DE2034543A1 - Disazo dyes - Google Patents

Description

FARBENFABRIKEN BAYER AG Patent department

K / Pr

Disazo dyes

The present invention relates to sulfonic acid groups Disazo dyes of the general formula

SO ₃ H

in which R ^ and R «represent a nonionic substituent X is a hydroxy, alkoxy or acylamino group means, R, and R. hydrogen, alkyl or aralkyl groups, m is an integer of O to 3 and η represent an integer from O to 2,

and their manufacture and use for dyeing and printing of natural and synthetic polyamide fiber materials.

Preferred dyes are those of the formula I in which X stands for an acylamino group.

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Suitable nonionic substituents R ₁ are, for example: halogen atoms, such as F, Cl and Br, optionally halogen-substituted alkyl radicals with 1 to 4 carbon atoms such as -CH ^, -C ₂ H ^, n- and i-σ, Ηγ, n-, i- and tC ^ H ^, -CH ₂ Cl and -CF ₃ ; Alkoxy radicals with 1 to 4 carbon atoms such as -OCH ,, -OC ₂ Hc, n ~ and 1-OC ₅ H ^ and n-OC.Hg; optionally by alkyl radicals with 1 to 4 carbon atoms, which in turn can carry further substituents, or by phenyl radicals substituted carbonamide and sulfonamide groups and carbon and sulfonic acid ester groups with 2 to 7 carbon atoms.

Particularly suitable non-halogenic substituents R ₂ are alkyl and alkoxy radicals, preferably methyl and methoxy radicals; Halogen such as fluorine, chlorine, bromine; Acylamino groups, preferably the formylamino group and also alkylcarbonylamino groups, with 1 to 4 carbon atoms in the alkyl radical, such as acetylamino and propionylamino.

Suitable radicals X are, in addition to OH and C ₁ -C 4 -alkoxy radicals, in particular the formylamino group and optionally substituted alkylcarbonylamino groups with 1 to 4 carbon atoms in the alkyl radical, such as acetylamino, hydroxyacetylamino, chloroacetylamino and propionylamino groups, and optionally substituted phenylcarbonylamino groups such as benzoylamino groups , 4-chlorobenzoyl, 3- or 4-methylbenzoyl, 3-CF, -benzoylamino groups and optionally carbamoylamino radicals substituted by alkyl radicals having 1 to 7 carbon atoms or by optionally substituted phenyl radicals, such as, for. B. NHCONHCH ,, NHCONHC.Hq

NHCONHCH ₂ OOh ₅ , NHC ONH - <^ y, NHCONH - ^^ - CI, NHC ONH-

Suitable alkyl radicals R ₅ and R. are optionally by halogen, such as fluorine, chlorine or bromine,., As well as by cyano, hydro

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109884/1548

xy-> C ₁ - 0. -alkoxy, C ₂ - Cc-alkylcarbonyl or C ₂ - .C ^ - alkoxyearbonyloxy groups substituted alkyl radicals with 1 to 4 carbon atoms, such as ζ. B. -CH ,, -C ₂ Hc, nC ~ H ™, η-Ο ^ Η «, 2-chloroethyl, 2-cyanoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-acetoxyethyl.

Suitable aralkyl radicals R, and R are in particular benzyl and phenylä-Üiylreettj which can have further substituents in the benzene nucleus, such as chlorine, C ₁ -C / "alkyl or C, -C -alkoxy radicals.

The new dyes of the formula I are obtained by Aminoazo compounds of the formula

N - / ^ _ ν

wherein R ₁ , R ₂ , m and η have the meaning given above,
diazotized, with compounds of the formula

III

in which X, R ^ and R ^ have the meaning given above, couples and - in the event that R and / or R are hydrogen - optionally then the -HR-R - group is alkylated or aralkylated.

Le A 13 156 - 3 -

10 98 8 4/15 Λ 8

The coupling takes place in the usual way, preferably in aqueous, weakly acidic medium; if appropriate, acid acceptors, for example pyridine, are added. The isolation normally takes place at pH 7, optionally by salting out with sodium chloride or potassium chloride.

The alkylation to be carried out if necessary . Aralky- . lation takes place by reaction with suitable compounds, such as esters of strong mineral acids or organic sulfonic acids and preferably low molecular weight alcohols, such as alkyl halides, aralkyl halides, dialkyl sulfates and aryl sulfonic acid esters.

Examples include: dimethyl sulfate, diethyl sulfate, methyl iodide, ethyl chloride, propyl bromide, benzyl bromide, methyl benzenesulfonate, ethyl p-toluenesulfonate and butyl p-chlorobenzenesulfonate.

The reaction with the alkylating or aralkylating agents takes place predominantly in alcoholic and / or alcoholic-aqueous solution in the presence of acid acceptors, such as, for example Alkali carbonates and bicarbonates. In this way, a monoalkylation or monoaralkylation is primarily achieved.

Some of the aminoazo compounds of the formula (II) are known. These compounds are obtained by acid coupling of a diazotised amine of the formula

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109884/1548

IV

wherein R ₁ and η have the meaning given above, with an amine of the formula

(V)

in which R « ^{and n have the} meanings given above.

If appropriate, N-methanesulfonic acid can be used instead of the amine (V) be used. The aminoazo compound can be obtained from the coupling product obtained in this way after alkaline saponification (II) obtained.

Suitable aminoazo compounds of the formula II are: 4-amino-azobenzene, 4 ^f -chloro-4-amino-ajobenzene _> 3'-chloro-4-amino-azobenzene, Z'-Ohlor ^ -amino-azobenzene, 2 ', 5' -Dichlor-4-amino-azobenzene, 2 ¹ , 4 ^l -Dichlor-4-amino-aBobenzene, 3 ^r , 4 * -Dichlor-4-amino-azobenzene, 4 ^l -Methyl-4-amino-azobenzene, 3 ' r methyl-4-amino-azobenzene, 2 ^l -methyl-4-amino-azobenzene, 4'-chloro-2-methyl-4-amino-azobenzene, 4 ¹ -chloro-2-acetylamino-4-amino-azobenzene, 2,3'-dimethyl-4-amino-a-benzene, 2,4'-dimethyl-4-amino-azobenzene, 2-methoxy-4-amino-azobenzene, 4'-chloro-2-methoxy-4-amino-azobenzene , 2,5-dimethoxy-4-aminoazobenzene, 2-methyl-5-methoxy-4-amino-azobenzene _> 2-methyl-5-

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ethoxy-4-amino-azobenzene, 2,3'-methyl-S-methoxy-4-aminoazobenzene, 4'-trifluoromethyl-4-amino-azobenzene, 2 ^f -trifluoromethyl-4'-chloro-4-amino-azobenzene, 2 · -Trifluoromethyl-4'-chloro-2-methyl-4-amino-azobenzene, 4'-trifluoromethyl-2-acetylamino-4-amino-azobenzene, 3'-chloro-4'-trifluoromethyl-4-amino-azobenzene , 3'-chloro-4'-trifluoromethyl-2-methyl-4-amino-azobenzene 4-amino-azobenzene-4'-sulfonic acid amide, 4-amino-azobenzene-3'-sulfonic acid (2-hydroxyethyl) amide, 4-Amino-azobenzene-3'-sulfonic acid anilide, 4-Amino-azobenzene-4'-carboxylic acid methyl ester, 4-Amino-azobenzene-4'-carboxamide _f

Suitable coupling components of the formula III are, for example:

2-Amino-4-acetylamino-benzenesulfonic acid, 2-N, N-dimethylamino-4-acetylamino-benzenesulfonic acid, 2-N, N-diethylamino-4-acetylamino-benzenesulfonic acid, 2-N-ethylamino-4-acetylamino-benzenesulfonic acid, 2-N-propylamino-4-acetylamino-benzenesulfonic acid, 2-N, N-bis (2-hydroethyl) -amino-4-acetylamino-benzenesulfonic acid , 2-N, N-diethylamino-4-benzoylamino-benzenesulfonic acid, 2-amino-4-phenylcarbamoylamino-benzenesulfonic acid, 2-amino-4-propionylamino-benzenesulfonic acid, 2-N, N-dimethylamino-4-propionylamino-benzenesulfonic acid, 2-N, N-diethylamino-4-chloroacetylamino-benzenesulfonic acid, 2-N, N-dimethylamino-4-formylamino-benzenesulfonic acid, 2-N, N-diethylamino-4-methylcarbamoyl aminobenzenesulfonic acid

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Z-Amino ^ -methylcarbamoylamino-benEoleulfonic acid, 2-Amino-4-hydroxy-benzenesulfonic acid, 2-amino-4-methoxy-benzenesulfonic acid, 2-N, N-dietliylamino-4-ethoxy-benzenesulfonic acid.

The new dyes are particularly suitable for dyeing and Printing of natural and synthetic fiber materials containing amide groups, for example those made of wool, Silk and synthetic super polyamide fibers. The dyeings obtained, especially those on synthetic polyamide materials, are characterized by good fastness properties; especially due to good wet fastness properties and very good light fastness properties. Also the neutral leasehold and the combination behavior with other suitable dyes for such Materials is remarkably good.

example 1

19.7 parts by weight (0.1 mol) of 4-aminoazobenzene are vigorously stirred with 200 parts of water and 28 parts of 28 foigex hydrochloric acid and diazotized in the customary manner with 70 parts of 10% nitrite solution. When the addition of nitrite is complete, the mixture is stirred for a further hour, clarified with activated charcoal if necessary, and excess nitrous acid is removed with amidosulfonic acid.

The diazonium salt solution is added to a solution of at 0-5 28.6 parts by weight (0.1 mole) of 2-N, N-diethylamino-4-acetylaminobenzenesulfonic acid in 2,000 parts of water and at the same time pyridine is added dropwise so that the pH remains constant at 3. After 5 hours 120 ml of pyridine are added (pH 5-6). It is left to react overnight. The reaction mixture is isolated using sodium hydroxide solution to pH 9-10, separates the precipitated dye and dries the paste at 100. The dye obtained corresponds in the form of free acid of the formula.

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84/1548

HHCOCH,

and represents a red powder that dissolves in hot water. Polyamide material is colored light- and wet-fast. As a nuance you get a scarlet red.

Dyeing process

50 milligrams of the dye are dissolved in 100 parts of hot water, 4 milliliters of 10 foige acetic acid are added and a 10 gram strand of polyamide fibers is introduced into the dyebath. The dyebath is brought to boiling temperature within 20 minutes and then held for 1 hour. It is then rinsed and dried at "JO to 80".

Other dyes of this type are listed in the following table: .-... '

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4-aminoazobenzene Table I · £ ■ · ■ 2034543 4-aminoazobenzene Coupling component hue Diazo component 4-trifluoromethyl-4-
amino-azobenzene benzenesulfonic acid Scarlet fever i> 4'-methoxy-2-methyl-
4-amino-azobenzene 2-H, N-Mmethylamino-4-acet-
aminobenzenesulfonic acid Scarlet fever 2) 2'-chloro-4-amino-
azobenzene 2-N, N-dimethylamino-4-acet-
aminobenzenesulfonic acid Red 3) 2'-chloro-4-amino-
azobenzene 2-N, N-dimethylamino-4-acet_
aminobenzenesulfonic acid Scarlet fever 4) 4'-chloro-4-amino-
azobenzene 2-amino-4-acetamino-
benzenesulfonic acid Red 5) 4'-chloro-4-amino-
azobenzene 2-N, H-diethylamino-4-acet-
aminobenzenesulfonic acid Red 6) 2 ■ ', 5 · -Dichloro-4-amino-
azobenzene 2-amino-4-acetaminö-
benzenesulfonic acid Scarlet fever 7) 2,3'-dimethyl-4-amino-
azobenzene 2-If, li-Diabhylamino-4-acet-
aminobenzenesulfonic acid Red 8th) (2-hydroxyäbhyl) -
aminosulfone 2-F, N-diethylamino-4-acet-
aminobenzenesulfonic acid Red 9) 4-aminoazobenzene-4 -
carboxamide benzenesulfonic acid Scarlet fever 10) carboxylic acid methyl ester 2-N, N-diethylamino-4-acet-
aminobenzenesulfonic acid Red 11) 2-methyl ~ 4-amino-
azobenzene 2-N, N-diethylamino-4-ace b-
aminobenzenesulfonic acid Red 12) 2-methyl-4-amino-
azobenzene 2-N, li-diethylamino-4-ace b-
aminobenzenesulfonic acid Red 13) 2-methoxy-4-amino- 2-amino-4-acebamino-
benzenesulfonic acid Scarlet fever 14) 2-N, N-diethylamino ^ -acet-
aminobenzenesulfonic acid Scarlet fever .15) 2-N, N- bis (2-hydroxyäbhyl) - Scarlet fever ■ 16)

azobenzene

17) 2-acet? Amino-4-aminoazobenzene

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amino-4-acetaminobenzenesulfonic acid

2-N, N-bis (2-hydroxyethyl) -amino-4-acetamino-benzene- sulfonic acid

■ - 9 -

Scarlet fever

δ ί for \ r ¹ W- -. «Uli;".

1098ÖA / .15A8

Diazo component

Coupling component

hue

18) 4-aminoazobenzene

19) 2-methyl-4-aminoazobenzene

20) 4-aminoazobenaol

21) 4-aminoazobenzene

22) 4-aminoazobenzene

23) 4-aminoazobenzene

24) 4-aminoazobenzene

25) 2 ~ methyl-4-aminoazobenzene 2-amino-4-phsnylcarbamoyl-orange aminobenzenesulfonic acid

2-amino-4-methylcarbamoyl orange aminobenzenesulfonic acid

2-amino-4-methoxymethyl orange carbamoyl-aminobenzenesulfonic acid

2-N, N-diethylamino-4 ^ benzoyl orange aminobenzenesulfonic acid

2-amino-4-hydroxy-benzene-orange sulfonic acid

2-Amino-4-methoxy-benzene ^ Orange sulfonic acid

2-N, N-dimethylamino orange

4-methoxy-benzenesulfonic acid

2-N, N-dimethylamino-4-meth-orange oxy-benzenesulfonic acid

Example 2

21.9 parts by weight (0.05 mole) of the dye

—N = N—

prepared according to Example 1 is dissolved in one liter of boiling ethanol and add 10.6 parts by weight (0.1 mole) of soda. Within one 12.6 parts by weight (0.1 mol) of benzyl chloride are added dropwise every hour and lets another group react. It is poured for insulation in 1 liter of ice-water and filtered off the precipitate. After this Drying gives a dye of the formula:

Le A 13 156 -XO-

0 a B B4 / I 5 4 8

ν! Ι

—HHCH ,. BHCOCH,

It represents a red powder, the polyamide fibers according to the ■ described Color proofs in bright scarlet tones.

In the following table II further dyes are listed which were subjected to alkylation.

Table II

Dye according to Table I Kr.

Alkylating agents 1

hue

1 1

■ 7 10 14 14 22 22 23

Dimethyl sulfate

Diethyl sulfate

Benzyl chloride

Diethyl sulfate

Diethyl sulfate

Benzyl chloride

Diethyl sulfate

Dimethyl sulfate

Ethyl chloride

Benzyl chloride

Scarlet Fever Scarlet Fever Eot

Scarlet Scarlet Scarlet Orange Orange Orange

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Claims (13)

Patent claims: are in which R, and R ^"is a non-ionogenic substituent, X represents a hydroxy, alkoxy or acylamino group, R ₅ and R. are hydrogen, alkyl or aralkyl, m is an integer from O to 3, and η a whole Represent number from 0 to 2. 2) Disazo dyes of the formula containing sulfonic acid groups in which R, · halogen atoms, optionally halogen-substituted alkyl radicals with 1 to 4 carbon atoms, alkoxy radicals with 1 to 4 carbon atoms, optionally by alkyl radicals with 1 to 4 carbon atoms or phenyl radicals subeti- Le A 13 156 - 12 - 10B884 / 15A8 tuated carbonamide and sulfonamide groups or carboxylic acid esters and sulfonic acid ester groups with 2 to 7 carbon atoms, R ₂ ^{denotes 1} methyl and methoxy radicals, halogen, the formylamino group or alkylcarbonyamino groups with 1 to 4 carbon atoms in the alkyl radical, X denotes a hydroxyl or Alkojcygruppe with 1 to 4 carbon atoms means and preferably for a formylamino group, one optionally through. Halogen-substituted alkylcarbonylamino group with 1 to 4 carbon atoms in the alkyl radical, a phenylcarbonylamino group optionally substituted by halogen, CP or alkyl or a carbamoylamino group optionally substituted by alkyl radical with 1 to 7 carbon atoms or phenyl radicals, R, 'and Ri ¹ hydrogen, optionally alkyl radicals with 1 to 4 carbon atoms substituted by halogen, cyano, hydroxy, C ₁ -C alkoxy, C «-Cc -alkylcarbonyloxy or Ο« - Cc alkoxycarbonyloxy groups, or optionally by chlorine, C _{1 -C -alkyl} or C ₁ -C alkoxy-substituted benzyl or phenylethyl radicals, m is an integer from 0-3 «and η is an integer from 0-2. 3) disazo dye of the formula Le A 13 156 - 13 - 10988 4/1548 4) disazo dye of the formula / Λ- N = N - ^ V N = H - SO ₃ H NHCOGH, 5) disazo dye of the formula SO ₃ H -N = N - <'7-N = N - ^ ~~ V NH- NHCOCH, 6) disazo dye of the formula CH ■ N = N N = N -Λ. NHCOCH, 7) disazo dye of the formula CH - N = N -CV- N = N- SO ₃ H NHCOCH, 8) disazo dye of the formula SO, H - NH * NHCOCH, Le A 13 156 - 14 - 109884/1548 7034543 9) disazo dye of the formula OCH, 10) Process for the preparation of sulfonic acid group-containing disazo dyes of the formula in which R ^ and R ₂ stand for a nonionic substituent, X is a hydroxy ,. Alkoxy or Acy denotes 1-amino group, R ₅ and R denote hydrogen, alkyl or aralkyl groups, m denotes an integer from 0 to 3 and η denotes an integer from 0 to 2, characterized in that aminoazo compounds of the form mel wherein R ₁ ,
to have, . m and η dio otcn given meaning Le A .13 156 - 15 - 109884/1548 2034643 diazotized, with compounds of the formula wherein X, R, and R. have the meaning given above, couples and - in the event that R, and / or R. is hydrogen mean - optionally then the -NR ^ R ^ group alkylated or aralkylated. 11) Process for dyeing and printing natural and synthetic polyamide fiber materials, characterized in that that one uses dyes of claims 1-9 » 12) Natural and synthetic polyamide fiber materials, dyed and / or printed with dyes of claims 1-9. 13) Disazo dyes containing sulfonic acid groups of claims 1-9, obtained by the process of claim 10. Le A 13 156 - 16 - 109884/1548