DE1285642B - Process for the production of azo dyes - Google Patents

Description

It has been found that valuable new azo dyes are obtained if acylating agents which is the rest of the general formula

C CH ₂ CH ₂

in the A the rest of one

denotes azo dyes bearing a plurality of sulfonic acid groups, Y preferably denotes a hydrogen atom or an advantageously low molecular weight alkyl radical, X has the meaning given in the explanation of the formula I and η denotes an integer which is greater than or equal to 1, preferably one of the numbers 1 or 2, stands. The new process is of particular technical interest for the production of monoazo dyes.

The azo dyes used as starting materials for the production of the new dyes or for Preparation of azo dyes suitable intermediates must have at least one acylatable amino group contain, but they can also have two or more acylatable amino groups.

Intermediate materials suitable for the production of azo dyes are not just coupling components and diazo components, but also compounds which can be converted into diazo components, for example Compounds which have a formylamino group instead of the primary amino lip to be diazotized or contain a nitro group. The intermediate substances mentioned are produced in a customary manner by coupling or, if necessary after conversion into diazo components, by diazotization and coupling completed to azo dyes.

Azo dyes which correspond in that of the diazo component and / or in that of the coupling component Part of the molecule containing acylatable amino groups are in the usual way by coupling available from diazo components with coupling components, at least one of the components an acylatable amino group or a group which can be converted into an acylatable amino group, e.g. B. a formylamino group or a nitro group, which after coupling into an acylatable Amino group is converted.

Diazo components which, in addition to the diazotizable amino group, have at least one further acylatable Amino group are, for example, 1,3-diaminobenzene - 4 - sulfonic acid, 1,4 - diaminobenzene-3-sulfonic acid, 1,4-diaminobenzene and 1,4-diamino-3-nitrobenzene.

As compounds which can be converted into diazo components and contain acylatable amino groups, are for example l-amino-4-nitrobenzene, 1-amino-3-nitrobenzene, Called l-amino-4-formylaminobenzene or 1-amino-3-formylammobenzene.

Coupling components which contain at least one acylatable amino group are for example Aminohydroxybenzenes, di- or polyaminobenzenes, aminohydroxynaphthalenes, di- or polyaminonaphthalenes, Aminophenylmethylpyrazolones and the N-alkyl, or also N-aryl, N-aralkyl and N-cycloalkyl derivatives these compounds and the corresponding sulfonic acids, sulfonic acid amides and sulfones.

The compounds mentioned can have further substituents on the aromatic nucleus, such as alkyl, Aralkyl, aryl, carboxyl, carboxylic acid, carboxamide, carboxylic acid ester, arylamino, nitro groups and / or halogen atoms.

The acylating agents which release the remainder of the general formula I can differ from one another derive ß-oxy- or / I-thiopropionic acids, for example from the jS-methoxypropionic acid, the / J-ethoxypropionic acid, the / J-methylmercapto-

optionally one or 45 propionic acid, the / i-ethyl mercaptopropionic acid, or

advantageously of an optionally substituted / i-phenoxy or ß-phenylthiopropionic acid, such as the / f-phenoxypropionic acid, the /? - (4-chlorophenoxy) propionic acid, the ß- {3- or 4-nitrophenoxy) propionic acid, the / i- (4-methylphenoxy) propionic acid, ß- (4-methoxyphenoxy) propionic acid, /? - phenylmercaptopropionic acid, ß- (4-methylphenyl) -mercaptopropionic acid, / I- (4-methoxyphenyl) -mercaptopropionic acid or der / J- (4-nitrophenyl) mercaptopropionic acid.

The acid halides obtainable from these carboxylic acids or acid anhydrides are usually used with the aforementioned azo dyes or for Preparation of azo dyes suitable intermediates in aqueous solution or slurry or in organic solvents such as formamide, dimethylformamide or N-methylpyrrolidone, or in aqueous mixtures with organic solvents and / or diluents at lower or lower slightly elevated temperature, advantageously in the presence of acid-binding agents such as sodium carbonate, Sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate,

give off, where X stands for the group —S — R or preferably represents the group - O — R ', R represents a Alkyl radical, an aralkyl radical, a cycloalkyl radical or an aryl radical and R 'an alkyl radical, a Aralkyl radical, a cycloalkyl radical, an aryl radical or a heterocyclic radical means with azo dyes or for the preparation of azo dyes suitable intermediates, the at least one acylatable Carry amino group, to /? - (propionic acid amide) -ether or -thioether derivatives and converts in the case of using the intermediate substances, the reaction products in a manner known per se completed to azo dyes.

Primary amino groups, but also secondary amino groups, are preferred as acylatable amino groups. Acylating agents which release the rest of the general formula I are, for example, the appropriately substituted .beta.-oxy or / f Thiopropionsäurehalogenide, such as the chlorides or bromides, or the substituted .beta. corresponding oxy or ß-Thiopropionsäureanhydride. The radicals R and R 'mentioned in the explanation of the general formula I are expediently a low molecular weight alkyl radical, for example a methyl, ethyl or propyl radical, or a benzyl radical or, preferably, an optionally substituted aryl radical, for example a naphthyl -1 radical, for a naphthyl-2 radical, for a phenyl radical, for a 4-chlorophenyl radical, for a 4-methylphenyl radical, for a 4-methoxyphenyl radical or for a 3- or 4-nitrophenyl radical.

The new dyes correspond to the general formula

CO-CH ₂ -CH ₂ -X;

II

Sodium hydroxide, potassium hydroxide, and / or organic nitrogenous bases, e.g. B. triethylamine or pyridine.

The dyes obtainable according to the invention can be separated off very easily from the reaction mixtures and can be easily removed from any adhering impurities by washing with water.

The new dyes can be used for dyeing and / or printing structures such as foils, films and Textile goods, e.g. B. fibers, threads, flakes, woven and knitted fabrics made of a wide variety of fiber-forming materials Kind, for example made of wool, silk, synthetic linear polyamides or polyurethanes or made of paper, serve. The dyes obtainable according to the invention are particularly suitable good for dyeing and / or printing textiles made from native and / or regenerated cellulose. Very good dyeings and prints are then obtained by methods customary for reactive dyes Fastness properties, in particular excellent wet, light and rub fastness. When printing of textile material made of cellulose according to the methods customary for reactive dyes, the new ones stand out Dyes due to the fact that the unfixed dye components are particularly easy to wash out.

From French patent specification 1,198,990 it is known that dyes with /? - chloropropionyl groups by virtue of their labile chlorine atom can be used as reactive dyes. It should However, it is surprising that the dyes obtainable according to the invention are among those for reactive dyes usual application methods with elimination of the ether or thioether group so smoothly with the Cellulose react.

The parts and percentages given in the examples are, unless otherwise stated, Weight units. The parts of the volume relate to the parts by weight as under normal conditions measured liters to the kilogram.

example 1

103 parts of // phenoxypropionic acid are dissolved in 100 parts by volume of N-methylpyrrolidone and mixed with 80 parts of thionyl chloride. The temperature rises to 50 to 60 ^° C. with evolution of hydrogen chloride. After stirring for 1 hour, the solution of the β-phenoxypropionic acid chloride thus obtained is slowly added in small proportions to a solution of 69 parts of 3-nitroaniline in 400 parts by volume of N-methylpyrrolidone. The temperature rises to 60 ^° C. during this process. After stirring for 3 hours at 60 ° C., the mixture is poured into 2000 parts by volume of ice water and the acidic solution is neutralized with dilute aqueous sodium hydroxide solution. The separated oil gradually crystallizes and the crystals are then filtered off with suction. To remove any adhering 3-nitroaniline, the crude product is stirred with about 1000 parts by volume of aqueous 10% strength hydrochloric acid while cooling with ice, filtered off with suction and washed free of acid. After drying, about 140 parts of an almost colorless crystal powder are obtained, which melts at about 92 ° C and, after recrystallization from ethanol, at 97 to 98 ° C.

Analysis: C ₁₅ H ₁₄ N ₂ O ₄ (molecular weight 286.3).
Found ... C 63.0, H 5.0, N 9.7%;
calculated ... C 62.9, H 4.8, N 9.8%.

130 parts of the 3-nitro- / i-phenoxypropionic anilide obtained in this way are hydrogenated in 1500 parts by volume of methanol using 5 parts of Raney nickel at 80 to 90 ° C. and under a pressure of 60 atmospheres hydrogen. After evaporation of the solvent, 110 parts of a colorless substance are obtained, which melts at about 95 ° C, and after recrystallization from ethanol at 107 ⁰ C.

Analysis: C ₁₅ Hj ₆ N ₂ O ₂ (molecular weight 256.3).

Found ... C 69.9, H 6.5, N 10.7%;
calculated ... C 70.3, H 6.3, N 10.9% ·

13 parts of the 3-amino-ß-phenoxypropionic anilide thus obtained are concentrated with ice cooling with 50 parts by volume of water and 12.5 parts by volume stirred aqueous hydrochloric acid. The sparingly soluble hydrochloride of the base is formed in the process. The mixture is then stirred with 100 parts by volume of water and 100 parts by volume of acetone and the amino compound diazotized by adding 16 parts by volume of an aqueous 23% sodium nitrite solution. The diazo solution is then in a solution of 12 parts of 1-hydroxynaphthalene-4-sulfonic acid and 50 parts of sodium acetate are added to 100 parts by volume of water and the mixture is stirred for a few hours. After that, will suctioned off the reaction material and washed with water. After drying, 29 parts are obtained of a red dye which is produced on cotton by the dyeing process customary for reactive dyes delivers red dyeings with very good wet fastness properties.

Other monoazo dyes are obtained by combining those mentioned in the table below and diazo component obtainable in the manner described above with the coupling components mentioned by diazotizing and doming. The dye 2 delivers on fabrics made from polycaprolactam and the dyes 3 to 15 replenish on cellulose tissue the dyeing and printing processes customary for reactive dyes in the methods given in the table Tones.

example

Diazo component

Coupling component

hue

0-CH ₂ -CH ₂ -CO-

the same
the same

l-phenyl-3-methylpyrazolone- (5)

1 - (3'-sulfophenyl) -3-methyl-

pyrazolone- (5)
1 - (4'-sulfophenyl) -3-methyl-

pyrazolone- (5)

yellow

yellow
yellow

5 Diazo component continuation Coupling component hue Example! / VO-CH ₂ -CH ₂ -CO-NH 1 - (2'-methyl-4'-sulfophenyl) - Geib 5 3-methylpyra, zolon- {5) the same H ₂ N 1 - (2'-chloro-5'-sulfophenyl) - yellow 6th 3-methylpyrazolone- (5) the same 1 - (6'-chloro-2'-methyl-4'-sulfo- Geib 7th phenyl) -3-methyl- pyrazolone- (5) the same l- (2 ', 6'-dichloro-4'-sulfophenyl) - yellow 8 ■ 3-methylpyrazolone- (5) the same 2-hydroxynaphthalene-3,6-di- Red 9 sulfonic acid the same 1 -hydroxynaphthalene- Red 10 5-sulfonic acid • the same. 1 -hydroxynaphthalene-S.S-di- Red 11 sulfonic acid the same 1 -Benzoylamino-8-hydroxy- BJaustichigrot 12th naphthalene-3,6-disulfonic acid the same 1 -acetylamino-8-hydroxy- Bluish red 13th naphthalene-3,6-disulfonic acid the same 1 -Benzoylamino-8-hydroxy- BJaustichigrot 14th naphthalene-4,6-disulfonic acid the same 2-acetylamino-5-hydroxy Red 15th naphthalene-7-sulfonic acid

Example 16

As described in Example 1, 103 parts of phenoxypropionic acid are converted into the acid chloride and added to a solution of 69 parts of 4-nitroaniline in 400 parts by volume of N-methylpyrrolidone. After stirring for 3 hours at 60 C ^r, the mixture is poured into 2000 parts by volume of ice water, the separated oil is separated off and the mixture is stirred under ice-cooling this with 1,000 parts of 10% aqueous hydrochloric acid. The compound, which has become crystalline, is then filtered off with suction and washed acid-free with water. After drying, 120 parts of a light yellow colored substance are obtained which, after recrystallization from ethanol, melts at 103 to 104 ° C.

Analysis: Q ₅ H ₁₄ N ₂ O ₄ (molecular weight 286.3).

Found ... C62.4, H 5.1, N9.7 ° _O ;
calculated ... C 62.9, H 4.9. N9.8 ° ".

30 parts of the 4-nitro- / i-phenoxypropionic anilide thus obtained are dissolved in 600 parts by volume of ethanol and 3 parts of Raney nickel at 80 to 90 C and hydrogenated under a pressure of 60atü hydrogen. After evaporation of the solvent 24 parts of a colorless substance are obtained, which after recrystallization from benzene at 107 to 108 C melts.

Analysis: C ₁₅ H ₁₆ N ₂ O ₂ (molecular weight 256.3).

Found ... C 70.5, H 6.4, N 11.1%;

^ calculated ... C 70.3, H 6.2. N 10.9%.

13 parts of this 4-amino-fJ-phenoxypropionsäureanilids are stirred into a mixture of 75 parts by volume of water and 12.5 parts by volume of aqueous hydrochloric acid and diazotized konzentnerter an aqueous 23 ° _'o solution of sodium nitrite by 16 parts by volume. The diazo solution is then added to a solution of 15 parts of (1- (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone- (5) and 50 parts of sodium acetate in 100 parts by volume of water. After stirring for about 3 hours, this becomes in water The poorly soluble reaction material is filtered off with suction, washed with water and dried. 21.5 parts of a yellow dye are obtained which, according to the dyeing processes customary for reactive dyes, give yellow dyeings on cotton with very good wet fastness properties Diazo components obtainable as explained above with the coupling components mentioned by diazotization and coupling. The dye 17 dyes fabrics made of polycaprolactam and the dyes 18 to 26 dye fabrics made of cotton by the dyeing processes customary for reactive dyes in the shades given in the table.

example Diazo component Coupling component hue 17th
18th S ^ V Q-CH ₂ - CH ₂ - CO - NH - ^ V NH ₂
the same 1-phenyl-3-methyl-
pyrazolone- (5)
l- (3'-sulfophenyl) -3-methyl-
pyrazolone- (5) Geib
yellow

continuation

example Diazo component Coupling component

hue

0-CH ₂ -CH ₂ -CO-NH

NH,

O-CH, -CH, -CO-NH

O CH ₂ CH ₂ CO NH

NH ₁

NH, 1 - (4'-sulfophenyl) -3-methylpyrazolone- (5)

1-hydroxynaphthalene-4-sulfonic acid

1-hydroxynaphthalene-5-sulfonic acid

1-hydroxynaphthalene-S.S-disulfonic acid

1 -Benzoylamino-8-hydroxynaphthalene-4,6-disulfonic acid

1-acetylamino-5-hydroxynaphthalene-7-sulfonic acid

1 - (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone- (5)

Monoazo dye of the formula
HO NH ₂

yellow

Red

Red

Red

Bluish red

Red

Golden yellow

blue

/ V

NQ ₂

Example 27

120 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid are added in a mixture of 5 (X) parts by volume of water and 500 parts by volume of acetone dissolved by about 20 parts of sodium hydroxide. A solution of 110 parts is stirred into this solution , i-phenoxypropionic acid chloride in 100 parts by volume

₄ o acetone while maintaining the pH of the mixture by adding dilute aqueous sodium carbonate solution at a value of 6 to 8. After the amino group of the I-amino-S-hydroxynaphthalene-7-sulfonic acid is completely acylated, the acetone is under reduced pressure evaporated and the compound of formula

HO., S - [jl] - NH - CO - CH ₂ - CH ₂ - O

OH

precipitated sodium chloride by acidifying at about 10 ° _o aqueous hydrochloric acid and salting-out and separated.

51 parts of the compound thus obtained are in 100 parts by volume of water with the addition of 4 parts Sodium hydroxide dissolved neutrally. Then 50 parts of sodium acetate are added to the solution and the mixture is stirred one from 18 parts of 1-aminobenzene-4-sulfonic acid in the usual way prepared diazo solution while maintaining the pH of the mixture by adding of aqueous dilute sodium carbonate solution at a value of 6 to 7. After addition of sodium chloride the reaction material is suctioned off, washed and dried. About 50 parts of one are obtained red dye, which is wet-fast in red after the dyeing process customary for reactive dyes Tones colors.

In a similar way, one can use 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid or 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid acylate with 7-phenoxypropionic acid. The coupling of the 1 - / <- phenoxypropionylamino - 8 - hydroxynaphthalene obtained in this way - 3,6- or -4,6 - disulfonic acid obtained with diazotized 1-aminobenzene-4-sulfonic acid Dyes dye cotton purple.

Example 28

15 parts of 1-amino-4-acetylaminobenzene are in diazotized in the usual way and alkaline coupled with 22.4 parts of 1 - hydroxynaphthalene - 4 - sulfonic acid. Sufficient sodium hydroxide is added to the dye solution obtained to make the content of the solution of sodium hydroxide is 10%, and the mixture is heated to the boil for 1 hour. Then cool one to room temperature, d. H. to about 15 to 30 ° C. by adding aqueous hydrochloric acid the pH of the mixture to a value of 6 to 8, add 200 to 300 parts by volume of acetone and stir at 0 to 10 C in the mixture a solution of 25 parts of i-phenoxypropionic acid chloride in 50 parts by volume

809 648 Ί 895

Acetone. The pH of the mixture is maintained by adding aqueous sodium carbonate solution a value of 6 to 8. The reaction material is now separated off with the aid of aqueous hydrochloric acid and sodium chloride. After drying, one obtains about 55 parts of the red dye of the formula

OH

γ ^ ϊν_ η ΓΊ.τ r> Lj γτλ

which is identical to the dye mentioned in Example 20.

Example 29

15th

70 parts of 3-nitroaniline are dissolved in 400 parts by volume of acetone. After adding 250 parts by volume of water, a solution of 74 parts of i-methoxypropionic acid chloride in 100 parts by volume of acetone is stirred into the mixture ^{at 0 to 10 ° C.} The pH of the mixture is kept at a value of 7 to 8 by adding dilute aqueous sodium carbonate solution. The reaction mixture initially goes into solution, but precipitates again after stirring for 2 hours at room temperature. The mixture is then poured into 1000 parts by volume of ice water, 300 parts by volume of concentrated aqueous hydrochloric acid are added, the mixture is stirred for half an hour at 0 to 10 ^° C., the reaction material is filtered off with suction, washed acid-free and dried. About 95 parts of the compound of the formula are obtained

NH-CO-CH ₂ -CH ₂ -O-CH ₃

35

in the form of almost colorless crystal powder that melts at 45 to 50 ° C.

Analysis: C ₁₀ N ₁₂ N ₂ O ₄ (molecular weight 224.2).

Found ... C 53.6, H 5.4, N 12.2%; calculated ... C 53.6, H 5.4, N 12.5%.

Catalytic hydrogenation gives approximately 83 parts of the abovementioned nitro compound 70 parts of the corresponding amino compound in the form of an oil, which when rubbed with 40 parts by volume of concentrated aqueous hydrochloric acid solidified to form a crystal slurry of the hydrochloride of the base.

After recrystallization from ethanol, the hydrochloride of the base melts at 222 ° C. with decomposition.

23 parts of the above hydrochloride are in a mixture of 100 parts by volume of water and 15 parts by volume of concentrated hydrochloric acid and mixed with 32 parts by volume of an aqueous 23% strength Diazotized sodium nitrite solution. The diazo solution is then added to a solution of 30 parts of l- (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone- (5), 4 parts of sodium hydroxide and 50 parts of sodium acetate in 150 parts by volume of water. After completing the coupling the dye is salted out, filtered off with suction and dried. 59 parts of a yellow dye are obtained, yellow dyeings on cotton fabric by the dyeing processes customary for reactive dyes of very good wet fastness properties.

SO ₃ H

Obtained in the same manner from / J-Methoxypropionsäurechlorid and 4-nitroaniline 4-nitroanilide melts at 107-108 ⁰ C. The hydrochloride of the corresponding obtained therefrom by hydrogenating p-Aminoanilids has a decomposition point of 213-215 ° C. Diazotization of this compound and subsequent coupling with 1- (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone- (5) gives a yellow dye. Coupling with 1-hydroxynaphthalene-4-sulfonic acid instead of 1- (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone- (5) gives a red dye.

Example 30

110 parts of i-phenylmercaptopropionic acid are converted into the acid chloride according to the procedure given in Example 1 and added to a solution of 69 parts of 4-nitroaniline in 200 parts of dimethylformamide. After 3 hours of stirring at 6O ⁰ C, the mixture is poured into 2000 parts by volume of ice water, filtered off the precipitate, stirred it under ice-cooling again with 1,000 parts of 10% aqueous hydrochloric acid, the residue is filtered off with suction and washed free of acid with water. After drying, 140 parts of a pale yellowish compound, melting after recrystallization from ethanol at 106-107 ⁰ C is obtained.

13.6 parts of the 4-nitro / 5-phenylmercaptopropionsäureanilids thus obtained are hydrogenated in 150 parts of methanol using 0.2 part of platinum oxide at 80 to 90 ⁰ C and under a pressure of hydrogen-60atü. After evaporation of the solvent, about 11 parts of a colorless oil are obtained, which crystallizes after a while.

11 parts of this 4-amino - ^ - phenylmercaptopropionic anilide are with ice cooling in a mixture of 75 parts by volume of water and 12.5 parts by volume concentrated aqueous hydrochloric acid and stirred by means of 16 parts by volume of an aqueous 23% Diazotized sodium nitrite solution. The diazo solution is then added to a solution of 15 parts of 1 - (2'-chloro-5'-sulfophenyl) -3-methylpyrazolone- (5) and 50 parts of sodium acetate in 100 parts by volume of water. After about After stirring for 3 hours, the reaction mixture is filtered off with suction and dried. You get approximately 20 parts of a yellow dye which is produced on cotton by the dyeing process customary for reactive dyes results in yellow dyeings of very good wet fastness properties.

Other azo dyes are obtained by combining those listed in the table below and as above explains available diazo components with the coupling components mentioned by diazotization and domes. These dyes dye fabrics made of cotton in the ranges given in the table Tones.

example CI- Diazo component Coupling component hue 31 CH ₃ - / ~~ VS — CH ₂ -CH ₂ -CO — NH- / ~~ J l- (4'-sulfophenyl) -
3-methylpyrazolone- (5) yellow 32 the same 1 -hydroxynaphthalene-
4-sulfonic acid Red 33 CH ₃ - ^ y ~ -S-CH ₂ -CH ₂ -CO-NH- ^ ^ 1 -hydroxynaphthalene-
4-sulfonic acid Red 34 / ~~% -S — CH ₂ -CH ₂ -CO-NH - / ^ 1 -hydroxynaphthalene-
4-sulfonic acid Red CH ₃ 35 ^ VS-CH ₂ -CH ₂ -CO-NH ^ ~ J 1 -hydroxynaphthalene-
4-sulfonic acid Red y- NH ₂ >"NH ₂ > -NH ₂

Claims (1)

Claim: Process for the preparation of azo dyes, characterized in that one acylating agents, the rest of the general formula -C-CH ₂ -CH ₂ specify, where X stands for the group —S — R or represents the group —O — R ', R represents an alkyl radical, an aralkyl radical, a cycloalkyl radical or an aryl radical and R 'an alkyl radical, an aralkyl radical, denotes a cycloalkyl radical, an aryl radical or a heterocyclic radical, with azo dyes or intermediate substances suitable for the production of azo dyes which contain at least one carry acylatable amino group, to / 3- (propionic acid amide) -ether- or thioether derivatives and, in the case of the use of the intermediates, the reaction products are known per se Way completed to azo dyes.