JP4951295B2 - Process for producing near-infrared absorbing dye compound - Google Patents

Description

  The present invention relates to a method for producing a near-infrared absorbing dye compound useful as an image forming material, an infrared thermosensitive recording material, an optical recording element, an optical film material, and the like. More specifically, the present invention relates to a cheap, simple and high-yield production method for aminium salts and diimonium salts which are near-infrared absorbing dye compounds.

Aminium dyes and diimonium dyes are useful as near-infrared absorbing dyes that do not substantially absorb visible light but absorb infrared rays, and have been actively studied (for example, Patent Documents 1 to 3).
Conventionally, in order to produce aminium dyes and diimonium dyes, a precursor amino compound is oxidized with Cu ²⁺ (for example, Patent Documents 4 and 5), a method of oxidizing with Fe ³⁺ (for example, Patent Documents 6 and 7), a solid catalyst. (For example, Patent Document 8), oxidation with peroxodisulfate (for example, Patent Document 9), oxidation with silver hexafluoroantimonate (for example, Non-Patent Document 1), and electrical oxidation (for example, Patent Although methods such as literature 10) are known, none of them is satisfactory in terms of yield, and there are problems such as high environmental burden and high cost by using heavy metal ions.
JP 2003-280247 A Japanese Patent Laid-Open No. 2003-29596 JP 2004-145036 A Japanese Patent Publication No.59-40825 JP-A-63-51462 Japanese Patent Laid-Open No. 2-311447 Japanese Patent Laid-Open No. 11-315054 JP-A-5-98243 JP 2003-55643 A JP-A 61-246391 Journal of Dispersion Science and Technology, 23, 555 pages (2002)

  An object of the present invention is to provide an inexpensive, simple, and high-yield production method for aminium salts and diimonium salts, which are near infrared absorbing dye compounds useful as image forming materials, infrared thermosensitive recording materials, optical recording elements, and optical film materials. It is to provide.

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

(1), characterized in that it comprises the following general formula reacting the salt of peroxomonosulfuric acid consisting composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4 and the compound represented by (I), the near infrared absorbing dye Compound production method.

In the general formula (I), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ , R ¹³² , R ¹⁴¹ and R ¹⁴² each independently represents a hydrogen atom, an aliphatic group or an aromatic group, R ¹⁰³ , R ¹¹³ , R ¹²³ , R ¹³³ and R ¹⁴³ each independently represent a substituent, and n ₁₀₃ , n ₁₁₃ , n ₁₂₃ , n ₁₃₃ and n ₁₄₃ each independently represent an integer of 0 to 4 .

In the general formula (II), R ²¹¹ , R ²¹² , R ²²¹ , R ²²² , R ²³¹ , R ²³² , R ²⁴¹ and R ²⁴² each independently represent a hydrogen atom, an aliphatic group or an aromatic group, R ²⁰³ , R ²¹³ , R ²²³ , R ²³³ and R ²⁴³ each independently represent a substituent, n ₂₀₃ , n ₂₁₃ , n ₂₂₃ , n ₂₃₃ and n ₂₄₃ each independently represent an integer of 0 to 4, and X is monovalent Or it represents a divalent anion, n ₂₅₃ represents 1 or 2, and the product of the valence of X and n ₂₅₃ is 2.
(2 ) The production method according to (1 ), wherein X is a divalent anion.
( 3 ) The production method according to (1) or (2) , wherein an acid or a salt thereof coexists in the step.
( 4 ) The production method according to ( 3 ), wherein the acid or a salt thereof is perchloric acid or a perchlorate.
( 5 ) The production method according to any one of (1) to ( 4 ), wherein at least the starting temperature of the reaction is −30 ° C. to 20 ° C.
( 6 ) The production method according to any one of (1) to ( 5 ), wherein the near-infrared absorbing dye compound produced by the reaction is obtained in a yield of 90% or more.

  The present invention provides an inexpensive, simple, and high-yield production method for aminium salts and diimonium salts, which are useful as near-infrared absorbing dye compounds as image forming materials, infrared thermosensitive recording materials, optical recording elements, and optical film materials. be able to.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, an aliphatic group means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The alkyl group may have a branch and may form a ring (that is, a cycloalkyl group). The number of carbon atoms in the alkyl group is preferably 1-20, and more preferably 1-18. The alkyl part of the substituted alkyl group is the same as the above alkyl group. The alkenyl group may have a branch, or may form a ring (that is, a cycloalkenyl group). The alkenyl group has preferably 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 above alkenyl group. The alkynyl group may have a branch, and may form a ring (that is, a cycloalkynyl group). The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 18 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. The alkyl part of the aralkyl group and the substituted aralkyl group is the same as the above alkyl group. The aryl part of the aralkyl group and the substituted aralkyl group is the same as the following aryl group.

  Examples of the substituent of the alkyl part of the substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group include a halogen atom (for example, chlorine atom, bromine atom, iodine atom), alkyl group [straight chain, branched, cyclic Represents a substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-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, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. 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 substituted groups having 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, that is, 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] 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, aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound A monovalent group in which one hydrogen atom is removed from, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2 -Pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group Preferably, it is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably having a carbon number) 6 to 30 substituted or unsubstituted aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably carbon 3 to 20 silyloxy groups such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, 1-phenyltetrazole- 5-oxy, 2-tetrahydropyranyloxy ,

Acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy , Stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy, N, N -Diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms) Aryloxycarbonyloxy group of, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or non-substituted with 1 to 30 carbon atoms) Substituted alkylamino groups, substituted or unsubstituted anilino groups having 6 to 30 carbon atoms such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), acylamino groups (preferably Or a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroyl Amino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as 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, Butoxycarbonyl, ethoxycarbonylamino, t-butoxycarbonylamino, n- octadecyloxycarbonylamino amino, N- methyl - methoxycarbonylamino)

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms such as methylsulfonylamino, Rusulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, For example, methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably Is a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted group having 0 to 30 carbon atoms). Substitute sulfamo Groups 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 substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, Methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms) Sulfoni Group, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substitution having 7 to 30 carbon atoms) Or an unsubstituted arylcarbonyl group, a heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p -N-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms such as phenoxycarbonyl, o- Chlorophenoxy Cicarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxy Carbonyl, 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- (methylsulfonyl) 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), an imide group (preferably N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, For example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphini 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 to 30 carbon atoms) A substituted or unsubstituted phosphinylamino group such as dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms such as trimethylsilyl , T-butyldimethylsilyl, phenyldimethylsilyl).

  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.

  Examples of the substituent of the aryl moiety of the substituted aralkyl group include the substituents of the following substituted aryl group.

  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. The number of carbon atoms in the aromatic group is preferably 6 to 40, more preferably 6 to 30, and still more preferably 6 to 20. Among them, the aryl group is preferably phenyl or naphthyl, particularly preferably phenyl.

  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 include the groups exemplified above as the substituent of the alkyl portion of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group.

Next, the compounds represented by the general formulas (I) and (II) will be described.
In general formula (I), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ , R ¹³² , R ¹⁴¹ and R ¹⁴² are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Preferably they are a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, and a C6-C20 aryl group, More preferably, it is C1-C20 An alkyl group having 10 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms and an aryl group having 6 to 8 carbon atoms, most preferably Is an alkyl group having 2 to 6 carbon atoms. It is also preferred that all of R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ , R ¹³² , R ¹⁴¹ and R ¹⁴² are the same.

R ¹⁰³ , R ¹¹³ , R ¹²³ , R ¹³³ and R ¹⁴³ are preferably halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, cyano groups, hydroxyl groups, carboxyl groups, alkoxy groups, aryloxy groups, silyloxy groups , 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, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group An acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group, more preferably a halogen atom, an alkyl group, Alkenyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, amino group, alkylthio group, arylthio group, imide group, silyl group, more preferably halogen atom, alkyl group , An aryl group, an alkoxy group, an aryloxy group, a silyloxy group, and an amino group, and most preferably an alkyl group. It is also preferred that all of R ¹¹³ , R ¹²³ , R ¹³³ and R ¹⁴³ are the same.

n ₁₀₃ , n ₁₁₃ , n ₁₂₃ , n _133, and n ₁₄₃ are preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and most preferably 0.

In the general formula (II), R ²¹¹ , R ²¹² , R ²²¹ , R ²²² , R ²³¹ , R ²³² , R ²⁴¹ and R ²⁴² are synonymous with the aforementioned R ^{111 and the} like, and preferred ranges are also the same. It is also preferred that all of R ²¹¹ , R ²¹² , R ²²¹ , R ²²² , R ²³¹ , R ²³² , R ²⁴¹ and R ²⁴² are the same.

R ²⁰³ , R ²¹³ , R ²²³ , R ²³³ and R ²⁴³ have the same meaning as R ¹⁰³ described above, and the preferred range is also the same. It is also preferable that all of R ²¹³ , R ²²³ , R ²³³ and R ²⁴³ are the same.

n ₂₀₃ , n ₂₁₃ , n ₂₂₃ , n ₂₃₃ and n ₂₄₃ have the same meanings as n ₁₀₃ described above, and the preferred ranges are also the same.

X represents a monovalent or divalent anion, and X as the monovalent anion is preferably a perchlorate ion, a carboxylate ion, a sulfonate ion, a hexafluorophosphate ion, a tetrafluoroborate ion or a hexavalent ion. A fluoroantimonate ion, more preferably a perchlorate ion, a sulfonate ion, a hexafluorophosphate ion, a tetrafluoroborate ion or a hexafluoroantimonate ion, and more preferably a perchlorate ion or a hexafluorophosphorus ion. Acid ion, tetrafluoroborate ion or hexafluoroantimonate ion, most preferably perchlorate ion. X that is a divalent anion is preferably carbonate ion, sulfate ion, oxalate ion, succinate ion, malonate ion, chromate ion, dichromate ion, tetraborate ion, more preferably carbonate ion, Sulfate ions, oxalate ions, and tetraborate ions, more preferably carbonate ions and sulfate ions, and more preferably sulfate ions.
n ₂₅₃ represents 1 or 2, and the product of the valence of X and n ₂₅₃ is 2.

Specific examples of the compounds represented by the general formulas (I) and (II) of the present invention are shown below, but the present invention is not limited thereto.
(Compound represented by formula (I))

(Compound represented by formula (II))

The salt of peroxomonosulfuric acid (molecular formula: H ₂ SO ₅ ) used in the present invention is 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ , and examples thereof include OXONE (trade name) of DuPont. It is done.

It is preferable that an acid or a salt thereof coexists in the oxidation step of the present invention.
Examples of such acids (protons) or salts thereof include perchloric acid, benzoic acid, hexafluorophosphoric acid, tetrafluoroboric acid, p-toluenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, An acid such as naphthalene-1,5-disulfonic acid, trifluoroacetic acid, hexafluoroantimonic acid, trifluoromethanesulfonic acid, molybdic acid or its ammonium salt, lithium salt, sodium salt, potassium salt, magnesium salt, preferably Chloric acid, hexafluorophosphoric acid, tetrafluoroboric acid, methanesulfonic acid, hexafluoroantimonic acid or trifluoromethanesulfonic acid proton, ammonium salt, sodium salt or potassium salt, more preferably perchloric acid, hexafluoro phosphoric acid Proton of tetrafluoroboric acid or hexafluoroantimonate, sodium and potassium salts, and most preferably perchloric acid, sodium perchlorate or potassium perchlorate.

  The ratio of the raw materials used for the reaction is preferably 0.1 to 10 moles, more preferably 1 to 6 moles, more preferably 1 to 1 mole of peroxomonosulfate with respect to 1 mole of the compound represented by the general formula (I). .5 to 5 mol, more preferably 2 to 4 mol is used.

  The acid or salt thereof is preferably 0.5 to 20 mol, more preferably 1 to 10 mol, and still more preferably 1.5 to 5 mol, relative to 1 mol of the compound represented by the general formula (I). More preferably, 2 to 4 mol is used.

  Examples of the solvent used in the reaction include water, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) sulfoxide solvents (for example, dimethyl). Sulfoxide), ureido solvent (eg tetramethylurea), ether solvent (eg dioxane, cyclopentylmethyl ether), ketone solvent (eg acetone, cyclohexanone), hydrocarbon solvent (eg toluene, xylene, n-decane), Halogen solvents (eg tetrachloroethane, chlorobenzene), alcohol solvents (eg methanol, ethanol, isopropyl alcohol, ethylene glycol, cyclohexanol, phenol), pyridine solvents (eg pyridine, γ- Choline, 2,6-lutidine), ester solvents (e.g. ethyl acetate, butyl acetate), carboxylic acid solvents (e.g. acetic acid, propionic acid) and nitrile-based solvents (e.g., acetonitrile) is used alone or in combination. Of these, water, amide solvent, sulfone solvent, sulfoxide solvent, ureido solvent, halogen solvent, alcohol solvent, pyridine solvent, ester solvent, carboxylic acid solvent, and nitrile solvent are preferable. Preferably, water, amide solvent, sulfone solvent, ureido solvent, halogen solvent, alcohol solvent, ester solvent and nitrile solvent, more preferably water, sulfone solvent, alcohol solvent, ester solvent. And nitrile solvents. It is also preferable to use water and another solvent in combination.

  The reaction temperature is −30 to 250 ° C., preferably −10 to 150 ° C., more preferably −5 to 100 ° C., still more preferably 0 to 70 ° C., and still more preferably 10 to 50 ° C. It is also preferable to carry out at 5 to 20 ° C. and raise the temperature to 25 to 100 ° C. from the middle.

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

Reference Example 1 Synthesis of Exemplary Compound (I-10) Exemplary Compound (I-10) was synthesized according to the following scheme.

Synthesis of compound 2:
Into a three-necked flask was placed 56.5 g of p-phenylenediamine, 495 g of p-nitrochlorobenzene (1), 173.7 g of potassium carbonate, 750 ml of 1-methyl-2-pyrrolidone, and 10 g of copper powder. Was stirred. This was cooled to room temperature, and the obtained crystal was washed with 1-methyl-2-pyrrolidone and water, and then air-dried to obtain 297.3 g of the target compound 2 (yield 96%). When the mass spectrum of this product was measured, M = 592 was obtained.
Melting point: 300 ° C or higher

Synthesis of compound 3:
Add a solution consisting of 160 g of compound 2, 0.32 g of iron (III) chloride and 160 ml of isopropyl alcohol, 8.1 g of activated carbon and 1340 ml of 1-methyl-2-pyrrolidone in a three-necked flask and heat to an internal temperature of 100 ° C. Stir. To this, 450 g of hydrazine monohydrate (80% aqueous solution (HH-80)) was added dropwise over 1 hour, and the mixture was heated and stirred for 5 hours at an internal temperature of 100 to 110 ° C. did. After filtering this product to remove activated carbon and the like, 800 ml of methanol and 1200 ml of water were continuously added dropwise thereto, and the resulting crystals were suction filtered and dried to obtain 125.2 g of the desired compound 3 (yield). Rate 98%). When the mass spectrum of this product was measured, M = 472 was obtained.
Melting point: 300 ° C or higher

Synthesis of Exemplified Compound (I-10):
In a three-necked flask, 47.3 g of Compound 3, 165.9 g of potassium carbonate, and 300 ml of 1-methyl-2-pyrrolidone were added and stirred while heating. At an internal temperature of 80 ° C., 220.8 g of 1-iodobutane was 1 It was added dropwise over time. After stirring for 3 hours at an internal temperature of 82 to 93 ° C., the mixture was cooled to room temperature, extracted by adding 1000 ml of ethyl acetate and 1000 ml of water, and the resulting ethyl acetate layer was washed with 1000 ml of water three times. The residue obtained by concentration on a rotary evaporator was purified by silica gel column chromatography to obtain 88.5 g of the desired exemplified compound (I-10) (yield 96%). When the mass spectrum of this product was measured, M = 920 was obtained.
Melting point: 104.5 ° C

Example 1 Synthesis of Exemplary Compound (II-3) Exemplary Compound (II-3) was synthesized according to the following scheme.

9.21 g of Exemplified Compound (I-10) was dissolved in 120 ml of ethyl acetate in a 3 neck Slasco, and 40 ml of acetonitrile was added and stirred at room temperature. DuPont Oxone here (OXONE; trade name, purchased from Sigma Aldrich _Japan, consisting of the composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4) and 12.3g of sodium perchlorate 2.44g in 40ml water The dissolved aqueous solution was added dropwise over 30 minutes and then stirred for 3 hours. This was separated, washed three times with a mixture of 60 ml of water and 10 ml of saturated brine, and then concentrated with a rotary evaporator. Ethyl acetate was added to the resulting residue, and the resulting crystals were filtered. It was dried to obtain 10.4 g of the target exemplified compound (II-3) (yield 93%). When the mass spectrum of this product was measured without ionization, a result of M / E = 460 was obtained. Further, when the DSC of this product was measured, the results were as follows: a heat generation start temperature of 186 ° C. and a heat generation amount of 1,420 J / g.

Example 2 Synthesis of Exemplary Compound (II-3) Exemplary Compound (II-3) was synthesized according to the following scheme.

9.21 g of Exemplified Compound (I-10) was dissolved in 120 ml of ethyl acetate in a 3 neck Slasco, and 40 ml of acetonitrile was added and stirred at room temperature. Here DuPont oxone (OXONE; trade name, purchased from Sigma Aldrich _Japan, consisting of the composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4) and 12.3g of potassium perchlorate 2.77g in 40ml water The dissolved aqueous solution was added dropwise over 30 minutes and then stirred for 3 hours. This was separated, washed three times with a mixture of 60 ml of water and 10 ml of saturated brine, and then concentrated with a rotary evaporator. Ethyl acetate was added to the resulting residue, and the resulting crystals were filtered. It was dried to obtain 10.6 g of the target exemplified compound (II-3) (yield 95%). When the mass spectrum of this product was measured without ionization, a result of M / E = 460 was obtained.

Example 3 Synthesis of Exemplary Compound (II-15) Exemplary Compound (II-15) was synthesized according to the following scheme.

10.3 g of Exemplified Compound (I-11) was dissolved in 120 ml of ethyl acetate in a 3 neck Slasco, and 40 ml of acetonitrile was added thereto and stirred at room temperature. Here DuPont oxone (OXONE; trade name, purchased from Sigma Aldrich _Japan, consisting of the composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4) and 12.3g of potassium perchlorate 2.77g in 40ml water The dissolved aqueous solution was added dropwise over 30 minutes and then stirred for 3 hours. This was separated, washed three times with a mixture of 60 ml of water and 10 ml of saturated brine, and then concentrated with a rotary evaporator. Ethyl acetate was added to the resulting residue, and the resulting crystals were filtered. It dried and obtained 11.2 g of target exemplary compound (II-15) (yield 91%). When the mass spectrum of this product was measured without ionization, a result of M / E = 516 was obtained.

Example 4 Synthesis of Exemplary Compound (II-7) Exemplary Compound (II-7) was synthesized according to the following scheme.

11.46 g of Exemplified Compound (I-15) was dissolved in 150 ml of ethyl acetate in a 3 neck Slasco, 50 ml of acetonitrile was added thereto and stirred at room temperature. Here DuPont oxone (OXONE; trade name, purchased from Sigma Aldrich _Japan, consisting of the composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4) and 12.3g over 30 minutes an aqueous solution prepared by dissolving in water 40ml After dropping, the mixture was stirred for 3 hours. Next, an aqueous solution in which 2.77 g of potassium perchlorate was dissolved in 40 ml of water was added thereto and stirred as it was for 1 hour. This was separated, washed three times with a mixture of 60 ml of water and 10 ml of saturated brine, and then concentrated with a rotary evaporator. Ethyl acetate was added to the resulting residue, and the resulting crystals were filtered. By drying, 12.10 g of the target exemplified compound (II-7) was obtained (yield 90%). When the mass spectrum of this product was measured without ionization, a result of M / E = 572 was obtained.

Example 5 Synthesis of Exemplary Compound (II-33) Exemplary Compound (II-33) was synthesized according to the following scheme.

In a three-necked flask, 9.21 g of Exemplified Compound (I-10) was dissolved in 120 ml of ethyl acetate, 40 ml of acetonitrile was added, and the mixture was stirred at room temperature. Here DuPont oxone (OXONE; trade name, purchased from Sigma Aldrich _Japan, consisting of the composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4) aqueous solution of 12.3g and 1.96g sulfuric acid was dissolved in 40ml water Was added dropwise over 30 minutes, followed by stirring for 3 hours. This was separated, washed three times with a mixture of 60 ml of water and 10 ml of saturated brine, and then concentrated with a rotary evaporator. Ethyl acetate was added to the resulting residue, and the resulting crystals were filtered. It dried and obtained 9.4g of target exemplary compound (II-33) (yield 92%). When the mass spectrum of this product was measured without ionization, a result of M / E = 460 was obtained.

Example 6 Synthesis of Exemplified Compound (II-3) 9.21 g of Exemplified Compound (I-10) was dissolved in 120 ml of acetonitrile in a 3-necked Slasco and stirred at room temperature. Here DuPont oxone (OXONE; trade name, purchased from Sigma Aldrich _Japan, consisting of the composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4) was added to 12.3 g, followed by stirring for 3 hours. After adding 3.9 g of sodium perchlorate to the filtrate obtained by filtering the crystals from this, the mixture was stirred as it was for 1 hour, 40 ml of ethyl acetate and 100 ml of water were added and stirred, and the resulting crystals were filtered, By drying, 11.0 g of the target exemplified compound (II-3) was obtained (yield 98%). When the mass spectrum of this product was measured without ionization, a result of M / E = 460 was obtained.

As described above, according to the present invention, by using peroxomonosulfuric acid as an oxidizing agent, a diimmonium compound was obtained with a high yield of 90% or more. In particular, when a divalent diimmonium compound is produced as described in the above examples, in Example 4 of JP-A-2003-55643, when peroxodisulfuric acid is used, the yield is as low as 60%. By using peroxomonosulfuric acid, it was possible to produce a diimmonium compound with a high yield exceeding 90%.

Claims (6)

Following the compound represented by the formula (I) is reacted with peroxomonosulfuric salts of sulfuric consisting composition of _{2KHSO 5 · KHSO 4 · K 2} SO 4, to obtain a diimmonium salt represented by the following general formula (II) A method for producing a near-infrared absorbing pigment compound, comprising:

In the general formula (I), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ , R ¹³² , R ¹⁴¹ and R ¹⁴² each independently represents a hydrogen atom, an aliphatic group or an aromatic group, R ¹⁰³ , R ¹¹³ , R ¹²³ , R ¹³³ and R ¹⁴³ each independently represent a substituent, and n ₁₀₃ , n ₁₁₃ , n ₁₂₃ , n ₁₃₃ and n ₁₄₃ each independently represent an integer of 0 to 4.

In the general formula (II), R ²¹¹ , R ²¹² , R ²²¹ , R ²²² , R ²³¹ , R ²³² , R ²⁴¹ and R ²⁴² each independently represent a hydrogen atom, an aliphatic group or an aromatic group, R ²⁰³ , R ²¹³ , R ²²³ , R ²³³ and R ²⁴³ each independently represent a substituent, n ₂₀₃ , n ₂₁₃ , n ₂₂₃ , n ₂₃₃ and n ₂₄₃ each independently represent an integer of 0 to 4, and X is monovalent Or it represents a divalent anion, n ₂₅₃ represents 1 or 2, and the product of the valence of X and n ₂₅₃ is 2. The production method according to claim 1, wherein X is a divalent anion. The method according to claim 1 or 2 , wherein an acid or a salt thereof coexists in the step. The said acid or its salt is a perchloric acid or a perchlorate, The manufacturing method of Claim 3 characterized by the above-mentioned. The production method according to any one of claims 1 to 4 , wherein at least a starting temperature of the reaction is set to -30 ° C to 20 ° C. Characterized in that to obtain a near infrared absorbing dye compound produced by the reaction with a yield of 90% or more, the production method according to any one of claims 1-5.