DE2603160A1 - NEW BASIC AZO DYES, THEIR PRODUCTION AND USE - Google Patents

Description

CfBA-GEiGY AG, CH-A002 "Basel

Case 1-9770

GERMANY

DIPL.-tNu. -, ryv: Z * ^r z ^Γ:; \ DR. GAND ^ AIR

PÄVi-h: "ANW Λ LT ii 8 MÖNCHEN 80 · M AU EHKIRCH EBSTR. 45

Lawyer File 26 605

January 28 , 1976

New basic azo dyes, their production and use .

The present invention relates to cationic azo dyes of the formula

A ^ C - N = N

wherein

R is an optionally substituted low molecular weight

The alkyl radical η O or I ₅ Z is a divalent radical which complements the ring A to form an azine or azole ring which fuses one

609832/0947

26G3160

May contain benzene ring,

Y is hydrogen or a low molecular weight alkyl radical, X ^ is an anion and

R .. and R "independently of one another are each hydrogen or one low molecular weight, optionally substituted · alkyl radical, where R, and R "together with the Nitrogen atom and optionally including a further nitrogen atom or an oxygen atom can form a ring. '

The term "low molecular weight" denotes residues here 1 to 4 carbon atoms.

Possible substituents of the alkyl radicals R, R- and R "are: aryl radicals, in particular the phenyl radical, chlorine, hydroxyl or cyano groups, C 1 -C 4 -alkoxy, in the case of R acyl and in the case of R ₁ and R ₉ also acyloxy groups, for example C 1 -C, -alkoxycarbonyl, C 1 -C, -alkanoyl, C -, -C, -alkoxycarbonyloxy and C 1 -C, -alkanoyloxy.

The ring A is preferably one of the following radicals containing a quaternized nitrogen atom: pyrazolium, Thiazolium, isothiazolium, thiadiazolium, isoxazolium or triazolium,

The anion X can be derived from strong inorganic acids, and then represents e.g. the -chlorine-, bromine-, Iodine, nitrate, sulphate, especially hydrogen sulphate and. Phosphate, especially dihydrogen phosphate ion. Come but also anions of organic acids in question, including

■ χ 809832/0947 '.

Aryl and alkyl sulfonate and carbonate ions are understood, in particular the benzenesulfonate ion and its with Nitro, chlorine, bromine, C, -C, -alkyl and C, -C, -alkoxy groups substituted derivatives, C -, - C, -alkyl sul foen at ions, anions aliphatic carboxylic acids with 1 to 4 carbon atoms and benzoates, the benzene ring bearing the same substituents can how. in the case of benzenesulfonate ion. Of special The anions of the low molecular weight, i.e. containing 1 to 4 carbon atoms, alkylsulfuric acid half-esters are important. Furthermore, the dyes can be present as double salts with heavy metal halides, in particular with zinc and Cadmium halides.

- Examples of such anions are: the benzenesulfonate, ρ-toluenesulfonate, p-methoxybenzenesulfonate, methanesulfonate, ethanesulfonate, formate, acetate, chloroacetate, propionate, lactate, tartrate, benzoate, methylbenzoate, Methyl sulfate, ethyl sulfate, ZnCl ₃ and CdCl ₃ -IOn.

The new dyes are generally produced by coupling a heterocyclic, nitrogen-containing diazo component on a fluoroaniline and quaternization or Alkylation of the azo dye obtained.

The invention thus relates to a method for Preparation of the dyes of the formula (1), which is characterized in that an azo dye of the formula

S03832 / 0947

A ^ C - N = N - () —N (2)

// Vl / ^x r ₂

(CH-CH) Γ ^Ζ

wherein Z, η, Y, R-, and R ^ are the same as in formula (1), with an alkylating agent which gives off the radical R, reacts.

As alkylating agents with which the azo compounds of the formula (2) are converted to cyclammonium salts of the formula (1), for example the following compounds of the formula

R-X

in question: optionally substituted, low molecular weight alkyl esters or aralkyl esters of a hydrogen halide, e.g. Methyl, ethyl, n-propyl, η-butyl, ß-cyanoethyl, ß-carbamoyla'thyl- or benzyl esters of hydrogen chloride, hydrogen bromide or hydrogen iodide, low molecular weight dialkyl sulfates, such as that Dimethyl or diethyl sulfate, C -, - C, -alkyl ester of an organic Sulfonic acid, such as methyl, B-chloroethyl, ethyl, propyl and butyl esters of benzenesulfonic acid, o- or p-toluenesulfonic acid, 4-chlorobenzenesulfonic acid or 4-nitrobenzenesulfonic acid, also the alkyl bromine or chloroacetic acid esters with 1 to 4 carbon atoms in the alkyl radical \

Other alkylating agents are alkenes and epoxy compounds. These can be used as precursors of alkanol esters

E09832 / 0947

Grasp type R — X. They will be in the presence of acids like HCl, HBr, formic acid or glacial acetic acid, with the ones to be quaternized Nitrogen compounds implemented. Examples of such alkylating agents are the following reagents mentioned in the first column, each of which is given in the second column Introduce remainder R into the nitrogen compound:

= CH-, - cn; - CH ₂ R. - CN CH ₂ = CE- COOCH ₃ - - - CH ₂ - CH ₂ - COOCH ₃ CH ₂ = CH - COOC ₂ H ₅ - CH ₂ - CH ₂ - COOC ₂ H ₅ CH ₂ CT CH ₂ - CH ₂ -CH ₂ - OH - CH -CH ₃ '' ^CH 2 - CH ₂ CH ₃ -CH-
OH

The alkylation is conveniently carried out by heating in an inert organic solvent, for example hydrocarbons such as benzene j toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride, tetrachloroethane, chlorobenzene, _t ο -dichlorobenzene or Nltrakahlenwasserstoffen as Nitromethant; Nitrobenzene or nitroaphthalene. Acid anhydrides, acid amides or nitriles, such as acetic acid anhydride, dimethylformamide or acetonitrile or also bimethyl sulfoxide can also be used as solvents in the alkylation. A large excess of a solvent can also be used

809 83 2/09

ORIGINAL INSPECTED

Use alkylating agents. In most cases, especially in the presence of organic solvents, it is necessary to heat the reaction mixture from outside in order to start the reaction. In some cases. _r, the alkylation in aqueous medium or uiitex using an alcohol, optionally in the presence ge -., of small amounts of potassium iodide are performed *.

The compounds of formula (2) are in _; . Usually obtained by diazotizing a heterocyclic amine and coupling onto a fluoroaniline. ,

Examples of suitable coupling components are;

3-fluoroaniline, -. . , .. · ..

2-fluoro-NjN-dimethylaniline,. . ,

2-fluoro-N-ethylaniline,
3-fluoro-N, N-dimethylaniline,

3-fluoro-6-methyl-N, N-dimethylaniline,.

Come as heterocyclic amines. e.g. the the following compounds in question: .., ·; . . 2-amino-thiazole, 2-amino-4- or -5-methyl-thiazole, 2-amino-4-n-butyl-thiazole, 2-amino-4-trifluoromethyl-thiazole, 2-amino-

7s.ti.329 “ORIGINAL INSPECTED

4-chloromethyl-thiazole, 2-amino-4- or -5-phenyl-thiazole, 2-amino-4- (3'-nitro) -phenyl-thiazole, 2-amino-4- (4'-nitro-phenylthiazole, 2-amino-4- (4'-methoxy) -phenyl-thiazole, 2-amino-4- (4'-bromo- or -chlor) -phenyl-thiazole, 2-amino-4- or -5-methoxy-thiazole, 2-amino-4-hydroxymethyl-thiazole, 2-amino-4- or -5-acetyl-thiazole, 2-amino-4-acetylamino-thiazole, 2-amino-4-dimethylaminomethyl-thiazole, 2-amino-4- or ~ 5-ethoxycarbonylthiazole, 2-amino-4- or -5-cyano-thiazole, 2-amino-5-nitrothiazole, 2-amino-5-methylsulfonyl-thiazole, 2-amino-5-methylmercapto-thiazole, 2-amino-5-phenoxycarbonyl-thiazole, 2-amino-5-bromo- or -chlorothiazole, 2-amino-5-rhodano-thiazole, 2-amino-4,5-dimethyl-thiazole, 2-amino-4-bromo-5-phenyl-thiazole, 3-amino-isothiazole, 3-amino-5-nitro-isothiazole, 3-amino-4,5-dimethyl-isothiazole, 3-amino-5-phenyl-isothiazole, 5-amino-3-methyl-isothiazole, 5-amino-3,4-dimethyl-isothiazole, ■ S-amino-S-phenyl-isothiazole, 5-amino-3-methyl-4-cyano-isothiazole, 5-Amino-3-phenyl-4-methyl-isothiazole, 5-Amino-3-methy 1-4-carbomethoxy-isothiazole, 5-amino-4-methyl-isothiazole, 5-amino-isoxazole, S-amino-S ^ -dimethyl-isoxazole, 3-amino-isoxazole, 2-amino-1,3,4-thiadiazole, 2-amino-5-methyi-1,3,4-thiadiazole, 2-Amino-5-phenyl-1,3,4-thiadiazole, 2-amino-5-methoxy-1,3,4-thiadiazole, 2-amino-5-methylmercapto-l, 3,4-thiadiazole, 2-amino-5- (athoxycarbonylmethylthio) -i, 3,4-thiadiazoi, 2-amino-5-methy1-sulfonyl-1,3,4-thiadiazole, 5-amino-1,2,4-thiadiazole, 5-amino-3-methyl-1,2,4-thiadiazole, 5-amino-3-phenyl-1,2,4-thiadiazole,

6O9832 / D9A7 ORIGINAL INSPECTED

l, 5-Amino-3-methoxy- or, S-Ämino-S-benzyloxy-l ^^ - thiadiazole, 5-amino-3-methylmercapto-l, 2,4-thiadiazole, 3-amino-1,2, 4-triazole, 3-amino-5-methyl- or -ethyl-l ^^ - triazole, S-amino-S-cyclohexyl-l, 2,4-triazole, 3-amino-5-phenyl-l ₃ 2, 4-triazole, 3-amino-5- (3'-methylphenyl) -1,2,4-triazole, 3-amino-S- (4'-nitrophenyl) -I, 2j4-triazole j S-amino-S- benzyl-l ^^ - triazole, 1-methyl-3-amino-1,2,4-triazolj 1-benzyl-3-amino-1,2,4-triazole, 1-phenyl-3-amino-1,2 , 4-triazole, 1-benzy1-5-methyl-3-amino-1,2,4-triazole, 1,5-dibenzyl-3-amino-1,2,4-triazole, 1-ethyl-5-phenyl -3-amino-1,2,4-triazole, 4-phenyl-5-amino-pyrazole, 4-methyl-5-amino-pyrazole, 4-cyano-5-amino-pyrazole, 4-nitro-5-amino -pyrazole, 1-phenyl-5-aminopyrazole, 3-aminopyrazole, 1-phenyl-3-aminopyrazole, 3-amino-4-cyanopyrazole, 3-amino-4-nitro-pyrazole, 3-amino -4-ethyl-pyrazole, 3-amino-4-ethoxycarbonyl-pyrazole, S-amino-1-phenyl-1-methoxycarbonyl-pyrazole, 1,4-diphenyl-5-amino-pyrazole, 1,4-dimethyl-5 -amino-pyrazole, 1-ethyl-4-methyl-5-amino-pyrazole, 1-n-Bu tyl-4-methyl-5-aminopyrazole, 1- (3'-methylphenyl) -3-methyl-5-aminopyrazole, 1- (4 ^! Methyl phenyl) -3-methyl-5-aminopyrazole, 1- (3 ⁱ -chlorophenyl) -3-methyl-5-aminopyrazole, 1- (3'-methoxyphenyl) -3-methyl-5- amino-pyrazole, 1- (3 ^Ί -methylsulfony! phenyl) -3-methyl-5-amino-pyrazole, 1- (4 ¹ -nitrophenyl) -S-pyrazole, 4,5-dicyano-2-aminoimidazole,

609832/0947

Among the diazo components mentioned are specifically the the following preferred groups are to be mentioned: thiazoles of the formula

^R 3

Ί ^ C - NH, fr *

where R ~ hydrogen, C-, -C, -alkyl, phenyl, chlorine, bromine, C1 -C4 alkoxycarbonyl or C1 -C4 alkanoyl.

- Triazoles, in one of their possible tautomeric forms of the formula

Ν —Ν

correspond, wherein R / hydrogen or a C -, - C, -alkyl, a Is benzyl or phenyl group.

- Thiadiazoles of the formula

N-N

• where R is hydrogen, C -, - C, -alkyl or phenyl

- Isothiazole, the formula

^R 6

wherein R ^ is C-, -C-, -alkyl or phenyl,

0 9 8 3 2 / € Γ9 4

- IU -

- Pyrazoles of the formula

R. .R

⁹ Vif ⁸

where RyHsC ₁ -Cz-AIlCyI _{3 is} benzyl, phenyl or phenyl substituted with chlorine, bromine, C ₁ -Cz-AIlCyI or C-, -C / -alkoxy and Rg and Ry are each hydrogen or a C - ^ - C ^ - Mean alkyl radical,

The thiazoles of the above formula, in particular 2-aminothiazole, are of particular importance.

The cationic dyes of the formula (1) fall as salts of the acids of the alkanol esters used for their preparation or aralkanol esters R — X, ie as salts of inorganic or organic acids. It is therefore primarily about halides, such as chlorides, bromides or iodides, alkyl sulphates, such as methosulfates and ethosulfates, benzenesulfonates or p-toluenesulfonates. If desired, can be doubled Reaction in a suitable polar solvent, salts of other acids can also be prepared, for example oxalates

609832/8947

by adding oxalic acid. You can also use double salts produce, for example with the dye halides and corresponding zinc halides.

The precipitation of the color salts formed is expediently completed by adding sodium chloride and / or zinc chloride in aqueous-acidic solution and then isolated by filtration.

The dyes obtained according to the invention are suitable for dyeing and printing materials made of polyacrylonitrile or polyvinylidenecyanide as well as other acid-modified materials Synthetic fibers such as acid modified polyamide or acid modified polyester.

Under polyacrylonitrile is meant especially polymers, for example, 85 to contain more than 857 _o, 100% acrylonitrile; They also contain 0 to 15% vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid, acrylic acid esters, methacrylic acid, methacrylic acid esters, etc.

On these fibers, which can also be dyed in a mixture with one another, one obtains intensive and with the new dyes level dyeings with unexpectedly good lightfastness and good general fastness properties, especially good washing, sweat, sublimation, wrinkle-proof, decatur, ironing, rubbing, carbonizing, water, Chi'or water, sea water, dry cleaning, over dyeing and Solvent fastness. Surprisingly, the lightfastnesses are better than the corresponding dyes containing instead of fluorine, chlorine, bromine or hydrogen. Which he-

€ 09832/0347. ORIGINAL

New dyes according to the invention also have a good one Stability and good affinity e.g. in aqueous solutions of different pH values.

The good ability to migrate should also be emphasized of the new dyes. It makes it possible even under critical dyeing conditions, for example at fast Heating up the dye bath and obtaining level dyeings without using retarders. Also suitable the new dyes for practically all acrylic fibers on the market and give up both quickly and level dyeings on slow-pulling types. As examples of suitable acrylic fibers, there are those below Brand names of commercial products sold: Acrilan, Creslan, Crylor, Courtelle, Dynel, Dolan, Euroacryl, Exlan, Orion, Velicren, Vonnel, Verel, Wolcrylon and Zefran.

The new dyes also work well for trichromatic staining as they blend well with already known ones combine basic dyes.

In the following examples, the parts are parts by weight, the percentages are percentages by weight and the temperatures are given in ^° C. The relationship between parts by weight and parts by volume is the same as that between

g and cm.

6 09832/0947 ORIGINAL INSPECTED

Example 1 ../- ". ^R - .-; .. · ■ ..-"'"■

; .5.0 parts of that obtained by diazotizing 2-arainothiazole and coupling of the resulting diazonium salt on 2-fluoro-N, N-dimethy! aniline accruing by customary methods Dye of the formula

-N

N = N

are dissolved in 75 parts by volume of chlorobenzql at 90 °. One drips onto it. 3 parts by volume of dimethyl sulfate to and keeps the reaction mixture for 2 hours at 90-100 °. It is allowed to cool and the precipitated dye of the formula is sucked off

CIL

-N =

CH ₃ SO ₄

This dye ?:. Dyes polyacrylonitrile from weakly acidic Dyebath, with a royal blue shade. The colorations are completely irrelevant and very lightfast.

ÖW3 2 /; 0 9:47.

ORIGINAL INSPECTED

Example 2 .-....- ::

5.0 parts of the resulting diazonium salt by diazotizing 2-aminothiazole and coupling the diazonium salt ^; on 3-fluoro-N, N-dimethylaniline by customary methods accruing dye of the formula """*""

—N

Ii

s

N = N

are dissolved in 75 parts by volume of chlorobenzene at 90 °. 3 parts by volume of dimethyl sulfate are then added dropwise and holds the approach for 2 hours at 90-100 °. One lets cool and soak up the precipitated dye of the formula ■. ■

CH ₃

CH "

-N- = N-

Li

This dye salt dyes polyacrylonitrile from weakly acidic Dye bath with a violet shade. The colors are completely irrelevant and very lightfast. Compared with the corresponding Dye made from 2-aminothiazole and m-chloro-N, N-dimethylaniline show colorations with the dye according to the application 1 to 2 grades better lightfastness. - ■ - · ■ - · -

ORIGINAL INSPECTED

g 0 9 8 3 2 7 Q 3 4 7. ^:

Example 3

2.5 parts of that obtained by diazotizing 1,3-dimethyl-5-aminopyrazole and coupling of the resulting diazonium salt to 3-fluoro-N, N-dimethylaniline according to customary methods Methods resulting dye of the formula

CH.

N = N

are dissolved in 40 parts by volume of dimethylformamide at 90-100 °. 2 parts by volume of dimethyl sulfate are then added dropwise and holds the approach for 2 hours at 90-100 °. The dimethylformamide is then reduced under Pressure distilled off and the dye residue in 100 Parts by volume of water added. The clear-filtered aqueous dye solution becomes the dye of the formula

= Ν ^ ^Γ Λ_Ν

ZnCl,

deposited by means of sodium chloride and zinc chloride. This dye salt dyes polyacrylonitrile from weakly acidic Dye bath with an orange shade. The colors are completely irrelevant and lightfast.

609832/0947

75.ii.329a ORIGINAL INSPECTED

Example 4

5.8 parts of the resulting diazonium salt by diazotizing 2-aminothiazole and coupling the diazonium salt for 1- (2-fluorophenyl) -3-methyl-4,5-dihydropyrazole customary methods obtained dye of the formula

-N = N

are dissolved in 100 parts by volume of chlorobenzene at 70-80 °. Two parts by volume of dimethyl sulfate are then added dropwise and the batch is kept at 70-80 ° for 1 hour. One lets cool and remove the precipitated dye formula

CH _Q / ³

~ N = N

N = C

CH ₃ SO ₄

5 parts of the resultant dried dye together with 10 parts of thiodiglycol, 25 parts of 40% acetic acid _s 225 parts of locust bean gum derivative (12? O-solution) and 235 parts of boiling water processed into a printing paste A polyacrylonitrile fabric is printed with this paste and the print is completed in the usual way.

A purely blue print with good fastness properties is obtained .

6 0 9 8 3 2! / J) 9 h 1

ORIGlNAL INSPECTED

Claims (12)

R is an optionally substituted low molecular weight alkyl radical η O or 1, Z is a divalent residue, 'which the ring A to a Azine or azole ring supplements, which may contain a fused benzene ring, Y is hydrogen or a low molecular weight alkyl radical, X ^ an anion and R, and R ^ independently of one another are each hydrogen or one mean low molecular weight, optionally substituted alkyl radical, where R-, and R ~ together with the Nitrogen atom and optionally including a further nitrogen atom or an oxygen atom can form a ring. 609832/0947 2. Cationic azo dyes according to claim 1, wherein the ring A is a pyrazolium, thiazolium, isothiazolium, thiadiazolium, isoxazolium or triazolium radical. 3. Cationic azo dyes according to Claims 1 and 2 of the formula -S N- R ¹ N = N (3) Ro hydrogen, C -, - C, -alkyl, phenyl, chlorine, bromine, C, -C, -alkoxycarbonyl or C-j-C, alkanoyl and R 'is a C-, -C, -alkyl radical or a benzyl radical and in which. Y, R ₁ and Rp and X ^ are the same as in claim 1. 4. Cationic azo dyes according to claim 3, wherein Y is hydrogen or methyl, R ~ hydrogen and R., and Rp are methyl. 5, cationic azo dyes according to claims 3 and 4 the formula 609832/0947 Γ " N "
R ¹ CiL OIL (4) wherein R 'is C-, -C, -alkyl or benzyl and one U is hydrogen and the other is fluorine and X · -' is an anion. 6. Process for the preparation of cationic azo dyes of the formula . X ² K / " ¹ A ^Λ R-NA C-N = N- <V-N (CH = CH) (D R is an optionally substituted low molecular weight Alkyl radicals O or 1, Z is a divalent radical which forms the ring A into one AzIn or azole ring complements which an annelated May contain benzene ring, Y is hydrogen or a low molecular weight alkyl radical, X ^ is an anion and 60983 2/0947 ORIGINAL INSPECTED R 1 and R _9, independently of one another, each denote hydrogen or a non-molecular, optionally substituted alkyl radical, where R 1 and R ₉ together with the nitrogen atom and optionally including a further one. Nitrogen atom or an oxygen atom can form a ring, characterized in that that you can use an azo dye of the formula (CH-CH) wherein Z, n, Y, R ₁ and R ₉ are the same as in formula (1) _loading; interpret with an alkylating agent donating the radical R. ■. 7. The method according to claim 6, characterized in that that one starts from a dye of the formula (2) in which the ring A is a pyrazolium, thiazolium, isothiazolium, Is thiadiazolium, isoxazolium or triazolium radical. 8. Process according to Claims 6 and 7, characterized in that one uses a dye of the formula ORIGINAL INSPECTED 3 \ ^ ~ N = N- / VN ^ ^λ (5) NX ₁ / \ _R where R ~ is hydrogen, C, -C, -alkyl, phenyl, chlorine, bromine, Cj -C, -alkoxycarbony 1 or C-, -C, ~ alkanoyl and Y, R ^ and R2 are the same as in claim 6, with an alkylating agent which gives off a C-, -C, -alkyl or a benzyl radical. 9. The method according to claim 8, characterized in that one starts from a dye of the formula (5) in which Y is hydrogen or methyl, R ~ hydrogen and R. and Ry are methyl. 10. The method according to claims 8 and 9, characterized in that a dye of the formula U
-S / -4 '/ CH ₃ CH ₃ wherein one U is hydrogen and the other is fluorine, with an alkylating agent of the formula R '- X
wherein R 'is a C - ^ - C ^ -alkyl or benzyl radical and X is chlorine, 6 0 9 8 3 2/0947 Bromine or the remainder of a C-, -C, -alkylsulfuric acid half-ester means. 11. Process for dyeing and printing textile materials made of polyacrylonitrile or acid-modified polyamide or polyester, characterized in that one the dyes defined according to claims 1 to 5 are used . 12. The material obtained according to claim 11. 809832/0947