JPS5945017B2 - Method for producing novel water-soluble benzoxanthene and benzothioxanthene compounds - Google Patents

Description

Detailed Description of the Invention From German Patent Application Publication No. 2017764, the following general formula (1) [wherein, X is oxygen or sulfur atom, Y is oxygen or] N-R group (in formula R is a hydrogen atom or an optionally substituted alkyl, cycloalkyl or aryl group, heterocyclic residue, hydroxyl or amino group, R/1 and R'2 are a hydrogen atom, a halogen atom,
Water-soluble benzoxanthin and benzothioxanthene dyes, meaning an alkyl or alkoxy group, and n being a number from 1 to 3, are known.

This compound of formula (1) is obtained by sulfonating a compound of the following general formula (I[) (wherein R'1, R:, X and Y have the above meanings) by a method known per se. It is manufactured by

In this document, there is no description at all regarding the position of the sulfo group in the benzoxanthin/benzothioxanthene combination.

This is because a mixture of isomers is clearly formed during sulfonation, and in this process the sulfonation is carried out exclusively on the aromatic ring.
This is because it is carried out particularly in the benzoxanthin- or benzothioxanthene-dye nucleus. Therefore, ]N in the side chain
There is also no description of a compound having a sulfonic acid group at the end as the -R group. In this known process, the nuclear sulfonation is carried out in particular using fuming sulfuric acid. At low temperatures of 70-100°C, a mixture of mono- and disulfonated products is formed (Example 1), whereas at high temperatures of 125-130°C, products are nuclearly sulfonated at two sites (Example 1). 2).

Furthermore, German Patent Application No. 2150879 states:
The use of such nuclear sulfonated dyes of the formula (1) for dyeing and printing textile materials made of natural and synthetic polyamides and polyurethanes is described.

Further, from this publication, a dye having a sulfonic acid group in the aliphatic side chain via an imide group', NR is known. However, the dyes additionally contain at least one other sulfonic acid group on the benzoxanthin or benzothioxanthene group. These mononuclear benzoxanthin and benzothioxanthene sulfonated dyes give very bright dyeings, but in some properties they do not fully meet the demands placed on dyes today. do not.

In particular, the dye obtained using the dye has poor alkali resistance. In addition, the dyes do not uniformly color materials consisting of textured polyamide fibers with different degrees of orientation. The present inventors have discovered new and better water-soluble compounds, especially those which contain no sulfo group in benzoxanthin and benzothioxanthene and which correspond to the following general formula (1) in the form of free acid. Alkali and alkaline earth metals and ammonium salts were found.

Alkaline salts include in particular the sodium and potassium salts. In the above general formula (1), each symbol has the following meaning: X is an oxygen atom or a sulfur atom,
, R2, R3 and R4 are the same or different and each has a hydrogen atom, an alkyl group having 1 to 4 C atoms, in particular a methyl or ethyl group or a 1 to 4 C atom. An alkoxy group, in particular a methoxy or ethoxy group, where the residues of the formula +B-(D)n together are alkylene residues having 1 to 6 C atoms, such as (wherein R is a hydrogen atom or means an alkyl group having 4 C atoms, and alkylene is an alkylene residue having 1 to 6 C atoms; w is a sulfonic acid group, a sulfato group (- 0S03H), phosphato group (-0P03H2) or thiosulfato group (
-SSO3H), and m is a number of 1 or 2.

or a trivalent nitrogen atom or a mononuclear or dinuclear aromatic group,
(C1-C4)-Alkyl aromatic or heterocyclic radicals, such as benzene mono- or naphthalene nuclei or benzyl radicals (the aromatic nucleus is substituted by an alkyl mono- or alkoxy group containing 1 to 4 C atoms or a chlorine atom) and/or may contain an alkylene group containing 1 to 4 C atoms), to which a residue w may be attached, and D is divalent or trivalent. benzene residues or naphthalene residues or aromatic or aliphatic carboxylic acids such as formic acid, acetic acid, valeric acid or benzoic acid or naphthoic acid esters, carboxylic acid amides or acyl residues, or aliphatic or Aromatic sulfonamide residues (especially of the benzene series, e.g. phenylsulfonic acid or p-toluenesulfonic acid), or monosulfonamide or carbonylamide residues, especially of the formula [wherein R is 1 to 6] a branched or straight-chain alkyl group containing 2 to 4 carbon atoms,
or phenyl group (this is a chlorine atom, methyl-, ethyl-
, optionally substituted with methoxy and/or ethoxy groups) or (C1-C4)-alkylenephenyl group, such as a group of the formula -CH2-CH2 or -CH2, w is a sulfonic acid group as a water-solubilizing group (which may be bonded to B and/or D);
Sulfato group (-0S03H), thiosulfato group (-
SSO3H), phosphate group (-0P03H2), phosphonic acid group (-PO(0H)2) or phosphonic acid half ester group (-PO(0R5)(0H)) (wherein R5 is lower alkyl or benzyl group ), and m is 1 or 2
and n is O or 1.

According to the present invention, the novel compound of formula (1) has the following general formula (
2) or (3) The dicarboxylic acid or its anhydride represented by the following general formula (4) (
In the above formula, X. Rl, R2, R3, R4, B. D.W.
m and n have the meanings given above) to form the imide in one reaction step, in a solvent at a temperature of 50 to 200°C, most preferably 80 to 150°C and optionally under pressure. It is also preferable to carry out the reaction at a pH of 4 to 10, especially 6 to 9.

Solvents include in particular dimethylformamide, alkyl glycols such as ethylene glycol-monomethyl mono- or monoethyl ether, lower alkanols such as methanol, ethanol or butanol, or mixtures of these solvents, mixtures of these solvents with water, preferably water. or the formula (au) (wherein R1, R2, R3, R4, B.D and n are the formula (
In formula (1), w is a sulfato group (
-0S03H) and m is 1, in which case in the case of this esterification reaction, especially local Care should be taken not to overheat the phosphate compound or the phosphate compound using concentrated phosphoric acid or polyphosphoric acid at a temperature of 80 to 200°C, especially 100 to 150°C. Of the compounds of formula (1) which are varied or prepared by b-(1) and b-(2), n=0 and B is from 1 to 6
an alkylene group containing one C atom, in particular a group of the formula -CH2- or -CH2-CH2-, or an aromatic residue, in particular a benzene residue, which may be substituted by an alkylene group, such as a residue of the formula Compounds are preferred.

A compound of formula 00 is prepared using an aryl disulfo monochloride or a sulfochloride of an arylcarboxylic acid such as benzoic acid-3-sulfochloride in pyridine.
In the above formula, X. Rl, R2, R3 and R4 have the above meanings, q represents a number from 1 to 6, and A is sulfonyl-
or a carbonyl group, and Ar represents an aromatic residue such as a phenylene group or a naphthylene group,
In that case (in the above formula, X..Rl, R2, R3, Ar and q have the above meanings, R5 is a hydrogen atom or
The sulfochloride of the aromatic carboxylic acid used can be reacted as a carboxylic acid chloride via a complex compound of pyridine, or the compound of the formula By reaction with sulfo-monochloride 2 (in which case the amide formation is carried out in a manner known per se in the presence of an acid binder in an organic solvent and/or water), a compound of formula It is reacted with an amine of the following formula in an organic solvent in the presence of an acid binder in a manner known per se to obtain an amine of the formula (in the above formula, R1, R2, R3, R4, X.q and R5 have the above meanings). and R means an alkylene group containing 1 to 6 C atoms, especially a methylene group or an ethylene group, or a group of the formula.

To isolate the compounds obtained by the various methods mentioned above, the reaction mixture is stirred, if necessary, in the customary manner with ice water and brought to a pH of 5-7 using soda solution.

The new compound is then salted out with sodium chloride or potassium chloride, filtered through a suction port and dried. Production of dicarboxylic acids of general formulas (2) and (3) and their anhydrides, as well as imides and acid chlorides thereof represented by general formulas (alternative), (auto), and eel, used as starting compounds The carboxylic acids required for
59 and German Patent Application Nos. 1,569,761 and 1,770,818.

The novel compounds of formula (1) have been found to be particularly suitable as brilliant dyes for dyeing and printing natural and synthetic fiber materials containing carbonamide groups, such as wool, silk, synthetic polyamide fibers or polyurethane fibers. did.

The compound produces a deep, reddish to greenish-yellow, very brilliant dyeing on these materials, which in places has a strong green fluorescence and is very high to high for the dye class.
It has excellent brightness and wet fastness). In this case, the dyeings and prints are generally characterized by very good light fastness in dry and wet conditions, good to very good fastness to washing (perborates or peroxides and other (even in the presence of bleaching agents, e.g. hypochlorite) and good acidic and alkaline perspiration fastness, cross dyeing, bottling, full, water, seawater, alkali, acid and rub fastness. Excellent in this respect. Furthermore, the new dyes have good dyeing properties and good build-up properties on the above-mentioned fibers and therefore high tinting strength. Furthermore, the dyeings obtained with the dyes are distinguished by a very good uniformity; the dyes uniformly color the textured polyamide materials. Furthermore, the new dye has very good water solubility even in cold water, causes no or very little agglomeration of the dye in the dye mixture during dyeing, and also provides good resist dyeing when dyeing mixed fabrics. behavior (in particular about 100
(at high temperatures of from 230 DEG C. to 230 DEG C.) and the aqueous dye solutions, padding baths and printing pastes can be distinguished by good viscosity behavior and low electrolyte sensitivity.

In particular, the dyes according to the invention have different dyeing properties and use and processing fastnesses, e.g. , outstandingly superior in terms of tinting strength, clear contour behavior, alkali fastness, and alkaline sweat fastness.

Moreover, on the above-mentioned textile materials some of the dyes are mixed with suitable blue dyes to give very bright green shades with very good sunlight and wet fastness properties. Another advantage of the new compound is that it can be easily manufactured industrially.

In particular, the general formula (2) or (3) used as starting material
) of benzoxanthin mono- or benzothioxanthene-dicarboxylic acids or their anhydrides can be prepared together with the amine of general formula (4) in only one reaction step to form the compounds according to the invention, which are usually in very high yields and very pure. (obtained in a state). Moreover, this reaction can be carried out in water. Among the novel compounds according to the invention, those in which the individual radicals of the general formula (1) have the following meanings are particularly preferred: R1 or R
2 or R3 is a methyl or methoxy group, in other cases a hydrogen atom, and R4 is a hydrogen atom, or R1, R2, R
3 and R4 are each a hydrogen atom, X is an oxygen atom or a sulfur atom, and the formula is +B-(D).

] The residue has a total of 1 to 6 C atoms, especially 2
an alkylene group containing 1 to 6 C atoms, or an alkylene group containing 1 to 6 C atoms, or an alkylene group containing 1 to 6 C atoms;
Alkyl then forms an alkyl group containing 1 to 4 C atoms, especially meaning a methyl or ethyl group.

w represents a sulfonic acid group, sulfato, phosphate or thiosulfate, and m is 1 or 2.

Particularly advantageous and preferred among these are compounds of the formula (
In 1) R,, R2, R3, R4 and x and w likewise have the abovementioned meanings and m is 1.

Among the compounds according to the present invention, a particularly excellent and representative example that can be synthesized conveniently is represented by the following general formula (5) (wherein B represents the following formula or group, and w represents a thiosulfato or phosphate group, particularly sulfo group or sulfato group).

? The following examples are illustrative of the invention and the parts stated therein are parts by weight.

Example 1 Benzothioxanthene-3,4-dicarboxylic anhydride 3
0.4 part was suspended in 330 parts of dimethylformamide,
and 14.2% of 2-aminoethanesulfonic acid in 180 parts of water.
Heat under reflux for 8 hours with a solution of 5 parts and 7.8 parts of potassium carbonate.

After cooling to room temperature, 200 parts of 15% potassium chloride solution are added to completely precipitate the imide compound obtained. After several hours, filter through the suction port, wash with 10% potassium chloride solution,
Then, dry at 100°C. Approximately 47 parts of benzothioxanthene-3,4-dicarboxylic acid-N-β-sulfoethylimide of the formula are obtained in the form of the potassium salt.

This new compound has an absorption maximum of 469 nm and a 1 molecule extinction coefficient of 15,380 and dissolves in water to give a yellow color and gives a brilliant, golden yellow color with good sunlight and wet fastness on wool and polyamide by conventional dyeing methods. Causes staining. Example 2 32 parts of 10-methoxybenzoxanthine-3,4-dicarboxylic anhydride are introduced into a solution of 13.7 parts of 2-aminoethanesulfonic acid and 5.3 parts of sodium carbonate in 500 parts of water and placed in a pressurized autoclave. 140℃ for 6 hours inside
Heat while stirring.

After cooling, the imide compound obtained is completely precipitated by adding 40 parts of sodium chloride, filtered through a suction port and washed with 10% sodium chloride solution. After drying, approximately 43 parts of a compound having the following formula are obtained in free acid form.

This is ground for easier use as a dye.

It has an absorption maximum of 447 nm, a molecular extinction coefficient of 18,360 and dissolves in water to give a yellow color and a fringe-coloured fluorescence, and is eminently suitable for dyeing and printing natural and synthetic polyamides, in which case it is an extremely bright, greenish-yellow color. The color tone is obtained. Example 39-Methyl-benzoxanthene-3,4-
15 parts of dicarboxylic anhydride to 18 parts of monoethyl glycol
0 parts of the compound and stirred autoclaved for 6 hours with a solution of 7.5 parts of 2-aminoethanesulfonic acid and 5.2 parts of sodium bicarbonate in 90 parts of water.
Three copies are obtained.

This compound has an absorption maximum of 457 nm and a 1-molecule extinction coefficient of 162.
It has 60. With this compound bright yellow dyeings can be obtained on synthetic polyamide fiber materials by customary dyeing methods. Example 5 29 parts of benzoxanthin-3,4-dicarboxylic anhydride was suspended in 450 parts of monoethyl glycol.
Heat to 0°C.

After cooling, the imide compound thus obtained is salted out with saturated sodium chloride solution, filtered through a suction port, washed and dried. Approximately 21 parts of a compound having the following formula in free acid form are obtained.

It can be dyed on wool and synthetic polyamides by industrially customary methods to give very bright greenish-yellow dyeings with good use fastnesses. Example 4 Analogously as described in Example 2, 32 parts of 6-methoxybenzoxanthine-3,4-dicarboxylic anhydride are reacted with 13.7 parts of 2-aminoethanesulfonic acid.

After salting out and washing with 10% sodium chloride solution, about 48 parts of a compound having the following formula are obtained in the form of the free acid.

This produces bright greenish-yellow dyeings with good use fastness on wool and polyamide. Example 6 17.3 parts of 2-aminoethanol sulfate are dissolved in 180 parts of water with 23 parts of sodium bicarbonate, then 250 parts of dimethylformamide are added, resulting in a compound of about 9.2 parts.
part is obtained as potassium salt.

This gives a very bright greenish-yellow dyeing with an absorption maximum of 446 nm and very good use fastness on synthetic polyamides. Example 8 14.5 parts of phenylhydrazine-2,5-disulfonic acid are dissolved in 40 parts of water with 2.8 parts of sodium acetate and 9 parts of sodium carbonate.

Next, add 200 parts of monoethyl glycol and 10 parts of monoethyl glycol.
-methoxybenzoxanthine-3 and 10-methoxybenzoxanthine-3,4
- 32 parts of dicarboxylic anhydride are introduced. The suspension is stirred for 8 hours at 95° C. and a pH value of 7 to 7.5. After the reaction has ended, the imide obtained is precipitated with 200 parts of 15% sodium chloride solution, filtered through a suction port, washed with 10% sodium chloride solution, dried at 80° C. and ground. Approximately 43 parts of an orange-yellow compound having the following formula are obtained in the form of the free acid. This has an absorption maximum of 448 nm and a single molecule extinction coefficient of 149.
20 and gives greenish-yellow, very bright dyeings and prints with good use fastness on wool and polyamide fibers by industrially customary dyeing and printing methods. Example 7 8.5 parts of 10-methoxybenzoxanthine-3,4-dicarboxylic acid-N-β-hydroxy-ethylimide are introduced into 90 parts of polyphosphoric acid and heated gradually to 140° C. with stirring.

°Stir at this temperature for 8 hours. The reaction mixture is then placed on ice, the resulting phosphate compound is salted out with potassium chloride, and filtered off with suction. The wet sipcake is stirred in water and neutralized with potassium carbonate. After clarification and spray drying of the solution, about 27 parts of a compound of the following formula are obtained as potassium mono/sodium salt.

It has an absorption maximum of 448 nm, a molecular extinction coefficient of 13010 and gives a bright yellow color on synthetic polyamide fibers by industrially common dyeing and printing processes. Example K 9 When 16 parts of 10-methoxybenzoxanthine-3,4-dicarboxylic anhydride and 20 parts of the sodium salt of 4-aminobenzyl sulfonic acid are reacted under the conditions listed in Example 8, a compound of the following formula: 25 parts are obtained as potassium mono- or sodium salt.

The resulting compound has an absorption maximum of 453 nm and an extinction coefficient of 2 per molecule.
4510. With this, very bright yellow dyeings with very good light fastness properties are obtained on synthetic polyamide fiber materials. Example 10 Benzoic acid-3
- Introducing 7 parts of sulfochloride.

It is then stirred for 1 hour at 30-40°C and for 2 hours at 40-50°C. In that case, it will dissolve completely. then 40
Add dropwise 50 parts of water at 60-70°C for another hour.
Stir with. 25°C to precipitate the formed compounds.
Add 200 parts of saturated sodium chloride solution, filter the precipitated product through the suction port, and wash with saturated sodium chloride solution.
It is then dried in vacuum at 60°C. 10.4 parts of a compound corresponding to the following formula are obtained in the form of the free acid. This dye has an absorption maximum of 449 nm, a molecular extinction coefficient of 11,110 and produces a brilliant greenish-yellow dyeing on synthetic polyamide fiber materials. Example 11 N-Methyltaurine (sodium 4.5 parts of the solution (as salt) are added dropwise.

Then at 10-20°C for 3 hours and at 20-3°C for 5 hours.
The mixture is stirred at 0° C. and the pH value is kept at 6-7. After the reaction, 100 parts of saturated sodium chloride and potassium chloride solutions are added. Pass the precipitate through the suction port. Wash the wet filter cake with saturated sodium chloride solution and then add 40 mL of water.
Stir in 0 parts. After clearing the solution and spray-drying, 3.4 parts of a compound of the following formula are obtained as potassium mono/sodium salt.

Claims (1)

[Claims] 1 In the form of a free acid, the following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) [In the formula, X is an oxygen or sulfur atom, and R_1, R_2, R_3 and R_4 are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 C-atoms, or an alkoxy group having 1 to 4 C-atoms; (D)_n■ together with alkylene residues or formulas having 1 to 6 C-atoms ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. is an alkylene residue having 6 C-atoms), W is a sulfone residue, sulfato-, phosphate- or thiosulfato group, and m is a number of 1 or 2. In order to produce the corresponding water-soluble benzoxanthene and benzothioxanthene compounds, the following formula (2) or (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲
There are mathematical formulas, chemical formulas, tables, etc.▼(3) (R_1 in the formula,
R_2, R_3, R_4 and X have the above meanings)
Benzoxanthene- or benzothioxanthene-dicarboxylic acid or its anhydride represented by the following general formula (4) ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼(4) Reacting with the amine represented by (residues in the formula ■B-(D)_n■, W, m, and n have the above meanings) to form an imide. The above method characterized by: 2 In the form of free acid, the following general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, X is oxygen or sulfur atom, and R_1, R_2, R_3 and R_4 are the same or They are different from each other and are respectively a hydrogen atom, an alkyl group having 1 to 4 C-atoms, or an alkoxy group having 1 to 4 C-atoms, and the residues of the formula ■B-(D)_n■ are Alkylene residues or formulas having together 1 to 6 C-atoms ▲Mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. water-soluble benzoxanthene and benzoxanthene residues corresponding to 1), where W is a sulfato or phosphate group, and m is a number of 1. To prepare thioxanthene compounds, the general formula (
10) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (10) (In the formula, R_1, R_2, R_3, R_4, X and the residue of the formula
B-(D)_n■ has the above meaning) is reacted with sulfuric acid at a temperature of 0 to 40°C or with concentrated phosphoric acid or polyphosphoric acid at a temperature of 80 to 200°C. The above method. 3 In the form of free acid, the following general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, X is an oxygen or sulfur atom, and R_1, R_2, R_3 and R_4 are the same or are different from each other and are each a hydrogen atom, an alkyl group having 1 to 4 C-atoms or an alkoxy group having 1 to 4 C-atoms and a residue of the formula ■B-4(D)_n■ is a residue represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula, alkylene is an alkylene residue having 1 to 6 C-atoms), W is a sulfo group, and m means the number 1] In order to produce water-soluble benzoxanthene and benzothioxanthene compounds corresponding to the formula (11) ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (11) (R_1 in the formula
, R_2, R_3, R_4, 4 In the form of free acid, the following general formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, X is oxygen or sulfur atom, and R_1, R_2, R_3 and R_4 are the same or They are different from each other and are respectively a hydrogen atom, an alkyl group having 1 to 4 C-atoms, or an alkoxy group having 1 to 4 C-atoms, and the residues of the formula ■B-(D)_n■ are General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, alkylene is an alkylene residue having 1 to 6 C-atoms, and R is a hydrogen atom or a hydrogen atom or
for producing water-soluble benzoxanthene- and benzothioxanthene-compounds corresponding to the residue represented by (meaning an alkyl group having an atom), W represents a sulfo group, and m is a number of 1. Then, the general formula (15)▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (15) (R_1 in the formula
, R_2, R_3, R_4, ) R-NH-alkylene-SO_3H (wherein alkylene and R have the above-mentioned meanings).