JPH0848687A - Production of dioxazine compound, coloring material and plate-like crystal - Google Patents

Abstract

PURPOSE:To obtain a fine compound capable of providing a pigment crude having good disperse stability, fastness, fluidity, gloss and coloring force and high production efficiency by carrying out cyclization reaction in the presence of a specific dioxazine derivative. CONSTITUTION:This method for producing a dioxazine compound of formula III is to cyclize a compound of formula II (R is H or a 1-8C alkyl; Z<1> and Z<2> are each H or a halogen) in the presence of a dioxazine derivative of formula I [R<1> is H or a 1-8C alkyl; Z<3> and Z<4> are each H or a halogen; X and Y are each a substituent group; (i) and (j) are each 0-6 and (i)+(j) is 1-6]. Furthermore, a compound of formula IV is exemplified as the compound of formula I.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing a dioxazine compound useful as a pigment, a coloring material and a plate crystal.

[0002]

2. Description of the Related Art In order to produce a compound of the following formula (1),
3-amino-9-alkylcarbazole represented by the following formula (5) and chloranil are condensed in an inert solvent in the presence of an acid binder to obtain a compound represented by the following formula (2), and then this compound A method for ring closure using a ring closure agent is known (PB Report 65657, Japanese Patent Publication No. 60-119).
86 etc.). Further, as a method for converting the pigment crude obtained by the above method into a pigment, methods described in JP-A-54-56630 and JP-A-58-120673 are proposed.

[0003]

However, this pigment crude is difficult to disperse, it is necessary to disperse very strongly, the production efficiency is poor, and it is difficult to obtain a high-quality pigment. Further, for dispersion, it has been proposed to grind with a surfactant or a dye derivative (JP-A-2-102272, JP-A-2).
-102273, US5275653), production efficiency is inferior, miniaturization is insufficient, and dispersion stability is inferior.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned drawbacks, the present inventors have found that by carrying out a ring-closing reaction in the presence of a derivative of a dioxazine compound represented by the following formula (3). It has been found that an excellent pigment crude can be obtained. That is, the present invention provides (1) Formula (3)

[0005]

[Chemical 4]

(In the formula, R'is a hydrogen atom or a carbon number of 1-8.
Indicates an alkyl group, Z ^3, Z ⁴ each independently represent a hydrogen atom or a halogen atom, X and Y each independently represent a substituent, i is the number of 0 to 6, j is the number of 0 to 6 Indicates. However, i + j is a number from 1 to 6. ) In the presence of a compound represented by the formula (2)

[0007]

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## STR1 ## wherein R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Z ¹ and Z ² each independently represent a hydrogen atom or a halogen atom. Characteristic, Formula (1)

[0009]

[Chemical 6]

A method for producing a dioxazine compound represented by the formula (wherein R, Z ¹ and Z ² are the same as above), (2) X in the formula (3) is -A- (CH ₂ ) ₁ -B, Y. But-
_{A '- (CH 2) n} -B' ( wherein, A and A 'is a direct bond or _{-SO 2 -, - CO -,} - S -, - CH 2
NHCO -, - O -, - CR 1 R 2 -, - CONR
³ −, −SO ₂ NR ⁴ −, −NR ⁵ − (where R ¹ ,
R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a saturated and unsaturated aliphatic or aromatic group (these groups may contain a chalcogen atom, a nitrogen atom and / or a halogen atom). Indicates. ), A divalent linking group selected from B) and B and B'each independently represent a hydrogen atom or-.
OR ⁶ (wherein R ⁶ represents a hydrogen atom, a metal atom, a saturated or unsaturated aliphatic or aromatic group (these groups may contain a chalcogen atom, a nitrogen atom and / or a halogen atom).) , -NR ⁷ R ⁸ and -R ⁹ represent a bonding group (wherein R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a saturated and unsaturated aliphatic or aromatic group ( These groups may include chalcogen atoms, nitrogen atoms and / or halogen atoms)), n and l
Each independently represents a number from 0 to 8. )), I is a number from 0 to 6 and j is a number from 0 to 6, (3) A is -SO _2- ,
—SO ₂ NR ⁴ —, l is an integer of 0 to 8, and B
There -OR ^6, -NR ⁷ R ^8, is -R ^9, A 'is -S
O ₂ −, n is 0, B ′ is —OR ⁶ ,
i is a number from 1 to 6 and j is a number from 0 to 5, (2) A method for producing a dioxazine compound,

(4) A is --O--, --CR ¹ R ² -,-
^{_{CH 2 NHCO -, - CONR 3}} - a and, l is 0 to 8
Of an integer, B is a hydrogen atom or -OR ^6, -NR ⁷
R ⁸ is a bonding group selected from —R ⁹ and i is 1 to 6
And j is 0, the method for producing the dioxazine compound of (2), (5) the compound of formula (3) is a sulfonic acid derivative of a compound of formula (1), a sulfonamide derivative (aminosulfonyl derivative), Alkyl ether derivative, alkylamide derivative (carboxylic acid amide alkyl derivative) or carbonamide derivative (aminocarbonyl derivative)
(1) A method for producing a dioxazine compound according to (1),
The sulfonic acid derivative is a compound in which —SO ₃ M (M is a hydrogen atom or a metal atom) is bonded to the compound of formula (1), and the sulfonamide derivative is an aminosulfonyl group in the compound of formula (1), A hydrazinosulfonyl group, an alkylaminosulfonyl group, an aminoalkylaminosulfonyl group, an alkylaminoalkylaminosulfonyl group or a formula —SO ₂ N (R ₁₁ ) ₂ (wherein R ₁₁ is (CH ₂ C
H ₂ O) _n H (where _n is an integer of 1 to 30). ) Is bound to the compound, the alkyl ether derivative is a compound of formula (1) to which an alkoxy group having 1 to 8 carbon atoms is bound, and the alkylamide derivative is a compound of formula (1) to phthalimide. An alkyl group,
A compound in which an onium alkylcarbonylaminoalkyl group, an oniumcarbonylaminoalkyl group, an alkylcarbonylaminoalkyl group, an aminoalkylcarbonylaminoalkyl group or an alkylaminoalkylcarbonylaminoalkyl group is bonded, and the carbonamide derivative is a compound of formula (1) A method for producing a dioxazine compound of (5), which is a compound in which a carbamoyl group, an alkylaminocarbonyl group, an aminoalkylaminocarbonyl group, or an alkylaminoalkylaminocarbonyl group is bound, (7) a compound of formula (3) is represented by formula (1) ) The method for producing a dioxazine compound of (1) which is a sulfonic acid derivative of the compound, (8) the sulfonic acid derivative has 1 to 6 sulfonic acids bonded as a substituent to the compound of the formula (1), Some or all Process for producing a dioxazine compound of a which are compounds become (7),

(9) A method for producing a dioxazine compound of (1), wherein the compound of formula (3) is a sulfonamide derivative of the compound of formula (1), and the sulfonamide derivative (10) is
In the compound of the formula (1), as a substituent, an alkylaminosulfonyl group, an alkylaminoalkylaminosulfonyl group or a formula —SO ₂ N (R ₁₁ ) ₂ (wherein R ₁₁ is (CH
₂ CH ₂ O) _n H (where _n represents an integer of 1 to 30). (9) a compound having 1 to 5 groups and 0 to 3 sulfonic acid groups or salts thereof bonded (total number of substituents: 1 to 6), the method for producing a dioxazine compound according to (9), ) A method for producing a dioxazine compound of (1), wherein the compound of formula (3) is an alkylamide derivative of the compound of formula (1). (12) A compound in which an alkylamide derivative has 1 to 5 onium alkylcarbonylaminoalkyl groups and 0 to 3 sulfonic acid groups or salts thereof bonded as substituents to the compound of formula (1) (11) The method for producing a dioxazine compound according to (11), wherein the onium alkylcarbonylaminoalkyl group is a pyridinium alkylcarbonylaminoalkyl group, and the counter ion thereof is chlorine ion, lactate ion or methylsulfate. A method for producing a dioxazine compound of (12) which is an ion, a method for producing a dioxazine compound of (8), (10) or (12), wherein the salt (14) is an alkali metal salt, and (15) represented by formula (3) The amount of the compound to be used is 0. to 1 part by weight of the compound represented by the formula (2).
The production method of the dioxazine compound of (1) is 005 to 0.3 parts by weight, and (16) the ring-closing reaction is carried out by adding 1 part by weight of the compound of the formula (2) to the compound of the formula (3). In the presence of 005 to 0.3 parts by weight and a ring-closing agent, 10
(1), (5), which is performed by heating to 0 to 200 ° C.
The method for producing the dioxazine compound of (7), (9) or (11), and the amount of the ring closure agent (17) used is 0.1 to 5 times mol per 1 mol of the compound represented by the formula (2). (1
6) a method for producing a dioxazine compound, (18) (1)
A coloring material containing a compound of formula (1) synthesized by the method described in (19), a coloring material containing a reaction product obtained by the reaction described in (1), (20) a formula (1) described in (1) A plate-like crystal of the dioxazine compound represented by 1), (2
1) A plate-like crystalline reaction product obtained by the reaction according to (1).

In the present invention, the ring closure reaction of the compound of formula (2) is carried out in the presence of the compound of formula (3). In the above formula (3), R'is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, etc., but preferably a methyl group, an ethyl group,
They are an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. For i and j, i + j is 1
A number of 0 to 6 provided that Z ³ ,
Z ^{4 s} are each independently a hydrogen atom or a halogen atom. Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is preferable.

X and Y are substituents. X is, for example, -A
_{- (CH 2) l -B,} Y is, for example -A '- (CH _2)
n −B ′ (where A and A ′ are a direct bond or —S
_{O 2 -, - CO -,} - S -, - CH 2 NHCO -, - O
^{-, - CR 1 R 2 -} , - CONR 3 -, - SO 2 NR 4
−, −NR ⁵ − (where R ¹ , R ² , R ³ , R ⁴ , R
Each of ⁵ independently represents a hydrogen atom, a saturated or unsaturated aliphatic or aromatic group (these groups may contain a chalcogen atom, a nitrogen atom and / or a halogen atom). ) Represents a divalent linking group selected from, B and B 'are each independently a hydrogen atom or -OR ⁶ (wherein R ⁶ is a hydrogen atom, a metal atom, the saturated and unsaturated aliphatic or aromatic group (these groups may also contain a chalcogen atom, a nitrogen atom and / or halogen atoms) shows ^{a), -. NR 7 R 8} , represents a bonding group selected from -R ⁹ (wherein, R ^7, R ⁸ and R ⁹ each independently represent a hydrogen atom, a saturated or unsaturated aliphatic or aromatic group (these groups may contain a chalcogen atom, a nitrogen atom and / or a halogen atom) and a table. To be done. here,
The metal atom is preferably an alkali metal such as lithium, sodium or potassium, and the chalcogen atom is preferably an oxygen atom or a sulfur atom. Examples of the saturated or unsaturated aliphatic or aromatic group which may contain a chalcogen atom, a nitrogen atom and / or a halogen atom include a methyl group, a chloromethyl group, an ethyl group, an n-propyl group, an isopropyl group and n-butyl. Group, isobutyl group, t
-Alkyl group such as butyl group, pentyl group, hexyl group, heptyl group, octyl group (preferably having 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms), ethenyl group, propenyl group, butenyl group, pentenyl group, etc. Alkenyl group (preferably having 2 to 8 carbon atoms, more preferably 2 to 8 carbon atoms)
5), a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group or a cyclohexyl group (preferably having a carbon number of 3 to 1).
0, and more preferably 4 to 8 carbon atoms, ester groups such as methoxycarbonyl group, ethoxycarbonyl group and benzyloxycarbonyl group, ether groups such as methoxy group, ethoxy group and phenoxy group, acyl groups such as acetyl group and propionyl group. Groups, phenyl groups, aryl groups such as chlorophenyl groups, pyridinium groups, chlorpyridinium groups, pyridyl groups, pyridonyl groups, piperidonyl groups, morpholino groups, furyl groups, oxazolyl groups, thienyl groups, chlorobenzyl groups, nitrobenzyl groups, etc. can give.

As the X and Y, for example, -SO ₃ M
(Where M represents a hydrogen atom or a metal atom), an alkylaminosulfonyl group, an alkylaminoalkylaminosulfonyl group, an alkoxy group having 1 to 8 carbon atoms, a phthalimidoalkyl group, an oniumalkylcarbonylaminoalkyl group, an alkylcarbonylaminoalkyl. Group, alkylaminoalkylcarbonylaminoalkyl group, -S
O ₂ N (R ₁₁ ) ₂ (wherein R ₁₁ is (CH ₂ CH ₂ O) _n
H (where _n is an integer of 1 to 30) is shown. ),
Examples thereof include an alkylaminocarbonyl group and an alkylaminoalkylaminocarbonyl group.

Examples of M in --SO ₃ M include a hydrogen atom, an alkali metal atom such as lithium, sodium and potassium, a metal atom such as an alkaline earth metal atom such as magnesium and calcium, and preferably a hydrogen atom. And alkali metal atoms, more preferably hydrogen atoms, sodium and potassium. Examples of —SO ₃ M include sulfonic acid, lithium sulfonate, sodium sulfonate, potassium sulfonate, magnesium sulfonate, calcium sulfonate and the like.

Examples of the alkylaminosulfonyl group include (C ₁ -C ₄ ) alkylaminosulfonyl groups such as N-methylaminosulfonyl group and N-ethylaminosulfonyl group, N-ethyl-N-methylaminosulfonyl group,
Examples thereof include di (C ₁ -C ₄ ) alkylaminosulfonyl groups such as dimethylaminosulfonyl group and dipropylaminosulfonyl group. The alkylamino alkylaminosulfonyl group, for example N- methylamino propylamino sulfonyl group, such as N- ethylamino propylamino sulfonyl group (C ₁ ~C ₄₎ alkylamino (C ₁ -C
₄ ) Alkylaminosulfonyl group, dimethylaminopropylaminosulfonyl group, diethylaminopropylaminosulfonyl group, dimethylaminomethylaminosulfonyl group, diethylaminomethylaminosulfonyl group, diethylaminoethylaminosulfonyl group, di (n-propyl) aminomethylaminosulfonyl group , Di (n-propyl) aminoethylaminosulfonyl group, di (n-propyl) aminopropylaminosulfonyl group, di (isopropyl) aminomethylaminosulfonyl group, di (isopropyl) aminoethylaminosulfonyl group, di (isopropyl) amino Di (C ₁ -C) such as propylaminosulfonyl group, dibutylaminopropylaminosulfonyl group, N-ethyl-N-methylaminopropylaminosulfonyl group, etc.
C ₄₎ alkylamino (C ₁ ~C ₄₎ alkylaminosulfonyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group,
Examples thereof include t-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group and octyloxy group. Examples of the phthalimidoalkyl group include phthalimido (C ₁ -C ₄ ) alkyl groups such as phthalimidomethyl group, nitrophthalimidomethyl group, monochlorophthalimidomethyl group and dichlorophthalimidomethyl group. Examples of the onium alkylcarbonylaminoalkyl group include a pyridinium alkylcarbonylaminoalkyl group and a tetraalkylammonium alkylcarbonylaminoalkyl group. Examples of the pyridinium alkylcarbonylamino group, e.g., pyridinium, such as pyridinium methyl carbonylamino methyl group (C ₁ ~C ₄₎ alkylcarbonylamino (C ₁ ~C ₄₎ alkyl group, and the like. Examples of the tetraalkylammoniumalkylcarbonylaminoalkyl group include tetra (C ₁
-C ₄₎ alkylammonium (C ₁ ~C ₄₎ alkylcarbonylamino (C ₁ ~C ₄₎ alkyl group, and the like. Non-chromogenic ion as a counter ion of onium,
For example, halogen ion such as fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, methyl sulfate ion, benzenesulfonate ion, sulfonate ion such as methanesulfonate ion, fatty acid ion such as acetate ion, lactate ion, etc. Examples thereof include oxy acid ion and benzoic acid ion. Examples of —SO ₂ N (R ₁₁ ) ₂ include a diethanolaminosulfonyl group and a di (polyethylene glycol) aminosulfonyl group. The degree of polymerization of polyethylene glycol is 1 to 30, preferably 20.
It is about 30. Examples of the alkylcarbonylaminoalkyl group include (C _{1 to} C) such as methylcarbonylaminopropyl group and ethylcarbonylaminobutyl group.
₄ ) Alkylcarbonylamino (C ₁ -C ₄ ) alkyl groups and the like. Examples of the alkylaminoalkylcarbonylaminoalkyl group include (C ₁ -C ₄ ) alkylcarbonylamino (C ₁ -C ₄ ) alkyl groups such as dimethylaminopropylcarbonylaminopropyl group and ethylaminomethylcarbonylaminobutyl group. To be Examples of the dialkylaminoalkylaminocarbonyl group include dimethylaminopropylaminocarbonyl group, diethylaminopropylaminocarbonyl group, N
-Methyl-N-propylaminopropylaminocarbonyl group and the like.

R'in the above equation (3),
Preferable combinations of Z ³ , Z ⁴ , X and Y are, for example, R ′ is methyl group, ethyl group, propyl group, Z ³ is hydrogen atom or chlorine atom, Z ⁴ is hydrogen atom or chlorine atom, and X is sulfonic acid. A salt of a group, an alkylaminoalkylaminosulfonyl group or an oniumalkylcarbonylaminoalkyl group, and Y is a sulfonic acid group. Also, for i and j, i is 1
-5, j is 0-5, and i + j is 1-6
Is the number of.

The compound of formula (3) can also be referred to as, for example, the following compound. That is, the compound of formula (3) is, for example, a sulfonic acid derivative, a sulfonamide derivative (aminosulfonyl derivative), an alkyl ether derivative, an alkylamide derivative (carboxylic acid amide alkyl derivative) or a carbonamide derivative of the compound of formula (1). (Aminocarbonyl derivative). The sulfonic acid derivative, as a substituent, for example, a compound of formula (1), -SO ₃ M (where M
Represents a hydrogen atom or a metal atom. ) Is bonded to the compound, and examples of the sulfonamide derivative (aminosulfonyl derivative) include a compound of the formula (1) having a substituent such as an aminosulfonyl group, a hydrazinosulfonyl group, and an alkylaminosulfonyl group (for example, see above). ), An aminoalkylaminosulfonyl group (for example, an amino (C ₁ -C ₄ ) alkylaminosulfonyl group such as an aminomethylaminosulfonyl group, an aminobutylaminosulfonyl group), an alkylaminoalkylaminosulfonyl group (for example, see above) or formula _{-SO 2 n (R 11) 2} ( where R ₁₁ is _{(CH 2 CH 2 O) n} H ( where _n is from 1 to 30
Indicates an integer. ). ) Is bonded to the compound, and examples of the alkyl ether derivative include compounds having a compound of the formula (1) to which an alkoxy group having 1 to 8 carbon atoms (for example, see above) is bonded as a substituent. Examples of the alkylamide derivative (carboxylic acid amidoalkyl derivative) include, for example, a phthalimidoalkyl group (for example, see above) and an oniumalkylcarbonylaminoalkyl group (for example, see above) as a substituent in the compound of the formula (1). An oniumcarbonylaminoalkyl group (for example, an oniumcarbonylaminomethyl group,
Onium carbonylamino (C ₁ -C ₄ ) alkyl groups such as oniumcarbonylaminobutyl group), alkylcarbonylaminoalkyl groups (for example, see above), aminoalkylcarbonylaminoalkyl groups (for example, aminomethylcarbonylaminomethyl group, amino) A compound having an amino (C ₁ -C ₄ ) alkylcarbonylamino (C ₁ -C ₄ ) alkyl group such as butylcarbonylaminomethyl group) or an alkylaminoalkylcarbonylaminoalkyl group (for example, see above) bonded thereto, As the carbonamide derivative (aminocarbonyl derivative),
For example, in the compound of the formula (1), as a substituent, a carbamoyl group, an alkylaminocarbonyl group (for example, see above), an aminoalkylaminocarbonyl group (for example, an aminomethylaminocarbonyl group, an aminobutylaminocarbonyl group and the like amino (C ₁ -C ₄₎ alkylaminocarbonyl) or alkylaminoalkyl aminocarbonyl group (e.g., compounds see above) it is bonded and the like. Specific examples of each of these substituents include the groups described above.

Among these compounds of formula (3), preferred are, for example, sulfonic acid derivatives, sulfonamide derivatives (aminosulfonyl derivatives) and alkylamide derivatives (carboxylic acid amide alkyl derivatives) of the compound of formula (1). Can be given. As the sulfonic acid derivative,
For example, a compound in which 1 to 6 sulfonic acids are bonded as a substituent to the compound of the formula (1) and a part or all of which is a salt is exemplified. Examples of the sulfonamide derivative (aminosulfonyl derivative) of the compound of the formula (1) include, for example, a compound of the formula (1) having a substituent such as an alkylaminosulfonyl group, an alkylaminoalkylaminosulfonyl group or a formula —SO ₂ N (R). ₁₁ ) ₂ (where R ₁₁ is (C
H ₂ CH ₂ O) _n H (where _n is an integer of 1 to 30). ) 1 to 5 groups, a sulfonic acid group or a salt thereof is bonded to 0 to 3 compounds (total number of substituents is 1 to 6), preferably 1 to 5 alkylaminoalkylaminosulfonyl groups , A compound in which 0 to 3 sulfonic acid groups or salts thereof are bonded (total number of substituents is 1 to 6
Individual). Examples of the alkylamide derivative (carboxylic acid amide alkyl derivative) of the compound of formula (1) include
For example, a compound in which 1 to 5 oniumalkylcarbonylaminoalkyl groups and 0 to 3 sulfonic acid groups or salts thereof are bonded to the compound of formula (1) as substituents (total number of substituents is 1 to 6) Preferred are compounds having 1 to 5 pyridinium alkylcarbonylaminoalkyl groups and 0 to 3 sulfonic acid groups or salts thereof (the total number of substituents is 1 to 6). In this case, the counter ion is preferably chlorine ion, methylsulfate ion, acetate ion, lactate ion or the like.

Typical examples of the compounds of the above formula (3) are shown below.

[0023]

[Chemical 7]

[0024]

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[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

In the present invention, the compound of formula (2) is the starting material, and the compound of formula (1) is the target. In the above formulas (1) and (2), R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t
-Butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. Z ¹ and Z ² are hydrogen atoms or halogen atoms. Examples of the halogen atom include a chlorine atom and a bromine atom, and a chlorine atom is preferable.

The easily dispersible dioxazine compound (1) obtained by the method of the present invention is prepared by reacting the compound represented by the formula (3) in the presence of the compound represented by the formula (3) in an inert organic solvent, if necessary, by adding the ring-closing agent. It can be obtained by subjecting the compound represented by (2) to a ring closure reaction at high temperature. At the time of ring closure reaction,
It is also possible to heat while reducing the pressure. The addition amount of the compound represented by the formula (3) is preferably 0.005 to 0.3 part by weight, more preferably 0.01 to 0.2 part by weight, relative to 1 part by weight of the compound represented by the formula (2). It is about a part. The compound represented by the formula (3) may be a mixture of compounds having different numbers and kinds of substituents, and the form is powder or water, for example,
A solution such as an organic acid or an organic solvent or a wet cake may be used.

The ring-closing reaction time is preferably 0.5 to 6 hours, more preferably 1 to 5 hours. The reaction temperature is preferably 100 to 200 ° C, more preferably 150 to 18 ° C.
0 ° C. As the inert solvent used in the reaction, halogenated aromatic solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, dibromobenzene, chloronaphthalene and chlorotoluene, dichlorotoluene, bromotoluene, toluene, xylene, mesitylene, ethylbenzene. , Alkylbenzene such as diethylbenzene and alkylated aromatic solvents such as methylnaphthalene, nitrobenzene, alkanes such as decane, dodecane, decene and dodecene, alkenes and the like. These can be used alone or in combination. The amount of this solvent used is preferably about 3 to 20 parts by weight, more preferably about 5 to 15 parts by weight, relative to 1 part by weight of the compound of formula (2).

Examples of the ring-closing agent include sulfonic acid halides such as benzenesulfonyl chloride, toluenesulfonyl chloride, chlorobenzenesulfonyl chloride and nitrobenzenesulfonyl chloride, acid halides such as benzoyl chloride, halides such as chloranil and dichloronaphthoquinone, and particularly benzene. Preferred are sulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, chlorobenzenesulfonyl chloride and the like. When a ring-closing agent is used, its amount is preferably 0. 0 relative to the compound of the above formula (2).
The molar ratio is 1 to 5, and more preferably 0.5 to 3 molar ratio.

After the reaction is completed, the solution containing the dioxazine compound is filtered to separate the desired product. After that, if necessary,
The obtained crystals may be washed with a solvent or the like. The production method of the present invention uses the compound of formula (2) as a starting material,
Equation (5)

[0034]

[Chemical 13]

(Wherein R is the same as above) and chloranil in the above-mentioned inert solvent in the presence of an acid binder at about 0 to 80 ° C.
The compound of formula (2) is obtained by condensation with, and the compound can be applied to the production method of the present invention without separation. Examples of the acid binder include organic or inorganic alkalis, for example, alkali metal salts of weak acids such as sodium carbonate and sodium acetate, trialkylamines such as trimethylamine and triethylamine, and the like. The compound represented by the formula (3) may be added before the condensation reaction between the compound represented by the formula (5) and chloranil.

The plate-like crystal of the dioxazine compound of the present invention has an aspect ratio of 1: 1 to 1 as the average crystal size.
1: 5, preferably about 1: 1 to 1: 4,
Further, as is clear from the electron micrograph of FIG. 1, it is a thin plate-like crystal. The crystals obtained by the conventional method are needle-like crystals or columnar crystals as is clear from the electron micrograph of FIG. 2, which is clearly different from the plate-like crystals of the present invention.
This plate-like crystal is particularly composed of a dioxazine compound derivative (6) having a sulfone group shown below (where X is S in the formula (3)).
A sulfone group such as O ₃ H or SO ₃ Na, Z ³ and Z ⁴ are each independently a hydrogen atom or a halogen atom, and i is 1 to 1
6, a compound in which j is 0) in the presence of the compound of formula (2).

[0037]

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As the coloring material in the present invention, for example, an ink, a paint, a synthetic resin film, a synthetic resin plate, a synthetic resin masterbatch, a fiber, a rubber, a pigment printing paste, a pigment printing dispersion or the like is used. Equation (1) obtained by
There are various materials colored with the compound. The dioxazine compound of formula (1) (pigment crude) obtained by the method of the present invention is very suitable as a pigment dye, particularly as a pigment for coloring a polymer material. That is, when the pigment crude obtained by the method of the present invention is pigmented by a conventional method and used for ink, paint, resin coloring or pigment printing, various fastnesses such as light resistance, heat resistance and migration resistance are good, and It has excellent properties such as excellent fluidity and luster of the pigment, high coloring power, high dispersion stability, and resistance to re-aggregation.

The compound represented by the above formula (3) is
It can be produced by a known conventional method. That is, as a typical example, a method of sulfonation of a dioxazine compound represented by the above formula (1) with fuming sulfuric acid, a method of chlorsulfonation of a dioxazine compound represented by the above formula (1), and then a reaction with an amine compound. A method of chlormethylating a dioxazine compound represented by the above formula (1) and then reacting it with an amine compound (JP-A-1-
217078, etc.), a method of chloroacetaminomethylating a dioxazine compound represented by the above formula (1) and then reacting with an amine, a dioxazine compound represented by the above formula (1) is reacted with N-methylolphthalimide in polyphosphoric acid. Method (Japanese Patent Laid-Open No. 4-246469, etc.).

[0040]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, all percentages and parts are percentages and parts by weight.

Example 1 20 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone, o
120 parts of dichlorobenzene are mixed, and further, the compound of the formula (7) (in the formula (6), R ′ is an ethyl group,
Z ³ and Z ⁴ are chlorine atoms, M is sodium, and i is 2) (0.5 parts) are added, the temperature is raised to 140 to 150 ° C. under reduced pressure, and 8 parts of p-toluenesulfonyl chloride is added at the same temperature. Add and stir at 165-175 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 17.5 parts of a dioxazine compound (in the formula (1), R is an ethyl group,
A plate crystal of a compound in which Z ¹ and Z ² are chlorine atoms was obtained.

Example 2 10 parts of 3-amino-9-ethylcarbazole, 7 parts of chloranil, 4 parts of sodium carbonate, 1 part of o-dichlorobenzene
Mix 00 parts and stir at 30-65 ° C. When the condensation reaction is complete, add 1.5 parts of the compound of formula (7),
Subsequently, under reduced pressure, the temperature was raised to 140 to 150 ° C., 7 parts of p-toluenesulfonyl chloride was added at the same temperature, and 165 to 165
Stir at 175 ° C. for 5 hours. After the completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 12.8 parts of the dioxazine compound (in the formula (1), R is an ethyl group, Z ¹ and Z ^2). Compounds in which is a chlorine atom) were obtained.

Example 3 20 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone, o
120 parts of dichlorobenzene are mixed, and further, the compound of the formula (8) (in the formula (6), R ′ is an ethyl group,
2 parts of a compound in which Z ³ and Z ⁴ are chlorine atoms, M is sodium, and i is 1 and 8 parts of p-toluenesulfonyl chloride are added, and the mixture is stirred at 165 to 175 ° C. for 5 hours. After the completion of the reaction, the reaction mixture was cooled and the obtained crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 17.3 parts of a dioxazine compound (R in the formula (1) is an ethyl group,
A compound in which Z ¹ and Z ² are chlorine atoms was obtained.

Example 4 10 parts of 3-amino-9-ethylcarbazole, 8 parts of chloranil, 3 parts of sodium carbonate, 1 part of o-dichlorobenzene
00 parts are mixed and stirred at 25-60 ° C. After completion of the condensation reaction, 2 parts of the compound of the formula (8) and 6 parts of p-toluenesulfonyl chloride were added, and the mixture was added at 165 to 175 ° C. for 5 minutes.
Stir for hours. After the completion of the reaction, the reaction mixture was cooled and the obtained crystals were filtered and washed with o-dichlorobenzene, methanol, and water.
It was dried to obtain 13.2 parts of a dioxazine compound (a compound of the formula (1) in which R is an ethyl group and Z ¹ and Z ² are chlorine atoms).

Example 5 14 parts of 3-amino-9-octylcarbazole, 8 parts of chloranil, 3 parts of sodium carbonate and 100 parts of o-dichlorobenzene are mixed and stirred at 25 to 60 ° C. After completion of the condensation reaction, 0.3 part of the compound of the formula (7) is added, the temperature is raised to 140 to 150 ° C., 6 parts of benzenesulfonyl chloride is added, and the mixture is stirred at 165 to 175 ° C. for 5 hours. After the reaction is complete, the reaction mixture is cooled, and the precipitated crystals are filtered to obtain o-
After washing with dichlorobenzene, methanol, water, and drying, 14.2 parts of the dioxazine compound (in the formula (1),
R is an octyl group and Z ¹ and Z ² are chlorine atoms)
To obtain a plate-like crystal.

Example 6 10 parts of 3-amino-9-ethylcarbazole, 8 parts of chloranil, 3 parts of sodium carbonate, 2 parts of the wet cake of the formula (7) and 100 parts of o-dichlorobenzene were mixed,
Stir at 25-60 ° C. When the condensation reaction is over 140
The temperature is raised to ° C, 6 parts of p-toluenesulfonyl chloride is added, and the mixture is stirred at 165 to 175 ° C for 3 hours. After the reaction,
The crystals obtained after cooling were filtered, washed with o-dichlorobenzene, methanol and then with water, and dried to obtain 12.8 parts of a dioxazine compound (in the formula (1), R is an ethyl group, Z ¹ ;
A plate crystal of a compound in which Z ² is a chlorine atom) was obtained.

Example 7 20 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone, o
120 parts of dichlorobenzene are mixed, and 0.1 part of the compound of formula (7) and the compound of formula (9) (in formula (6), R'is an ethyl group, Z ³ and Z ⁴ are chlorine atoms). , M is sodium, and i is 3), and an aqueous solution of 0.5 part of the mixture is added, and the temperature is gradually raised to 140 to 150 ° C. under reduced pressure. 8 parts of p-toluenesulfonyl chloride was added at the same temperature, and the mixture was stirred at 165 to 175 ° C. for 5 hours. After completion of the reaction, the resulting crystals were cooled, filtered, washed with o-dichlorobenzene, methanol and then with water, and dried to obtain 17.5 parts of a dioxazine compound (in the formula (1), R is an ethyl group, Z ¹ and Z ^2). Compounds in which is a chlorine atom) were obtained.

Example 8 10 parts of 3-amino-9-ethylcarbazole and 6.5 parts of chloranil, 3 parts of sodium carbonate, and the above formula (7)
Compound of formula (9), compound of formula (9) 0.7 part, compound of formula (10) (in formula (6), R ′ is an ethyl group, Z ³ and Z ⁴ are chlorine atoms, and M is Sodium, i is 4
0.2 parts, a compound of the above formula (11) (a compound of the formula (6), wherein R ′ is an ethyl group, Z ³ and Z ⁴ are chlorine atoms, M is sodium and i is 5) 0 An aqueous solution of 1 part of the mixture and 100 parts of o-dichlorobenzene are mixed and stirred at 30 to 65 ° C. When the condensation reaction is completed, the temperature is raised to 140 to 150 ° C. under reduced pressure, 6 parts of p-toluenesulfonyl chloride is added at the same temperature, and the mixture is stirred at 165 to 175 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 12.6 parts of the dioxazine compound (formula (1)
In, a compound in which R is an ethyl group and Z ¹ and Z ² are chlorine atoms is obtained.

Example 9 20 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone, o
- mixed dichlorobenzene 120 parts, in addition the compound of formula (12) (Formula (3), R 'is an ethyl group, Z ^3, Z ⁴ is a chlorine atom, X is _{SO 2 NH (CH 2) 3} N (CH
₃ ) ₂ , a compound in which i is 3 and j is 0) 0.8 part of an acetic acid solution is added, the temperature is raised to 140 to 150 ° C. under reduced pressure, and 8 parts of p-toluenesulfonyl chloride is added at the same temperature. 16
Stir for 3 hours at 5-175 ° C. After completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 17.4 parts of the dioxazine compound (in the formula (1), R is an ethyl group, Z ¹ and Z ^2). Was a chlorine atom).

Example 10 10 parts of 3-amino-9-ethylcarbazole, 7 parts of chloranil, 2.8 parts of sodium carbonate and 100 parts of o-dichlorobenzene are mixed and stirred at 30 to 65 ° C. When the condensation reaction is completed, the compound of the formula (13) (in the formula (3), R ′ is an ethyl group, Z ³ and Z ⁴ are chlorine atoms, and X is
SO ₂ NH (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂ , a compound in which i is 3 and j is 0) (1.5 parts) is added, and the temperature is raised to 140 to 150 ° C. under reduced pressure. Then, 6 parts of benzenesulfonyl chloride is added at the same temperature, and the mixture is stirred at 165 to 175 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then with water, and dried to obtain 12.4 parts of the dioxazine compound (formula (1)
In, a compound in which R is an ethyl group and Z ¹ and Z ² are chlorine atoms is obtained.

Example 11 20 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone, o
Mixing 120 parts of dichlorobenzene, and further adding 0.2 parts of the compound of formula (7) and 0.4 of the compound of formula (9).
Part, a compound of the above formula (14) (in the formula (3), R ′
Is an ethyl group, Z ³ and Z ⁴ are chlorine atoms, and X is SO ₂ NH (CH
₂ ) ₃ N (CH ₃ ) ₂ , i is 4, and j is 0)
0.5 parts of an aqueous solution of the mixture was added and the pressure was reduced to 140-1.
The temperature is raised to 50 ° C., 8 parts of p-toluenesulfonyl chloride is added at the same temperature, and the mixture is stirred at 165 to 175 ° C. for 5 hours.
After completion of the reaction, the reaction mixture was cooled and the obtained crystals were filtered, washed with o-dichlorobenzene, methanol and then with water, and dried to 17.5.
To obtain a dioxazine compound (a compound of the formula (1) in which R is an ethyl group and Z ¹ and Z ² are chlorine atoms).

Example 12 10 parts of 3-amino-9-ethylcarbazole, 7 parts of chloranil, 3 parts of sodium carbonate, 1 part of o-dichlorobenzene
Mix 00 parts and stir at 30-65 ° C. When the condensation reaction is completed, the compound of the formula (15) (in the formula (3), R'is an ethyl group, Z ³ and Z ⁴ are chlorine atoms, and X is SO ₂
NH (CH ₂ ) ₃ N (CH ₃ ) ₂ , i is 3, Y is SO ₃ H, j is 1
1.0 part of acetic acid solution is added, then the temperature is raised to 140 to 150 ° C. under reduced pressure, 7 parts of p-toluenesulfonyl chloride is added at the same temperature, and 165 to 175 ° C.
Stir for 2 hours. After the completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 12.6 parts of the dioxazine compound (formula (1)
In, a compound in which R is an ethyl group and Z ¹ and Z ² are chlorine atoms is obtained.

Example 13 10 parts of 3-amino-9-ethylcarbazole, 6 parts of chloranil, 4 parts of sodium carbonate, a compound of the above formula (16) (in the formula (3), R'is an ethyl group, Z ³ and Z) ⁴ is a chlorine atom, X is SO ₂ NH (CH ₂ ) ₃ N (CH ₃ ) ₂ , i is 2, Y
Is SO ₃ H, a compound in which j is 2) 0.5 part of a wet cake, and 100 parts of o-dichlorobenzene are mixed, and
Stir at 65 ° C. After the condensation reaction is completed, the temperature is raised to 140 to 150 ° C. under reduced pressure, 7 parts of p-toluenesulfonyl chloride is added at the same temperature, and the mixture is stirred at 165 to 175 ° C. for 5 hours. After the completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 12.3 parts of a dioxazine compound (formula (1)
In, a compound in which R is an ethyl group and Z ¹ and Z ² are chlorine atoms is obtained.

Example 14 10 parts of 3-amino-9-ethylcarbazole, 7 parts of chloranil, 3 parts of sodium carbonate, a compound of the above formula (17) (in the formula (3), R'is an ethyl group, Z ³ and Z) ⁴ is a chlorine atom, X is OC ₈ H ₁₇ , i is 2 and j is 0)
1.5 parts and 100 parts of o-dichlorobenzene are mixed, and 3
Stir at 0-65 ° C. After the condensation reaction is completed, the temperature is raised to 140 to 150 ° C. under reduced pressure, 6 parts of benzenesulfonyl chloride is added at the same temperature, and the mixture is stirred at 165 to 175 ° C. for 5 hours. After the completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then water, and dried to obtain 12.2 parts of the dioxazine compound (formula (1)
In, a compound in which R is an ethyl group and Z ¹ and Z ² are chlorine atoms is obtained.

Example 15 10 parts of 3-amino-9-ethylcarbazole, 7 parts of chloranil, 4 parts of sodium carbonate, a compound of the above formula (18) (in the formula (3), R'is an ethyl group, Z ³ and Z) ⁴ parts of chlorine atom, X is a phthalimidomethyl group, 2 parts of a compound in which i is 2 and j is 0) and 100 parts of o-dichlorobenzene are mixed and stirred at 30 to 65 ° C. After completion of the condensation reaction, the temperature was raised to 140 to 150 ° C. under reduced pressure, and 7 parts of p-toluenesulfonyl chloride was added at the same temperature.
Stir for 5 hours at 5-175 ° C. After completion of the reaction, the reaction mixture was cooled and the resulting crystals were filtered, washed with o-dichlorobenzene, methanol and then with water and dried to obtain 12.3 parts of the dioxazine compound (in the formula (1), R is an ethyl group, Z ¹ and Z ^2). Was a chlorine atom).

Example 16 2,5-Dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone 20 parts, o
120 parts of dichlorobenzene are mixed, and further 0.2 parts of the compound of formula (7) and the compound of formula (19) (in formula (3), R'is an ethyl group, Z ³ and Z ⁴ are chlorine atoms). , X is CH ₂ NHCOCH ₂ -Py lactate, a compound in which i is 4, and j is 0) (0.8 parts), and the mixture is heated under reduced pressure to 140 to 150 ° C. -Add 7 parts of toluenesulfonyl chloride and stir for 5 hours at 165-175 ° C. After completion of the reaction, the crystals obtained are cooled and filtered to obtain o
-Dichlorobenzene, methanol, and then washed with water and dried to obtain 17.0 parts of a dioxazine compound (a compound of the formula (1), wherein R is an ethyl group, Z ¹ and Z ² are chlorine atoms).

Comparative Example 1 20 parts of 2,5-dichloro-3,6-bis (9-ethyl-3-carbazolylamino) -1,4-benzoquinone, o
-Mix 120 parts of dichlorobenzene, 140-
The temperature is raised to 150 ° C., 8 parts of p-toluenesulfonyl chloride is added at the same temperature, and the mixture is stirred at 165 to 175 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled and the obtained crystals were filtered, washed with o-dichlorobenzene, methanol, then with water and dried.
6.7 parts of dioxazine compound (in the formula (1), R
Was a ethyl group and Z ¹ and Z ² were chlorine atoms) to obtain needle crystals.

Example 17 To 22 parts of the dioxazine compound obtained in Example 1 was added 33 parts of ethylene glycol and 150 parts of ground salt, and dispersion pigmentation was carried out with a kneader for 7 hours. When the resulting pigment was stirred and mixed with an ink varnish with a paint shaker to form an ink, it was excellent in gloss and tinting strength. In addition, when a paint test with an alkyd resin was performed, the hue was rapidly reddish due to excellent dispersibility, and the coloring power was large and clear.

Examples 18 to 19 According to Example 17, the dioxazine compounds obtained in Examples 8 and 9 were used in place of the dioxazine compound obtained in Example 1, and dispersed pigmentation was carried out for 7 hours with a kneader. went.

Comparative Example 2 According to Example 17, the dioxazine compound obtained in Comparative Example 1 was used in place of the dioxazine compound obtained in Example 1, and the pigment was dispersed for 7 hours with a kneader.

Comparative Example 3 According to Example 17, 21 parts of the dioxazine compound obtained in Comparative Example 1 instead of 22 parts of the dioxazine compound obtained in Example 1 and 1 part of the compound represented by the above formula (7) were used. Was used to disperse the pigment in a kneader for 7 hours.

The compound pigmented with the above kneader was dispersed as
A dark enamel paint was prepared using each alkyd resin varnish for paint. Further, a dark enamel was mixed with a titanium oxide paint to prepare a light enamel. For the above, the hue, density, and gloss were compared. The results are shown in Table 1.

[0063]

Table 1 Table 1 Examples Dioxazine compounds used Hue Concentration Luster 17 Example 1 Redness 110 Good 18 Example 8 Redness 120 Good 19 Example 9 Redness 115 Very good Comparative Example 2 Comparative Example 1 Standard Standard ( 100) Standard Comparative Example 3 Comparative Example 1 + Compound 7 Blue 95 Equivalent

The hue and density of the pigment obtained were applied to art paper with a light-colored enamel, and the sample of Comparative Example 2 was used as a standard for visual judgment. The density was determined by comparing the ink densities of various contents of the standard sample with the density of the ink containing the standard amount of the standard sample and the same amount of the sample, and setting the ink concentration of the standard sample of the standard amount to 100. The gloss was evaluated visually by applying dark enamel on art paper.

[0065]

EFFECTS OF THE INVENTION According to the present invention, a high-quality pigment crude can be easily obtained, and a pigment produced by using the pigment crude can be used for coloring paints, resins, or for pigment printing.
It has various fastnesses such as migration resistance, excellent fluidity and gloss, and high coloring power.

[Brief description of drawings]

FIG. 1 is an electron micrograph (× 3000) of a dioxazine crystal produced by the method of Example 1.

FIG. 2 is an electron micrograph (× 3000) of a dioxazine crystal produced by the method of Comparative Example 1.

Claims (21)

[Claims] 1. A formula (3): (In the formula, R'represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Z ³ and Z ⁴ each independently represent a hydrogen atom or a halogen atom, X and Y each independently represent a substituent, i Is a number from 0 to 6 and j is a number from 0 to 6.
i + j is a number from 1 to 6. ) In the presence of a compound represented by the formula (2) (Wherein R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and Z ¹ and Z ² each independently represent a hydrogen atom or a halogen atom). , Formula (1) (In the formula, R, Z ¹ and Z ² are the same as the above.) A method for producing a dioxazine compound. 2. X in the formula (3) is -A- (CH ₂ ) _l.
-B, Y is _{-A '- (CH 2) n} -B' ( wherein, A and A 'is a direct bond or _{-SO 2 -, - CO -,} - S
_{-, - CH 2 NHCO -,} - O -, - CR 1 R 2 -, -
_{^{CONR 3 -, - SO 2 NR}} 4 -, - NR 5 - ( ^{wherein, R 1, R 2, R} 3, R 4, R 5 each independently represent a hydrogen atom, an aliphatic or aromatic, saturated and unsaturated Group (which may contain a chalcogen atom, a nitrogen atom and / or a halogen atom), and B and B ′ each independently represent a hydrogen atom or OR ⁶ (where R ⁶ is a hydrogen atom, a metal atom,
A saturated and unsaturated aliphatic or aromatic group (these groups may contain a chalcogen atom, a nitrogen atom and / or a halogen atom) is shown. ), —NR ⁷ R ⁸ and —R ⁹ represent a bonding group (wherein R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a saturated and unsaturated aliphatic or aromatic group). (These groups may include a chalcogen atom, a nitrogen atom and / or a halogen atom).
n and l each independently represent a number from 0 to 8. )), I is a number from 0 to 6, and j is a number from 0 to 6. The method for producing a dioxazine compound according to claim 1. Wherein A _{is, -SO 2 -, - SO 2} NR 4 - and is, l is an integer from 0 to 8, B is -OR ^6, -NR ⁷
R ^8, is -R ^9, A 'is -SO ₂ - is, n is 0
Wherein B ′ is —OR ⁶ , i is a number from 1 to 6, and j is a number from 0 to 5. 3. The method for producing a dioxazine compound according to claim 2, wherein 4. A is —O—, —CR ¹ R ² —, —CH ₂
NHCO -, - CONR ³ - a and, l is an integer from 0 to 8, B is a hydrogen atom or -OR ^6, -NR ⁷ R ^8,
The method for producing a dioxazine compound according to claim 2, wherein the dioxazine compound is a bonding group selected from —R ⁹ , i is a number from 1 to 6, and j is 0. ， 5. The method for producing a dioxazine compound according to claim 1, wherein the compound of formula (3) is a sulfonic acid derivative, a sulfonamide derivative, an alkyl ether derivative, an alkylamide derivative or a carbonamide derivative of the compound of formula (1). 6. A sulfonic acid derivative becomes a compound of formula (1)
SO ₃ M (where M represents a hydrogen atom or a metal atom)
Wherein the sulfonamide derivative is a compound of formula (1) having an aminosulfonyl group, a hydrazinosulfonyl group, an alkylaminosulfonyl group, an aminoalkylaminosulfonyl group, an alkylaminoalkylaminosulfonyl group or a formula —SO ₂ N (R ₁₁ ) ₂ (where R
₁₁ shows the _{(CH 2 CH 2 O) n} H ( where _n is an integer of 1 to 30.). ) Is a compound having a group bonded thereto, and the alkyl ether derivative is a compound having a compound of the formula (1) bonded to an alkoxy group having 1 to 8 carbon atoms,
The alkylamide derivative is bonded to the compound of formula (1) with a phthalimidoalkyl group, an oniumalkylcarbonylaminoalkyl group, an oniumcarbonylaminoalkyl group, an alkylcarbonylaminoalkyl group, an aminoalkylcarbonylaminoalkyl group or an alkylaminoalkylcarbonylaminoalkyl group. 6. The production of a dioxazine compound according to claim 5, wherein the carbonamide derivative is a compound in which a carbamoyl group, an alkylaminocarbonyl group, an aminoalkylaminocarbonyl group or an alkylaminoalkylaminocarbonyl group is bonded to the compound of the formula (1). Method. 7. The method for producing a dioxazine compound according to claim 1, wherein the compound of formula (3) is a sulfonic acid derivative of the compound of formula (1). 8. The sulfonic acid derivative is a compound in which 1 to 6 sulfonic acids are bonded to the compound of the formula (1) as a substituent, and a part or all of them is a salt.
A method for producing a dioxazine compound. 9. The method for producing a dioxazine compound according to claim 1, wherein the compound of formula (3) is a sulfonamide derivative of the compound of formula (1). 10. A sulfonamide derivative is the compound of formula (1), wherein the substituent is an alkylaminosulfonyl group,
Alkylaminoalkylaminosulfonyl group or formula-
SO ₂ N (R ₁₁ ) ₂ (wherein R ₁₁ is (CH ₂ CH ₂ O)
_n H (where _n is an integer of 1 to 30). )
10. The method for producing a dioxazine compound according to claim 9, which is a compound in which 1 to 5 groups represented by and a 0 to 3 sulfonic acid group or a salt thereof are bonded (the total number of substituents is 1 to 6). 11. The method for producing a dioxazine compound according to claim 1, wherein the compound of formula (3) is an alkylamide derivative of the compound of formula (1). 12. An alkylamide derivative comprising a compound of formula (1) having 1 to 5 onium alkylcarbonylaminoalkyl groups and 0 to 3 sulfonic acid groups or salts thereof as substituents (substitution (The total number of groups is 1 to 6)
The method for producing a dioxazine compound according to claim 11, which is 13. The method for producing a dioxazine compound according to claim 12, wherein the onium alkylcarbonylaminoalkyl group is a pyridinium alkylcarbonylaminoalkyl group and the counter ion thereof is chloride ion, lactate ion or methylsulfate ion. 14. The salt according to claim 8, which is an alkali metal salt.
A method for producing a 0 or 12 dioxazine compound. 15. The amount of the compound represented by formula (3) used is
0.005 with respect to 1 part by weight of the compound represented by the formula (2)
The amount of the dioxazine compound is about 0.3 part by weight. 16. The ring-closing reaction is carried out in an amount of 0.005 of the compound of the formula (3) per 1 part by weight of the compound of the formula (2).
~ 0.3 parts by weight and 100-200 in the presence of a ring-closing agent.
The method according to claim 1, 5, 7, 9 or 11 which is performed by heating to ℃
A method for producing a dioxazine compound. 17. The use amount of the ring-closing agent is 0.1 to 5 times mol per 1 mol of the compound represented by the formula (2).
6. The method for producing a dioxazine compound of 6. 18. A coloring material containing a compound of formula (1) synthesized by the method according to claim 1. 19. A coloring material containing a reaction product obtained by the method according to claim 1. 20. A plate crystal of the dioxazine compound represented by the formula (1) according to claim 1. 21. Obtained by the reaction according to claim 1,
Plate-like crystalline reaction product.