JP4916161B2 - New azo dye compounds - Google Patents

Description

  The present invention is used for dyeing textile fibers such as cotton, hair, or synthetic fibers, leather, paper, plastic, fur, etc., for food, for hair dyes, for ink, for inkjet printing, for laser printing, and for copying. , For thermal transfer image formation, for optical recording materials, for organic EL light emitting materials, for lasers, for organic semiconductors, for solar cells, for fluorescent probes, for non-linear optical materials, for solid imaging tubes and other various filters, and for color The present invention relates to an azo dye compound and an azo dye useful as dyes used for displays such as liquid crystals.

Azo dyes have many excellent properties such as high dyeability, fastness to heat, light and washing, and low production costs, and have long been used for textile fibers such as cotton, wool, or synthetic fibers, and leather. It has been widely used for dyeing paper, plastic, or fur, and for food. Today, in addition to these traditional applications, for paint pigments, inks, inkjet printing, laser printing, copying, thermal transfer image forming, optical recording materials, organic EL light emitting materials, lasers Used in the widest range of applications, for organic semiconductors, solar cells, fluorescent probes, nonlinear optical materials, solid-state imaging tubes and other filters, color liquid crystal displays, and hair dyes. Is a dye skeleton. Non-patent document 1 widely describes specific application examples thereof.
However, azo dyes are known to produce aromatic amine compounds when they are reductively metabolized in vivo, and recently there have been concerns about their safety (for example, see Non-Patent Document 2). ). Therefore, the development of azo dyes that are more difficult to reduce is demanded in consideration of the influence in vivo.
Recently, the synthesis of novel heterocyclic compounds having an azo group in the ring, 1,10-heterodisubstituted benzo [c] cinoline derivatives, has been reported, with a focus on the mechanism of ring formation and structural chemistry. (For example, refer nonpatent literature 3).
K. Hunger, Industrial Dyes, Chemistry, Properties, Applications, Wiley-VCH, 2003 RKLynn et al., Toxicol. Appl. Pharmacol., 56, 248, 1980 V. Benin et al., J. Org. Chem., 65, 6388, 2000

  An object of the present invention is to provide an azo dye compound and an azo dye which are stable under reducing conditions, improve the influence in vivo, and exhibit high dyeability and colorability.

The above problems can be solved by the following means.
(1) A compound represented by the following general formula ( III ).

［式中、Ｖ_１ はスルホンアミド基を表し、Ｖ_２はニトロ基、シアノ基またはアルコキシカルボニル基を表わす。ｒは１〜４を表わす。Ｍ _１は陽イオンを表し、ｍ_１は電荷を中和するのに必要な数を表す。］
（２） 前記一般式(III)において、Ｖ _２ がシアノ基またはアルコキシカルボニル基であり、ｒが１である（１）に記載の化合物。
（３） 前記一般式(III)において、Ｖ _２ がシアノ基である（２）に記載の化合物。

[Wherein, V ₁ represents a sulfonamide group, and V ₂ represents a nitro group, a cyano group, or an alkoxycarbonyl group . r represents 1-4 . M ₁ represents a cation , and m ₁ represents a number necessary for neutralizing the charge. ]
(2) The compound according to (1), wherein in the general formula (III), V ₂ is a cyano group or an alkoxycarbonyl group, and r is 1.
(3) The compound according to (2), wherein in the general formula (III), V ₂ is a cyano group.

  Since the azo dye compound of the present invention is stable even under reducing conditions, it improves the influence in vivo, exhibits high dyeability and colorability, and realizes low production costs. Furthermore, this compound has an effect as a pigment.

In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or substituted with one or more (up to the maximum possible) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group.
Therefore, as long as there is no notice in particular, the substituent substituted by the compound of this invention may be what kind of substituent, and the substituent represented by the following W may be sufficient as it.

The substituent represented by W is not particularly limited, and examples thereof include a halogen atom, an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group). ), Alkynyl group, aryl group, heterocyclic group (may be referred to as 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 (including alkylamino group, arylamino group, heterocyclic amino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonyl Amino group, aryloxy Carbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl Group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group And ureido group, boronic acid group (—B (OH) ₂ ), phosphato group (—OPO (OH) ₂ ), sulfato group (—OSO ₃ H), and other usual substituents.

  More specifically, examples of W include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group [a linear, branched, cyclic 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 carbon atoms). A substituted or unsubstituted bicycloalkyl group having ˜30, 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] heptane-2 -Yl, bicyclo [2,2,2] octane-3-yl) and tri Black structure is intended to encompass such.

  An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl 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 having 3 to 30 carbon atoms). A substituted or 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-cyclohexene-1- ), A bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, one hydrogen atom of a bicycloalkene having one double bond is removed. For example, bicyclo [2,2,1] hept-2-en-1-yl, It is intended to include cyclo [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), an aryl group (preferably a substituted or unsubstituted group having 6 to 30 carbon atoms) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl),

  A heterocyclic group (preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, condensed with a benzene ring or the like; More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, and 1- A cationic heterocyclic group such as methyl-2-pyridinio and 1-methyl-2-quinolinio), a cyano group, a hydroxyl group, a nitro group, a carboxyl group, and an alkoxy group (preferably having a carbon number of 1 to 30 substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryl An oxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy ), A silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy),

  Heterocyclic oxy group (preferably substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group A substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 7 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, Morpholinocar Nyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxy Carbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy groups (preferably substituted or unsubstituted aryloxycarbonyloxy groups having 7 to 30 carbon atoms, such as phenoxy Carbonyloxy, 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 arylamino group having 6 to 30 carbon atoms, such as amino, methylamino, dimethylamino; , Anilino, N-methyl-anilino, diphenylamino), ammonio groups (preferably ammonio groups, substituted or unsubstituted alkyls having 1 to 30 carbon atoms, aryls, ammonio groups substituted by heterocycles, such as trimethylammonio , Triethylammonio, diphenylmethylammonio), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted group having 6 to 30 carbon atoms) Arylcarbonylamino groups such as formylamino, aceto Ruamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms) , For example, 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, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms, such as methylsulfonyl) A Mino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted having 1 to 30 carbon atoms) An alkylthio group such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), hetero A ring thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, 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 substituted or unsubstituted alkylsulfinyl having 1 to 30 carbon atoms) Groups, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl or arylsulfonyl groups (preferably having 1 to 3 Substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl A carbonyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms A heterocyclic carbonyl group bonded to a group, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-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-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl) An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably a carbon A substituted or unsubstituted carbamoyl group having 1 to 30 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), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted with 2 to 30 carbon atoms or An unsubstituted phosphino group such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms such as phosphinyl, dioctyloxyphosphine Finyl, diethoxyphosphinyl),

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino, phospho group, silyl group (preferably having 3 carbon atoms). -30 substituted or unsubstituted silyl groups such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino groups (preferably substituted or unsubstituted hydrazino groups having 0 to 30 carbon atoms such as trimethylhydra Dino), ureido groups (preferably substituted with 0 to 30 carbon atoms) Unsubstituted ureido group, for example N, N-dimethyl ureido), and the like.

  In addition, two Ws can be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring or naphthalene. Ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, Phenanthroline ring, Ntoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

Among the above substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents, -CONHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group ). More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

First, the compound represented by formula (I) will be described.

X ₁ and X ₂ each independently represent a carbon atom or a hetero atom, and at least one of X ₁ or X ₂ represents a hetero atom. X ₁ is preferably a heteroatom. The heteroatom is preferably a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, more preferably a nitrogen atom, a sulfur atom, an oxygen atom, and a selenium atom, Particularly preferred is a nitrogen atom.

Z ₁ represents an atomic group necessary for forming an aromatic ring, and Z ₂ represents an atomic group necessary for forming an aromatic heterocycle. In the present invention, the aromatic ring means an aromatic carbocycle or an aromatic heterocycle unless otherwise specified.
Examples of the aromatic carbocycle formed by Z ₁ include a benzene ring, a naphthalene ring, anthracene, phenanthrene, and a benzene ring condensed with an aromatic heterocycle described below.
Examples of the aromatic heterocycle formed by Z ₁ include a 5-, 6-, 7-, or 8-membered aromatic heterocycle. The aromatic heterocycle formed by Z ₁ is preferably a 5- or 6-membered nitrogen-containing heterocycle. The 5- or 6-membered nitrogen-containing heterocycle may be any 5- or 6-membered nitrogen-containing heterocycle, or a benzene ring or other heterocycle may be condensed to form a polycyclic heterocycle structure. Good.

Examples of the aromatic heterocycle formed by Z ₂ include a 5-, 6-, 7-, or 8-membered aromatic heterocycle. The aromatic heterocycle formed by Z ₁ and Z ₂ is preferably a 5- or 6-membered nitrogen-containing heterocycle. The 5- or 6-membered nitrogen-containing heterocycle may be any 5- or 6-membered nitrogen-containing heterocycle, or a benzene ring or other heterocycle may be condensed to form a polycyclic heterocyclic ring structure. Good.

The hetero atom contained in the aromatic heterocycle formed by Z ₁ and Z ₂ is preferably a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom, and more Preferred are a nitrogen atom, a sulfur atom, an oxygen atom, and a selenium atom, more preferred are a nitrogen atom, a sulfur atom, and an oxygen atom, and particularly preferred are a nitrogen atom and a sulfur atom.

  Specifically preferred as these aromatic heterocycles are furan ring, pyrrole ring, thiophene ring, imidazole ring, pyrazole ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, triazole ring, tetrazole ring, Thiadiazole ring, oxadiazole ring, pyran ring, dioxane ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, thiadiazine ring, oxadiazine ring, oxatriazole ring, thiatriazole ring, indolizine ring, and benzo condensed Ringed benzothiazole ring, benzoxazole ring, benzotriazole ring, benzothiadiazole ring, benzooxadiazole ring, pyranone ring, pyrylium ring, triazine ring, tetrazine ring, indole ring, quinolidine ring, quinoline ring, phthala Down ring, a quinoxaline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, a phenanthroline ring, an acridine ring, and, purine, pteridine and the like.

  These heterocyclic rings may be substituted or condensed with any substituent, and examples of the substituent include W described above. Moreover, the tertiary nitrogen atom contained in the heterocyclic ring may be substituted to become quaternary nitrogen. It should be noted that any case where another tautomeric structure of the heterocycle can be written is chemically equivalent and included in the present invention.

V ₁ represents a substituent and is preferably substituted on the aromatic ring formed by Z ₁ . r represents the number of substituents V ₁ , preferably a number of 1 to 4, more preferably a number of 1 to 3, and particularly preferably 1 to 2. V ₂ represents a substituent, and is preferably substituted with an aromatic ring formed by Z ₂ . s represents the number of substituents _{V 2,} preferably a number from 1 to 4, more preferably a number from 1 to 3, 1 to 2 is particularly preferred.
V ₁ and V ₂ are preferably substituted by at least one group.
At least one group of V ₁ and V ₂ is preferably the following substituent represented by W1, and examples of the substituent other than W1 include the substituents described above for W. .
As a combination of the substituents represented by V ₁ and V ₂ , the substituent represented by V ₁ and V ₂ is preferably selected from the following substituents W1 or W2, and the substituent V ₁ is the substituent W1. In some cases, the substituent V ₂ is preferably the substituent W 2, and when the substituent V ₁ is the substituent W 2, the substituent V ₂ is preferably the substituent W 1.

W1 represents a hydroxy group, a primary to tertiary amino group, an acylamino group, or a sulfonamide group. Specifically, the proton is dissociated or non-dissociated hydroxy group, amino (NH ₂ ) group, alkyl or arylamino group having 1 to 60 carbon atoms (eg, methylamino, ethylamino, propylamino, butylamino, octyl) Amino, dodecylamino, benzylamino, phenylamino, naphthylamino), dialkyl or diarylamino groups having 2 to 60 carbon atoms (eg, dimethylamino, diethylamino, dipropylamino, dibutylamino, dioctylamino, didodecylamino, di Benzylamino, N-butyl-N-ethylamino, N-methyl-N-ethylamino, N-methyl-N-benzylamino, diphenylamino, dinaphthylamino, N- (4-tolyl) -N-phenylamino) N-alkyl having 6 to 60 carbon atoms -Arylamino group (for example, N-methyl-N-phenylamino), acylamino group having 2 to 10 carbon atoms (for example, acetylamino, n-butanamide, octanoylamino, benzoylamino, nicotinamide), carbon atoms 1-60 sulfonamide groups (for example, methanesulfonamide, 4-butanesulfonamide, 8-octanesulfonamide, p-toluenesulfonamide, pentafluorobenzenesulfonamide, chlorobenzenesulfonamide) may be mentioned. In addition, these may further have a substituent such as a substituent W.

W1 is preferably a proton-dissociated or non-dissociated hydroxy group, amino (NH ₂ ) group, alkyl or arylamino group having 1 to 20 carbon atoms (for example, methylamino, ethylamino, propylamino, butylamino, octyl) Amino, dodecylamino, benzylamino, phenylamino, naphthylamino), dialkyl or diarylamino groups having 2 to 20 carbon atoms (eg, dimethylamino, diethylamino, dipropylamino, dibutylamino, dioctylamino, didodecylamino, di Benzylamino, N-butyl-N-ethylamino, N-methyl-N-ethylamino, N-methyl-N-benzylamino, diphenylamino, dinaphthylamino, N- (4-tolyl) -N-phenylamino) N- of 6 to 20 carbon atoms Alkyl-N-arylamino group (for example, N-methyl-N-phenylamino), acylamino group having 2 to 10 carbon atoms (for example, acetylamino, n-butanamide, octanoylamino, benzoylamino, nicotinamide), Examples thereof include a sulfonamide group having 1 to 20 carbon atoms (for example, methanesulfonamide, 4-butanesulfonamide, 8-octanesulfonamide, p-toluenesulfonamide, pentafluorobenzenesulfonamide, chlorobenzenesulfonamide).

W1 is more preferably a proton dissociated or non-dissociated hydroxy group, amino (NH ₂ ) group, a substituted or unsubstituted alkylamino group having 1 to 18 carbon atoms, a substituted or unsubstituted group having 2 to 18 carbon atoms Examples include a dialkyl or diarylamino group, a substituted or unsubstituted acylamino group having 1 to 18 carbon atoms, and a substituted or unsubstituted sulfonamide group having 1 to 18 carbon atoms, and more preferably, a proton is dissociated or non-dissociated. Hydroxy group, amino (NH ₂ ) group, methylamino, ethylamino, propylamino, butylamino, octylamino, dimethylamino, diethylamino, dipropylamino, di (2-hydroxyethyl) amino, dioctylamino, didodecylamino Dibenzylamino, N-butyl-N-ethylamino, N-methyl-N-ethylamino, N-methyl-N-benzylamino, acetylamino, n-butanamide, nicotinamide, methanesulfonamide, 4-butanesulfonamide, 8-octanesulfonamide, p-toluenesulfonamide, Examples include pentafluorobenzenesulfonamide and chlorobenzenesulfonamide.

  W1 is particularly preferably a hydroxy group, dimethylamino group, methanesulfonamide, 4-butanesulfonamide, p-toluenesulfonamide, or pentafluorobenzenesulfonamide group in which protons are dissociated or non-dissociated.

  W2 is nitro group, cyano group, alkoxycarbonyl group, aryloxycarbonyl group, alkyl or arylsulfonyl group, carbamoyl group, sulfamoyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, carboxyl group, heterocyclic oxy group, It represents an ammonio group, an alkyl and arylsulfinyl group, a sulfo group, an alkyl or arylsulfonyl group, an acyl group, an aryl or a heterocyclic azo group. Specifically, a nitro group, a cyano group, an alkenyl group (preferably having 2 to 10 carbon atoms, for example, vinyl, allyl, oleyl), an aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl, p- Tolyl, naphthyl), acyl groups (preferably having 1 to 20 carbon atoms, such as acetyl, benzoyl, butanoyl, 4-chlorobenzoyl), sulfonyl groups (preferably having 1 to 20 carbon atoms, such as methanesulfonyl, butanesulfonyl) , Toluenesulfonyl), alkyl or arylsulfinyl group (preferably having 1 to 20 carbon atoms, for example, methyl sulfoxide, phenyl sulfoxide, 4-chlorophenyl sulfoxide, 4-nitrophenyl sulfoxide), carbamoyl group (having 1 to 10 carbon atoms) Preferably, for example, N, N-dimethyl Rubamoyl), sulfamoyl group (having 0 to 10 carbon atoms, for example, N, N-dimethylsulfamoyl), sulfo group, carboxyl group, alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonyl) , Ethoxycarbonyl, benzyloxycarbonyl), aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, for example, phenyloxycarbonyl, p-tolyloxycarbonyl, naphthyloxycarbonyl, p-chlorophenyloxycarbonyl), heterocyclic group ( The number of carbon atoms is preferably 0 to 20, preferably selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom of the ring structure, and including a carbon atom in addition to the hetero atom as the ring atom More preferably, preferably 3 ring members -8, more preferably 5-6, for example, the group represented by the aforementioned W), and the above may further have a substituent such as the substituent W.

  W2 is preferably a nitro group, a cyano group, an aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl, p-tolyl, naphthyl), an acyl group (preferably having 1 to 20 carbon atoms, for example, acetyl, Benzoyl, butanoyl, 4-chlorobenzoyl), sulfonyl groups (preferably having 1 to 20 carbon atoms, such as methanesulfonyl, butanesulfonyl, toluenesulfonyl), alkyl or arylsulfinyl groups (preferably having 1 to 20 carbon atoms, , Methyl sulfoxide, phenyl sulfoxide, 4-chlorophenyl sulfoxide, 4-nitrophenyl sulfoxide), carbamoyl group (preferably having 1 to 10 carbon atoms, for example, N, N-dimethylcarbamoyl), sulfamoyl group (having 0 to 10 carbon atoms) Is preferred, for example N, N-dimethylsulfamoyl), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, For example, phenyloxycarbonyl, p-tolyloxycarbonyl, naphthyloxycarbonyl, p-chlorophenyloxycarbonyl).

  W2 is more preferably a nitro group, a cyano group, an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl) or an aryloxycarbonyl group (preferably having 6 to 20 carbon atoms). Represents, for example, phenyloxycarbonyl, p-tolyloxycarbonyl, naphthyloxycarbonyl, p-chlorophenyloxycarbonyl), an alkyl or arylsulfonyl group, a carbamoyl group, a sulfamoyl group, and an acyl group.

  Particularly preferred as W2 is a cyano group, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, phenyloxycarbonyl, p-tolyloxycarbonyl, naphthyloxycarbonyl, p-chlorophenyloxycarbonyl, methylsulfonyl group, carbamoyl group, sulfamoyl group, acyl group It is.

On the aromatic heterocycle formed by Z ₁ and Z ₂ , there may be other substituents in addition to the substituent represented by V ₁ or V ₂ . Examples of these substituents include the above-described substituent represented by W.

M ₁ represents a cation or an anion necessary for neutralizing the charge of the compound molecule. The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-toluene ion). Chlorobenzenesulfonate ion), aryl disulfonate ion (eg, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (eg methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Further, an ionic polymer may be used. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium ion).

m ₁ represents the number of cations or anions necessary to neutralize the charge. m ₁ may be 0 when neutralization is not required, and a number of 0 to 10 is preferable, and a number of 0 to 5 is more preferable.

式中のＺ_２で表わされる原子群、Ｖ_１およびＶ_２で表される置換基、ｒおよびｓの数、Ｍ_１で表わされる対イオン、ｍ_１で表わされる数、ならびにＸ_１およびＸ_２で表わされる原子は、一般式（Ｉ）で説明したものと同様であることが好ましい。
式中、Ｚ_２は芳香族へテロ環を形成するのに必要な原子群であることが好ましい。Ｖ_１およびＶ_２は置換基を表わし、少なくとも一方の一つの基はヒドロキシ基、１〜３級アミノ基、アシルアミノ基、またはスルホンアミド基であることが好ましい。ｒは置換基Ｖ_１の数を表わし１〜４が好ましく、１〜３がより好ましく、１〜２が特に好ましい。ｓは置換基Ｖ_２の数を表わし１〜４が好ましく、１〜３がより好ましく、１〜２が特に好ましい。前記一般式（II）で表わされる化合物はさらにＶ_１およびＶ_２以外の置換基を有していてもよい。Ｍ_１は対イオンを表し、ｍ_１は電荷を中和するのに必要な数であり０〜１０の数が好ましく、０〜５の数がより好ましい。Ｘ_１およびＸ_２は炭素原子もしくはヘテロ原子であり、少なくとも一方はヘテロ原子である。
Will now be described compound represented by a general formula (II).

In the formula, an atomic group represented by Z ₂ , a substituent represented by V ₁ and V ₂ , the number of r and s, a counter ion represented by M ₁ , a number represented by m ₁ , and X ₁ and X ₂ The atoms represented by are preferably the same as those described in formula (I).
In the formula, Z ₂ is preferably an atomic group necessary for forming an aromatic heterocycle. V ₁ and V ₂ represent a substituent, and at least one group is preferably a hydroxy group, a _primary to tertiary amino group, an acylamino group, or a sulfonamide group. r represents the number of substituents V ₁ , preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2. s represents the number of substituents V ₂ , preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 to 2. The compound represented by the general formula (II) may further have a substituent other than V ₁ and V ₂ . M ₁ represents a counter ion, and m ₁ is a number necessary for neutralizing the electric charge, preferably a number from 0 to 10, more preferably a number from 0 to 5. X ₁ and X ₂ are carbon atoms or heteroatoms, and at least one is a heteroatom.

式中のＶ_１ はスルホンアミド基を表し、Ｖ _２ はニトロ基、シアノ基またはアルコキシカルボニル基を表わす。ｒは１〜４を表わす。Ｍ _１ は陽イオンを表し、ｍ _１ は電荷を中和するのに必要な数を表す。
ここで、Ｖ_１およびＶ_２ における上記置換基、ｒの数、Ｍ_１で表わされる陽イオン、ｍ_１で表わされる数は、一般式（Ｉ）で説明したものと同様であることが好ましい。
ｒは１〜３が好ましく、１〜２が特に好ましい。ｍ _１は電荷を中和するのに必要な数であり０〜１０の数が好ましく、０〜５の数がより好ましい。
なお、一般式（Ｉ）、（II）で表わされる化合物、または本発明の一般式（III）で表わされる化合物は、アゾ色素として好ましく用いることができ、それぞれ一般式（Ｉ）、（II）、または（III）で表わされるアゾ色素とすることができる。
Next, the compound represented by the general formula (III) of the present invention will be described.

In the formula, V ₁ represents a sulfonamide group, and V ₂ represents a nitro group, a cyano group, or an alkoxycarbonyl group. r represents 1-4. M ₁ represents a cation, and m ₁ represents a number necessary for neutralizing the charge.
Here, the substituents in V ₁ and V ₂ , the number of r, the cation represented by M ₁ , and the number represented by m ₁ are preferably the same as those described in the general formula (I).
r is 1 to 3 is good better rather, 1-2 is particularly preferred. m ₁ is a number necessary to neutralize the electric charge, and is preferably a number from 0 to 10, more preferably a number from 0 to 5.
The compounds represented by the general formulas (I) and (II) or the compounds represented by the general formula (III) of the present invention can be preferably used as azo dyes, and are represented by the general formulas (I) and (II), respectively. Or an azo dye represented by (III).

The intramolecular azo bond in the general formulas (I), (II), and (III) is obtained by a method for intramolecular azo coupling of a bi (hetero) aryl compound having an amino group (for example, V. Benin et al., J Org. Chem., Volume 65, page 6388 (issued in 2000)), a method in which an amino group on a bi (hetero) aryl compound is reacted with a nitrogen-containing compound (for example, For example, a method of reacting with nitrite in the presence of an acid. The method for synthesizing the bi (hetero) aryl compound having an amino group can be determined according to the structure of the target compound having the substituents V ₁ and V ₂ .
The substituents V ₁ and V ₂ may be introduced in any reaction process, but are preferably introduced before the intramolecular azo coupling. When introduced in the initial stage or in the middle of the reaction process, the substituent can be appropriately protected and deprotected to obtain a compound having the desired structure.

Next, although the specific example of the compound of this invention is shown, this invention is not limited to these.
Here, the following compounds 1 to 7, 9, 10, and 17 to 24 are reference examples.
Et in the chemical formula represents an ethyl group.

  When the compound of the present invention has a plurality of asymmetric carbon atoms in the molecule, there are a plurality of stereoisomers for the same structure, but the present invention includes all the stereoisomers and a plurality of stereoisomers. Even one of the bodies may be used as a mixture.

  The compound of the present invention is used for dyeing textile fibers such as cotton, hair, or synthetic fibers, leather, paper, plastic, fur, etc., for foods, for hair dyes, for inks, for inkjet printing, for laser printing, For copying, thermal transfer image forming, optical recording materials, organic EL light emitting materials, lasers, organic semiconductors, solar cells, fluorescent probes, nonlinear optical materials, solid imaging tubes and other various filters, And it can use suitably for displays, such as a color liquid crystal.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
Example 1
Exemplary Compound 8 was synthesized as shown in Scheme 1 below.

(A)化合物８−ａの合成
m-ニトロフェニルヒドラジン硫酸塩75gにエタノール240mlを加え攪拌下、トリエチルアミン55mlを添加した。この液を加熱還流し、これにエトキシメチレンマロノニトリル76gのエタノール50ml溶液を滴下した。滴下終了後、3時間加熱還流攪拌した。その後、反応液を全量で150mlぐらいになるまで減圧濃縮した。濃縮された反応液を水冷し、得られた結晶を濾取、乾燥することで化合物８−ａを63.6g(収率75％)得た。

(A) Synthesis of compound 8-a
240 ml of ethanol was added to 75 g of m-nitrophenylhydrazine sulfate, and 55 ml of triethylamine was added with stirring. This solution was heated to reflux, and a solution of 76 g of ethoxymethylenemalononitrile in 50 ml of ethanol was added dropwise thereto. After completion of the dropwise addition, the mixture was heated to reflux with stirring for 3 hours. Thereafter, the reaction solution was concentrated under reduced pressure to a total volume of about 150 ml. The concentrated reaction liquid was cooled with water, and the obtained crystals were collected by filtration and dried to obtain 63.6 g of Compound 8-a (yield 75%).

(B) Synthesis of Compound 8-b Iron powder (104 g), ammonium chloride (11.4 g), and water (85 g) were mixed and stirred at an external temperature of 100 ° C. for 10 minutes. To this was added 850 ml of 2-propanol, and 81.8 g of compound 8-a was slowly added in portions over 30 minutes while stirring under heating. After completion of the addition, the mixture was further heated to reflux for 1 hour. The reaction solution was filtered with celite while hot, then the filtrate was concentrated under reduced pressure, water was added thereto, and the mixture was allowed to stand at room temperature for 3 hours. The precipitated crystals were collected by filtration, and the crystals washed with methanol were dried to obtain 60 g (yield 84%) of Compound 8-b.

(C) Synthesis of Compound 8-c Compound 8-b, 30 g, was dissolved in 150 ml of dimethylacetamide at room temperature, 18.5 ml of α-picoline was added thereto, and then cooled to 0 ° C. While maintaining the internal temperature at 10 ° C. or lower, 13.2 g of methanesulfonyl chloride was slowly added dropwise. After completion of the addition, the mixture was stirred at room temperature for 3 hours. The reaction solution was slowly poured into a stirred mixture of 1 L of ice water and 5 ml of acetic acid, and stirred as it was for 1 hour. The crystals were collected by filtration and dried to obtain 36.7 g (yield 87%) of compound 8-c.
(D) Synthesis of Compound 8

After 14 g of compound 8-c and 60 g of phosphoric acid are dissolved by heating, the mixture is cooled and stirred in a salt-ice water bath until the internal temperature reaches 0 ° C. While stirring at an internal temperature of 0 ° C., 4.2 g of sodium nitrite was slowly added as a solid. After further stirring for 0.5 hour at this temperature, the reaction solution was poured into 500 ml of water, and the precipitated crystals were collected by filtration. The crystals were added to 70 ml of methanol, dissolved by adding 3 ml of triethylamine, stirred, filtered, and 7 ml of acetic acid was added to the filtrate with stirring to precipitate crystals. The crystals were collected by filtration, washed with methanol, and dried to obtain 9.1 g of Compound 8 (yield 63%). The melting point was 283-285 ° C.
Compound 8 had an absorption λmax (absorption maximum wavelength) in DMF (N, N-dimethylformamide) of 461.6 nm and an ε max (molar maximum absorption coefficient) of 3.26 × 10 ⁴ cm ⁻¹ M ⁻¹ . Further, the NMR spectrum was as follows.
¹ H NMR (300 MHz, DMSO-d ₆ ) δ (ppm): 3.33 (3H, s) 7.68-7.72 (1H, dd, J = 8 Hz, 1.0 Hz) 8.16-8.17 (1H, d, J = 1.0 Hz) 8.67-8.74 (1H, d, J = 8Hz) 9.01 (1H, s) 11.40 (1H, broad)

(Example 2)
Exemplified Compound 11 was synthesized as shown in Scheme 2 below.

(A)化合物１１−ａの合成
化合物８−ｂ、4.0gをピリジン30mlに溶解させ、外温0℃に冷却しながら、パラトルエンスルホニルクロリド（スキーム２中ではパラトルエンスルホニル基を「Ｔｓ」と表示）4.2gをゆっくり分割添加した。添加終了後、室温で3時間攪拌した。反応液に1M塩酸水と酢酸エチルを加え酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、硫酸マグネシウム乾燥、濃縮したのち、シリカゲルカラムクロマトグラフィーで精製することで、化合物１１−ａを5.29g(収率75％)得た。
(B)化合物１１の合成
化合物１１−ａ、5.29gをリン酸80mlに加温溶解させた後、塩-氷水バスで内温0℃になるまで冷却攪拌する。内温0℃で攪拌下、亜硝酸ナトリウム1.14gを固体のまま、ゆっくり加えた。この温度でさらに0.5時間攪拌した後、反応液を水500mlに注ぎ、析出した結晶を濾取した。結晶をメタノール70mlに加え、トリエチルアミン3mlを加え攪拌することで溶解させ、ゴミとり濾過後、濾液に攪拌下酢酸7mlを加えたところ結晶が析出した。結晶を濾取し、メタノールでかけ洗いし、結晶を乾燥することにより、化合物１１を3.09g(収率57％)得た。融点は２６６〜２６９℃であった。
化合物１１のＤＭＦ（Ｎ，Ｎ−ジメチルホルムアミド）にＤＢＵ（１，８−ジアザビシクロ［５．４．０］−７−ウンデセン）を３滴添加した溶液中の吸収λmax（吸収極大波長）は462.8nmであり、ε max（モル最大吸光係数）は3.30×10⁴cm^-1M^-1であった。この色素は、図１の吸収スペクトルのとおり（横軸は吸収波長を示し、縦軸は吸光度を示す）、色相が良好であった。さらに、ＮＭＲスペクトルは下記のとおりであった。
¹H NMR (300MHz, DMSO-d_６)δ(ppm)：2.33(3H, s) 6.67(2H, s) 7.41〜7.44(2H, d, J=8Hz) 7.64〜7.67(1H, m) 7.85〜7.88(2H, d, J=8Hz) 8.07(1H, s) 8.64〜8.67(1H, d, J=8Hz) 8.98(1H, s)

(A) Synthesis of Compound 11-a Compound 8-b, 4.0 g, was dissolved in 30 ml of pyridine and cooled to an external temperature of 0 ° C., while paratoluenesulfonyl chloride (in the scheme 2, the paratoluenesulfonyl group was changed to “Ts”). Display) 4.2 g was slowly added in portions. After completion of the addition, the mixture was stirred at room temperature for 3 hours. 1M aqueous hydrochloric acid and ethyl acetate were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography to give compound 11-a. 5.29 g (yield 75%) was obtained.
(B) Synthesis of Compound 11 After dissolving 5.29 g of Compound 11-a in 80 ml of phosphoric acid with heating, the mixture is cooled and stirred until the internal temperature reaches 0 ° C. in a salt-ice water bath. Under stirring at an internal temperature of 0 ° C., 1.14 g of sodium nitrite was slowly added as a solid. After further stirring for 0.5 hour at this temperature, the reaction solution was poured into 500 ml of water, and the precipitated crystals were collected by filtration. The crystals were added to 70 ml of methanol, dissolved by adding 3 ml of triethylamine, stirred, filtered, and 7 ml of acetic acid was added to the filtrate with stirring to precipitate crystals. The crystals were collected by filtration, washed with methanol, and dried to obtain 3.09 g (yield 57%) of Compound 11. The melting point was 266-269 ° C.
Absorption λmax (absorption maximum wavelength) in a solution obtained by adding 3 drops of DBU (1,8-diazabicyclo [5.4.0] -7-undecene) to DMF (N, N-dimethylformamide) of Compound 11 is 462.8 nm. Ε max (molar maximum extinction coefficient) was 3.30 × 10 ⁴ cm ⁻¹ M ⁻¹ . As shown in the absorption spectrum of FIG. 1 (the horizontal axis indicates the absorption wavelength and the vertical axis indicates the absorbance), this dye has a good hue. Further, the NMR spectrum was as follows.
¹ H NMR (300 MHz, DMSO-d ₆ ) δ (ppm): 2.33 (3H, s) 6.67 (2H, s) 7.41 to 7.44 (2H, d, J = 8 Hz) 7.64 to 7.67 (1H, m) 7.85 to 7.88 (2H, d, J = 8Hz) 8.07 (1H, s) 8.64 to 8.67 (1H, d, J = 8Hz) 8.98 (1H, s)

(Example 3)
Exemplary Compound 12 was synthesized as shown in Scheme 3 below.

(A)化合物１２−ａの合成
化合物８−ｂ、8.0gをピリジン60mlに溶解させ、外温0℃に冷却しながら、パラクロロベンゼンスルホニルクロリド9.3gをゆっくり分割添加した。添加終了後、室温で3時間攪拌した。反応液に1M塩酸水と酢酸エチルを加え酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、硫酸マグネシウム乾燥、濃縮したのち、シリカゲルカラムクロマトグラフィーで精製することで、化合物１２−ａを11.62g(収率78％)得た。なお、ＮＭＲスペクトルは下記のとおりであった。
¹H NMR (400MHz, DMSO-d_６)δ(ppm)：6.67(2H, s) 7.11〜7.14(1H, d, J=8Hz) 7.17〜7.20(1H, d, J=8Hz) 7.25(1H, s) 7.36〜7.41(1H, t, J=8Hz) 7.64〜7.67(2H, d, J=8Hz) 7.76〜7.80(3H, m) 10.67(1H, s)

(A) Synthesis of Compound 12-a Compound 8-b, 8.0 g, was dissolved in 60 ml of pyridine, and 9.3 g of parachlorobenzenesulfonyl chloride was slowly added in portions while cooling to an external temperature of 0 ° C. After completion of the addition, the mixture was stirred at room temperature for 3 hours. 1M aqueous hydrochloric acid and ethyl acetate were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography to give compound 12-a. 11.62 g (yield 78%) was obtained. The NMR spectrum was as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 6.67 (2H, s) 7.11 to 7.14 (1H, d, J = 8 Hz) 7.17 to 7.20 (1H, d, J = 8 Hz) 7.25 (1H, s) 7.36 to 7.41 (1H, t, J = 8Hz) 7.64 to 7.67 (2H, d, J = 8Hz) 7.76 to 7.80 (3H, m) 10.67 (1H, s)

(B) Synthesis of Compound 12 After dissolving 11.3 g of Compound 12-a in 150 ml of phosphoric acid with heating, the mixture is cooled and stirred in a salt-ice water bath until the internal temperature reaches 0 ° C. Under stirring at an internal temperature of 0 ° C., 2.3 g of sodium nitrite was slowly added as a solid. After further stirring at this temperature for 0.5 hour, the reaction solution was poured into 800 ml of water, and the precipitated crystals were collected by filtration. The crystals were added to 200 ml of methanol, dissolved by adding 15 ml of triethylamine and stirred. After removing dust, 25 ml of acetic acid was added to the filtrate with stirring to precipitate crystals. Crystals were collected by filtration, washed with methanol, and dried to obtain 10.55 g (yield 90%) of Compound 12. The melting point was 232 to 236 ° C.
Absorption λmax (absorption maximum wavelength) in a solution obtained by adding 3 drops of DBU (1,8-diazabicyclo [5.4.0] -7-undecene) to DMF (N, N-dimethylformamide) of Compound 12 is 458.3 nm. And ε max (molar maximum extinction coefficient) was 3.20 × 10 ⁴ cm ⁻¹ M ⁻¹ . As shown in the absorption spectrum of FIG. 2 (the horizontal axis indicates the absorption wavelength and the vertical axis indicates the absorbance), this dye has a good hue. Further, the NMR spectrum was as follows.
¹ H NMR (300 MHz, DMSO-d ₆ ) δ (ppm): 7.65 to 7.71 (3H, m) 7.96 to 7.99 (2H, d, J = 8 Hz) 8.09 (1H, s) 8.66 to 8.69 (2H, d, J = 8Hz) 8.99 (1H, s)

Example 4
Exemplary Compound 13 was synthesized as shown in Scheme 4 below.

(A)化合物１３−ａの合成
化合物８−ｂ、7.0gをピリジン40mlに溶解させ、外温0℃に冷却しながら、1-ブタンスルホニルクロリド5.5mlをゆっくり分割添加した。添加終了後、室温で3時間攪拌した。反応液に1M塩酸水と酢酸エチルを加え酢酸エチルで抽出し、有機層を飽和食塩水で洗浄し、硫酸マグネシウム乾燥、濃縮したのち、シリカゲルカラムクロマトグラフィーで精製することで、化合物１３−ａを9.0g(収率100％)得た。

(A) Synthesis of Compound 13-a Compound 8-b, 7.0 g, was dissolved in 40 ml of pyridine, and 5.5 ml of 1-butanesulfonyl chloride was slowly added in portions while cooling to 0 ° C. After completion of the addition, the mixture was stirred at room temperature for 3 hours. 1M aqueous hydrochloric acid and ethyl acetate were added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography to give compound 13-a. 9.0 g (yield 100%) was obtained.

(B) Synthesis of Compound 13 Compound 13-a, 8.5 g, was dissolved in 100 ml of phosphoric acid with heating, and then cooled and stirred in a salt-ice water bath until the internal temperature reached 0 ° C. While stirring at an internal temperature of 0 ° C., 2.5 g of sodium nitrite was slowly added as a solid. After further stirring at this temperature for 1 hour, the reaction solution was poured into 500 ml of water, and the precipitated crystals were collected by filtration. The crystals were added to 100 ml of methanol and dissolved by adding 5 ml of triethylamine and stirred. After removing dust and filtering, 8 ml of acetic acid was added to the filtrate with stirring to precipitate crystals. The crystals were collected by filtration, washed with methanol, and dried to give 5.13 g (yield 60%) of Compound 13. The melting point was 249-251 ° C.
Absorption λmax (absorption maximum wavelength) in a solution obtained by adding 3 drops of DBU (1,8-diazabicyclo [5.4.0] -7-undecene) to DMF (N, N-dimethylformamide) of Compound 13 is 465.0 nm. And ε max (molar maximum extinction coefficient) was 3.20 × 10 ⁴ cm ⁻¹ M ⁻¹ . As shown in the absorption spectrum of FIG. 3 (the horizontal axis indicates the absorption wavelength and the vertical axis indicates the absorbance), this dye has a good hue. Further, the NMR spectrum was as follows.
¹ H NMR (300 MHz, DMSO-d ₆ ) δ (ppm): 0.81 to 0.85 (3H, t, J = 7 Hz) 1.31 to 1.42 (2H, m) 1.68 to 1.76 (2H, m) 3.44 to 3.40 (2H, t, J = 7Hz) 7.69-7.72 (1H, d, J = 8Hz) 8.17 (1H, s) 8.71-8.73 (1H, d, J = 8Hz) 9.02 (1H, s) 11.37 (1H, broad)

(Example 5)
Exemplary Compound 14 was synthesized as shown in Scheme 5 below.

(A) Synthesis of Compound 14-a Compound 8-b, 8.0 g was dissolved in 40 ml of pyridine, and 9.4 g of 1-octanesulfonyl chloride was slowly added in portions while cooling to an external temperature of 0 ° C. After completion of the addition, the mixture was stirred at room temperature for 3 hours. 1M aqueous hydrochloric acid and ethyl acetate are added to the reaction mixture, and the mixture is extracted with ethyl acetate. The organic layer is washed with saturated brine, dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography to give compound 14-a. 10.66 g (yield 71%) was obtained. The NMR spectrum was as follows.
¹ H NMR (400 MHz, DMSO-d ₆ ) δ (ppm): 0.81 to 0.87 (3H, t, J = 7 Hz) 1.15 to 1.27 (8H, m) 1.27 to 1.36 (2H, m) 1.62 to 1.70 (2H, m) 3.10-3.16 (2H, t, J = 7Hz) 6.70 (2H, broad) 7.17-7.24 (2H, m) 7.33 (1H, s) 7.43-7.48 (1H, t, J = 8Hz) 7.78 (1H, s) 10.03 (1H, s)
(B) Synthesis of Compound 14 After 10.2 g of Compound 14-a is dissolved in 150 ml of phosphoric acid by heating, the mixture is cooled and stirred in a salt-ice water bath until the internal temperature reaches 0 ° C. Under stirring at an internal temperature of 0 ° C., 2.06 g of sodium nitrite was slowly added as a solid. After further stirring at this temperature for 1 hour, the reaction solution was poured into 600 ml of water, and the precipitated crystals were collected by filtration. The crystals were added to 300 ml of methanol, dissolved by adding 12 ml of triethylamine and stirred. After removing the dust and filtering, 20 ml of acetic acid was added to the filtrate with stirring to precipitate crystals. The crystals were collected by filtration, washed with methanol, and dried to give 9.04 g (yield 86%) of Compound 14. The melting point was 197-201 ° C.
Absorption λmax (absorption maximum wavelength) in a solution of compound 14 in which 3 drops of DBU (1,8-diazabicyclo [5.4.0] -7-undecene) is added to DMF (N, N-dimethylformamide) is 465.5 nm. Ε max (molar maximum extinction coefficient) was 2.75 × 10 ⁴ cm ⁻¹ M ⁻¹ . This dye had a good hue as shown in the absorption spectrum of FIG. 4 (the horizontal axis represents the absorption wavelength and the vertical axis represents the absorbance).

(Test example)
The reduction test was conducted by the following method.
Example Compound 1 of Reference Example, Example Compounds 8, 11, 12, 13, and 14 of the present invention , and the following Comparative Compounds A, B, and C were mixed with 5 equivalents of sodium hydrosulfite in methanol-water, For 48 hours.

反応液をＬＣ／ＭＳで分析したところ、比較化合物Ａの場合、比較化合物Ａは９５％以上消失し、スキーム６に示す還元生成物１Ａ、および還元生成物２Ａが生成していた。同様に、比較化合物Ｂの場合、比較化合物Ｂは９５％以上消失し、スキーム６に示す還元生成物３Ｂおよび還元生成物４Ｂが生成していた。一方、参考例の例示化合物１、本発明の例示化合物８、１１、１２、１３、及び１４の場合、全く同じ条件で処理しても各例示化合物は１００％残存していた。また、比較化合物Ｃも同じ条件で１００％残存していたが、この化合物は可視域に吸収を示さなかった。

When the reaction solution was analyzed by LC / MS, in the case of the comparative compound A, the comparative compound A disappeared by 95% or more, and the reduction product 1A and the reduction product 2A shown in Scheme 6 were produced. Similarly, in the case of the comparative compound B, the comparative compound B disappeared by 95% or more, and the reduction product 3B and the reduction product 4B shown in Scheme 6 were generated. On the other hand, in the case of Exemplified Compound 1 of Reference Example and Exemplified Compounds 8, 11, 12, 13, and 14 of the present invention, 100% of each exemplified compound remained even when treated under exactly the same conditions. Comparative compound C also remained 100% under the same conditions, but this compound did not absorb in the visible region.

さらに、化学物質の変異原性評価の際に代謝酵素として通常使用されるＳ−９ＭＩＸに４８時間以上曝した場合にも、比較化合物ＡおよびＢが還元されたのに対し、参考例の例示化合物１、本発明の例示化合物８、１１、１２、１３、及び１４は還元されないことが確認できた。
上記の試験結果より本発明の化合物が還元条件下において安定性が極めて高いことが明らかである。

Furthermore, the comparative compounds A and B were also reduced when exposed to S-9MIX, which is usually used as a metabolic enzyme in the evaluation of the mutagenicity of chemical substances, for 48 hours or more, while the exemplified compounds of the reference examples 1. It was confirmed that the exemplified compounds 8, 11, 12, 13, and 14 of the present invention were not reduced.
From the above test results, it is clear that the compound of the present invention has extremely high stability under reducing conditions.

2 is an absorption spectrum of Exemplary Compound 11. 2 is an absorption spectrum of Exemplary Compound 12. 2 is an absorption spectrum of Exemplary Compound 13. 2 is an absorption spectrum of Exemplary Compound 14.

Claims (3)

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

[Wherein , V ₁ represents a sulfonamide group, and V ₂ represents a nitro group, a cyano group, or an alkoxycarbonyl group. r represents 1-4 . M ₁ represents a cation, and m ₁ represents a number necessary for neutralizing the charge . ] In Formula (III), V ₂ is a cyano group or an alkoxycarbonyl group, the compound according to claim 1 r is 1. The compound according to claim 2, wherein in the general formula (III), V ₂ is a cyano group.

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