KR830001369B1 - How to prepare basic dye - Google Patents

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Description

How to prepare basic dye

The present invention relates to the following compounds of the general formula (III) in the presence of catalytic amounts of halogen or cyano-substituted benzoqui or nitro-substituted phenanthrenequinones and catalytic amounts of nitrogen oxides (except nitrogen dioxide) or The present invention relates to a process for preparing a basic dye of formula (I), characterized by oxidizing with oxygen in the presence of a substance which produces the same nitric oxide.

In the above formula

A and B independently of each other represent a hetero-aromatic group or a group of the following general formula (II)

Group,

Y represents a hydrogen or nonionic substituent,

n represents 1 to 4,

R ₁ and R ₂ are hydrogen or alkyl; Aryl or aralkyl optionally substituted by a nonionic or acidic group, or together or together with Ar in the 0-position to form a heterocyclic ring,

D is hydrogen; Alkyl; Aryl optionally substituted by a neutral or acidic group; Or a hetero-aromatic group

X ⁻ represents an anion.

In general formula, an alkyl group is a C1-C4 alkyl group especially. Alkyl groups carry, for example, one to three nonionic or acidic substituents. Such substituents include halogen, hydroxyl, alkyl of 1 to 4 carbon atoms, cyano, alkoxy of 1 to 4 carbon atoms, alkoxycarbonyl of 1 to 4 carbon atoms, alkylcarbonyloxy of 1 to 3 carbon atoms, aminocarbonyl, sulfo Or carboxyl.

Halogen is preferably fluorine, chlorine or bromine.

Particularly suitable aryl groups are optionally substituted phenyl or naphthyl groups.

Particularly suitable aralkyl groups are optionally substituted benzyl, α- or β-phenylethyl or α-, β- or γ-phenylpropyl groups.

These isocyclic groups may carry 1 to 3 substituents such as, for example, halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, sulfo or carboxyl.

The R ₁ and R ₂ groups together or together with the 0-position of Ar form, for example, a 5-membered or 6-membered ring;

For example, the R ₁ and R ₂ groups together may be piperidine; To form a pyridine, morpholine or piperazine ring; R ₁ and R ₂ together with Ar in the 0-position form a tetrahydroquinoline, indolin, zulolidine, phenomorpholine, tetrahydroquinoxaline or carbazole ring.

Heteroaromatic rings D mentioned include especially indol-3-yl, pyrazol-4-yl and pyrazolin-5-one-4-yl rings. Heterocyclic rings are substituted, for example, by alkyl groups or phenyl having 1 to 4 carbon atoms.

Among the dyes described above, the compounds of the following general formula (IV) can be prepared particularly easily.

In the above formula

R ₃ and R ₅ are independently of each other hydrogen, alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms, cyanoethyl, alkoxyalkyl having 3 to 5 carbon atoms, and alkoxy carbo having 3 to 8 carbon atoms Nylalkyl, alkylcarbonyloxyalkyl having 3 to 8 carbon atoms in total, halogenoalkyl having 1 to 4 carbon atoms, sulfoalkyl having 2 to 4 carbon atoms, cyclohexyl, benzyl, phenyl, phenethyl; Halogen or phenyl substituted with alkyl or alkoxy having 1 to 4 carbon atoms, or sulfobenzyl,

R ₄ and R ₆ independently of each other, alkyl having 1 to 4 carbon atoms, hydroxyalkyl having 2 or 3 carbon atoms, cyanoethyl, halogenoalkyl having 1 to 4 carbon atoms, alkoxyalkyl having 3 to 5 carbon atoms in total, and total carbon atoms Alkoxycarbonylalkyl of 3 to 8, alkylcarbonyloxyalkyl or benzyl of 3 to 8 carbon atoms in total, or

or

R ₃ and R ₄ and / or R ₅ and R ₆ together form a pilidine, piperidine, morpholine or piperazine ring, optionally substituted with alkyl of 1 to 4 carbon atoms, or

R ₃ , R ₄ , R ₅ and / or R ₆ together with a phenyl ring in the 0-position, tetrahydroquinoline, indolin, zulolidine, phenomor, optionally substituted with alkyl, phenyl or benzyl having 1 to 4 carbon atoms To form a Pauline, tetrahydroquinoxaline or carbazole ring,

R ₇ and R ₈ represent hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy or halogen of 1 to 4 carbon atoms,

n represents an integer of 1 to 4,

E is phenyl; Phenyl or naphthyl monosubstituted or disubstituted with halogen, alkyl of 1 to 4 carbon atoms, alkoxy, nitro, carboxyl group or sulfonic acid group of 1 to 4 carbon atoms; Or a heterocyclic group of the general formula (V)

(Wherein R ₉ represents hydrogen, alkyl having 1 to 4 carbon atoms, phenyl, alkyl ester having 1 or 2 carboxylic acids; carboxylic acid amide optionally N-substituted with alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms) ,

or

E represents a group of the following general formula (VI) or

Wherein n, R ₃ , R ₄ and R ₇ are as described above, or

E represents a group of the following general formula (VII) or (VII)

Wherein R ₁₀ represents hydrogen, alkyl of 1 to 4 carbon atoms or halogen, in particular chlorine or bromine, and n, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as described above;

X ⁻ is as described above.

The following compound of formula (VII) is used as a starting material for preparing the dye of formula (IV).

In the above formula

n and R ₃ to R ₈ are as described above,

F is the same as E or is a group of the following general formula (XI) or (XII).

In the above formula

n, R ₃ to R ₈ and R ₁₀ are as described above.

R ₃ and R ₅ independently of one another represent hydrogen, methyl ethyl, hydroxyethyl, propyl or butyl, R ₄ and R ₆ independently of one another represent methyl, ethyl, sulfobenzyl or sulfoethyl, and R ₇ and R ₈ These independently represent hydrogen, methyl, methoxy or chlorine,

E is phenyl; Phenyl substituted with chlorine, methoxy or sulfonic acid groups; P-dimethylaminophenyl; P-diethylaminophenyl; Particular preference is given to dyes of the general formula (IV) which represent P-bishydroxyethylaminophenyl or a group of formula (V) wherein R ₉ is hydrogen, methyl or phenyl and R ₃ is methyl or phenyl .

Anions are derived from inorganic or organic acids and are generally determined by the preparation process to be performed and the purification of crude dyes.

Generally dyes are in the form of zinc chloride double salts, acetates, methosulfates, ethosulfates or halides (especially chlorides or bromide). Anions can be replaced with other anions according to known methods.

The quinones used as oxidants are tetrachloro-, tetrabromo-, tetrafluoro-, tetracyano- or dicyanodichloro-1,4-benzoquinone, tetrachloro- or tetrabromo-1,2-benzoquinone Or 2-nitro-, 2,7-dinitro- or 4 5-dinitro-phenanthrenequinone. Tetrachloro- and tetrabromo-1,4-benzoquinones are preferred. Quinone is used in the amount of 10 ^-3 to 10 ^-1 mole based on the molar amount of the compound of formula (III). Instead of quinones the corresponding hydroquinones may be used.

Suitable catalysts are nitrogen oxides or nitrogen dioxide or substances which liberate nitrogen oxides under reaction conditions, especially in acid solvents, for example ferric nitrate or sodium nitrite. The catalyst uses a concentration of 1 to 20 mole percent with respect to the substrate.

New method quinone 10 about equal to the molar amount of compound of the formula (Ⅲ) compound 0 to and at 150 ℃, preferably 20 to 70 ℃ dissolved or suspended in an aqueous or organic solvent in neutral or acidic, in the formula (Ⅲ) ^- After adding ³ to 10 ^-1 mol, the reaction solution is strongly mixed with the supplied oxygen, usually pure oxygen or air, and 1 to 20 mol% of nitrate or nitrite is added or 1 to 20 mol% of nitrogen oxide total is added during the reaction. It can proceed by weighing and adding. Oxides can be metered from an oxygen outlet or from a separate metering device. It is necessary to mix the gas and solution vigorously to obtain a high reaction rate. The reaction can also be run under pressure.

Examples of suitable solvents for oxidation include methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, benzene, toluene, xylene, cumene, acetic acid, propionic acid, lactic acid, dichloroethane, methanol, ethanol, propanol, isopropanol, butanol, glycol , Methylglycol, dimethyl, glycol, tetrahydrofuran, dioxane, ethyl acetate, dimethylformamide, N-methylpyridone or acetone or mixtures thereof. The reaction may also proceed in aqueous solution or suspension or in a mixture of water and a solvent that can be miscible with water. The pH of the reaction solution should be in the range of neutral to acidic, depending on the dye.

Preference is given to an acidic pH range of pH 1-4.

The following examples illustrate the invention. Unless otherwise indicated, parts relate to weight.

Example 1

99 parts of leuco-malachite green, 6 parts of chloranyl and 600 parts of glacial acetic acid are treated strongly with air at 30 ° C. During the reaction-after a reaction time of about 12 hours-a total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide, produced by treating sodium nitrite with sulfuric acid, are added in an equal metered amount. At the end of the reaction, 95% of the leuco-malachite green used is converted to malachite green. After evaporation of glacial acetic acid, the dye is treated with sodium hydroxide solution and precipitated as a carbinol base. The carbinol base is warmed to 70 ° C. with oxalic acid, the mixture is filtered and cooled to precipitate very clean crystalline malachite green oxalate.

If instead of nitric oxide, 2.5 parts of sodium nitrite or 2.5 parts of ferric nitrate are added during atmospheric oxidation, similarly good results are obtained.

Example 2

A mixture of 109.5 parts of the compound of the following structural formula, 300 parts of glacial acetic acid, 300 parts of chlorobenzene and 6 parts of chloroanyl is treated vigorously with air at 50 캜.

During the reaction, a total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide are continuously metered in. At the end of the reaction, chlorobenzene and some glacial acetic acid are evaporated in vacuo, the residue is taken up in hot water, the aqueous mixture is acidified with dilute hydrochloric acid, heat filtered and the dye precipitated with sodium chloride. The dye is obtained in 90% yield. Similar results are obtained if sodium nitrite or ferric nitrate is used instead of nitrogen oxide as a catalyst.

Example 3

A suspension of 31.8 parts of the compound of the following structural formula, 1 part of chloranyl and 450 parts of water is treated with oxygen at 70 ° C. with vigorous stirring.

During the reaction, a total of 0.5 parts of a mixture of nitrogen monoxide and nitrogen dioxide are continuously metered in. At the end of the reaction, 88% of the starting compounds used are oxidized to dyes. The dye can be separated by treating the reaction solution with sodium chloride. Similar results are obtained by using sodium nitrite or ferric nitrate instead of nitrogen oxide as a catalyst.

Example 4

107 parts of leuco-diamond green and 6 parts of chloroanyl are dissolved in 60 parts of glacial acetic acid and 500 parts of chloroform.

At 30 ° C., the air stream is passed violently through this solution. A total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide were added to the reaction during the reaction. At the end of the reaction, the reaction solution contained diamond green in 92% yield.

Example 5

Then 118 parts of the structural compound and 6 parts of chloro anil are dissolved in 60 parts of glacial acetic acid and 500 parts of chloroform.

While stirring this solution vigorously, air is passed through it at 50 ° C. A total of 1.2 parts of a mixture of nitrogen monoxide and nitrogen dioxide are added at the same time as the air outflow.

At the end of the reaction, chloroform is evaporated in vacuo, the residue is dissolved in warm water, the aqueous mixture is filtered, and the dye is salted with sodium chloride solution. Dye is obtained in a yield of 87%.

The following leuco-compounds can also be oxidized in good yields by the invention according to the invention.

Claims (1)

The compounds of formula (III) are then subjected to such nitrogen oxides in the presence of catalytic amounts of halogen or cyano-substituted benzoquinones or nitro-substituted phenanthrenequinones and catalytic amounts of nitrogen oxides (except A method for preparing a basic dye of the following general formula (I), characterized by oxidizing with oxygen in the presence of a substance to produce.

In the above formula A and B independently of each other represent a hetero-aromatic group or a group of the following general formula (II)

Group, Y represents a hydrogen or nonionic substituent, n represents 1 to 4, R ₁ and R ₂ are hydrogen or alkyl; Aryl or aralkyl optionally substituted by a nonionic or acidic group, or together or together with Ar in the 0-position to form a heterocyclic ring, D is hydrogen; Alkyl; Aryl optionally substituted by a neutral or acidic group; Or a hetero-aromatic group and X ⁻ represents an anion.