DE2838616A1 - FIBER REACTIVE AZO DYES - Google Patents

Description

BAYER AKTIENGESELLSCHAFT

Central area

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Bayerwerk My / Th

Fiber-reactive azo dyes

D-N = N

HO ₈ S

OH

(D

wherein

where R ₃

stands for halogen such as fluorine, chlorine or 3roa _e C ₁ -C ₄ -AlCyI, C ₁ -C ₄ -AIkOXy, a sulfo-, carbosyl, acylamino or 4-sulfophenylazo group,
O ₃ H

SO ₃ H

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Sr

where R ₃

for hydrogen, C ₁ -C ₄ -AllEyI or an acylamino =

group stands,

R = hydrogen, methyl, ethyl, 5 R ₁ = hydrogen, methyl,

X = hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -AlkOXy, halogen such as Fluorine, chlorine or bro, a carboxy, sulfo group

or acylaitiino group (especially acetyl-formyl- ^

Oxalylamino or ureido). ₁₀ examples of Aaine der Forael

D-NH ₂ (II)

are the following:

1-aaino-2-sulfo-4-ethylbenzene, 1-aaino-2-sulfo-4-β-ethylbenzene, 1-aaino-2-sulfo-2-chloro-benzene, 1-aaino-2-sulfo ⁵ 4 -aethoxy-benzene, 1-aaino-2-sulfo-4-ethoxy-benzene, 1-aaino-2-sulfo-4-arboxy-benzene, 1-aaino-2,4-disulfobenzene, 1-aino-2 -sulfo-4- (4 * -eulfophenylazo) -benzene, 1-amino-2-sulfo-4-acetylamino-benzene, 1-amino-2,5-disulfobenzene, 1 · ^ Aaino-2,5 "* disulfo— 4i-ethyl-benzene, 1-aaino-2, 5 *** disulfo-4-aoetylaaino-benzene

Preferred dyes correspond to the formulas SO ₃ H
-NsN

wherein

X and R _{1 have} the abovementioned meaning hfban and R ₄ s chlorine, methyl, methoxy, ethoxy, sulfo, carboxy, aoetylaaino or 4-sulfophenylazo.

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(IV)

in which R ₁ and X have the meaning given above and R 3 is hydrogen, methyl or aoetylanino.

Dyes of the formulas III and IV are also preferred, in which

R ₁ = hydrogen and dyes of the form III and IV, in

those
X and R ₁ = hydrogen «

The invention furthermore relates to a process for the preparation of the compounds of the formula (I). It consists in that you can dye pen formula

DN = N ^0H

CX

HO ₁ S NH R

where D and R has the meaning given above: nit 2,4,6-trifluoro-1,3,5-t: riazln with elimination of hydrofluoric acid Ί ₅ condenses and the resulting difluoro compounds with an amine of the formula '

/ ^R 1 HN. ^ ( _VI )

under spin-off

converts hydrofluoric acid to (i) "

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The condensation of the dyes (v) with the 3-triflaor = triazine is preferably carried out in aqueous solution or suspension, at low temperature and at weakly acidic, neutral to slightly alkaline pH value,

Condensation in the pH range of 3-5 is advantageous executed. The released hydrogen fluoride is through

Addition of aqueous alkali metal hydroxides, carbonates or bioyrbo = nate dulled. The reaction of the difluoro compound with the amines (vi) is likewise preferably carried out in an aqueous solution Solution or suspension, at low temperature and at weakly acidic to neutral to almost alkaline pH. The hydrogen fluoride released during condensation is converted into carbon dioxide by adding aqueous alkali metal hydroxides nate or bicarbonate neutralized. Isolation of the difluoro compound is generally dispensed with.

The dyes (y) 1 are obtained by coupling the diazotized amines (II) with I-acid under single conditions = It is obvious that the coupling is preferably carried out in the ortho-position to the hydroxyl group of the I-acid. However, it is in the In general, coupling with an N-acylated I-acid is preferred, with the acyl radical then duroh Warming = men is split off in an acidic or alkaline medium. Particularly acetyl, carbamoyl, meth = come as aeyl radical oxycarbonyl, ethoxycarbonyl or -CO- (l-acid urea

25 through reaction with phosgene).

Examples of AMine (VI) are as follows:

Aniline, N-methyl-aniline, 4-methyl-aniline, 4-iso-propylaniline, 4-ethylaniline, 4-chloroaniline, 4-sulfo-aniline, 4-carboxy-aniline,% -aoetylaeino-aniline, 4-methoxy-aniline, 4-thoxy-aniline, 4-iso-propoxy-aniline, N-methyl-4-ethyl- • niline, N-methyl-it-aiethoxy-aniline.

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In case that

X = sulfo or carboxy, the dyes (i) can also be used Manufacture so that nan first p-sulfanilic acid or 4-carboxy-aniline is reacted with s-trifluorotrlazine and then carries out the condensation with the dye (v).

There is another possibility for the production of (i) in that one diazotized amines (II) with coupling components of the formula

OH

HO ₃ S f- ^ jy-NH - ^ - X (VII)

F 1 o wherein

X and R have the meaning given above, in the black acidic, neutral to black alkaline range united.

The new dyes are suitable for dyeing and printing of materials containing hydroxyl or amide groups, such as textile fibers, threads and fabrics made of wool, silk, synthetic polyamide ·; and polyurethane fibers and for washable dyeing and printing of native or regenerated Cellulose, the treatment of cellulose materials expediently in the presence of acid-binding agents Means and optionally by the action of heat according to the methods that have become known for reactive dyes.

The formulas given for the dyes are those of the corresponding ones free acids. The dyes were generally in the form of the alkaline potassium salts, especially the sodium salts isolated and used for dyeing.

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example 1

50.3 g of the aminoazo dye 2,5-disulίο-benzene ^ l azo 2} l-hydroxy-3-sulfo-6-anino-naphthalene are dissolved in a mixture of 300 μl of water and 200 g of ice. 13.5 g of 2,4,6-trifluorotriazine are then added dropwise and the pH is maintained between 3.5 and 4.5 by the simultaneous addition of dilute sodium hydroxide solution. When the condensation is complete, 9.3 g of aniline are added to the clear solution and the pH is maintained between 5 and 6 with dilute sodium hydroxide solution. The temperature during the second condensation stage is between 0 and 10 *. Naohden nan sioh duroh a Dünnechiohtohrona = togrann has convinced of the end of the acylation, the dye is salted out with common salt, filtered off, dried and ground. An orange dye powder is obtained which dissolves easily in water. The dye conforms to the formula

SO ₃ H

The dye used as the starting material is obtained ten duroh dlazotier of l-aaino-2,5-disulfo-benzene, Coupling with N-Aoetyl-I-SHure, subsequent saponification of the Aoetyl group with dilute sodium hydroxide solution at 80-90 * and isolation Duroh salting out in sohwaoh alkaline range.

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Staining examples Printing specification

If you print cotton nettle with a printing paste that per kilogram 20 g of the dye shown in Example 1, 100 g of urea, 300 ml of water, 500 g of alginate thickening (60 g sodium alginate / kg thickening) and 10 g soda, and which was made up to 1 kg with water, dry, steam for 1 minute at 103 ° C, rinse with hot water and ■ soap at the boil, this gives lan a clear, orange »print τοη good wet and lioateohtaeit.

10 Blocking regulation

30 parts of the dye shown in Example ^ l ' are dissolved in 1000 parts of water. With this solution, a cotton fabric is fouladed and weight loss is achieved pressed by 90%. The still moist cotton is in a bath at 70 ° for 30 minutes which dissolved in 1000 parts of water 300 parts of calcined sodium sulfate and 10 parts of calcined sodium carbonate contains, treated. The Färbuo * will then be completed in the usual way. You get a brilliant » te-s traag · "Bit rorztifli'ohen wet and liohteohtheiten.

Color rule

In a staining beaker with a content of 300 ml, which is located in a heatable water bath, 168 ml of water are removed from 20 - 25 ° presented. 0.3 g of that of Example 1 is pasted the dye obtained with 2 ml of cold water and add 30 ml of hot water (70 °) to; the Dye on. The dye solution is added to the water added and 10 g of cotton yarn kept constantly in motion in this dye liquor. Within 10 minutes

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th, the temperature of the dye liquor is increased to 40 50 °, 10 g of anhydrous sodium sulfate are added and dyeing continues for 30 minutes. Then 4 g of anhydrous sodium carbonate are added to the dye liquor and dyeing is carried out at kO - 50 ° for 60 minutes. Man. then removes the dyed material from the dye liquor, removes the adhering liquor by wringing out or squeezing it off and rinses the material first with cold water and then with hot water until the rinsing liquor is no longer bled. The colored material is then soaped in 200 ml of a liquor containing 0.2 g of sodium alkyl sulfate for 20 minutes at the boiling point, rinsed again and at 60-70. dried in a Trookensohrank · A brillana tea trftaf · of good washing and moisture resistance is obtained.

If one proceeds according to the information in Example 1, however instead of the aminoazo dye used there, Verbin = fertilization begins, which is achieved by diazotizing the in column 1 listed diazo component !!, coupling with the aoetyl = compounds of the coupling components mentioned in column 2 =:

th and saponification.der acetyl group are available and instead of aniline one of the Aeine described in column 3 is used, this also results in valuable dyes, the cotton naöh one of the dyeing processes listed in one of the listed in column h

Color 25 tones.

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Example column 1

Column 2

Column 3

2 l-aaino-2 _y 5-di- It l-hydroxy-3-eulXo- N-methylaniline eulfo-benzene It 6-amino-naphtha1ine 3 η N p-toluidine 4th η η ρ-chloroaniline 5 N N p-anisidine 6th N H p-phenetidine 7th l-aaino-2,4-di- η aniline sulfo-benzene 8th H η N-methylaniline 9 η η p-tolnidine 10 It p-Gh1orani1in 11 It p-anisidine 12th It η p-phenetidine 13th l-amino-2-sulfo- aniline 4-oa rboxy-benz ο1 14th It η N-methylaniline 15th η It p-tolnidine 16 l-avino-2,5-di- η aniline βηΙίο-4-ethyl- benzene 17th η N-methylaniline 18th η p-toluidine

Orange column

π η it η η

η η η π η η

Q) ti

Example column 1

split

Column 3

Column k

1-amino-2,5-disulio-4-methylbenzene

"

1-Amino-2,5-d isulfo - ^ - acetylamino-benzene 1-amino-2-sulfo-4-methoxy-benzene

1-hydroxy-3-sulfo-6-aminonaphthalene

It

p-chloroaniline

p-anisidine aniline

p-sulfanilic acid

orange

Scarlet fever

23 η Il 11 It It 24 η ti η 4-carboxy aniline It 25th η H N p-anisidine It 26th η It It p-phenetidine Il 27 l-Auino-2-sulfo- l-amino-2-BUlfo- η aniline orange benzene 4-methyl-benzene 28 M. η V-methylaniline . It 29 η p-sulfanilic acid It 30th It 4-carbocyte aniline It 31 H p-anisidine It 32 ti aniline It 33 η N-methylaniline reds »orange

example Column 1 η Column 2 Column 3 Column 4 34 l-amino-2-sulfo- It l-hydroxy-3-sulfo- p, anisidine red orange 4-ethyl-benzene η 6-anino-naphtha1ine 35 M. π π p-sulfanilic acid η 36 Π η 4-Carboacy — ani 1 in π 37 l-amino-2-sulfo- η aniline orange 4-chloro-benzene η 38 η N η N-methylanine η 39 M. H η p-anisidine η 40 η η p-sulfanilic acid η 41 N η 4-Carboxy-ani1ine η 42 l-amino-2-sulfo- η aniline Scarlet fever 4-acetylaminoben = zol 43 η N-methylaniline N 44 η p-Sul f ani 1 s a'ur e η 45 H 4-carboxy-ani1ine π 46 l-hydroxy-3-sulfo- aniline M. 6-methylamino naphthalene 47 H N-M «thylaniline N 48 Il 4-carboxy- * niline Il 49 « V-SuIfo-aniline M.

example Column 1 Column 2 50 l-amino-2-sulfo- l-hydroxy-3-suifo- (4'-sulfo-phenyl- 6 — methylanino— amino) benzene naphthalene 51 η R. 52 η R. 53 R. R. 54 η l-hydroxy-3-sulfo- 6-amino-naphtha1ine 55 R. R. 56 N H 57 l-A «ino-2-sulfo- R. 4-ne th oxy-benz ο1 58 η R. 59 R. H 6o R. R. 61 R. H 62 R. R. 63 l-amino-2-sulfo- R. 4-ethoxy benzoil 64 H R. 65 R. " 66 R. R.

Column 3

split

aniline

N-methylaniline
p-toluidine
p-chloroaniline
aniline

p-toluidine

p-sulfanilic acid

aniline

N-methylaniline
p-sulfanilic acid
4-carboxy-aniline
p-anisidine
p-toluidine
aniline

p-sulfanilic acid
4-carboxy-ani1ine
N-methylaniline

Scarlet fever

H R H R

R R R

R R

R H R H

R H R

Example 67

45.3 g of the dye 2-sulfo-4-methoxy-benzene <^ 1 azo 2 ^) l-Hydroxy-3-sulfo-6-amino-naphthalene are in one Mixture with 400 ml of water and 100 g of ice. An ice-cold solution of 28.8 g of 2,4-difluoro-6- (4'-sulfophenyl) -amino-1,3,5-triazine is then used and maintains a pH of 5-6 during the condensation. Addition of dilute soda solution · Temperature 5-10 ° · After acylation is complete the dye is salted out, filtered off, dried and ground. The dye is identical to the one after Example 59 produced product.

Example 68

A solution of 50.7 g of the secondary condensation product of 1 mole each of p-sulfanilic acid, 1-hydroxy-3-sulf0-6-aminonaphthalene and 2,4,6-trifluorotriazine in 600 ml

Water is partially mixed with an aqueous suspension

the diazo compound obtained from 20.3 g of l-amino-2-sulfo-4-methoxy-benzene is obtained, and a pH of 5-6 is achieved by simultaneous addition of dilute soda solution hold · After the coupling is complete, the dye is salted out, filtered off, dried and ground. Of the The dye is identical to the product prepared according to Example 59.

The dye of Example 60 is also obtained if «an according to the instructions in Example 67 or 68 = drives, but it starts from products that have an equivalent instead of the p-sulfanilic acid used there Amount of 4-carboxy-aniline used.

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Claims (1)

Claims l) dyes of the formula D-N = N wherein D = SO ₃ H where R ₃ for halogen, such as fluorine, chlorine or Brob, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -AlkOXy, a sulfo-, carboxy-acylamino, or 4-sulfophenylaxogroup, SO ₃ H SO ₃ H where B ₃ for hydrogen, C _t -C ₄ -alkyl or an acylamino = group stands,
R ₁ = hydrogen, methyl,
X = hydrogen, C _t -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen such as Fluorine, chlorine or bromine, a sulfo-, carboxy or Acylamino group. R = hydrogen, methyl, ethyl. Le A 19 133 030011/0402 2) dyes of the formula HO ₃ S wherein X and R _{1 have} the meaning given in claim l) and R ₄ = chlorine, methyl, methoxy, ethoxy, sulfo, carboxy, acetylamino or 4-sulfophenylazo. 3) dyes of the formula ^{σΛ | Η} OH ^{1 H} ° 3 ^S η r ¹⁰ wherein X and R _{1 have} the meaning given in Claim l) and R ₅ = hydrogen, methyl or acetylamino k) dyes of claims 2) and 3), in which R ₁ = hydrogen. 5) dyes of claims 2) and 3), in which R ₁ and X = hydrogen. Le A 19 133 03001 1/0402 6) Process for the production of dyestuffs in forests 1 wherein
D, R, I ₁ and X have the meaning given in Claim l) have, daduroh marked that nan color fabrics of the Forael D-N-N ■ it 2,4,6-trlfluorotriazine with elimination of τοη Reacts 1 mol FlußsKure and the resulting difluon Connection old Asiinen of the formula B-: / ^B > in which X and S _{1 have} the meaning given in claim 1), with elimination of τοη 1 mol of flow rate condenses. 7) Use of the dyes of claims l) to 5) to « Dyeing and printing τοη hydroxyl groups or fiber materials containing anide groups Le A 19 133 030011/0402