DE1960818A1 - Disazo dyes - Google Patents

Description

COLOR FACTORY BAYERAG 196081 » LEVIRKU S EN-Bayezwuk Pttcat-AbttUuaf Q QC7 IQCJCl

M / Wk

Diaazo dyes

The invention relates to new sulfonic acid groups containing disazo dyes of the formula

Process for their production and their use for dyeing nitrogen-containing fiber materials.

In the general formula (I) stand

Rj for hydrogen, chlorine, bromine, a straight-chain or branched alkyl radical with 1 - 4 carbon atoms, such as methyl, ethyl, n-propyl, ieo-propyl, η-butyl, iso-butyl, tert.-butyl, a trifluoromethyl group, an alkoxy radical with 1-4 carbon atoms, such as methoxy, ithoxy, n- and iso-propoxy, and n- and iao-butoxy, and also alkylsulfonyl | such as methyl and ethyl sulfonyl, alkanoyl

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amino such as formylamino, aeetylamino, propionylamino, hydroxyacetylamino, optionally mono- or di-alkylated sulfonamide, nitro, cyano, methyl carbonyl, ethyl carbonyl, methoxy or itoxy carbonyl, R ₂ for hydrogen, halogen such as chlorine or bromine _{r is} methyl, ethyl, methoxy or ethoxy and m is an integer from 1-5.

A "particularly valuable group of dyes in the frame the formula (I) corresponds to the formula

(Ia)

wherein R ^ and R ¹ «are independently hydrogen or a methyl group.

Very particularly valuable dyes in the context of the formula (I) correspond to the formula

(Ib)

wherein R ¹ ^ is hydrogen or a methyl group .

The new disazo dyes (I) are prepared by adding amines of the formula

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7 Vhh,

(H)

(R ₁ ),

where R and m have the meaning given above, diazotized and with cL-ITaphthylainin (III) or its in the Amino group protected derivatives (IV) or (V)

(III)

(V)

coupled, whereby one monoazo dyes of the formulas

(R ₁ X

(VI)

respectively.

-ΪΙ = N-T

<* i> « ^xv "

(VII)

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respectively. '

"~" \ - N = N - / _ Λ-MHCH ₂ SO ₃ H (VIII)

where R- and m have the meaning given above, receives.

The amino group in dyes (VII) and (VIII) is then exposed by acidic or alkaline saponification. The monoazo dyes thus obtained are diazotized and with amines of the formula

(IX)

wherein R ₂ ^d ^ ^e has the meaning given above, coupled.

Diazo components of the formula (II) are, for example:

Aniline, 2-aminotoluene, 3-aminotoluene, 4-aminotoluene, 2-aminoethylbenzene, 3-amino-ethylbenzene, 4-amino-ethylbenzene, 2-aminoisopropylbenzene, 2-trifluoromethyl-aniline, 3-trifluoromethyl-aniline, 4-trifluoromethyl-aniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 1-amino-2,3-dimethyl-benzene, 1-amino-2,4-dimethyl-benzene, 1-Ami.no-2,5-dimethyl-benzene, 1-Amino-2,4-diethylbenzene, 2,3-dichloro-aniline, 2,4-dichloro-aniline, 2,5-dichloro-aniline, 3,4-dichloro-aniline, 2,4-dibromo-aniline, 2,5-

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Dibromo-aniline, 2-cyano-aniline, 3 ~ cyano-aniline, 4-cyano-aniline | 4-amino-phtnalaäure-dinitrile, 4-amino-iaophthalsäure di.nitrilt-4-chloro-2-amino-benzonitrile _f t-amino-2,4,5-trimethyl-benzene, 1-amino-2,3 »5 trimethyl-benzene, 2,4,5-2richloro-aniline, 2,3,4,5-tetrachloro-aniline, penta-chloro-aniline, 4-chloro-2-aminotoluene, 5-chloro-2-aminotoluene , 4-chloro-2-trifluoromethylaniline, 3-chloro-2-methyl-aniline, 2-methyl ~ 4,5-dichloro-aniline, e-chloro-1-methyl-aniline, 5-trifluoromethyl-2-chloro-aniline , 4-chloro-3-methyl-aniline, 4,6-diciilor-3-methyl-aniline, 3-chloro-4-methyl-aniline, 2-amino-anisole, 3-amino-anisole, 4-amino-aniaol , 2-amino-plienetol, 3-amino-plienetol, 4-aminophenetol, 4-chloro-2-amino-aniaol, 5-chloro-2-alnino-ani8ol, 4 »5-ilichlor-2-amino -aniaol, 3-aminoformanilide, 3-aminoaoetanilide, 4-amino-acetanilide, glycolic acid (3-amino-anilide), glycolic acid (4-amino-anilide), 3-aminobenzolaulfonic acid amide ,. 3-Aminobenzolaulfonsäuremethylainid, 3-Amtnobenzolsulfonsäurephenylamid, 3-Aminobenzolaulfonaäure-lT-beta-hydroxyäthylamid, 4-Aminobenzolaulfonaäureamid, 4-Aminobenzolsulfonaäuremethylamid, 4-Aminobenzolaulfonaäurephenylamid, 4-Aminobenzolaulfonaäure-N-ß-hydroxyäthylamid, p-Kitranilin, 4-Aminoaceteph. enone, anthranic acid methyl ether, anthranic acid ethyl ether, 3-aminobenzoic acid methyl ether, 3-aminobenzoic acid ethyl ether, 4-aminobenzoic acid methyl ether, 4-aminobenzoic acid ethyl ether.

End components of formula (IX) are beiapielaweiae:

N-hienyl-naphthylamine-1-aulphonic acid-8, no-tolyl-naphthylamine-1-sulphonic acid-8, Nm-tolyl-naphthylamine-i-aulphonic acid-e, H-p-tolyl-naphthylamine-1-eulphonic acid-8 _t No-lthylphenyl-naphthylamine-1-sulfonic acid-8, Nm-lthylphenyl-naphthylamine-1 -aulfona acid-8, Np-lthylphenyl-naphthylamine-i-sulfona acid-S, H - (^ - methoxyphenyl) -naphthylamine-1-sulfonic acid- 8, H- (3-methoxyp: ienyl) -naphthylamine-1-sulfonic acid-8 | H- (4-methoxyphenyl) -

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(196081B

8, N- (2-lthoxyphenyl) -naphthylamine <-1-sulf @ nsäur @ -8, N = (3-lthoxyphe.nyl) -naphthylamine 1-sulfo »3 acid <=> 8, M- (4-lthoxyphenyl) -naphthylamine-1-sulfonic acid-8, 1- (2 »GhloPphenjl) -naphthylamine-1-sulfonic acid-8, IT- (3-chlorophenyl) -naplitliylamine-1-sulfonic acid-8, N- (4-chlorophenyl) -naphthylamines -1-sulfonic acid-8.

The diazo components of the formula (II) are used in the well-known manner _& "for example in acidic, aqueous solution with sodium nitrite solution" at Ö «. 5 ° C and combined with the coupling components (III), (IY) or "(V). The coupling can be carried out, for example, in a strongly acidic to weakly acidic pH range in an aqueous or organic-aqueous medium. Coupling component ( III) can expediently be used in the form of an emulsion, which is obtained, for example, with an emulsifier based on sulfated castor oil, or as a finely crystalline precipitate from hydrochloric acid solution using sodium acetate solution. The aminoazo dyes (VI) obtainable in this way are insoluble in water and are therefore easy to isolate. If the coupling component (IV) or (V) is used, the water-insoluble monoazo dyes (VI) are easily obtained by acidic or alkaline saponification of (VII) or (VIII).

The Weiterdiazotierung the aminoazo (Vl) can, for example in acid, aqueous dispersion, in organischwäßrigem or in suitable organic medium such as ethylene glycol monoethyl ether, formamide or dimethylformamide _ö carried out with sodium nitrite solution or in concentrated sulfuric acid, the Diazotierungstemperaturen can be between 0 ° and 30 ° G. The coupling with the end components (IX) to give the disazo dyes (I) is likewise carried out in a manner known per se, for example in a neutral, weakly or strongly acidic aqueous medium or in an aqueous-organic medium. The disazo dyes of formula (I) are

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usually very sparingly soluble in an acid medium and can therefore can be isolated by simple filtering off. If the dyes (I) are impure, they can be precipitated in the usual way hot water, possibly with the addition of alkali. The sparingly water-soluble, acid-isolated dyes (I) can thereby be made more soluble in water by, for example, using salts from strong Bases and weak acids, for example trisodium phosphate, disodium hydrogen phosphate, "sodium tetraborate, latrium metaphosphate, Sodium silicate or sodium carbonate, mixed.

The dyes of the formula (i) are suitable for dyeing nitrogenous materials such as wool and silk, but preferably synthetic super polyamide and super polyurethane fibers in blue tones with good to very good general fastness properties. The dyes draw from both acidic as well as from a neutral dye bath on polyamide fibers.

In the following examples, parts mean parts by weight, Percentages by weight.

Example 1:

93 parts of aniline are in the usual way in hydrochloric acid, ice-cold Solution with 69 parts of I sodium nitrite dissolved in 250 Parts of water, diazotized. The diazonium salt solution thus prepared runs to a finely crystalline <^ - uaphthylamine suspension, which was prepared as follows: 143 parts of dunaphthylamine are converted into 3400 parts at 98 ° G Entered water, dissolved with HO parts of concentrated hydrochloric acid, cooled at 30 ° 0 with 1850 parts of ice to 0 ° C and tm thin stream with 270 parts of sodium acetate, dissolved in Parts of water are added. The pH of the coupling is 4.5.

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After the coupling is complete, it is concentrated with 340 parts Hydrochloric acid made Congo acidic, cooled to 0 ° C. with about 2800 parts of ice and treated with 75 parts of sodium nitrite, dissolved in 310 parts Water, diazotized rapidly, the monoazo dye largely going into solution with a brown color. The temperature is left rise to 10 ° G and filtered from undissolved constituents. The diazonium salt solution then runs to a pH 4 adjusted solution of 321 parts of the sodium salt of li-phenyl-naphthylamine-1-sulfonic acid-8 in approx. 2500 parts Water. By adding sodium acetate solution at the same time the pH is kept at 3.5-4 during the coupling. When the coupling is complete, the dye has the formula

^W ■ ■ U> - ^S0 3 ^H

vacuumed and dried. 510 parts of an almost black powder are obtained.

Staining example

0.1 g of the dye is dissolved in 100 ml hot water, 5 ml of 10 % ammonium acetate solution are added and the solution is diluted to a volume of 500 ml of water. 10 g of polyamide fibers are added to the dyebath, the dyebath is brought to the boil within 20 minutes, 4 ml of 10% acetic acid are added and the mixture is kept at boiling temperature for one hour. It is then rinsed and dried at 70-80 ° C. The dark blue colored polyamide material has good to very good fastness properties.

An equivalent color is obtained if no acetic acid is added to the dyebath.

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Example 2; JJ

93 parts of aniline are diazotized as described in Example 1, coupled to ck-naphthylamine and further diazotized. The diazonium salt solution runs to one adjusted to pH 4 Solution of 335 parts of the sodium salt of U-p-tolyl-naphthylamine-1-sulfonic acid-8 in about 2500 parts of water. By adding sodium acetate solution at the same time, the pH value of the Clutch release held at 3.5-4 ·. Bach ended clutch the dye is suctioned off and dried. 520 parts of dye of the formula are obtained

k = π- / ' Vhh-K' Vch

The dye dyes polyamide fibers from an acidic or neutral dye bath in dark blue tones with good to very good Fastnesses.

If the sodium salt of N-p-methoxyphenyl-naphthylamine-i-sulfonic acid-e is used as the final component, the result is one the dye of the formula

which dyes polyamide fibers dark blue with similar properties.

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Example 3:,

JIG

10.7 parts of o-toluidine are used in the usual way at 0-5 ° C diazotized. To this diazonium salt solution runs with the help of an emulsifier based on sulphated Rieinueöl at 75 ° C produced emulsion of 14.3 parts of oC-ffaphthylamine in 50 parts of water. The coupling is stirred at 10 ° C., the pH being adjusted by the dropwise addition of sodium acetate solution is gradually increased to 3-3.5. When the coupling is complete, the pH is reset to 1 with a little hydrochloric acid, half a value Stirred for an hour and the monoazo dye is filtered off with suction. It is washed 2-3 times with weakly acidified water, in 500 parts of water were stirred, 30 parts of concentrated hydrochloric acid were added and the mixture was stirred for half an hour. Then it will be cooled to 0 ° C. by adding ice and rapidly diazotized with 6.9 parts of sodium nitrite (as a 30 # aqueous solution). The temperature is then slowly increased to 20 ° C, the undissolved material is filtered off and the coupling is carried out as described in Example 1, to 30 parts of the sodium salt of N-phenyl-naphthylamine-1-sulfonic acid-8 at pH 3.5-4. After the coupling has ended the resulting dye of the formula

W- ^S0 3 ^H

vacuumed and dried. 47 parts of an almost black powder are obtained, which are made of eaurem or polyamide threads neutral dye bath in dark blue shades of good to very good fastness properties.

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Example 4:

10.7 parts of o-toluidine are, as described in Example 3 , diazotized at 0-5 ° C., coupled to flC-naphthylamine and further diazotized. The solution of the diazonium salt is filtered and then combined with 30 parts of the sodium salt of Np-tolyl-naphthylamine-1-sulfonic acid-8, as described in Example 2. The isolated and dried dye of the formula

^, - SO ₃ H

dyes polyamide threads from acidic or neutral baths in a dark blue tinge of green with good to very good properties. The same dye is obtained if _{7 parts of o-toluidine are diazotized 1Q f} , coupled to 29.9 parts of 1-naphthylamine-N-sulfonic acid at pH 11, and after coupling is complete, acidified to the Congo by adding 100 ml of hydrochloric acid, and heating for three hours The sulfonic acid residue is split off at 60-65 ° C., cooled to 10 ° C., the aminoazo dye formed is diazotized as described above and coupled to Np-toluene-naphthylamine-1-sulfonic acid-8.

If the final component is replaced by N-p-methoxyphenylnaphthylamine-1-sulfonic acid-8, this gives the dye of the formula

Vh = H- / Vb = έ- / ' VmM' Vooh

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ft

of the polyamide threads dark blue with very similar own liability colors.

In the following table, more are according to the invention obtained dyes atif out, the polyamide threads in the color specified tones.

constitution

Nuance on polyamide

O ₂ H ₅ .

reddish navy blue

Z ₇ -SO ₅ H

Navy blue

CH (CH ₃ ) ₂

-Έ = N-

-HH-

Navy blue

-Έ = H-

-H = H-

-HH-

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reddish navy blue

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Constitution.

Nuance on polyamide

OH,

Navy blue

Navy blue

CH,

CH ₅ W //

rotsticMg

Navy blue

CH

-H = N-

-CH,

greenish

Navy blue

CH ₃ W

-NH-

Navy blue

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Constitution

Nuance on polyamide

GH,

CH ₃

Navy blue

Cl

greenish

Navy blue

Cl

greenish

Navy blue

01- / Λ-ΒΓ

-Ν = IT- <^> -NH-

-OCH springeth ichig ^ Navy

-JM a JM-A 'V-N = N-

green tiohig navy blue

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constitution

A.

Huance on polyamide.

Cl '

greenish navy blue

greenish navy blue

greenish navy blue

CH,

Cl-

Navy blue

OCH,

Dark blue

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Constitution Nuance on polyamide

^ _N = H- / \> - U = if-

OCH,

reddish

Navy blue

OC "H _C

<L

-CH,

reddish dark blue

CH ₃ O-

Navy blue

f7> -S0, H

Dark blue

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KorLS.t.i.tut.icai Iuanee on loljaaid

-N = N- fty -M

-CH, navy blue

NHCOCH,

λ // " ^S0 3 ^H

Navy blue

NHCOCH ₃ W // \ N

-S0, H

greenish

Navy blue

-Ν = H- ^

greenish

Navy blue

HOCH ₂ CONH- e ^N > -N = N-Le A 12 691

Λ greenish * navy blue

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constitution

Nuance on polyamide

Η00Η _ο σ0ΝΗ - <^ ~ Λ-Ν = N - <^ % -Ή = N-

greenish

Navy blue

OCH,

HHCOCH,

Λ /> - SO, H rotstiohig

Navy blue

SO ₂ NH ₂

-SO.H dark blue

SO ₂ NH ₂

-Ν = N- <^ Λ -NH- f \ -CH

I green

Dark blue

SO ₂ NH ₂

green ti cn ig

Dark blue

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constitution

Nuance on polyamide

SO ₂ NHCH ₂ CH ₂ OH \ J /

reddish navy blue

-N = Ν-

SO ₂ NHCH ₂ CH ₂ OHV

_y -SO ₃ H

green in Marinetilau

-ir = H-A-H = Ν-

So ₂ NHCH ₂ CH ₂ OHV

reddish navy blue

-H = H-

SO ₂ NHCH ₂ CH ₂ OH

Navy blue

Cl

greenish navy blue

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Constitution Nuance on polyamide

,, green etiohig

Navy blue

V // " ^S0 3 ^H

Navy blue

-CH, dark blue

ν /> - S0, H

Η, Ο-00-γΛ-Ν = Η-

Navy blue

COOCH

-N = Ν-

Navy blue

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Konatitutton

Nuance on polyamide

Navy blue

H ₃ C

reddish

Navy blue

OH,

H ₃ C

reddish

Navy blue

Dark blue

-Η = N- C \ -H - H-

Dark blue

constitution

Nuance on polyamide

CH ₃ O

-SO.H navy blue

CH ₃

Dark blue

u ^ -SO ₃ H _CHi

Navy blue

CH,

-H = N-f ^ -BH-

Dark blue

Cl

Navy blue

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Claims (4)

Claims; Μ. ¹ disazo dyes of the general formula containing sulfona acid groups where R- stands for hydrogen, chlorine, bromine, a straight chain or branched alkyl radical with 1-4 carbon atoms, a trifluoromethyl group, an alkoxy radical with 1-4 carbon atoms, Alkylsulfonyl, optionally substituted Alkanoylamino, optionally mono- or di-alkylated by methyl and / or ethyl and / or hydroxyethyl Sulfonamide, nitro, cyano, methylcarbonyl, ethyl carbonyl, methoxy or ethoxycarbonyl, R _{2 stands} for hydrogen, chlorine, bromine, methyl, ethyl, methoxy or ethoxy and m stand for an integer from 1-5. 2. Disazo dyes containing sulfonic acid groups of the general types formula - 23 Le A 12 691 103 824 / 7-0? 31 * wherein R ¹ ^ and R ¹ ^ are independently hydrogen or a methyl group ·. 3. Disazo substances containing sulfonic acid groups; Alles common formula / "Λ-Η = Ν- / Λ-Η = Ν - / ^ - ΚΚ- <ΓΛ-σΚ, where R ^ _{1 stands} for hydrogen or a methyl group, 4. Process for the preparation of disazo dyes the general formula (R ₁ ) Vm (D Le A 12 691 - 24 - 109824/7003 wherein R- stands for hydrogen, chlorine, bromine, a straight-chain or branched alkyl radical with 1-4 carbon atoms, a trifluoromethyl group, an alfcoxy radical with 1-4 carbon atoms »alkylsulfonyl, alkanoylamino, optionally by methyl and / or ethyl and / or Hydroxyethyl mono- or di-alkylated sulfonamide, Έ ±% το ₉ Cyaii, Hethylcairbonjrl, ethylcarbonyl, Methozy- or Itho ^ ycaribonylj E ₂ for ^ hydrogen, chlorine, bromine, methyl, ethyl, methoxy or Ethoay imd m stand for an integer from 1 - 5, characterized in that one is an amino compound of general formula (Hi) ₁ wherein R ₁ and m have the meaning given above, diazotized and with a coupling component of the general formula wherein R _{2 has} the meaning given above, combined. 5 Use of the disazo dyes of claims 1-3 for dyeing nitrogen-containing fiber materials 6 · Hit disazo dyestuffs of claims 1-5 colored nitrogenous fiber materials Jm A 12 691 - 25 - ■ 109824/2003 BATH ORIGINAL