DE2851787A1 - DISAZO DYES - Google Patents

Description

BAYER AKTIENGESELLSCHAFT 5090 Leverkusen, Bayerwerk Central area My / AB

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Disazo dyes

The invention relates to new yellow disazo dyes of the general formula I.

in which S _{1 is} hydrogen, halogen, alkoxy, acylamino, B ₈ and B ₅ independently of one another hydrogen, halogen, alkyl,

Alkoxy, acylamino
and B _{4 is} halogen, OB ₆ , SB ₅ , NB ₆ B ₇ , where E _{0 is} vase material, low molecular weight alkyl, aryl, hetaryl, aralkyl or cycloalkyl and

B ₆ and B ₇ independently of one another are hydrogen, amino,

low molecular weight alkyl, aryl, hetaryl, aralkyl or cycloalkyl or together, optionally

including one or more heteroatoms, Λ

5 in particular oxygen and / or nitrogen, a VK

5- or 6-part hing, *

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where alkyl, aryl, hetaryl and aralkyl can in turn be substituted, and in which the rings A and B are optionally substituted could be, and a method for their manufacture thereby

marked,

that one hol of a cyanuric trihalide in any order with one hol of an aminoazo compound each general formula II

II 10

(HO ₈ S)

in which R ₁ , R ₂ and R _{8 have} the abovementioned meaning, a hol of an aminoazo compound of the general formula III

H ₈ N- (®) -N = N- (φ) III

in which the rings A and B can optionally be substituted, and optionally a compound of the general Formula IV

HR ₄ IV

in which R _{4 has} the above meaning, is reacted in the presence of an acid-binding agent, the aminoazo compounds of the general formulas II and III being prepared in a known manner.

Advantageous dyes are those of the general formula V

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.N = N.

in which Rj, B ₈ , E ₈ and B ₄ have the same meaning, ο, ρ, ς, r, B equals O or 1,

o + p + q + r + B but is equal to 2 and in which the hinges A and B may optionally be substituted.

Particularly advantageous dyes are those of the general formulas I and "V, in which

B * / ° t Pf »υ and B have the above meaning and B ₁ - NHCOCH ₈ , NHCONH ₁ , means when H ₂ and H ₈ stand for H or * t * H, CH ₄ , OCHj, OC ₈ H ₆ , when B _{1 and} B _{5 are} H and in which the hinges A and B can optionally be substituted.

Very particularly advantageous dyes are those of the general formulas I and Y ₁ in which E ₁ , Bg, E ₈ , o, p, q, r and s have the meanings given above,
B ₄ - OH, OCB ₈ , OCjH ₄ OCH ₈ , NH ₂ , NHC ₈ H ₄ OH, N (C ₈ H ₄ OH) ₈ , HC ₈ H ₄ OC ₂ H ₄₁ , NHCeH ₈ , N (CH ₈ ) C ₈ H ₈ , NH (J-CeH ₄ SO ₈ H) or

HHU-C ₆ H ₄ SO ₈ H) means
and bings A and B may optionally be substituted.

Interesting dyes are those of the general formulas ι and T, in which B ₁ , E ₈ , B ₈ , o, p, q, r and s have the meaning given above,

B ₄ HH ₂ , HHC ₈ H ₄ OH or N (C ₈ H ₄ OH) ₂ and the bings A and B can optionally be substituted.

Dyes of the general formulas I and V are preferred, for their preparation as compounds of the general formula III those of the general formula VI can be used

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H ₂ N- / ®V- N = N- / <§) \ VI

in which R ₈ and R ₉ independently of one another are H, Cl, OH, OCH ₈ , OC ₈ H ₆ ,

OCOCH ₈ , OCOC ₆ H ₆ , OSO ₂ CH ₅ , OSO ₂ C ₆ H ₆ , CH ₅ , CH ₂ SO ₅ H, NH ₂ , NHCOCH ₅ , NHCOCH ₈ OH, NHCOC ₆ H ₅ , NHCONH ₂ , NHSO ₂ CH ₃ , NHSO ₂ C ₆ H ₆ , COOH, SO ₅ H and in which the ring B can optionally be substituted.

Dyes of the general type are particularly preferred Formulas I and V, for their preparation as compounds of the general formula III those of the general formula VII are used,

VII

in which R _{10 is} H, CH ₅ , Cl, OCH ₅ , OC ₂ H ₆ , SO ₅ H and R _{11 is} H, CH ₅ , Cl, OCH ₅ , OC ₂ H ₆ , NHCOCH ₃ , NHGONH ₂
and in which the ring B may optionally be substituted.

Dyes of the general type are very particularly preferred Formulas I and V, for the preparation of which compounds of the general formula III are those of the general formula VIII be used,

BglL ^ ® VJJ = N- ((BrT "1 VIII

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40

in the R ₁₂

S ₁ and S ₈ ^

mean

and in which the ring Δ may optionally be substituted.

H, Cl, CH ₈ , OCH ₈ , OC ₈ H ₈ , OH and independently of one another H, SO ₈ H, COOH,

Particularly interesting dyes are those of the general formulas I and V, for their preparation as compounds of general formula III those of the general formula VIII are used in the

R _{12 is} 4-H, 4-CH ₃ , 4-OH or 4-OCH ₅ when S _{1 is} 3-SO ₃ H, 3-COOH or 3-CH ₂ SO ₈ H and S _{2 is} H,

or 3-H if

5 ₁ for 4-SO ₃ H, 4-COOH or 4-CH ₂ SO ₈ H and

5 _{2 represents} H and in which the ring Δ may optionally be 5 substituted.

Dyes of the general formula IX are of very particular interest

(HO ₈ S)

(SO ₅ H) \,

(HO ₈ S)

(HO ₅ S)

N = N-V

IX

in which o, p, q, r and s equal 0 or 1, o + p + q + r + s but equals 2 and in the

R _{1 is} NHCOCHj or NHCONH ₂ when R ₂ and R ₃

stand for H, or
R ₂ H, OCH ₈ , OC ₂ H ₆ , when R ₁ and R _{3 are} H,

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E ₄ NH ₈ , NHC ₈ H ₄ OH, N (C ₁₆ H ₄ OH) ₈ , E ₁₀ H, CB ₈ , Cl, OCB ₈ , OC ₈ H ₆ , SO ₈ H, E ₁₁ H, CH ₈ , Cl, OCH ₈ , OC ₈ H ₆ , NHCOCH ₈ , NHCONH ₈ and E _{18 is} 4-H, 4-CH ₈ , 4-OH or 4-0CH ₈ when S is

3-SO ₈ H, 3-COOH or 3-CH ₈ SO ₈ H, or 3-H if

S is SO ₈ H, 4-COOH or 4-CB ₈ SO ₈ H.

Aminoazo compounds of the general formula II are for example those that can be obtained by diazotizing and coupling 2-aminonaphthalenedisulfonic acids, such as 2-aminonaphthalene-1,5-disulfonic acid, 2-aminonaphthalene-3,6-disulfonic acid, 2-aminonaphthalene-3,7-dieulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid to aminobenzenes optionally substituted in the 2-position or in the 3-position, such as aniline, 2-methylaniline, 2-methoxyaniline, 2-ethoxyaniline, 2-chloroaniline, 3-acetylaniline, 3-aminophenylurea is obtained; can just as well as coupling components the CJ-methane sulfonic acids of the aminobenzenes mentioned above are used, wherein the protective group is split off again after the coupling by treatment with acids or alkalis.

Aminoazo compounds of the general formula III are for example those that can be obtained by diazotizing and coupling optionally substituted aminobenzenes, such as aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, 2-ethoxyaniline, 3-ethoxyaniline, 4-ethoxyaniline, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, Anthranilic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 5-amino-2-hydroxybenzoic acid, 5-amino-2-methylbenzenesulfonic acid, 3-aminophenyl methanesulfonic acid, 4-aminophenyl methanesulfonic acid, optionally substituted aminobenzenes, such as aniline, 2-methylaniline, 3-methylaniline, 2-methoxyaniline, 3-methoxyaniline, 2-ethoxyaniline, 3-ethoxyaniline, 2-methoxy-5-methylaniline, 2-ethoxy-5-niethylaniline, 5-methoxy-2-methylaniline, 2-aminophenol,

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3-aminophenol, 2,5-dimethylaniline, 3,5-dimethylaniline, 2,5-dimethoxyaniline, 3-acetylaminoanilin, 3-methylsulfonylaminoanilin, 3-aminophenylurea, 1,3-diaminobenzene, 3-amino-4-methylbenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 3-amino-4-niethoxybenzenesulfonic acid, 3-aminophenylmethanesulfonic acid is obtained; The u -> - methanesulfonic acids can just as well be used as coupling components of the above aminobenzenes can be used, the protective group after coupling by treatment with acids or alkalis is split off again.

Aminoazo compounds of the general formula III are for example those obtained by diazotizing and coupling of optionally further substituted 4-Nitroaminobenzol. ^':' N, such as 4-nitroaniline, 4-nitro-2-methoxyaniline, 4-N ^ ¹⁰⁵¹¹¹ Ui ¹¹ -2-sulfonic acid, 4-nitro-5-methoxyaniline-2-sulfonic acid on optionally substituted hydroxybenzenes, such as phenol, salicylic acid, 3-hydroxybenzoic acid, 2-hydroxy-6-methylbenzoic acid, 2-hydroxybenzenesulfonic acid, 3-hydroxybenzenesulfonic acid and subsequent reduction of the Nitroazo to ATiinoazoverbindungen is obtained.

Aminoazo compounds of the general formula III are also, for example, those which are obtained in the treatment of other aminoazo compounds of the general formula III with agents such as sulfuric acid, oleum, sulfur trioxide, with which sulfonic acid residues can be introduced, e.g. 4- '

Compounds of the general formula IV are e.g. water, methanol, Ethanol, glycol, 2-methoxyethanol, phenol, thiophenol, AvTL-noniak, Hydrazine, methylamine, ethylamine, dimethylamine, diethylamine, ethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, Glycine, N-methylglycine, taurine, N-methyltaurine, amino

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rs

methanesulphonic acid, N-methylaminomethanesulphonic acid, aniline, N-methylaniline, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-aminonaphthalene-4 ^ 8-dlsulfonsäurβ, 2-aminopyridine, 2-aminothiazole, Benzylamine, pyrrolidine, piperidine, morpholine.

The conversion of the cyanuric halides, e.g. cyanuric fluoride, cyanuric chloride, Cyanur bromide, with the aminoazo compounds of the general formulas II and III and the compounds of the general Formula IY takes place in any order in three stages, the first stage being carried out at about 0-10 °, the second at about 35-50 ° and the third at about 80-110 ° and the resulting acid with alkaline agents, such as sodium acetate, sodium bicarbonate, soda, caustic soda, Lithium carbonate, lithium hydroxide, potassium carbonate, potassium hydroxide, is neutralized.

Advantageously, those aminoazo compounds or compounds of the general formula IV are reacted first, that carry water-solubilizing groups.

The dyes are precipitated from the solution by adding salt, isolated and dried or isolated by spray drying; they are generally obtained in the form of the salts , in particular the alkali salts, preferably the sodium salts. The formulas given are those of the free acids

The new dyes dye cellulosic materials in clear shades of yellow.

In the examples below, "parts" mean parts by weight, "percentages" mean percentages by weight and the temperature data Celsius degrees.

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Example 1;

29 »5 parts of the aminoazo compound of the general formula II 2-aminonaphthalene-4,8-disulfonic acid and aniline are dissolved in 1000 parts of water and at 0 ° with a solution of 15 »5 parts Added cyanuric chloride in 100 parts of acetone, the hydrochloric acid released by adding 46 »5 parts of an aqueous 20? 6 soda solution is neutralized. After finishing the first Reaction stage are 22.2 parts of the aminoazo compound of the general formula III from 3-aminobenzenesulfonic acid and 2-methoxyaniline dissolved in 1000 parts of water and added. The temperature is increased to 40 ° and the hydrochloric acid released is added by adding neutralized by 46.5 parts of 20 $ soda solution. Subject termination 15> 2 parts of diethanolamine are added to the second reaction stage. The temperature is increased to 90 °, then another 3 Stirred for hours at this temperature. The dye is precipitated and isolated by adding 450 parts of potassium chloride. After drying, an orange-colored powder is obtained, the aqueous solution of which gives cellulose-containing materials a greenish yellow Colors tones.

Example 2 and 5:

Very similar dyes are obtained if, instead of the one in the example 1 diethanolamine used 18 parts of an aqueous 25% ammonia solution or 8.9 parts of ethanolamine.

Example 4:

18.6 parts of the aminoazo compound of the general formula * III, the by diazotizing and coupling 4-nitroaniline to salicylic acid and subsequent reduction is obtained, are dissolved in 1000 parts of water and at 0 ° with a suspension of 13 »5 parts of cyanuric chloride reacted in 100 parts of water, the hydrochloric acid released by adding 46.5 parts of an aqueous 20

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Soda solution is neutralized. After completion of the first reaction stage are 29.5 parts of the aminoazo compound of the general Formula II from 2-aminonaphthalene-4j8-disulfonic acid and aniline dissolved in 1000 parts of water and added. The temperature is increased to 40 °, then proceed as in Example 1. An orange powder and its aqueous solution are obtained dyes cellulose-containing materials in greenish yellow tones.

Example 5 and 6:

Very similar dyes are obtained if, instead of the diethanolamine used in Example 4, 18 parts of an aqueous 25% ammonia solution or 8.9 parts ethanolamine are used.

Example 7-96;

If the procedure 5 given in Examples 1-6 is followed, the compound of the general formula II is used the product of 2-aminonaphthalene-4,8-disulfonic acid and aniline and, as compounds of the general formulas III and IV, in given in the following table, yellow dyes are also obtained for cellulosic materials:

E.g. Connection of the general formula III Connection of
general formula IV 7th 4-aminobenzenesulfonic acid and aniline Diethanolamine 8th Il Ethanolamine 9 Il ammonia 10 3-aminobenzenesulfonic acid and aniline Diethanolamine 11 Il Ethanolamine 12th Il ammonia 13th 4-aminobenzoic acid and aniline Diethanolamine 14th Il Ethanolamine 15th Il ammonia

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E.g. Connection of the general formula III Connection of
general formula IV 16 3-aminobenzoic acid and aniline Diethanolamine 17th It Ethanolamine 18th Il ammonia 19th 5-amino-2-methyrbenzenesulfonic acid and aniline Methanol amine 20th Il Ethanolamine 21st M. ammonia 22nd 4-Amino phenylmethanesulfonic acid and aniline Diethanolamine 2; ί Il Ethanolamine 24 Il ammonia 2! 5 3-aminophenyl methanesulfonic acid and aniline Diethanolamine 2ύ Il Ethanolamine 27 Il ammonia 28 4-aminobenzenesulfonic acid and 2-methoxyaniline Diethanolamine 29 Il Ethanolamine 30th Il ammonia 31 3-aminobenzenesulfonic acid and 2-methoxyaniline Diethanolamine 32 Il Ethanolamine 33 Il ammonia 34 4-aminobenzoic acid and 2-methoxyaniline Diethanolamine 35 Il Ethanolamine 36 Il ammonia 37 3-aminobenzoic acid and 2-methoxyaniline Diethanolamine 38 Il Ethanolamine 39 It ammonia 40 5-amino-2-methylbenzenesulfonic acid and
2-methoxyaniline Diethanolamine 41 Il Ethanolamine 42 Il ammonia 43 4-aminophenyl methanesulfonic acid and
2-methoxyaniline Diethanolamine 44 Il Ethanolamine 45 Il ammonia

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E.g. Compound of the general formula III Connection of
general formula IV 46 3-aminophenylmethynesulfonic acid and 2-
Methoxyaniline Diethanolamine , 47 Il Ethanolamine 48 Il ammonia 49 4-aminobenzenesulfonic acid and 3-acetyl
aminoaniline Diethanolamine 50 Il Ethanolamine 51 Il ammonia 52 3-aminobenzenesulfonic acid and 3-acetyl
aminoaniline Diethanolamine 53 Il Ethanolamine 54 Il ammonia 55 4-aminobenzoic acid and 5-acetylaminoaniline Diethanolamine 56 Il Ethanolamine 57 Il ammonia 58 3-aminobenzoic acid and 3-acetylaminoaniline The thanolamin 59 Il Ethanolamine 60 Il ammonia 61 5-amino-2-methylbenzenesulfonic acid and
3-acetylaminoaniline Diethanolamine 62 Il Ethanolamine 65 Il ammonia 64 4-aminophenylmethaneulfonic acid and
3-acetylaminoaniline Diethanolamine 65 Il Ethanolamine 66 Il ammonia 67 3-aminophenyl methanesulfonic acid and
3-acetylaminoaniline Diethanolamine 68 Il Ethanolamine 69 Il ammonia 70 4-aminobenzenesulfonic acid and 3-aminophenyl
urea Diethanolamine 71 Ii Ethanolamine 72 Il ammonia

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-rf-

E.g. Compound of the general formula III Connection of
general formula IV 73 3-iminobenzenesulfonic acid and 3-aminophenyl
urea Diethanolamine 74 Il Ethanolamine 75 Il ammonia 76 4-aminobenzoic acid and 3-aminophenylureas Diethanolamine 77 Il Ethanolamine 78 Il ammonia 79 3-aminobenzoic acid and 3-aminophenylurea Diethanolamine 80 Il Ethanolamine 81 Il ammonia 62 5-amino-2-methylbenzenesulfonic acid and
3-aminophenylurea Diethanolamine 83 Il Ethanolamine 84 η ammonia 85 4-aminophenyl methanesulfonic acid and
3-aminophenylurea Diethanolamine 86 Il Ethanolamine 87 Il ammonia 88 3-aminophenyl methanesulfonic acid and
3-aminophenyl urine to ff Diethanolamine 89 Il Ethanolamine 90 It ammonia 91 4-nitroaniline and salicylic acid Diethanolamine 92 Il Ethanolamine 93 ■ I ammonia 94 4-aminoazobenzene and 2 Hol SO ₈
(4-iminoazobenzene-2,4'-disulfonic acid) Diethanolamine 95 η Ethanolamine 96 η ammonia

Similar good dyes are obtained if, instead of those in the examples 1-96 compounds of the general formula II used are those from 2-aminonaphthalene-4 | 8-disulfonic acid and 2-methoxyaniline or 3-acetaminoaniline or 3-aminophenylurea is used.

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Claims (12)

Claims; 1. Dyes of the general formula (HO ₅ S) in which R _{1 is} hydrogen, halogen, alkoxy, acylamino, R ₂ and R _{3 are} independently hydrogen, halogen, alkyl, Alkoxy, acylamino
and R _{4 is} halogen, OR ₆ , SR ₆ , NR ₈ R ₇ , where R _{6 is} hydrogen, low molecular weight alkyl, aryl, hetaryl, aralkyl or cycloalkyl
and R ₀ and R ₇ independently of one another are hydrogen, amino, mean low molecular weight alkyl, aryl, hetaryl, aralkyl or cycloalkyl or together, optionally including one or more heteroatoms, in particular oxygen and / or nitrogen, a 5- or 6-membered ring, where alkyl, aryl, hetaryl and aralkyl can in turn be substituted, and in which the rings A and B are optionally substituted could be. Le A 19 334 0 30 024/0204 2. Dyes of the general formula (SO ₃ H)! _ (HO ₅ S) ^ Jy ^ - N = N- Ο) -NN ξ _ ^ \ _{N = N} in the R ₁ , R ₂ , R ₃ and R _{4 are} those specified in claim 1,. Have meaning o, p, q, r, s is equal to O or 1, o + p + q + r + s but is equal to 2 and in which the Rings A and B optionally substituted could be. 3. Dyes of claims 1 and 2, in which R., o, p, q, r and s specified in claims 1 and 2 Have meaning and R _{1 is} NHCOCH ₃ , NHCONH ₂ when R ₂ and R _{3 are} H stand or
R ₂ H , CH ₃ , OCH ₃ , OC ₂ H ₅ when R ₁ and R ₃ stand for H and in which the rings A and B can optionally be substituted. 4. Dyes of claims 1-3, in which R ₁ , R ₂ , R ₃ , o, p, q _r r and s have the meaning given in claims 1-3, R ₄ OH, OCH ₃ , OC ₂ H ₄ OCH ₈ , NH ₂ , NHC ₂ H ₄ OH, K (C ₂ H ₄ OH) ₂ , NC ₂ H ₄ OC ₂ H ₄ -) , NHC ₆ H ₅ , N Means (CH ₈ ) C ₆ H ₅ , NH (3-C ₆ H ₄ SO ₅ H) or NH (4-C ₆ H ₄ SO ₃ H) and in which rings A and B are optionally substituted could be. Le A 19 334 030024 / 020A 5. Dyes of claims 1-4, in which R ^, R ₂ o, p, q, r and s have the meaning given there, R ₄ denotes NH ₂ , NHC ₂ H ₄ OH or N (C ₂ H ₄ OH) ₂ and in which the rings A and B can optionally be substituted. 6. Dyes of claims 1-5, with a radical of the formula N = N-- in the He and R ₉ independently of one another H, Cl, OH, OCH ₃ , OC ₂ H ₅ , OCOCH ₃ , OCOC ₆ H ₅ , OSO ₂ CH ₃ , OSO ₂ C ₆ H ₆ , CH ₃ , CH ₂ SO ₅ H, NH ₂ , NHCOCH ₃ , NHCOCH ₂ OH, NHCOC ₆ H ₅ , IiECONH ₂ , NHSO ₂ CH ₃ , NHSO ₂ C ₆ H ₅ , COOH, SO ₃ E and in which the ring B can optionally be substituted. 7. Dyes of claims 1-6, with a radical of the formula P10 in which H ₁₀ 'H, CH ₃ , Cl, OCH ₃ , OC ₂ H ₆ , SO ₈ H and R ₁₁ denote H, CH ₅ , Cl, OCH ₃ , OC ₂ H ₆ , NHCOCH ₃ , NHCOITE ₂ and in which ring B can optionally be substituted. Le A 19 334 030024/0204 - yr - 8. Dyes of claims 1-7, with a radical of the formula IS in which R _{12 is} H, Cl, CH ₃ , OCH ₃ , OC ₂ B ₈ , OH and S ₁ and S ₂ independently of one another H, SO ₅ H, COOH, CHp ^ mean and in which the ring A can optionally be substituted. 9. dyes of claim 8, wherein E _{12 is} 4-H, 4-CE ₅ , 4-OH or 4-OCE ₅ if 5 ₁ for 3-SO ₃ H, 3-COOH or 3-CH ₂ SO ₃ H and 5 ₂ stands for H,
or 3-H if 5 ₁ for 4-SO ₃ H, 4-COOH or 4-CH ₂ SO ₃ H and 5 ₂ stands for H. and in which the ring A can optionally be substituted. 10. Dyes of the general formula Le A 19 334 IX S = IT 030024/0204 in which ο, ρ, q, r and s equal 0 or 1, but ο + ρ + q + r + s is equal to 2 and in which R ₁ denotes NHCOCH, or HHCONH ₂ when R ₂ and E ₃ stand for H, or R ₂ H, OCH ₃ , OC ₂ H ₅ , when R ₁ and R _{3 are} H, R ₄ NH ₂ , NHC ₂ H ₄ OH, N (C ₂ H ₄ OH) ₂ , R ₁₀ E, CH ₃ , Cl, OCH ₃ , OC ₂ E ₅ , SO ₅ H, R ₁₁ H, CE ₃ , Cl, OCH ₃ , OC ₂ H ₆ , NHCOCH ₃ , NHCONH ₂ and H ₁₂ 4-H, _4-CH3, 4-OH or ₃ 4-0CH means if S is 3-SO ₃ e, 3-COOH or 3-CE represents ₂ SO ₃ H, or 3-H if S is SO ₃ H, 4-COOH or 4-CE ₂ SO ₃ H. 11. Use of the dyes of claims 1-10 for dyeing of cellulosic materials. 12. The cellulosic dyed with dyes of claims 1-10 Materials. Le A 19 334 03002A / 0204