JP4919629B2 - Croconium dye - Google Patents

Description

  The present invention relates to a novel croconium dye useful as an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, and the like.

  As a near-infrared absorbing dye that does not substantially absorb visible light but absorbs infrared light, a croconium dye is useful and has been actively studied (for example, see Patent Documents 1 to 5). As known croconium dyes, as shown in the general formulas (I) to (III) described in Patent Document 2, a polymethine substituent having a carbocyclic ring or a heterocyclic ring at the terminal is a croconic acid mother nucleus. In which 1 and 3 positions are substituted. Among these, as dyes composed of polymethine having a carbocyclic ring at the end, those having a carbocyclic ring of 2-hydroxy-4-dialkylaminobenzene are known. As this 4-amino group substituted at the 4-position of benzene, a dialkylamino group is known. Changing the functional group on the alkyl group of this dialkylamino group is effective in controlling the various physical properties of the dye (solubility, melting point, association, etc.), but only ether has been known as a substituent on the alkyl group so far. (See, for example, Patent Documents 3 and 5).

JP-A-5-155145 Japanese Patent Laid-Open No. 6-8644 JP 2001-117201 A JP 2001-294785 A JP 2002-286931 A

  An object of the present invention is to provide a novel croconium dye useful as an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material and the like.

  As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the following means.

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

[In the general formula (I), R ¹¹ represents a substituent having a proton with a pKa value of 18 or less, and R ¹² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. However, the total number of atoms other than hydrogen atoms in combination of R ¹¹ and R ¹² bonded to one nitrogen atom is 11 or more. n13 represents an integer of 0 to 4. When n13 is 2 or more, the plurality of R ¹³ may be the same or different and may be bonded to each other to form a ring. ]

(2) The compound according to (1), wherein R ¹¹ in the general formula (I) is a substituent having a proton with a pKa value of 10 to 17.
(3) The compound according to (1) or (2), wherein R ¹¹ in the general formula (I) is a substituent having a hydroxyl group.
(4) The compound according to (1) or (2), wherein R ¹¹ in the general formula (I) is a substituent having two or more hydroxyl groups.
(5) The compound according to any one of (1) to (4), wherein R ¹¹ in the general formula (I) is a substituent having an ether bond.

  ADVANTAGE OF THE INVENTION According to this invention, the novel croconium pigment | dye useful as an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, etc. can be provided.

Hereinafter, embodiments of the present invention will be described in detail. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The compound of the present invention (croconium dye) is represented by the following general formula.

〔一般式（Ｉ）中、Ｒ¹¹はｐＫａ値が１８以下のプロトンを有する置換基を表し、Ｒ¹²は水素原子、脂肪族基、芳香族基または複素環基を表す。ただし、一つの窒素原子に結合するＲ¹¹とＲ¹²とを合わせた水素原子以外の原子の総数は１１以上である。Ｒ¹³は置換基を表す。ｎ１３は０〜４の整数を表す。ｎ１３が２以上の場合、複数のＲ¹³は同一でも異なっていてもよく、互いに結合して環を形成してもよい。〕

[In the general formula (I), R ¹¹ represents a substituent having a proton with a pKa value of 18 or less, and R ¹² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. However, the total number of atoms other than hydrogen atoms in combination of R ¹¹ and R ¹² bonded to one nitrogen atom is 11 or more. R ¹³ represents a substituent. n13 represents an integer of 0 to 4. When n13 is 2 or more, the plurality of R ¹³ may be the same or different and may be bonded to each other to form a ring. ]

  The compound of the present invention can be used as a croconium dye useful as an image forming material, an infrared thermosensitive recording material, an optical recording element and an optical film material.

  In the present specification, the “aliphatic group” is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, a cycloalkyl group, a substituted cycloalkyl group, a cycloalkenyl group, a substituted cycloalkenyl group, Cycloalkynyl group means a substituted cycloalkynyl group. Of these aliphatic groups, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, a cycloalkyl group, a substituted cycloalkyl group, a cycloalkenyl group, and a substituted cycloalkenyl group are preferable.

The alkyl group may be linear or branched. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 18 carbon atoms. The alkyl part of the substituted alkyl group is the same as the alkyl group.
The alkenyl group may be linear or branched. The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkenyl part of the substituted alkenyl group is the same as the alkenyl group.
The alkynyl group may be linear or branched. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the alkynyl group.
The number of carbon atoms of the cycloalkyl group and the cycloalkenyl group is preferably 3 to 20, and the number of carbon atoms of the cycloalkyl part of the substituted cycloalkyl group and the cycloalkenyl part of the substituted cycloalkenyl group is a cycloalkyl group or a cycloalkenyl group. It is the same.

Examples of the substituent in the above-described substituted alkyl group, substituted alkenyl group, substituted alkynyl group, substituted cycloalkyl group, substituted cycloalkenyl group and substituted cycloalkynyl group include the following groups.
Halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl or cycloalkyl group [represents a linear, branched, cyclic substituted or unsubstituted saturated aliphatic group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl. ), A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, such as bicyclo [1,2,2] heptan-2-yl, Bicyclo [2,2,2] octane-3-yl) and a tricyclo structure having more ring structures It is intended to encompass such. An alkyl group (for example, an alkyl group of an alkylthio group) in the partial structure of the substituent described below also represents such an alkyl group. The same applies to a cycloalkyl group. ];

Alkenyl or cycloalkenyl group [represents an aliphatic group having a linear, branched, or cyclic substituted or unsubstituted double bond. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or unsubstituted 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, i.e., a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2 2] is intended to encompass oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 or A monovalent group obtained by removing one hydrogen atom from a 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, more preferably a 5- or 6-membered aromatic having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 30 carbon atoms) Substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyl Xy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having a carbon number of 2 30 substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl group having 2 to 30 carbon atoms) Carbonyloxy group, 6 to 30 carbon atoms Or an unsubstituted arylcarbonyloxy group such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted group having 1 to 30 carbon atoms) Carbamoyloxy group such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxy A carbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn- Hexadecyloxyphenoxycarbonyloxy),

An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms) Groups such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino groups (preferably substituted with 1 to 30 carbon atoms) Or unsubstituted aminocarbonylamino, eg , Carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, Methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonylamino groups such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamo A ruamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl Or an arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonyl Amino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably having 2 to 2 carbon atoms) 30 substituted or unsubstituted heterocyclic thio groups such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio),

Sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N- Acetylsulfamoyl, N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms) , 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl or arylsulfonyl groups (preferably substituted or unsubstituted having 1 to 30 carbon atoms) Replace Alkylsulfonyl group, 6-30 substituted or unsubstituted arylsulfonyl group such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, C2-30 substitution) Or an unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, for example, , Acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably substituted with 7 to 30 carbon atoms or Unsubstituted aryloxy A rubonyl group such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, For example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl)

A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl), aryl or heterocyclic azo group (preferably substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p- Chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted or non-substituted having 2 to 30 carbon atoms) Substituted phosphino groups such as dimethylphosphino, diphenylphosphine , Methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (Preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group (preferably having 2 carbon atoms) -30 substituted or unsubstituted phosphinylamino groups, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, For example, trimethylsilyl, tert-butyldimethylsilyl, phenyldi Chirushiriru)
Etc.

  Among the above functional groups, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl.

  In the present specification, the “aromatic group” means an aryl group and a substituted aryl group. These aromatic groups may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. 6-40 are preferable, as for the carbon atom number of an aromatic group, 6-30 are more preferable, and 6-20 are more preferable. Among them, the aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group.

  The aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group are the same as those described above as examples of the substituent of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, the substituted cycloalkyl group, the substituted cycloalkenyl group, and the substituted cycloalkynyl group. It is.

  In the present specification, the “heterocyclic group” is preferably a 5-membered or 6-membered saturated or unsaturated heterocyclic group. Further, an aliphatic ring, an aromatic ring or another heterocyclic ring may be condensed with the heterocyclic ring of the group. Examples of heteroatoms of the heterocycle include B, N, O, S, Se and Te. Of these, N, O and S are preferred as heteroatoms. The heterocyclic ring preferably has a valence (monovalence) in which the carbon atom is free (the heterocyclic group is bonded at the carbon atom). The number of carbon atoms of a preferable heterocyclic group is 1-40, More preferably, it is 1-30, More preferably, it is 1-20. Examples of the saturated heterocyclic ring include a pyrrolidine ring, a morpholine ring, a 2-bora-1,3-dioxolane ring, and a 1,3-thiazolidine ring. Examples of the unsaturated heterocyclic ring include imidazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, benzoselenazole ring, pyridine ring, pyrimidine ring and quinoline ring. The heterocyclic group may have a substituent. Examples of the substituent are the same as those described above as examples of the substituent of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, the substituted cycloalkyl group, the substituted cycloalkenyl group, and the substituted cycloalkynyl group.

Next, the compound represented by formula (I) will be described.
In the general formula (I), R ¹¹ represents a substituent having a proton with a pKa value of 18 or less. For the definition and description of pKa, see J.H. It is described in pages 248-272 of Advanced Organic Chemistry by March (4th edition, Wiley Interscience, published in 1992). A preferable pKa value is 6 to 18, more preferably 10 to 17, further preferably 12 to 17, and most preferably 14 to 17.
Preferable protons having a pKa of 18 or less include hydroxyl, mercapto, carbamoyl, sulfamoyl, carboxyl, acylamino, sulfo, and sulfonamide protons. More preferably, it is a proton of a hydroxyl group, a carbamoyl group, a sulfamoyl group, a carboxyl group, an acylamino group or a sulfonamide group, more preferably a proton of a hydroxyl group, an acylamino group or a sulfonamide group, and most preferably a hydroxyl group. The proton of the group.

The preferred number of pKa18 or less protons R ¹¹ has is 1 to 5, more preferably 1 to 3, more preferably 1 to 2, and most preferably 2.

The substituent represented by R ¹¹ is preferably an aliphatic group, an aromatic group or a heterocyclic group, and these groups are as described above. R ¹¹ is preferably an aliphatic group or an aromatic group, more preferably an aliphatic group having 1 to 40 carbon atoms or an aromatic group having 6 to 40 carbon atoms. More preferably, it is a C1-C20 aliphatic group, More preferably, it is a C1-C15 alkyl group, Most preferably, it is a C2-C10 alkyl group. However, these substituents have at least one pKa18 or less proton, that is, a substituent substituted with a group having the proton.
From the above viewpoint, in the compound of the present invention, R ¹¹ is preferably a substituent having a hydroxyl group, and more preferably a substituent having two or more hydroxyl groups. Moreover, as said R11, the substituent which has an ether bond is also preferable.

It is also preferred that a substituent is further bonded to R ¹¹ in addition to a group having a pKa 18 or less proton. Examples of the substituent are the same as those described above as examples of the substituent of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group, substituted cycloalkyl group, substituted cycloalkenyl group and substituted cycloalkynyl group. It is done. Of these, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, nitro groups, alkoxy groups, aryloxy groups, silyloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups are preferred. , Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, alkylthio group, arylthio group, Heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, imide group Phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, silyloxy Group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino Group, aryloxycarbonyl group and alkoxycarbonyl group, more preferably halogen atom, alkyl group, aryl group, cyano group, alkoxy group, aryloxy group and silyloxy group, Mashiku is an alkoxy group and an aryloxy group, and most preferably an alkoxy group.

In the general formula (I), R ¹² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and these groups are as described above. R ¹² is preferably a hydrogen atom, an aliphatic group and an aromatic group, more preferably a hydrogen atom, an aliphatic group having 1 to 40 carbon atoms and an aromatic group having 6 to 40 carbon atoms. R ¹² is more preferably a hydrogen atom and an aliphatic group having 1 to 30 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom or an unsubstituted C 1 to C 1 group. Or an alkyl group having 1 to 20 carbon atoms substituted by a hydroxyl group, a halogen atom, a heterocyclic group, a cyano group, a carboxyl group, an alkoxy group or a sulfo group.

In the general formula (I), the total number of atoms other than hydrogen atoms in combination of R ¹¹ and R ¹² bonded to one nitrogen atom is 11 or more. The total number of atoms is preferably 11-40.

In the general formula (I), R ¹³ represents a substituent. Examples of the substituent include substitution of the aforementioned substituted alkyl group, substituted alkenyl group, substituted alkynyl group, substituted cycloalkyl group, substituted cycloalkenyl group and substituted cycloalkynyl group. The thing similar to what was mentioned as an example of group is mentioned. R ¹³ is preferably a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group , Acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or aryl Sulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl , Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, more preferably halogen atom, alkyl group , Aryl group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group , Sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group A phosphinyloxy group, a phosphinylamino group, and a silyl group, and more preferably a halogen atom, an alkyl group, an aryl group, a cyano group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, a silyloxy group, and an amino group. Group, acylamino group, alkylthio group, arylthio group, acyl group, carbamoyl group, silyl group, more preferably halogen atom, cyano group, hydroxyl group, carboxyl group, and alkyl group having 1 to 20 carbon atoms, alkoxy group, A silyloxy group, an amino group, an acylamino group, an alkylthio group, an acyl group, a carbamoyl group, a silyl group, and an aryl group having 6 to 20 carbon atoms, an aryloxy group, an arylthio group, and more preferably a halogen atom, a cyano group, a hydroxyl group A group and 1 to 1 carbon atoms 12 alkyl groups, alkoxy groups, amino groups, and aryl groups and aryloxy groups having 6 to 12 carbon atoms, more preferably halogen atoms, hydroxyl groups, and alkyl groups and alkoxy groups having 1 to 8 carbon atoms. . Most preferred R ¹³ is a hydroxyl group.

R ¹³ is preferably bonded to R ¹¹ or R ¹² to form a 5- to 7-membered ring.

n13 represents the integer of 0-4, Preferably it is 0-3, More preferably, it is 1-2, More preferably, it is 1. When n13 is 2 or more, the plurality of R ¹³ may be the same or different and may be bonded to each other to form a ring.

  Next, although the specific example (Exemplary compound (1)-(C-30) of a compound represented by general formula (I) of this invention is shown, this invention is not limited to these.

  The compound of the present invention can be synthesized by dehydration condensation of croconic acid and an aniline compound with reference to the method described in Liebigs Annalen der Chemie, pages 935 to 939 (1993). The molar ratio of the aniline compound to 1 mol of croconic acid is preferably 1.5 to 3, more preferably 1.8 to 2.5, and particularly preferably 1.9 to 2.1. Examples of the solvent that can be used for the dehydration condensation include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane). ), Sulfoxide solvents (eg, dimethyl sulfoxide), ureido solvents (eg, tetramethylurea), ether solvents (eg, dioxane, cyclopentyl methyl ether), ketone solvents (eg, acetone, cyclohexanone), hydrocarbons Solvent (for example, toluene, xylene, mesitylene, n-octane), halogen-based solvent (for example, tetrachloroethane, chlorobenzene), alcohol-based solvent (for example, 1-butanol, ethylene glycol, cyclohexanol), carboxylic acid solvent (for example, vinegar ) Can be used alone or in combination with. In the dehydration condensation, preferably no solvent, hydrocarbon solvent, halogen solvent, alcohol solvent, ether solvent and carboxylic acid solvent, more preferably hydrocarbon solvent, halogen solvent and alcohol solvent. It is.

  The reaction temperature in the dehydration condensation is from 0 to 250 ° C., preferably from 50 to 200 ° C., more preferably from 60 to 150 ° C., preferably in the range of the reaction time from 5 minutes to 30 hours.

  In the dehydration condensation, it is also preferable to remove by-product water out of the system during the reaction. As a method of removing the by-produced water out of the system, a method of distilling alone or with a solvent under reduced pressure or normal pressure, a method using an absorbent such as molecular sieve, or a dehydrating condensing agent such as acetic anhydride is used. The method used is preferably used.

  The aniline compound as the raw material of the present invention can be synthesized with reference to the method described in JP-A-10-29976.

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

[Example 1]
Based on the following reaction, an exemplary compound (C-2) of the present invention was synthesized.

  Into a three-necked flask, 57.1 g of compound (1), 14.2 g of compound (2), 400 ml of 1-butanol, and 700 ml of toluene were added and stirred for 1 hour while partially distilling off the solvent under heating and reflux conditions. The obtained sample was cooled to room temperature, and the precipitated crystals were collected by filtration and dried to obtain 35.2 g of the target exemplified compound (C-2) (yield 52%). About the obtained compound, the spectral absorption of the diluted solution which uses tetrahydrofuran as a solvent was measured, and (lambda) max = 828nm was observed.

[Example 2]
Based on the following reaction, Exemplified Compound (C-5) was synthesized.

  92.3 g of compound (3), 14.2 g of compound (2), 600 ml of 1-butanol, and 700 ml of toluene were placed in a three-necked flask, and the mixture was stirred for 1 hour under heating and refluxing conditions while partially distilling off the solvent. The obtained sample was cooled to room temperature, and the precipitated crystals were collected by filtration and dried to obtain 48.4 g of the target exemplified compound (C-5) (yield 47%). About the obtained compound, the spectral absorption of the diluted solution which uses tetrahydrofuran as a solvent was measured, and (lambda) max = 828nm was observed.

[Example 3]
Based on the following reaction, Exemplified Compound (C-8) was synthesized.

  Into a three-necked flask, 57.1 g of compound (4), 14.2 g of compound (2), 800 ml of 1-butanol and 500 ml of toluene were added and stirred for 1 hour while partially distilling off the solvent. The obtained sample was cooled to room temperature, and the precipitated crystals were collected by filtration and dried to obtain 28.4 g of the target exemplified compound (C-8) (42% yield). About the obtained compound, the spectral absorption of the diluted solution which uses tetrahydrofuran as a solvent was measured, and (lambda) max = 831nm was observed.

[Example 4]
Based on the following reaction, Exemplified Compound (C-17) was synthesized.

  In a three-necked flask, 53.9 g of compound (5), 14.2 g of compound (2), 500 ml of 1-butanol, and 700 ml of toluene were added and stirred for 1 hour while partially distilling off the solvent. The obtained sample was cooled to room temperature, and the precipitated crystals were collected by filtration and dried to obtain 31.6 g of the target exemplified compound (C-17) (yield 49%). About the obtained compound, the spectral absorption of the diluted solution which uses tetrahydrofuran as a solvent was measured, and (lambda) max = 830nm was observed.

  The compounds of the present invention are useful as near infrared absorbing dyes. For this reason, the compound of the present invention is useful as an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, and the like, and has high industrial applicability.

Claims (3)

A compound represented by the following general formula (I):

[In general formula (I), R ¹¹ represents a substituent having a hydroxyl group , and R ¹² represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. However, the total number of atoms other than hydrogen atoms in combination of R ¹¹ and R ¹² bonded to one nitrogen atom is 11 or more. R ¹³ represents a substituent. R ¹³ may combine with R ¹¹ or R ¹² to form a 5- to 7-membered ring. n13 represents an integer of 0 to 4. When n13 is 2 or more, the plurality of R ¹³ may be the same or different and may be bonded to each other to form a ring. ] The compound according to claim 1 , wherein R ¹¹ in the general formula (I) is a substituent having two or more hydroxyl groups. The compound according to claim 1 or 2 , wherein R ¹¹ in the general formula (I) is a substituent having an ether bond.