウムカチオンを表す。］
［２］Ｒ^１が、架橋環式炭化水素基である［１］記載の化合物。
［３］Ｘ^１が、＊−Ｏ−ＣＯ−（＊は、Ｌ^１との結合位置を表す。）である［１］又は［２］記載の化合物。
［４］Ｒ²が、シアノ基である［１］〜［３］のいずれかに記載の化合物。
［５］［１］〜［４］のいずれかに記載の化合物を有効成分とする染料。
［６］［５］記載の染料を含む着色組成物。

[In formula (I), ^{X 1} represents a -CO-O-.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have an alkyl group having 1 to 8 carbon atoms as a substituent.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group.
R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, It represents a nitro group, a cyano group, or —NR ¹¹ R ¹² , and —CH ₂ — contained in the alkyl group, the alkoxy group and the aromatic hydrocarbon group may be replaced by —O— or —CO—. Good. R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.
R ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ]
[2] The compound according to [1], wherein R ¹ is a bridged cyclic hydrocarbon group.
[3] The compound according to [1] or [2], wherein X ¹ is * —O—CO— (* represents a bonding position with L ¹ ).
[4] The compound according to any one of [1] to [3], wherein R ² is a cyano group.
[5] A dye comprising the compound according to any one of [1] to [4] as an active ingredient.
[6] A coloring composition containing the dye according to [5].

  The compound of the present invention has a high molar extinction coefficient and a high spectral concentration.

  The compound of the present invention is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). The compounds of the present invention also include tautomers thereof.

[In formula (I), ^{X 1} represents a -CO-O-.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have an alkyl group having 1 to 8 carbon atoms as a substituent.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group.
R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, It represents a nitro group, a cyano group, or —NR ¹¹ R ¹² , and —CH ₂ — contained in the alkyl group, the alkoxy group and the aromatic hydrocarbon group may be replaced by —O— or —CO—. Good. R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.
R ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ]

X ¹ is * —CO—O— or * —O—CO—, preferably * —O—CO— (* represents a bonding position with L ¹ ). When X ¹ is an ester bond, the solubility in an organic solvent tends to be high, which is preferable.

L ¹ is an alkanediyl group having 1 to 8 carbon atoms, preferably an alkanediyl group having 1 to 4 carbon atoms, and more preferably an alkanediyl group having 1 to 3 carbon atoms.
Examples of the alkanediyl group having 1 to 8 carbon atoms include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and butane-1 , 3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms in R ¹ include monocyclic rings such as a cyclopropyl group, a cyclobutyl group, a cyclobutenyl group, a cyclopentyl group, a cyclopentenyl group, a cyclohexyl group, and a cyclohexenyl group. Alicyclic hydrocarbon group;
And a bridged cyclic hydrocarbon group such as an adamantane-1-yl group, an adamantane-2-yl group, a bicyclo [2.2.1] heptyl group, a tricyclo [5.2.1.0 ^2.6 ] decyl group. It is done.

Examples of the alkyl group having 1 to 8 carbon atoms that the alicyclic hydrocarbon group may have as a substituent include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Linear alkyl groups such as n-hexyl group, n-heptyl group, n-octyl group;
Isopropyl group, isobutyl group, sec-butyl group, isopentyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1- Methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-propylbutyl Group, 1- (1-methylethyl) butyl group, 1- (1-methylethyl) -2-methylpropyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group Group, 5-methylheptyl group, 6-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl 4-ethylhexyl group, 1-n-propylpentyl group, 2-propylpentyl group, 1- (1-methylethyl) pentyl group, 1-butylbutyl group, 1-butyl-2-methylbutyl group, 1-butyl-3 -Methylbutyl group, 1- (1,1-dimethylethyl) butylbutyl group, tert-butyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3- Dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4- Dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethyl Rupentyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1, 1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3- Dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl Group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group 3-ethyl-2-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, 1-propyl-1-methylbutyl group, 1-propyl-2-methylbutyl group, 1 -Propyl-3-methylbutyl group, 1- (1-methylethyl) -1-methylbutyl group, 1- (1-methylethyl) -2-methylbutyl group, 1- (1-methylethyl) -3-methylbutyl group, Examples thereof include branched alkyl groups such as 1,1-diethylbutyl group and 1,2-diethylbutyl group.

  Examples of the monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms having an alkyl group having 1 to 8 carbon atoms as a substituent include methylcyclohexyl group, butylcyclohexyl group, 2-methyladamantan-2-yl Group, 2-methyladamantan-1-yl group, 3-methyladamantan-1-yl group and the like.

R ¹ is preferably a bridged cyclic hydrocarbon group which may have an alkyl group having 1 to 8 carbon atoms as a substituent, and may have an alkyl group having 1 to 8 carbon atoms as a substituent. An adamantyl group is more preferable, and an adamantyl group and a methyladamantyl group are more preferable. When R ¹ is any of these groups, the compound of the present invention has a high spectral concentration and exhibits solubility in an organic solvent.

Preferable -L ¹ -X ¹ -R ¹ includes, for example, groups represented by formula (k-1) to formula (k-7). In formula (k-1) to formula (k-7), * represents a bonding position with a nitrogen atom on the pyridone ring. From the viewpoint of solubility in organic solvents, groups represented by formulas (k-1) to (k-3) are preferred.

R ² is a hydrogen atom, a cyano group, or a carbamoyl group. Among these, a cyano group is preferable because the raw materials are easily available.

R ³ is an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group.
Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, It is a nitro group, a cyano group or —NR ¹¹ R ¹² , and —CH ₂ — contained in the alkyl group, the alkoxy group and the aromatic hydrocarbon group may be replaced by —O— or —CO—. . R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.

R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxy group, a nitro group, or a cyano group. Or it is preferable that it is -NR < ¹¹ > R < ¹² >.

R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, a hydroxy group, a nitro group, or a cyano group. It is more preferable that
When R ^{4 to} R ⁷ are these groups, it is easy to obtain raw materials, and the compound of the present invention tends to exhibit a high spectral concentration.

Examples of the alkyl group having 1 to 8 carbon atoms in R ⁴ to R ^7, for example, same as the above.
Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and the like. .

Examples of the group in which —CH ₂ — contained in the alkyl group is replaced by —O— or —CO— include an alkoxyalkyl group having 2 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a group having 2 to 9 carbon atoms. An alkanoyl group and a C3-C9 alkoxy alkoxycarbonyl group are mentioned.
Examples of the group in which —CH ₂ — contained in the alkoxy group is replaced by —O— or —CO— include an alkoxycarbonyloxy group having 2 to 8 carbon atoms, an alkanoyloxy group having 2 to 9 carbon atoms, and 2 to 2 carbon atoms. 8 alkoxyalkoxy groups.

  Examples of the alkoxyalkyl group having 2 to 8 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, 1-ethoxypropyl group, 2-ethoxypropyl group, 1-ethoxy- 1-methylethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- (1-methylethoxy) propyl group, 1- (1-methylethoxy) -1-methyl Examples include an ethyl group, 2- (1-methylethoxy) -1-methylethyl group, and 3-ethoxypropyl group.

Examples of the alkoxycarbonyl group having 2 to 8 carbon atoms include a methoxycarbonyl group and a tert-butoxycarbonyl group.
Examples of the alkanoyl group having 2 to 9 carbon atoms include acetyl group, propionyl group, isobutyryl group, valeryl group, and isovaleryl group.
Examples of the alkoxyalkoxycarbonyl group having 3 to 9 carbon atoms include a methoxymethoxycarbonyl group, a methoxyethoxycarbonyl group, an ethoxyethoxycarbonyl group, a propoxyethoxycarbonyl group, a butoxyethoxycarbonyl group, and a pentyloxyethoxycarbonyl group.

Examples of the alkoxycarbonyloxy group having 2 to 8 carbon atoms include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an isopropoxycarbonyloxy group, an n-butoxycarbonyloxy group, and an isobutoxycarbonyloxy group. , Sec-butoxycarbonyloxy group, n-pentyloxycarbonyloxy group and the like.
Examples of the alkanoyloxy group having 2 to 9 carbon atoms include an acetyloxy group and a pivaloyloxy group.
Examples of the alkoxyalkoxy group having 2 to 8 carbon atoms include 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 4-methoxybutyl group and 4-ethoxybutyl group. Is mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a benzyl group, and a phenylethyl group.
Examples of the group in which —CH ₂ — contained in the aromatic hydrocarbon group is replaced by —O— or —CO— include a phenoxy group, a benzyloxy group, a benzoyloxy group, a phenoxycarbonyloxy group, and the like.

R ¹¹ and R ¹² are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 2 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include the same groups as those described above.
Examples of the alkenyl group having 2 to 8 carbon atoms include a vinyl group, an isopropenyl group, a pentenyl group, and a hexenyl group.
Examples of the acyl group having 2 to 8 carbon atoms include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, pivaloyl group, and benzoyl group.

Examples of —NR ¹¹ R ¹² in R ^{4 to} R ⁷ include N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, N-propylamino group, N , N-dipropylamino group, N-butylamino group, N, N-dibutylamino group, N-pentylamino group, N-acetylamino group and the like.
Examples of —NR ¹¹ R ¹² in which R ¹¹ and R ¹² are bonded to each other to form a ring containing a nitrogen atom include a 1-pyrazolyl group, a pyrrolidino group, a piperidino group, and a morpholino group.
Among these, N-acetylamino group is preferable in terms of spectral density.

A ⁺ is hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms.
The tetraalkylammonium cation is a quaternary ammonium cation having four alkyl groups, and one alkyl group has 1 to 4 carbon atoms.
Examples of the tetraalkylammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, and a dimethyldibutylammonium cation, and a tetrabutylammonium cation is preferable.

Examples of compound (I) include compound (I-1) to compound (I-78). Y ¹ represents -L ¹ -X ¹ -R ¹ . In Table 1, Y ¹ column, mark the expression number of groups exemplified above.

  Of these, compound (I-49) is preferred because of its high spectral density.

  Compound (I) can be produced by forming a complex using a compound represented by formula (d) (hereinafter sometimes referred to as “compound (d)”) and a chromium compound.

[In formula (d), R ^{1 to} R ⁷ , L ¹ and X ¹ represent the same meaning as described above. ]

As a method for producing the compound (d), it can be produced by diazo coupling a diazonium salt and a pyridone compound as described in JP-B-7-88633.
Specifically, the compound (d) can be produced by diazo coupling a diazonium salt represented by the formula (b) and a pyridone compound represented by the formula (c). The diazonium salt represented by the formula (b) can be obtained, for example, by diazotizing the amine represented by the formula (a) with nitrous acid, nitrite or nitrite.

[In formula (a), formula (b) and formula (c), R ^{1 to} R ⁷ , L ¹ and X ¹ represent the same meaning as described above. A ¹ represents an inorganic anion or an organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like. Examples of the organic anion include CH ₃ —COO ⁻ and C ₆ H ₅ —COO ^— . Preferred are chloride ion, bromide ion and CH ₃ —COO ^— .

Compound (d) in which X ¹ is * —O—CO— (* represents a bonding position with L ¹ ), that is, a compound represented by the formula (da) (hereinafter referred to as “compound (da)”) Will be described.

[In formula (da), R ^{1 to} R ⁷ and L ¹ represent the same meaning as described above. ]

  By diazo coupling a diazonium salt represented by the formula (a2) and a compound represented by the formula (b1) in an aqueous solvent, a compound represented by the formula (ea) (hereinafter “compound”) (E-a) "may be manufactured. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include N-methylpyrrolidone and the like.

[In formula (b1) and formula (ea), R ^{2 to} R ⁷ and L ¹ represent the same meaning as described above. ]

  Next, the compound (da) and the compound represented by the formula (b2) (hereinafter may be referred to as “compound (b2)”) are reacted in the presence of an organic solvent, whereby the compound (da ) Can be obtained. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

[In formula (b2), R ¹ represents the same meaning as described above. Z ¹ represents a chlorine atom or a bromine atom. ]

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform, alcohol solvents such as methanol, ethanol and butanol, and nitro hydrocarbon solvents such as nitrobenzene. And ketone solvents such as methyl isobutyl ketone, and amide solvents such as 1-methyl-2-pyrrolidone.

  The amount of compound (b2) to be used is preferably 1 mol or more and 8 mol or less, more preferably 1 mol or more and 4 mol or less, per 1 mol of compound (ea).

Next, the compound (d) in which X ¹ is * —CO—O— (* represents the bonding position with L ¹ ), that is, the compound represented by the formula (db) (hereinafter “compound (d -B) "may be described.

[In formula (db), R ^{1 to} R ⁷ and L ¹ represent the same meaning as described above. ]

  In the same manner as described above, the diazonium salt (a2) and the pyridone compound represented by the formula (b3) are converted into a compound represented by the formula (eb) in an aqueous solvent (hereinafter referred to as “compound (eb)”. Can be manufactured). The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. Examples of the aqueous solvent include the same solvents as mentioned above.

[In Formula (b3) and Formula (eb), R ^{2 to} R ⁷ and L ¹ represent the same meaning as described above. ]

Next, the compound (eb) and the compound represented by the formula (b4) (hereinafter may be referred to as “compound (b4)”) are reacted in the presence of an organic solvent to give the compound (db). ) Can be obtained. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 50 ° C to 120 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.
R ¹ —OH (b4)
[In formula (b4), R ¹ represents the same meaning as described above. ]
As an organic solvent used here, the same solvent as what is used by reaction with a compound (ea) and a compound (b2) is mentioned.

  The amount of compound (b4) to be used is preferably 1 mol or more and 8 mol or less, more preferably 1 mol or more and 4 mol or less, relative to 1 mol of compound (eb).

In the reaction, it is more preferable to add an acidic catalyst so that the reaction proceeds smoothly.
Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.
Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01 mol or more and 4 mol or less with respect to 1 mol of compounds (b4), More preferably, it is 0.8-2 mol.

  The method for obtaining the target compound (d) (that is, the compound (da) or the compound (db)) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (for example, acetic acid and the like) and water, and the precipitated crystals are collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, and further preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of acid, it is preferable to stir about 0.5 to 2 hours, hold | maintaining at the said temperature. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  In the compound (I), the compound (d) is reacted with the chromium compound in an aqueous solvent (for example, N, N-dimethylformamide, N-methylpyrrolidone, etc.), preferably at 70 to 150 ° C. for 3 to 10 hours. Can be manufactured.

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, ammonium sulfate chromium, and preferably chromium formate, ammonium sulfate, and the like.
It is preferable that the usage-amount of a chromium compound is 0.5-1 mol with respect to 1 mol of compounds (d).

In order to promote the reaction, an inorganic base can be present together.
Examples of the inorganic base include sodium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate, sodium acetate, calcium acetate and the like, preferably sodium carbonate and sodium acetate.

  The method for obtaining the target compound (I) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, it is preferable that the reaction mixture is mixed with an inorganic salt (for example, sodium chloride) and water, and the precipitated crystals are collected by filtration. The inorganic salt is preferably prepared by preparing an aqueous solution of an inorganic salt in advance and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and further preferably 10 ° C. or higher and 25 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an inorganic salt, it is preferable to stir about 0.5 to 2 hours, hold | maintaining at the said temperature. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The compound of the present invention thus obtained is useful as a dye. In addition, since the compound of the present invention has a high spectral density, it is useful as a dye used in color filters, fiber materials, etc. of display devices such as liquid crystal display devices that display colors using reflected light or transmitted light.

The dye of the present invention is a dye containing the compound of the present invention as an active ingredient.
The colored composition of the present invention preferably contains the dye of the present invention as a colorant (hereinafter sometimes referred to as “colorant (A)”) and further contains a resin (B). More preferably, the colored composition of the present invention further contains at least one selected from the group consisting of a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

In addition to the dye of the present invention, the colorant (A) may further contain a pigment and / or a dye different from the dye of the present invention.
As dyes different from the dyes of the present invention, the Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, reactive, direct And dyes classified as (Direct), Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

Examples of the pigment include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metal compounds. Oxides or mixed metal oxides may be mentioned. Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment under the Color Index (published by The Society of Dyers and Colorists). More specifically, the following color index (C.I.
) Numbered pigments, but are not limited thereto.

C. I. Pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the colorant (A) is preferably 5 to 60% by mass with respect to the solid content in the colored composition. Here, solid content means the sum total of the component except a solvent in a coloring composition.
The content of the dye of the present invention contained in the colorant (A) is preferably 3 to 100% by mass.
Dyes and pigments different from the dye of the present invention may be used alone or in combination of two or more with the dye of the present invention.

  The resin (B) is not particularly limited, and any resin may be used. The resin (B) is preferably an alkali-soluble resin, and more preferably a resin containing a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Specific examples of the resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.
The acid value of the resin (B) is preferably 50 to 150, and more preferably 60 to 135.
Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a coloring composition, More preferably, it is 13-60 mass%.

  The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical, an acid, or the like generated from the polymerization initiator (D). For example, the compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned.

The polymerizable compound (C) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The photopolymerizable compounds (C) may be used alone or in combination of two or more.
It is preferable that content of a polymeric compound (C) is 5-65 mass% with respect to solid content of a coloring composition, More preferably, it is 10-60 mass%.

As said polymerization initiator (D), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.
Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.
The polymerization initiators (D) may be used alone or in combination of two or more.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

  Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Chill, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Content of the solvent (E) in a coloring composition becomes like this. Preferably it is 70-95 mass% with respect to a coloring composition, More preferably, it is 75-90 mass%.

  The coloring composition of the present invention may be added as necessary, such as surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc. An agent may be included.

The compounds of the present invention are useful as dyes. Since it has a high molar extinction coefficient and a high spectral density, it is particularly useful as a dye used in a color filter of a display device such as a liquid crystal display device.
In addition, the coloring composition containing the compound of the present invention has various colorings such as a display device (for example, a known liquid crystal display device, an organic EL device) having a color filter as a part of its constituent parts, and a solid-state imaging device. It can be used in a known manner for devices related to images.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on mass unless otherwise specified.

  In the following Examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) and mass spectrometry (LC: Agilent 1200 type, MASS: Agilent LC / MSD type). The maximum absorption wavelength (λmax) was measured with a UV-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm) by preparing a 0.028 g / L ethyl lactate solution. .

[Example 1]
After adding 80 parts of water to 19.4 parts of 5- (N-acetylamino) anthranilic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  On the other hand, 26.0 parts of acetoacetic acid ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.8 parts of methyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.4 parts of 2-aminoethanol (manufactured by Wako Pure Chemical Industries, Ltd.) The parts were mixed and stirred at 95 ° C. for 24 hours. The reaction solution was cooled to room temperature, added to a mixed solution of 304 parts of water and 35 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a residue of suction filter and dried to obtain 20.4 parts represented by the formula (c-1).

  Next, 20.4 parts of the compound represented by the formula (c-1) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 39.1 parts of the compound represented by the formula (d-1).

Next, 37.6 parts of acid chloride (Wako Pure Chemical Industries, Ltd.) represented by the formula (e-1) is added to 39.9 parts of the compound represented by the formula (d-1). The mixture was stirred in methyl pyrrolidone at 70 ° C. for 3 hours. After completion of the reaction, the product was charged in water to obtain 43.8 parts of a compound represented by the formula (d-2). The obtained compound was yellow and the maximum absorption wavelength (λmax) was measured in an ethyl lactate solvent to show 458 nm. The structure was confirmed by ¹ H-NMR.
¹ H-NMR: 1.50 (6H, m), 1.68 (6H, m), 1.78 (6H, m), 2.07 (3H, s), 2.55 (3H, s), 4.12 (2H, t), 4.21 (2H , t), 7.89 (1H, m), 7.99 (1H, d), 8.35 (1H, d), 10.23 (1H, s), 15.73 (1H, s).

  Next, 150 parts of N, N-dimethylformamide, 7.7 parts of ammonium chromium sulfate and 2.6 parts of sodium acetate are added to 9.6 parts of the compound represented by the formula (d-2), and the mixture is about 6 at 135 ° C. Stir for hours to give a dark orange solution. This solution was poured into 20% brine, and the resulting orange solid was filtered, followed by vacuum drying at 60 ° C. to obtain 5.8 parts of a compound represented by the formula (I-49).

Identification of compound represented by formula (I-49) (mass spectrometry) ionization mode = ESI−: m / z = 1170.1 [M−Na] ⁻
Exact Mass: 1193.13

<Measurement of absorbance>
A solution having a concentration of 0.028 g / L was prepared by dissolving 0.35 g of the compound in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to 100 cm ³ . The absorbance at the maximum absorption wavelength (λmax) and the maximum absorption wavelength (λmax) of the solution was measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). It was measured. The results are shown in Table 2.

  In the table, compound (R-1) is C.I. I. Solvent Yellow 21 (Oleosol Fast Yellow 2G; manufactured by Taoka Chemical Industry Co., Ltd.).

[Example 2]
(Preparation of coloring composition)
(A) Colorant: Compound (I-49): Compound synthesized in Example 1 20 parts (B-1) Resin: Methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg KOH / g) 70 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts (D-1) photopolymerization initiator: benzyl dimethyl ketal (Irgacure 651; BASF Japan) 15 parts (E-1) Solvent: 680 parts of ethyl lactate are mixed to obtain a colored composition.

[Production of color filters]
On the glass, the colored composition obtained above is applied by spin coating to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, development is performed with an aqueous potassium hydroxide solution, and the color filter is obtained by heating to 200 ° C. in an oven.

  From the results in Table 2, it can be seen that the compound of the present invention has a high absorbance because of its high absorbance. Moreover, the coloring composition containing the said compound has the outstanding color performance, and it is possible to produce a high quality color filter.

  The compounds of the present invention are useful as dyes. Since the compound of the present invention has a high molar extinction coefficient and a high spectral density, it is particularly useful as a dye for use in a color filter of a display device such as a liquid crystal display device.

Claims (6)

A compound represented by formula (I).

[In formula (I), ^{X 1} represents a -CO-O-.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms.
R ¹ represents a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms which may have an alkyl group having 1 to 8 carbon atoms as a substituent.
R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group.
R ^{4 to} R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, It represents a nitro group, a cyano group, or —NR ¹¹ R ¹² , and —CH ₂ — contained in the alkyl group, the alkoxy group and the aromatic hydrocarbon group may be replaced by —O— or —CO—. Good. R ⁴ and R ⁵ , R ⁵ and R ⁶ , and R ⁶ and R ⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.
R ¹¹ and R ¹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ¹¹ and R ¹² may be bonded to each other to form a ring containing a nitrogen atom.
A ⁺ represents a hydrone, a sodium cation, a potassium cation or a tetraalkylammonium cation having 1 to 4 carbon atoms. ] The compound according to claim 1, wherein R ¹ is a bridged cyclic hydrocarbon group. The compound according to claim ¹ , wherein X ¹ is * —O—CO— (* represents a bonding position with L ¹ ). The compound according to any one of claims 1 to 3, wherein R ² is a cyano group.   The dye which uses the compound in any one of Claims 1-4 as an active ingredient.   A coloring composition comprising the dye according to claim 5.