DE1644200C3 - Water-soluble monoazo dyes and process for their preparation - Google Patents

Description

New water-soluble, greenish-tinged yellow monoazo dyes have been found, which are in the form of the free Acids correspond to the general formula (1)

CH ₁

CO

A-N = N-CH

CO-NH-B

- (X) _n - (SO ₃ H) _n , (1)

Acetoacetic acid phenylamide of the general formula (4)

CH ₃ CO

in which A is the phenyl radical or a phenyl radical substituted in ο-, m- and / or p-position to the azo group by halogen, methoxy, ethoxy, phenoxy, methyl, acetylamino and / or benzoylamino group or the naphthyl (1 ) Radical B denotes the phenyl radical or a phenyl radical substituted by halogen, methyl, methoxy, acetylamino and / or benzoylamino groups represents the ^ uIfonsäuregruppen are bonded to A and / or B, m stands for a number from 1 to 3, X is a group of formula (2) or (3) bonded to A and / or B

-N-SO ₂ -CH ₂ -CH ₂ -Y (2)

-N-SO ₂ -CH = CH ₂ (3)

denotes in which R represents a lower alkyl group, preferably a methyl group, and Y represents a halogen atom, such as chlorine atom, the dialkylamino, acetoxy, p-toluenesulfonyloxy, thiosulfate or sulfate radical and π represents the number 1 or 2

The present invention further relates to processes for the preparation of the abovementioned new dyes of the formula (1). This is how the new dyes in produced according to the invention by a

CH ₂ -CO-NH-B

(SO ₃ H) _-1

in which B and X have the abovementioned meanings -, «, ^., ^^ .-, m is a number from 0 to 3 and m is the number Q, 1 per 2, with a diazo compound of an amine of the general formula (5)

A-NH ₂

in which A and X have the abovementioned meanings, im a number from 0 to 3 and m the number 0.1 or 2, at a pH between about 6 and about 7 in an aqueous or aqueous-organic medium Couples where you choose the components so that the

Sum of nn and im equal to 1,2 or 3 and the sum

of m and m is 1 or 2

Modifications of this method according to the invention

consist in that one (a) the dyes thus obtained of the formula (1), which contain a group of the formula (2) in which R has the meaning given above and Y stands for the sulfate, p-toluenesulfonyloxy or acetoxy group or for chlorine with one Dialkylamine to the corresponding new dyes with an N- {0-dialkylaminoethyl) -N-alkyl-sulfonylamino group or (b) the thus obtained Dyes which oppose a group of the formula (3) with salts of thiosulfuric acid, preferably the alkali or ammonium salts, in the corresponding new dyes with an N - (/) - Thiosulfatoäthyl) -N-alkylsulfonylamino group or (c) the so obtained dyes of the formula (1) with a reactive group of the formula (2) with R and Y of there given meaning with alkaline acting

Agents such as sodium hydroxide into the

corresponding dyes with a group of

Formula (3) transferred Furthermore, new dyes of the formula

(1) with the reactive radical of the formula (2), in which Y stands for the sulfate, acetoxy or p-toluenesulfonyloxy radical is available if you have diazo and / or azo components of the formulas

CH ₁ CO

CH ₂ -CO-NH-B

or.

(SO ₃ H) ₁₁₁₁

. A-NH ₂

(SO ₃ H) _{1112 is} used in which A, B, im, im, m and m continue

have the meanings given above and X the rest of formula

-N-SQ ₂ -CH ₂ -CH ₂ -OH R

with R represents the above meaning, and in the azo compounds obtained in this way, the hydroxyl group of the radical X by treatment with the corresponding the inorganic or organic acids or their derivatives, such as sulfuric acid, amidosulfuric acid, acetyl chloride or p-toluene sulfonic acid esters, before sulfato, acetoxy or p-toluenesulfonyloxy group

Another modification of the process is that for the preparation of the dye Shape! (1) Diazo and / or azo components used which, instead of the above-mentioned groupings of formers (2) or (J), at least one Grouping of the formula (6)

-N-SO ₂ -CH ₂ -CHj-OH

(61

in which R has the stated meaning, contain, and this group in the monoazo dyes obtained in a known manner by treatment with inorganic ones or organic acids or their derivatives, such as sulfuric acid, sulfamic acid, acetyl chloride or p-toluenesulfonic acid esters, into one Group of the formula (2) mentioned

The diazotization of serving as diazo components aminobenzenes or aminonaphthalenes in a customary manner in an aqueous or aqueous-organic medium is between about O and about 15 ° G Coupling of the diazo compound obtained by the arylamides of acetoacetic acid of the formula (4) is carried out between about O and about IS ⁰ C A water / acetone or water / dioxane mixture, for example, can be used as the aqueous-organic medium for the coupling.

The monoazo dyes formed are made using sodium or potassium chloride or mixtures thereof deposited from the coupling solution, filtered off and washed or isolated by spray drying the dye solution

The following can be considered as diazotizable amines which can be used for the preparation of the monoazo dyes obtainable according to the process:

2-amino-anisole-4-sulfonic acid, 4-amino-anisole-3-sulfonic acid, 2-amino-anisole-5-sulfonic acid, 4-amino-anisole-2-sulfonic acid, 4-amino-acetylaminobenzene-2 sulfonic acid, 4-amino-acetylaminobenzene-3-sulfonic acid, 4-amino-1, S-xylene-6-sulfonic acid, S-Amino ^ -acetaminoanisoM-sulfonic acid, S-AmimM-methoxy-toluene-ö-sulfonic acid, H

py

^ Amino-pheno ^ -benzene- ^ sulfonic acid, 2-amino-4-dilor-aniso] -5-suVonsäiire, 2-An ^ c-6-Cuor-toluene-4-sulfonic acid, ^ Amino-N-methyl-N-athionylaminobenzene, 3-Amino-N-methy] -N-ethionylaminobenzene, 4-Amino-2-methoxy-N-methyl-N-ethionylaminobenzoJ,

4-amino-N-ethionylaminobenzene, b ^ Nlh \ ^

l-naphthylamine-S.e-disulfonic acid, l-naphthylamine-aj-disulfonic acid, 1-naphthylamine-47-disulfonic acid, l-naphthytamine- ^ e-disulfonic acid, 2-naphthylamine-1,5-disulfonic acid,

4-Amino-N-n-butyI-N-ethionyl-aminobeiizole,

4-Amino-N-methyl-N-ß-thiosuIfatoäthylsulfonyI-

aminobenzoL

4-Amino-N-methyl-N-ß-chloroethylsulfonyl-

aminobenzene,

l- (4 '- (N-methyl-N-j? -chk) räthylsulfonyl6mino) -

benzoyl-amino) -4-amino-benzene-3-sulfonic acid,

2-naphthylamine-1,5,7-trisulfonic acid.

The azo components include, for example, the N-acetoacetyl compounds of the following amines in fractions ge:

4-amino-anisole-2-sulfonic acid, 4-amino-acetylaminobenzene-2-sulfonic acid, 4-amino-1 ^ -xylene-δ-sulfonic acid,

4-Amino-N-methyl-N-ithionyl-amino-benzene,

3-Amino-N-methyl-N-ethionyl-aminobenzene,

4-Amino-2-methoxy-N-methyl-N-ethionyl-

aminobenzene,

4-amino-N-ethionyl-aminobenzene,

4-Amino-N-methyl-N-vinylsulfonylaminobenzoI,

4-Amino-N-methyl-N-jS-thiosulfatoäthylsulfonyI-

aminobenzene,

4-Amino-N-n-butyl-N-ethionyl-aminobenzene,

4-amino-N-methyl-N-ß-chloroethylsutfonyl-

aminoberizole,

l- (4 '- (N-methyl-N-j? -chloroethylsulfonyI-amino) -

benzoyl-amino) -4-amino-benzene-3-sulfonic acid,

furthermore, in general, aminobenzenesulfonic acids, which have further substituents, such as alkyl groups, may contain.

The N-acetoacetyl compounds used as azo components are prepared according to known methods, for example by reacting the corresponding amines with diketene in weakly acetic acidic aqueous solution Medium, received. For the manufacture of the dyes is

_S a not required to deposit it at the acetoacetyl compounds before.

The monoazo dyes produced according to the process are primarily used for dyeing and printing Cellulose material made from natural or regenerated Cellulose very suitable you will for this purpose using a dyeing or printing process customary for reactive dyes on the textiles mentioned applied and in conjunction with a treatment with an acid-binding agent at ordinary or Fixed at an elevated temperature The monoazo dyes obtainable according to the process produce strong greenish-yellow shades on cellulose material good washing. and lightfastness properties. They can also be used for dyeing or printing on, wool,

Find silk or polyamide fibers, where they are applied from acidic, neutral or weakly alkaline dye baths or printing pastes will. . '". · ..

16 4 4 2 UiU

Compared to the closest comparable, in the German patent specification = 1 · 2 Ö4? 762 "beSehfiebeneM" ^ Färbstöff er formula '· ^; '<'■■ - ^' is: h ^ -r.-'- i'jiitwwiy; - "- ■■ ¹ : nL ^^ m ^j as% Mc &"^

the formula

HO ₃ SO-CH ₂ -CH ₂ T-SO ₂ -N-

the "dyes obtainable according to the process are distinguished by a significantly greater color strength Cotton prints and cotton dyes. ι s

Furthermore, the dyes according to the invention have the closest structurally comparable properties Dyes of German patent specification 12 76 844 and US-PS 34 09 541 in surprising and by no means predictably a decidedly higher tinting strength; on cotton they provide strong, greenish yellow, clear dyeings of pure nuances.

Furthermore, precisely because of the very similar constitutions, it is surprising that the one for comparison used, inventive dye compared to the dye of Table Example 2 on p. 29 of the French patent 13 95 283 has a much better, even very good tartaric acid fastness.

example 1

203 parts by weight of 2-amino-anisole-4-sulfonic acid are dissolved with sodium carbonate at pH 7 in 200 parts by volume of water and mixed with 25 parts by volume of 4N sodium nitrite solution diazotized to 5 ⁰ C by the addition of saturated sodium carbonate solution to the diazo solution at 0 to 5 ° C is at 0 so the pH-value of the diazo solution at 63 to 7.0, and at 0 to 15 ° C. 39.4 parts by weight of 4-acetoacetylamino-N -methyl-N-ethionyl-aminobenzene. dissolved with sodium carbonate in 180 VolumteHen water at pH 6, the pH being kept at 63 to 7.0 during the coupling reaction with sodium carbonate. After coupling has ended, the mixture is salted out with potassium chloride, filtered off, washed with potassium chloride solution and dried. A yellow powder is obtained which dissolves in water with a yellow color

The dye obtained is in the form of the free acid the formula

N = N-CH-CO-NH ^{: LL} r ^

the agents on cotton have clear greenish yellow dyeings and prints with very good wet fastness properties.

Example 2

34.8 parts by weight of l-naphthylamine-9.7 * disulfonic acid (87%) are dissolved with sodium carbonate at pH 7 in 200 parts by volume of water and mixed with 25 parts by volume of 4N sodium nitrite solution. The solution obtained is added dropwise to a mixture of 25 parts by volume of concentrated hydrochloric acid and 100 parts by weight of ice and diazotized so at 0 to 5 ° C by the addition of saturated sodium carbonate solution to the diazo suspension at 0 to 5 ⁰ C the pH is adjusted value of the mixture at 63 to 7.0 and at 0 to 15 ° C 39.4 parts by weight of 3-acetoacetylamino-N-methyl-N-ethionyl-aminobenzene, dissolved with sodium carbonate at pH 6 in 180 parts by volume of water, the pH value during the Coupling reaction is maintained at 63 to 7.0 with sodium carbonate. After coupling has ended, the mixture is salted out with sodium chloride, filtered off, washed with sodium chloride solution and dried. The dye obtained is in the form of the free acid of the formula

N (CH, 1- SO ₂ -CH ₂ -CH ₂ -O-SO ₃ H NH - CO - CH - CO - CH,

N = N

> - SO ₃ H

H ₃ CN-SO, -CH ₂ -CH ₂ -O-SO ₁ H

SO ₃ H

corresponds to, forms a yellow powder that dissolves in water dissolves with yellow color. In the presence of alkaline agents, the dye gives brilliant greenish yellow prints and dyeings on cellulose fibers of good wet fastness properties.

feelspiet Ϊ ^U: *

Dissolved water, too, with the pH during the Coupling reaction is kept at 6.5 to 7.0 with sodium carbonate. When the coupling is complete, press Salted out sodium chloride, filtered off, washed with sodium chloride solution and dried. You get a yellow powder that dissolves in water with a yellow color. The dye that makes up the formula

H _-1 CN-SO ₂ -CH ₂ -CH ₂ -O-SOjH

N = N ^CH <υ

H ₃ C-CO-CH-CO-NH- </ ~) y-CH ₃

SO ₃ H

corresponds to produces clear greenish yellow on cellulose fibers in the presence of alkaline agents Dyeings of good wet and rub fastness properties.

Example 4

26.0 parts by weight of 5-amino-2-acetamino-anisole-4-sulfonic acid are dissolved with sodium carbonate at pH 7 in 200 parts by volume of water and with 25 parts by volume 4 N sodium nitrite solution are added. The solution obtained is added dropwise to a mixture of 25 Parts by volume of concentrated hydrochloric acid and 100 parts by weight of ice and diazotized so at 0 to 5 ° C Addition of saturated sodium carbonate solution to the diazotization mixture at 0 to 5 ° C is set pH value to 63 to 7.0 and gives 42.4 parts by weight of 2-methoxy-4-acetoacetylamino-N-methyl-N-ethionyl-aminobenzene at 0 to 15 ° C, with sodium carbonate at pH 6 dissolved in 180 parts by volume of water, the pH is maintained at 63 to 7.0 with sodium carbonate during the coupling reaction. After finished The coupling is salted out with sodium chloride, filtered off, washed with sodium chloride solution and dried A yellow powder is obtained which dissolves in water with a yellow color formula

V 10

Example 5 ^f »i""3

> ■ i ", 7»]

26.0 parts by weight of 5-amino-2-acetamino-anisole-4> sulfonic acid with sodium carbonate at pH t! Ftf 200 parts by volume of water dissolved and mixed with 25 Volumteiliei ¹ 4 N sodium nitrite solution. The LÖSüh obtained | i is added dropwise to a mixture of D = parts by volume of concentrated hydrochloric acid and 100 ÖVI weight parts of ice and diazotized so at 0 to 5 ⁰ C. Pieter $ addition of saturated sodium carbonate reheater | i diazotization mixture at 0 to 5 ° C provides mäh «#U ^! pH value to 6.5 to 7.0 and at 0 to 15 ⁰ C 40 parts by weight of 4-acetoacetylamino-N-methyl = -N ^ Hthi6j3 sulfatoäthylsulfönyl-aminobenzol, dissolved with sodium CarboWai at pH 6 in 180 parts by volume of water, to, the pH being maintained at 6.5 to 7.0 with sodium carbonate during the coupling reaction. After coupling is complete, the mixture is salted out with a mixture of sodium and potassium chloride, filtered off, washed with sodium chloride solution and dried. A yellow powder is obtained which dissolves in water with a yellow color. The dye, in the form of the free acid of the formula

H ₃ CN-SO ₂ -CH ₂ -CH ₂ -S-SO ₃ H

NH-CO-CH-CO-CH ₃

SO, H

NH-COCH ₃

45

H ₃ CN-SO ₂ -CH ₂ -CH ₂ -O-SO ₃ H

OCH ₃

NH - CO - CH - CO - CH ₃

50 OCH ₃

corresponds to natural and regenerated cellulose fibers under the action of alkaline fibers Medium clear greenish yellow dyeings with good wet fastness properties.

The following table contains further greenish-tinged yellow monoazo dyes, which were made according to the information given above Examples can be made. They result on cellulosic materials, wool, or silk Polyamide fibers also have greenish yellow prints and dyeings with similarly good fastness properties.

Bei-diazo component game

Azo component

55

NH-COCH ₃ ^w S-seBoHS & flse ■ ·

65

6 2-amino-aniso! -

£ 1534 *

IB 44 20Oi

Fortseföywg ' . Diazo component Aiokoniponehte at
game 4-amino-phenetol-
3-sulfonic acid 4-acetoacetylamino
N-methyl-N-ethioenyl-
aminobenzene 11th 4-amino-acetylamino> -
benzene-3-sulfonic acid - the same 12th 1 -naphthylamine ^ J-di-
sulfonic acid 4-acetoacetylamino
N-methyi-N-ethhibnyl-
aminobenzene 13th 1 -naphthylamine ^ .e-di-
sulfonic acid the same 14th 2-naphthylamine-1,5-di-
sulfonic acid the same 15th 2-naphthylamine-4,8-di-
sulfonic acid the same 16 2-napthylamine-3,6-di-
sulfonic acid the same 17th 3-amino-4-methoxy-
toluene-6-sulfonic acid 3-acetoacetylamino
N-methyl-N-ethionyl-
aminobenzene 18th S-amino ^ -acetamino-
anisole-4-sulfonic acid 3-acetoacetylamino
N-methyl-N-ethionyl-
aminobenzene 19th 3-amino-4-methoxy-
toluene-6-sulfonic acid 2-methoxy-4-acetoace-
tylamino-N-methyl-
N-ethionyl-aminobenzene 20th 4-amino-N-methyl-
N-ethionylamino-
benzene 4-acetoacetylamino
anisole-2-sulfonic acid 21 4-amino-phenoxy-
benzene-3-sulfonic acid 4-acetoacetylamino
N-methyl-N-ethionyl-
aminobenzene 22nd 4-amino-N-methyl-
N-ethionylamino-
benzene 2-acetoacetylamino
e-chlorotoluoM-sulfone-
acid 23 2-amino-4-chloro
anisole-5-sulfonic acid 4-acetoacetylamino
N-methyl-N-ethionyl-
aminobenzene 24

. Example .28, '"-', .... _t . · ,,., 120 parts by weight 'of the approximately 60% strength dye' of the formula. - ^; ι> ι '« Ρ., "Ji'

H ₃ CN-SO ₂ -CH ₂ -CH ₂ -O-SO ₃ H

IO NH-CO-CH-CO-CH ₃

N = N

25 SO ₃ H

SO ₃ H

are dissolved in 400 parts by volume of water while warming. After cooling to 20 ° C, it is added Stir 130 parts by weight of a 16.5 weight percent Sodium hydroxide solution and stir for a short time. The reaction mixture is then treated with dilute hydrochloric acid weakly acidified and the dye salted out with sodium chloride. The filtered off and dried Dye forms a yellow powder that dissolves in water with a yellow color. The dye that makes up the formula

H ₃ CN-SO ₂ - CH = CH ₂

NH-CO-CH-CO-CH ₃

N = N

SO ₁ H

35

40 SO ₃ H

corresponds to, produces brilliant, greenish yellow on cellulose fibers in the presence of alkaline agents Dyeings and prints with good light, wet and perspiration fastness properties.

Example 29

87 parts by weight of the 70% strength dye of the formula H ₃ CN-SO ₂ - CH = CH ₂

it is added dropwise at room temperature within 30 minutes, salted out with potassium chloride and dried. Man Minute oiljS pe ^ jcjitsteile. * Diethylatnin and stirs 8 receives a yellow powder that turns yellow in water Hours at room temperature. The dye will dissolve colori The dye that corresponds to the formula

H ₃ CN- SO ₂ -CH ₂ -CH ₂ -N

C, H <

NH-CO -CH-CO -CH ₁

CH,

SO ₃ H

corresponds to, results in: Cellulose materials under the action of alkaline compounds greenish yellow colorations with good wet fastness properties.

Claims (6)

Patent claims: Water-soluble monoazo dyes of the general formula S : f ' CO A-N = N-CH ' CO-NH-B -OiL • 5 , _ "A is the phenyl radical or one ^{substituted in o-, m r} or p-Stelhing to the azo group by halogen, •""TS ethojgr, phenoxy, methyl, acetylamif or benzoylamino groups ..". JSt or the naphthyi (1) radical; B generally represents the phenyl radical or a phenyl radical which is substituted by halogen, methyl, methoxy, acetylamino and / or benzoylamino groups, the sulfonic acid groups are bonded to A and / or B, m stands for a number from 1 to 3, X stands for a and / or B bonded group of the formula or -N-SO ₂ -CH ₂ -CH ₂ -Y R -N-SO ₂ -CH = CH ₂ 35 means in which R is a lower alkyl group and Y is a halogen atom, the dialkylaniino, acetoxy, p-toluenesulfonyloxy, thiosulfato or sulfate radical represents, and π represents the number 1 or 2 2. Process for the preparation of the compounds defined in claim 1, characterized in that as an acetoacetic acid phenyl amide of the general formula CH ₃ CO CH ₂ -CO-NH-B 45 wherein B and X have the meanings given in claim 1, on is a number from 0 to 3 and m _{5S is} the number O, 1 or 2, with a Dazo compound of an amine of the general formula A-NH ₂ 60 in which A and X have the meanings mentioned in claim 1, to a number of O to 3 and / or 12 did number O. J represents 2, at a pH value between about 6 and about 7 in aqueous or An aqueous-organic medium is coupled, väe components being chosen so that the sum of an and whether 1,2 or 3 and the sum of m and m is 1 or 2 3. Modification of the. The method according to claim 1, characterized in that the dyes obtained according to claim 1, which are a group of Formula of the formula (2) given in spoke 1, in which R is given in claim 1 Has meaning and Y stands for the sulfate, p-toluenesulfonyloxy or acetoxy group or for chlorine, with a dialkylamine to give the corresponding .Farbstoffen according to claim 1 with an N- {0-DialkyIaminoäthjrl) -N-alkyl-sulfony] aniino group 4. Modification of the method according spoke 1, characterized in that the dyes obtained according to claim 1, which are a group of formula -N-SO ₂ -CH = CH ₂ R with R as defined in claim 1, with salts of thiosulfuric acid in the corresponding dyes with an N-QMIüosulfatoäthyl) -N-alkyl-sulfonylamino group 5. Modification of the method according to claim 1, characterized in that the dyes obtained according to claim 1, which are a group of formula —N— SO ₂ -CH ₂ -CH ₂ -Y R with the meanings of R and Y mentioned in claim 1, with alkaline agents into the corresponding dyes with a group of the formula -N-SO ₂ -CH = CH ₂ R with the meaning of R given in claim 1 6. Modification of the method according to claim 1, characterized in that one diazo and / or Azo components of the formers CH ₁ CO CH ₂ -CO-NH-B A-NH ₂ used in which A, B, m, im, m and m die in Claim 2 have the meanings mentioned and X is the remainder of the formula -N-SO ₂ -CH ₂ -CH ₂ -CH R where R has the meaning given in claim ί represents, and in those obtained according to the process Azo compounds the hydroxy group of the radical X by handling with the appropriate acid or their derivative in the group of the formula -N-SO ₂ -CH ₂ -CH ₂ -Y converted, m which Y stands for the sulfate, acetoxy or p ~ toluenesulfonyloxy radical and R the im Claim 1 has the meaning mentioned