DE2036505C3 - Cationic dyes, processes for their preparation and their use - Google Patents

Description

wherein R- has the meaning given above. with the addition of an anion X yielding Condensing agent with f'yrazolinen of the general formula

M N

CM. (II.

wherein R "has the meaning given above. condense! and if * R- stands for hydrogen

If desired, an alkyl for this purpose. Cyclohexyl or aralkyl radicals in the description above Kind of introduces.

13. The method according to claim 12, characterized in that a compound is rooted as diphenylamine carbonic acid in which R ₇ is hydrogen .

14. The method according to claims 7 13, characterized in that you use phosphorus oxychloride as the water abs paltable agent !.

15. The method according to claim 14, thereby ge indicates that the phosphorus oxychloric is phosphorus pentoxide or phosphorpene chloride puts.

16. Method of dyeing. Printing and dyes (colors in bulk) of materials the completely or predominantly from polymerized system acrylonitrile or asymmetric Dicyanäthylet and or of acid-modified polyesters and which consist of acid-modified polyamide characterized in that dyes de claims 1-6 are used.

17. The use of dyes of claim '6, and I for dyeing leather, tannin-treated cotton, writing fluids, pastes pressure UNR ¹ of lignin-containing fibers.

Subject of the [all around: Mtid canonical dyes of the general formula

■ α i> nn

\ you remaining links / completing one Bcn / -i * _. Iji-; ndo! -. Atridine or anthrapyridine

ringes.
R is an Arvlresi or a heterocyclic radical

aromatic < rurakters the following Λπ.
R _{1 is} hydrogen or another nonionic

Rest.
R _{2 is} hydrogen or another nonionic

Rest.
Rj is hydrogen or another nonionic

Rest.
R ^ hydrogen or another nonionic

Rest.
R _{5 is} hydrogen or another nonionic

Rest.
R _{s is} hydrogen or another nonionic

Rest.
Rr hydrogen, an alkyl. Cyclohexyl-. Aralkyl

or aryl radical of the type mentioned below. m the numbers zero or one.
η the numbers zero or one and

X means tin anion

and in which the radicals R. R ₁ . R ₂ . R and R ₄ can be connected to one another and R- can be connected to a ring fused to A and in which the carbocyclic and heterocyclic rings contained in these formulas and the acyclic radicals are cationic and nonionic dyes customary in chemistry May contain substituents.

Process for their production and their use for dyeing and printing.

Suitable nonionic substituents customary in chemistry with basic dyes are, for. B. alkyl-hydroxy, Alkyloxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amidocarbonyl, nitrile, nitro-amino, Acylamino, alkylamino, dialkylamino sulfonyl, Mercapto, alkyl mercapto and aryl mercapto groups and halogen atoms of the following mentioned Art.

Alkyl radicals are methyl, ethyl, n-propyl, iso-propyl η-butyl. iso-butyl, n-amyl, iso-amyl. neo-pentyl Allyl and its substitution products such as / J-cyano-

ethyl. | / - ('chloroethyl,, / - M'tlioxyüthyl, (- ethoxyiilhyl. , / - ethoxyairbonylethyl.

Aralkyl radicals are benzyl, i-phenylethyl. 1-phenylpropyl and phenylpropyl (2,2) -Rcsl.

Aryl radicals are phenyl. 2-, 3- and 4-methylphenyl. 2-. 3- and 4-ethylphenyl, 4-isopropylphynyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, 4-bisphenylyl. Phenyl-4,; · (etramethylene, 2-.3- and 4-chlorophenyl. 2,4-dichlorophenyl, 2-, 3- and 4-bromophenyl, 4-fluorophenyl, 4-trifluorophenyl, 4-acetylphenyl, 4-cyanophenyl. 4-Methoxycarbonylphenyl. 4-Ethoxycarliony I phenyl. 4-Methylsulfonylaminophenyl. 3-Met hy! Sulfonyl phenyl. 2-, 3- and 4-Methoxyphenyl. 2-, 3- and 4-Athoxyphenyl, 4-Isnpropoxyphenyl. 4-Methylmercaptophenyl, Naphthyl-I.

Heterocyclic radicals are thienyl-2. 1-uryl -2, pyridyl-2. Benzoxazolyl-2. Benzothiazolyl-2.

Halogen atoms are fluorine. Chlorine and bromine.

The liquid basic dyes, customary organic and inorganic anions, may be used as anionic Resie X ", for example: chloride". Bromide ", CH ₁ SO _4. C ₂ H ₅ SO ₄ , p-toluenesulfonate. HSO ₄ , SO ₄ "", benzenesulfonate, p-chlorobenzene sulfonate. Dihydrogen phosphate, phosphate. Acetate. Chloroacetate, formate, propionate, lactate, crotonate. NO , ", Perchlorate, ZnCl ₃ and the anions of saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid and maleic acid. Citric acid. Oxalic acid, itaconic acid. Succinic acid, glutaric acid. Adipic acid. Pimelic acid and suberic acid. Preference is given to colorless anions; for dyeing from an aqueous medium, preference is given to those anions which do not impair the water solubility of the dye too much. For dyeing from organic solvents, preference is also given in many cases to those anions which promote the solubility of the dyestuff in organic solvents or at least do not adversely affect it.

The dyes of the formula (I) can be prepared by adding compounds of the formula

C-O

in the

in which A, R ₅ , R ₆ , R ₇ and η have the meaning given above , or compounds of the formula

(IH)

N =

in which A, R ₅ , R ₆ and η have the meaning given above and Xj is an anionically removable radical,

or compounds of the formula

f C. C. C. x, I.
N R. R ₁ . R ^

wherein A. R ₅ . R ₆ . R- and η have the meaning given above. X ₁ denotes an anionically removable radical and X 'denotes an anion, or their precursors with the addition of a condensing agent with pyrazolines of the formula which provides an anion X

R ₄ R ₁ R,

CCR ₁

Il N

(V)

N ΟΙΟΙ CU) ,,, R

wherein R. R ,. R ₂ . R.,. R ₄ and m have the meaning given above.

and if R _{7 is} hydrogen, if desired, it introduces an alkyl, cyclohexyl or aralkyl radical of the type mentioned above. The reaction of compounds of the formulas III with V and the possible introduction of alkyl, cyclohexyl or aralkyl radicals of the type mentioned above result in dyes of the formula I. wherein R _{7 is} hydrogen, an alkyl, cyclohexyl or aralkyl radical of the type mentioned above stands.

Compounds of the formula (II) which are suitable for carrying out the process according to the invention are, for example

Naphtholactam- (1.8),

4-chloro-naphtholactam- (l, 8),

4-bromo-naphtholactam- (1.8),

S-chloro-naphtholactam-f 1.8),

5-bromo-naphtholactam- (1.8),

2.4-dichloro-naphtholactam- (1.8).

2,4-dibromo-naphtholactam- (1,8).

2,4,5-trichloro -; aphtholactam- (1,8).

4-methoxy-naphtholactam- (1,8), 4-ethoxy-naphtholactam- (1,8), 2-meth yl-naphtholactam- (1,8), 2-ethyl-naphtholactam- (1,8 ) and 6 -Hydroxy-naphtholactam- (1.8),

N-methyl-naphtholactam-O ^), N-ethyl-naphtholactam- (1,8), N-n-propyl-naphtholactam- (1,8), N-iso-propyI-naphtholactam- (l, 8), N-n-butyl-naphtholactam- (1,8), N-iso-AmyI-naphtholactam- (1,8), N-n-hexyl-naphtho1actam- (1,8), N-Cyclohexyl-naphtholactam-i 1,8), N-benzyl-naphtholactam- (1,8), N-0-phenylethyl-naphtholactam- {1,8), N-y-phenyl-n-propylnaphtholactam-f 1,8), N-phenyl-naphtbolactam-il ^), N-methoxycarbonylmethyl-naphtholactam-i 1,8), N - /? - cyanoethyl-naphlholactam- (l, 8),

Il

N-, i-chloroithyl-naphtholaetam- (1,8).

N- / f-Ethoxycarbonylethyl-naphtholactam- (1.8).

N - // - methoxyethyl-naphtholactam- (1,8), N-zi-dimethylamino-ethyl-naphtholactam-l 1.8).

N-zi-morpholino-ethyl-naphtholactam-ll ^).

N-MethyM-chloinaphtholactam-f 1,8), N-ethyl-4-bromo-naphtholactam- (1,8), N-ethyl- ^ hydrcxy-naphtholactam-l 1,8), N-ethyl-4-methoxy-naphtholactam- (1.8), N-ethyl-4-n-butoxy-naphtholactam- (l, 8), N -ethyl-4-dimethylamino-naphtholaetam- (1.8).

N -ethyl-4-nitro-naphtholactam- (1,8).

N-Ethyl ^ -acetyl-naphtholactam-l 1,8).

N-ethyl-4-methyl-naphtholactam- (1.8).

N-methyl-5-chloronaphtholactam- (1,8).

N-methyl ^ -ethyl-naphtholactam-l 1,8), N-ethyl-2,4-dichloro-naphtholactam- (t .8), N-ethyl-2,4-dibromo-naphtholactam- (1,8), N-n-Buiyi-4-bromo-naphinoiaciam-i .8), N-methyl-T-methoxy-naphtholactam-1.1.8).

N-ethyl-4- / f-methoxy-ethoxynaphtholactam- (1,8), N, 2-trimethylene-naphtholactam- (1,8), N, 2-trimethylene-4-chloro-naphtholactam- (1.8).

N.2-trimethylene-4-bromo-naphtholactam- (1.8).

Acridone,

N-methyl acridone.

N-ethyl acridone, N-n-propyl acridone.

N-iso-propyl-acridone, N-n-butyl-acridone, N-iso-butyl-acridone, N-n-amyl-acridone, N-iso-amyl-acridone.

N-n-hexyl-acridone, N-neo-pentyl-acridone, N-phenyl-acridone, N-benzyl-acridone, N-Zi-Phenylethyl-acridon, N-cyclohexyl-acridone, N-allyl-acridone, l-chloro-acridon., 2-chloro-acridon.

3-chloro-acridone, 4-chloro-acridone.

l-bromo-acridone.

2-bromo-acridone, 3-erom-acridone, 4-biom-acridone and their N-methyl and N-ethyl derivatives.

1-methoxy-acridone, 2-methoxy-acridone, 3-methoxy-acridone, 4-methoxy-acridone, 1-ethoxy-acridone, 2-ethoxy-acridone, 3-ethoxy-acridone, 4-ethoxy-acridone, 2-n-butoxy-acridone, 2-phenoxy-acridone, 2-methylmercapto-acridone, 2-methylsulfonyl-acridone, 2-dimethylamino-acridone, 2-diethylaminoacridone, 2-methylacridone, 4-methyl-acridone, 2-ethyl acridone, 4-ethyl asridone, 4-iso-propyl-acr'done.

3-hydroxy-acridone,

1,4-Dimethoxy-aeridon.

2,4-dimethyl acridone,

2.7-ljimethoxy-acridone,

2.7-diethoxy-acridone,

2-methoxy-7-chloro-acridone.

N ^ -trimethylcn-acridone,

N-zi-cyanoethyl acridone,

N-zi-chloroethyl acridone.

N - ^ - Methoxyethyl-acridone.

Ν-, ί-ethoxyethyl acridone,

N '/ i-ethoxycarbonyl-acridone.

N-Methoxycarhonylmethyl-acridon and N-zf-Dimethylaminoäthyl-acridon.

Anlhrapyridone (Formula VI).

N-methyl-anthrapyridone,

N-n-butyl anthrapyridone,

rN-zf-Aihoxy-aihyi-anihrapyrition.

2-methyl-anthrapyridone.

6-methyl-anthrapyridone,

4-dimelhylamino-anthrapyridone and 4-anilino-anthrapyridone.

N-- H

Cl

(VII)

Suitable compounds of the formula (III) are, for example, 2-methylmercapto-benz- (c, d) -indole. 2-chloro-benz- (c, d) -indole, 9-chloro-acridine, 9-fluoroacridine and py-chloro-anthrapyridine (formula VII) and the chloro-acridines which, when treating the diphenylamine-2 -carboxylic acids in which R _{7 is} hydrogen are formed with phosphorus oxychloride and / or phosphorus pentachloride.

Suitable compounds of the formula (IV) are, for example, the hydrochloric acid, the sulfuric acid or acetic acid salts of the abovementioned compounds (III) or their z. B. with dimethyl sulfate, diethyl sulfate, Methyl toluenesulfonate or benzyl chloride obtained quaternary salts.

According to the invention, suitable precursors for the preparation of the compounds of the formulas (II), (III) and (IV) diphenylamine-1-carboxylic acids of the formula

(VIII)

wherein R _{7 is} hydrogen, an alkyl, cyclohexyl,

Aralkyl or aryl radical of the orslehend mentioned Kind of represents.

The term "precursors" is not intended to mean, however, that the diphynylamine carboxylic acids in in each case first to acridindcrivatcii cyclisicrt and only then condensed with pyrazolines; the reaction steps can rather be also swap, d. that is, it first becomes a compound of the formula

R.

R,

R ₁

C (C II CHI ,,, R

R ₄
Ο
C.

N
R-

wherein R ₇ . R, R ₁ . R ₂ . R ₃ . R ₄ and m have the meaning given.

generated by cyclization with (formal) elimination of water (presumably via at least one further intermediate stage) forms the dye.

Suitable compounds of the formula (VIII) are, for example, those compiled in the table below Diphenylamine-2-carboxylic acids:

Hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen Hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen

COOH

(IX)

Tabel Substituents

methyl

Benzyl

Phenyl

methyl

methyl

/ J-cyanoethyl

/ i-cyanoethyl

/ i-chloroethyl

/ i-methoxyethyl

/ i-dimethylamino-

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

hydrogen

4'-methyl 4'-methoxy

4'-ethoxy 4'-ethoxy 4 \ 5'-dimethoxy

3'-methyl 4'-methyl 6'-methyl 3 ', 4'-dimethyl 4 ', 6'-dimethyl

Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen Hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen

Hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen

14th

Substituents

4-ethyl

4-iso-propyl

4'-cyclohexyl

4'-hydroxy

4'-methoxy

4'-ethoxy

4'-n-propoxy

4-iso-propoxy

4'-n-butoxy

4-iso-amyloxy

4-ethoxy

4.4-diethoxy

-V.4 '- [5iiii! IuAy

.V.5'-diethoxy

4'.6'-diethoxy

4-chloro-4'.6'-diethoxy

4-dimethylamino

4-diethylamino

4 - ('hlor-4'-diethykimino

3.4 benzo

3.4-Benzo-4-ethoxv

2'.3'-Bcnzo

3'.4'-benzo

4'-methoxycarbonyl

3'-ethoxycarbonyl

4'-acetyl

4-chloro-4'-acetyl

3'.4'-DiChIOr

3'.4'.4-trichloro

4-bromine

4'-Fiuor

4-methylsulfonylamino

4-dimethylamidoc- .rbonyl-

amino

4-methoxycarbonylamino

4'-methylsulfonyl

4'-trifluoromethyl

3-methyl-4'-methoxy

5-methoxy-4'-methyl

6-methoxy-4'-ethoxy

4,5-dichloro-4'-ethoxy

Further suitable compounds of the formula (VIII) are, for example, the compounds of the following structure:

COOH O CH ₂

// x

COOH

N-

0-2-0- ° -

-C = O

-CH ₂

CH,

C = O

H - = - H Ο —CH,

COOH

C = O

CH ₃ CH ₃

H ¹

COOH

C = O 3- (4'-MethoxycarbonyIphenyl) -pyrazo | in (12), 3- (4'-Ethoxycarbonylphenyl) -pyrazoline- (12), 3- (4'-Methylsulfonylphenyl) -pyrazole! N- (12), 3- (4'-MethyIsulfonylaminophenyl) -pyrazolin- (12),

3- (4'-methoxyphenyD-pyrazoline- (12). 3- (4'-Ethoxyphenyl) -pyrazoline- (12), 3- (4'-Phenoxyphenyl) -pyrazoline- (12). 3- (4'-Isopropoxyphenyl) -pyrazoIin- (12), 3-styryl-5-phenyl-pyrazoline- (12), 3- (p-chloΓstyryί) -5- (4'-chloφhenyl) -pyrazoline- (. 12),

3- (o, p-dichlorostyryl) -5- (2 ', 4'-dichloφhenyl) -pyrazoline- (12),
3- (2'-thienyl) -pyrazoline- (12), 3- (5'-methylthienyl-2 ') -pyrazoline- (12), 3- (2'-furyl) -pyrazoline- (12),

H - = - H CH,

COOH

"; - Ν -.

COOH

'- N ^{- x} - H

COOH

C = O

CH ₃ H, H ₂ pyrazoline- (. 12),
3-i4'-Pyr; dy!) - pyrazo! In- {! 2),
3- (2'-Benzoxazolyl) -pyrazoline- (12), 3- (2'-BenzthiazoIyl) -pyrazoline- (12). 3- (1'-naphthyl) -pyrazoline- (12), 3- (2'-naphthyl) -pyrazoline- (12). 3-phenyl-4,5-tetramethylene-pyrazoin- (12). 3,4-diphenyl-pyrazoline- (12),
3,5-Dipheny! -Pyrazoline- (12)
and the pyrazoline derivative

N-N-H

CH,

H,

4i, Of the dyes of the general formula (I) those of the formulas P (I) or P (II) are preferred

H / - _> H ₂ N- ) H ₂ /
\
\ H ₂ H ₂

CH, -CH,

R-N = C-N

N =

Suitable pyrazolines of the formula V are, for example:

3-phenyl-pyrazoline- (12). 3- (4'-methylphenyl) -pyrazoline- (12), 3- (2'-ethylphenyl) -pyrazoline- (. 12). 3-14'-Isopropylphenyl) -pyrazoline- (. 12), 3- (4'-tert-butylphenyl) -pyrazoline- (12). 3- (4'-Cyclohexylphenyl) pyrazoline- (12). 3- (4'-bisphenylyl) -pyrazoline- (12), 3- (4'-ChlorophenyI) -pyrazoline- (12). 3-Jl'-chlorophenyl) pyrazoline- (12).

3-i; 2'-chlorophenyl) -pyrazolin- (12), 3- ^(2-l .4' Dichloφhenyl) -pyrazolin- (12). 3- (3'.4'-dichlorophenyl) pyrazoline- (12). 3- (4'-Bromophenyl) -pyrazoline- (12), 3- (4-Fluorophenyl) -pyrazoline- (I 2). 3- (4'-Trifluonethyl) -pyrazoline- (12). 3- (4-acetylphenyl) pyrazoline- (12). 3- (4'-Cyanophenyl) -pyrazoline- (12), (Xl)

CH ₅ -CH,

P (II)

in which R ₇ and X have the meaning given above, R _{8 stands} for an aryl radical of the type mentioned above or for a thienyl radical and in which the rings and acyclic radicals can contain nonionic substituents customary in the chemistry of cationic dyes.

809 640/164

Dyes of the formula (XI) can be prepared or be by making compounds of the formulas

R, - N-C = O

N = C-X,

(el (XIIIl

wherein R _{7 has} the meaning given above and can be bonded to the naphthalene ring, X _{2 represents} an anionically removable radical, in particular a mercapto group or a halogen atom, X 'is an anion and wherein R ₇ and the naphthalene ring are more cationic in chemistry Dyes can contain customary nonionic substances,
with pyrazolines of the general formula

CH, - CH,

H-N

(XIVi

N == C

wherein R _{8 has} the meaning given above. condensed and - if R is hydrogen - if desired introduces an alkyl, cyclohexyl or aralkyl radical of the type mentioned above. Dyes of the formula (XII) can be prepared by adding compounds of the formulas

N
R-

■ "■ / \

R-

X ' ¹

(XV)

or their precursors of the formula (VIII)

in which R _{7 has} the meaning given above, X _{1 stands} for an anionically removable radical, X 'is an anion and in which the acridine or acridone ring can contain nonionic substituents customary in the chemistry of cationic dyes,

condensed with pyrazolines of the general formula (XIV) and - if R _{7 is} hydrogen - if desired introduces an alkyl, cyclohexyl or aralkyi radical of the type mentioned above. If a starting product of the form in (a) is used to prepare the dyes of the formulas (XI) or (XII), it is necessary to carry out the condensation with the addition of a condensing agent which provides an anion X ″.

To carry out the process according to the invention, a compound of the formula (II) or (VIII) is heated with an equivalent amount of a pyrazoline of the formula (V) in an inert diluent with the addition of a condensing agent which provides an anion X. One of the components can also be used in excess. Suitable diluents are preferably liquids which are inert towards the condensing agent and which - if appropriate under reduced pressure
Can easily be removed again by distillation, such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichlorethylene, dichloroethane, chlorobenzene, dichlorobenzene, benzene or toluene. Acid chlorides, for example phosphorus oxychloride, phosphorus oxybromide, phosphorus tri- and pentachloride, are suitable as condensing agents. Thionyl chloride and phosgene. These condensation agents can often also be used in such an excess that they also serve as solvents or diluents. This is particularly true of phosphorus oxychloride. The rate of condensation can be increased by the additional use of water-splitting agents such as aluminum chloride. Titanium trachloride or phosphorus pentoxide are increased.

In one process variant, a compound of the formula (III) or (IV) is condensed with a pyrazoline of the formula (V) or (XIV). For this embodiment, the addition of a condensing agent is generally not necessary; Rather, it is sufficient to warm the compound (III) or (IV) in a suitable solvent with the pyrazoline.The optimum temperature depends on the structure of the components and can be very easily determined by a preliminary experiment, since condensation will occur is associated with a color effect; In general, lir warmth up to approx. 160 C will achieve the goal. Suitable solvents are /. B. alcohols such as methanol. Ethanol, n- and iso-propanol. iso-amyl alcohol. Glycol. Olympic mono-

methyl ether and Glyceririi ethers such as diethylene glycol dimethyl and diethyl ether and dioxane, also pyridine, quinoline, dimethylformamide, N-methylpyrrolidone, Tetrachloroethane, chlorobenzene and o-dichlorobenzene. The high-boiling, water-soluble solvents are preferred because they are particularly easy to work with.

The nature of the anion X is generally determined by the manufacturing process and that which may have been carried out Purification of the raw dye given. Generally the dyes are present as halides (especially as chlorides or bromides) or as methosulphates, ethosulphates, sulphates, benzene or toluenesulphonates or as acetates. The anions can be used in any way against other anions such as tetrafluoroborate, phosphate, chlorozincate. Nitrate, perchlorate, oxalate, propionate, formate, citrate, Tartrate, lactate or benzoate ions are exchanged.

In order to achieve solubility in the media suitable for dyeing from organic solvents, these anions are exchanged for, for example, 2-ethylcaproic acid, lauric acid, oleic acid, linoleic acid, a mixture of aliphatic carboxylic acids with 15-19 carbon atoms (Versatic acid 1519 from Shell) , a mixture of aliphatic carboxylic acids with 9-11 carbon atoms (Versatic acid 911 from Shell), coconut fatty acid first runnings, tetradecanoic acid. Undecylenic acid, dimethylpropanoic acid, dimethyl acetic acid. Carboxylic acids, the carbon chain of which is interrupted by heteroatoms, such as nonylphenol tetraethylene gl j koläthcrpropionäure, nonylphenol diethyienglykolälherprcpionskVje, dodecyltetraäthyleneglykolätherpropions ^; iure, 3-iNonyloxy) propionic acid, 3- (isotridecyloxy (propiolic acid. 3- (isotridecyloxy / diethylglycol ether propionic acid) ether propionic acid of the alcohol mixture with 6-10 carbon atoms, nonylphenoxyacetic acid, aromatic carboxylic acids such as cyclohexanoic acid, cyclohexanoic acid, cyclohexanoic acid, cyclohexanoic acid. Abietic acid and sulfonic acids such as tetrapropylene benzene sulfonic acid and dodecyl benzene sulfonic acid.

The new products are valuable dyes that are used for dyeing and printing materials Leather, tannier cotton, cellulose, synthetic super polyamides and super polyurethanes as well as for Dyeing lignocentric fibers like coconut, jute and sisal can be used. You are further suitable for the production of writing fluids. Stamp inks, ballpoint pen pastes and can also use in rubber printing.

In particular, however, the basic dyes of the above general formula are suitable for dyeing from aqueous liquor or from organic solvents - and printing on threads, ribbons, Woven or knitted fabrics made from polyacrylonitrile or from copolymers of acrylonitrile with others Vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl acetate, vinyl pyridine, vinyl imidazole, Vinyl alcohol, acrylic and methacrylic acid esters and amides, as. Dicyanethylene, or flakes, fibers, Threads. Tapes, fabrics or knitted fabrics made from acid-modified aromatic polyesters as well as acid modified polyamide fibers. Acid modified aromatic polyesters are, for example, polycondensation products from Sulfotcrephthalic acid and Ethylcnglycol. d. H. Polyethylene glycol terephthalates containing sulfonic acid groups, such as those in the Belgian U.S. Patent 5,490,179 and U.S. Patent 2,893,816.

The dyeing may be made from weakly acidic liquor to give "C enters into the dyeing bath conveniently at 40-60 and dyes then at boiling temperature. It can be colored even under pressure at temperatures above 100 ^c C. Furthermore, the dyes dopes be used to produce Add pc! yacrylonitrilhaltiger fibers or apply them to the undrawn fiber.

The dyeings and prints are particularly noticeable on the last-mentioned materials
by excellent fastness properties, especially light, wet, decatur, sublimation, perspiration and rubbing fastness, and in many cases by the extraordinary clarity of the color shade. The new dyes show the desired reservation effects, that is, selected accompanying fibers, such as wool or polyester, are not stained.

To apply the dyes to the materials to be colored, the known methods of Dyeing or printing including dyeing from organic solvents (e.g. chlorinated hydrocarbons) be applied.

The parts given in the examples are parts by weight.

example 1

19.7 parts of N-ethyl-naphtholactam-11.8) and 14.6 parts of 3-phenyl-pyrazoline- (12) are in 60 parts Dissolved chloroform. You can run in 20 parts of phosphorus oxychloride, the temperature up to The boiling of the solvent increases, and then keeps the mixture boiling for about 1 hour. Of the remaining after the chloroform has been distilled off The crude dye is dissolved in 700 parts of boiling water and treated with activated charcoal. From the The bulk of the dye of the formula separates out of the filtrate when it cools

C ₂ H ₅ -N = CN

CH, -CH,

he

'■ 7

crystalline from; the rest is precipitated by adding table salt. The dye is suitable for dyeing. Printing and mass coloring of materials that consist entirely or predominantly of polyacrylonitrile in extraordinarily real, very clear and fluorescent yellow tones.

Used instead of 3-phenyl-12-pyrazoline the equivalent amount of 3-4'-methylphenyl-, 3-4'-ethylphenyl-, 3-3'-methylphenyl-, 3-4'-methoxyphenyl-, 3-4'-Ethoxyphynyl-, 3-3 ', 4'-Dimethoxyphynyl-, 3 »4' ■ Chiorphenyk 3 = 4'-Bromphenyh 3-4'-cyanophenyl- or 3-x-thienyl-12-pyrazoline. so With the otherwise unchanged procedure, very real, yellow dyes are also obtained.

Example 2

169 parts of naphtholactam-! 1,8) and 146 parts 3-Phenyl-pyrazoline- (12) are in 750 parts of chlorine

benzene 2'stirred for ₂ hours at 80-100 C ^D with 150 parts of phosphorus oxychloride, followed by decomposing the residual Kondensationsrnittel by dropwise addition of water and the solvent is removed by distillation with water vapor, is thus obtained an aqueous dye solution. When it cools, the dye of the formula separates

CH ₁ -CH ₁

N = C-N

N =

in crystalline form. It is suitable for dyeing polyacrylonitrile in very real yellow tones.

The dye can in a conventional manner, for. B. by Stir with dilute, aqueous iodine solution at about 50'C. into the color base of the formula

If, instead of the dimethyl sulfate, the "equivalent amount of diethyl sulfate, ethylene chlorohydrin, / i-dimethylamino-ethyl chloride, / f-diethylamino-ethyl chloride, ff-piperidinyl ethyl chloride, ff-morpholino-ethyl chloride, / f-ethoxy-ethyl chloride, ^ -Chlor- or ff-bromo-propionitrile or 1-iodobutane, this also gives very real, yellow dyes.

+ i Example 4

ι »27.6 parts of N-AthyM-brom-US-naphthoIactam and Cl ¹ "'14.6 parts of 3-phenyl-12-pyrazoline are with

100 parts of freshly distilled phosphorus oxychloride are stirred for 2-4 hours at 70-80 ° C. After that, the Main amount of phosphorus oxychloride under verminii distilled off at a pressure below 80 ° C. The residue is initially mixed with 750 parts of water decomposed and then boiled. The dye of the formula separates from the filtrate

CH ₁ -CH ₁

N = C-N

N =

be convicted. This compound melts after recrystallization from methylcyclohexane or from Toluene at 186-188 ° C.

Example 3

29.7 parts of the color base of the formula obtained according to the information in Example 2

N = C-N

CH ₂ -CH ₂

are in 50-100 parts of dry dimethylformamide solved. At about 100 ° C., 13.0 parts of acid-free dimethyl sulfate are run in while stirring, and the mixture is stirred for another 1–3 hours at about 100 ° C and diluted the dye solution, cooled to about 50 ° C., with 900 parts of water. Separates by adding table salt one the dye of the formula

CH ₁ -CH,

CH ₃ -N = CN

N =

= C

egg'-'

2 (1

he, —CH,

C ₂ H ₅ -N = CN

= C

in out. which dyes polyacrylonitrile with very good fastness properties in very clear, strongly reddish-yellow shades.

If one of the following compounds is used instead of the naphtholactam derivative given above in an equivalent amount in each case, one obtains

Ji also very real, colouristically similar dyes: N - methyl - 4 - bromo, N - η - propyl - 4 - bromo, N - iso-propyl - 4 - bromo, N - η - butyl - 4 - bromo, N - iso - amyl-4- bromine-, N-n-hexyl-4-bromo-, N-methyl-4-chloro-, N-ethyl-2,4-dichloro, N-methyl-5-chloro, N-methyl

• »n 2,4,5-trichloro-, N-methyl-5-bromo-, N-ethyl-4-acetyI-, N-ethyl-4-acetylamino-, N-ethyl-4-methylsulfonylamino-, N-ethyl-4-dimethylamino-, N-ethyl-4-methoxy, N-methyl-δ-methoxy- and N-N-ethyl-o-methylamino -naphtholactam- (1,8).

45

Example 5

209 parts of N, 2-trimethylene-naphtholactam- (l, 8), and 146 parts of 3-phenyl-12-pyrazolin be with 750 parts of freshly distilled phosphorus oxychloride, with the addition of 70-150 parts phosphorus pentoxide 4-6 hours at about 60 ⁰ C stirred. The cooled mixture is then poured into 5000 parts of water to decompose the excess condensing agent. When the hydrolysis is complete, the deposited dye becomes

the formula

CH ₂ -CH ₂

(+1

by recrystallization from water with addition

Drr Farhslnff rrcriht on Ma-

Polyacrylonitrile materials very real, luminous greenish tinged dyes and prints.

Used instead of N, 2-trimethylnaphtholactam the equivalent amount of 2-methyl-. 2-ethyl-, 2-iso-propyl- or N-methyl-2-iithylnaphtholactam- (1.8). in this way, with the otherwise unchanged working method, one also obtains very genuine, greenish-yellow ones Dyes.

Example 6

222 parts of N- (i-cyanoethyl-1.8-naphtholactam and 152 parts of 3 - \ - thienyl-12-pyrazoline are in 750 parts Chloroform condensed with 150-200 parts of phosphorus oxychloride as described in Example 1 The dye of the formula is obtained

NCCH ₂ CH ₂ N CN

CII, CH,

N C S

Cl '

which on polyacrylonitrile very real, yellow colorations and Prints results.

Is used instead of cyanoethyl naphtholactam the equivalent amount of N-Methoxyearbonylmethyl-. N - ethoxycarbonylmethyl-. N - / (- methoxycarbonylethyl-. N -, (- ethoxycarbonylethyl. N -, .- dimethylaminoeth> l-. Ν-, ί-diethylaminoethyl-. N-.i-ethoxyethyl-. N-Benzyk N-4'-methoxybenzyl-. N -.; - Phenylethyl-. N-phenyl-. N-4-hydroxyphenyl- or N-4'-ethoxyphenyl-1,8-naphtholactam. so receives with the otherwise unchanged procedure, very real, deep dyes are also used.

32.5 tons

B ice ρ ι L-1 7
of the salt of the formula

s <

and I ". ^ file 3-4'-Metho \\ phen \ l-! Z-pyrazohn ncrden finished in Kh'p 7-JiIt-Ti dimethviformamid bi> / ur Elimination of methyl mercaptan heated to 100 I 10 C. After diluting with water, the dei resulting dye of the formula

CW _x NC N

CH, CH,

N C

CH ₁ SOi '

OCH,

isolated in the usual way. Fr gives on polyacrylonitrile brilliant, very real yellow colorations and prints

Example 8

22. ^ parts of N-n-Butv! -Naphtholactam-! 1.8) and 22.2 parts of 3.5-diphenyi- 12-pyrazoline are used according to condensed with one another as in Example I The dye of the formula is obtained

; CH, -CH ₇ CH ₇ CH, -N = CN

CH - CH ₂

χ; - - (- he

who are going to dye. Bulk dyeing and printing of polyacrylonitrile in very real, yellow tones is suitable. If, instead of the 3,5-diphenyl-12-pyrazolines, the equivalent amount of one of the following .1-2-pyrazolines of the general formula V is used, very real, yellow dyes are also obtained:

Phenyl hydrogen hydrogen hydrogen hydrogen Phenyl methyl methyl hydrogen R,. R ₄ = Cyclohexyl hydrogen hydrogen hydrogen R ₅ + ■ R _h = hydrogen R ₄ + R ₅ = Cyclohexyl hydrogen hydrogen methyl hydrogen hydrogen hydrogen hydrogen Water peat hydrogen Example 9 Kiiic Lösüii μ VLMi in, / ι rush ΐΉιίμιιι tiusi _y ■ y i-niiiu-

chloride (produced according to the information in the German Offenlegungsschrift 14 45 624. Example I b) in KX) 150 Parts of anhydrous chlorobenzene are 14.6 parts 3-phenyl-12-pyrazoline added. Heat slowly to about 120 C, the mixture is kept at this temperature for about 20 minutes and then distilled Remove the solvent with steam. The dye of Example 2 is obtained in this way.

Example 10

193 parts of N-methyl-acridone and 146 parts of 3-phenyl-2-pyrazoline are in 1000 parts of o-dichlorobenzene with 250 parts of phosphorus oxychloride for 5 hours for about Heated to 120 C. Then the mixture is allowed to cool, decomposes the excess phosphorus oxychloride by carefully adding water and drives off the o-dichlorobenzene with steam. The aqueous solution obtained in this way shows itself the resulting dye partially disappears when it cools. The excretion is achieved by adding table salt completed. The dye of the formula hydrogen hydrogen hydrogen obtained in this way Hydrogen cyclohexyl hydrogen methyl hydrogen hydrogen

IO condensed together. The strongly reddish-tinged yellow dye of the formula is obtained

Phenyl I. Phenyl 0 Phenyl 0 Phenyl 0 Phenyl 0 Phenyl 0 Phenyl 0 p-methoxyphenyl 0 > - 'T hicnvl 0

H N

N C

CII, CH,

Cl ¹

OCH ₅

which gives very real dyes and prints on the materials mentioned.

If, instead of the 2-ethoxy-acridone, the respective amount equivalent to that in the following is used Table given acridones, one gets the corresponding dyes, which are very real, in the Colorings and prints on polyacrylonitrile material given in the table result in:

CH, -

j CH ₃ - N

CT 'Acridone

can be purified by recrystallization from water with the addition of charcoal. It is suitable for Dyeing, printing and mass dyeing of materials containing gani; or predominantly made of polyacrylonitrile or acid modified polyesters or acid modified polyamides consist of outstandingly genuine, yellow tones.

It is used instead of 3-phenyl-pyrazoIins the equivalent amount in each case of one of the pyrazolines mentioned in Example 1, last paragraph, is obtained also very real, yellow dyes.

Example 11

239 parts of 2-ethoxy-acridone and 146 parts of 3-phenyl-12-pyrazoline are according to the information in the example

2-methoxy-acridone, 2-n-propoxy-acridone, 2-n-butoxy-acridone 2-iso-butoxy-acridone 2-beiizyloxy-acridone 3-methoxy-acridone 4-phenoxy-acridone 2,7-dimethoxy-acridone 1,4-diethoxy-acridone 2,7-diethoxy-acridone 1,4-dimethoxy-acridone 4,7-dimethoxy-acridone 1-chloro-acridone 2-chloro-acridone 3-chloro-acridone 4-chloro-acridone 2-bromo-acridone 2,7-dichloro-acridone 2,7-dibromo-acridone

Clay on polyacrylonitrile

reddish yellow

yellowish yellow

reddish yellow

reddish yellow

reddish yellow

rotsüchiggclb

yellow

reddish orange

orange

reddish orange

orange

orange

reddish yellow

reddish yellow

reddish yellow

yellow

reddish yellow

reddish yellow

reddish yellow

Fortsel / img
Acridone

2-methyl-acridone

2-ethyl acridone

4-iso-propylene acridone

3-phenyl-acridone

2-cyclohexyl acridone

2-dimethylamino-acridone

2-diethylamino-acridone

Clay on polyacrylonitrile

reddish yellow

reddish yellow

yellow

rotstichiggclb

reddish yellow

violet

violet

C'hlorbenzol slowly heated to 120 130 "C and held for 2- 3 hours at this temperature. Thereafter, the solvent is distilled off with steam. The residue is stirred with excess lime slurry or sodium hydroxide solution, whereby the color base of the formula

OC

Example 12

213 parts of diphenylamine-2-carboxylic acid with 500 parts of phosphorus oxychloride I ¹ Z ₂ hours to about CU, CII,

IWU ^ CIWHIIIIl. L / UIIII gllM lllilll UCI ClWii JVI V.

146 parts of 3-phenylpyra / .olin- (12) are added in portions. the mixture is stirred for 2 '/ ₂ hours at about 50 C and allowed to then run water with rapid stirring and sufficient cooling in about 1000 parts. A yellow suspension is obtained. After complete hydrolysis of the phosphorus oxychloride, it is filtered off with suction and washed with cold water. The dye of the formula obtained with very good hatching

n-N

cn, cn,

Cl ¹

can be purified by recrystallization from water, but this is generally not necessary. It is suitable for coloring polyacrylonitrile in real, yellow tones.

The dye is converted into the dye base of the formula by stirring with dilute soda solution

N-

ficigciViiiciii wiiu. DiCSO compound l.iiji SiC / i uUi'ci'i recrystallization from toluene purify. Orange-red crystals are obtained which melt at 210-214.degree. The salts of this compound with inorganic and organic acids such as hydrochloric acid, hydrobromic acid,, sulfuric acid, methylsulfuric acid, phosphoric acid. Sulfamic acid, methanesulfonic acid. Benzene and para-toluenesulfonic acid. Formic acid. F. acetic acid. Lactic acid, chloro-, di- and trichloroacetic acid c. Propionic acid, butyric and isobutyric acid and the quaternary salts - z. B. with the quaternizing agents mentioned in Example 3 - are suitable for dyeing, printing and mass dyeing the materials mentioned in the various examples in very genuine, reddish-yellow shades.

Example 14

257 parts of 4'-ethoxy-diphenylamine-2-carboxylate; iurc and 4 (X) 500 parts of phosphorus oxychloride are heated for 2 'I ₁ hours about 90 "C Thereafter nian are at ^r 40 50'C 152 parts of 3- <A. -Thienyl) -pyrazoline- (12), the mixture is stirred for a further 2 hours at about 50 ° C. and worked up according to the instructions in Beisr / ^: els 12. The dye of the formula is obtained

CH, - CH,

convicted. This connection can be z. B. Recrystallization from methylcyclohexane and then melts at 158 ° C. By Quatrnierung this color base with dimethyl sulfate in toluene at 70-100 ⁰ C is obtained the dye of Example 10 as methosulfate; with diethyl sulfate or another of the quaternizing agents mentioned in Example 3, true, yellow dyes are also obtained.

Example 13

213.5 parts of 9-chloro-acridine and 176 parts of 3- (4'-methoxyphenyl) -pyrazoline- (. 12) come with 750 parts

OC, H ₅

H N

N- C

C \ U CFl,

Cl

the orange-red colorations which are outstandingly fast on the materials mentioned in the above examples and prints supplies.

If the equivalent amount is used instead of the 4'-ethoxy-diphenylamine-2-carboxylic acid 4'-methoxy-, 4'-n-propoxy-, 4'-iso-butoxy-, 4'-phenoxy-, 3 ', 4'-dimethoxy, 2', 4'-dimethoxy, 2 ', 5'-dimethoxy, 2', 5'-diethoxy, 3 ', 5'-diethoxy, 4,4'- Diethoxy, 4-chloro-4'-ethoxy-, 4,4'-dichloro-4'-methyl-, 4'-ethyl-, 4'-phenyl-, 4'-cyclohexyl- or 4'-benzyldrp'.enyiamine-2 -carboxylic acid, this also gives very real, orange-red dyes. Used instead of of the thienylpyrazoline the equivalent amount of 3-4'-methoxyphenyl-, 3-4'-ethoxyphenyl-,

3-4'-n-butoxyphenyl or 3-4'-iso-Amyloxyphenyl-12-pyrazoline, so gets hurt ¹ is also very fast dyes orange-red hue. These dyes can be converted in the usual way into the color bases on which they are based, which can be quaternized with suitable alkylating agents. The quaternary salts obtained in this way with the quaternizing agents mentioned in Example 3 give outstandingly fast dyeings and prints on polyacrylonitrile.

Example 15

A mixture of 13.0 parts of N-methyl-anthrapyridone, 7.3 parts of 3-phenyl-pyrazoline- (12), 75 parts of o-dichlorobenzene and 10 parts of phosphorus oxychloria is heated to about 120 ° C. for 5 hours. When it cools, the dye of the formula separates

O-

V-N

CH, CH,

Cl

in crystalline form. It is enough for cleaning. the crude product with a (.suitable solvent. /. B. benzene or ethylene chloride. to wash, but the dye can also be removed by recrystallization Water to be purified. It dyes polyacrylonitrile with orange under lightfastness.

Used instead of phenylpyrrazoline. the equivalent amount of 3 - (\ - Thienvl) -pyrazoline - (12). 3 - (4 '- methoxyphenyl) pyrazoline - (12). 3- (4'-Ethoxyphenyl) -pyrazoline 12) or 3- (4- Diethylaminoäthoxyphenyl) - pyrazoline - (12). in this way, with the same procedure, dyes, the polyacrylonitrile, are obtained Dye red-orange with very good lightfastness.

Example 16

A polyacrylonitrile fabric is printed with a printing paste, which is produced in the following manner became: 30 parts by weight of the dye of the formula

CH ₁ -CH,

C, H, -N = C-N

Cl ¹

50 parts by weight of thiodiethylene glycol, 30 parts by weight of cyclohexanol and 30 parts by weight of 30% acetic acid are poured with 330 parts by weight of hot water and the resulting solution is added to 500 parts by weight of crystal gum (gum arabic as thickener). Finally, 30 parts by weight of zinc nitrate solution are added. The resulting print is dried for 30 minutes

steamed and then rinsed. A yellow print with very good fastness properties is obtained.

Example 17

Acid modified polyglycolti.ixphthalate fiber are introduced into an aqueous bath at 20 C in a liquor ratio of 1:40, containing 3 to 10 g per Liier Sodium sulfate. 0.1 l g of Olcylpolyglykolälhcr (50 mol of ethylene oxide). 0 15 g of dimethyl-bcn / .yl-dodecylammonium chloride and 0.15 g of the dye of the formula

CH, CH,

CH ₅ N-CN

he

Y Ί ¹ I )

contains and was adjusted to pH 4 5 with acetic acid. It is heated up within 30 minutes KKl C and reverberate the bath for 60 minutes! ' Temperature. The fibers are then rinsed and dried. A yellow color of very is obtained good fastness properties.

Example IS

Polyvinyl nitrile fibers are placed in an aqueous bath at 40 C in a liquor ratio of!: 4 (). 0.75 g of 30% acetic acid per Liier. 0.38 g of sodium acetate and 0.15 g of the dye of the formula

C ₂ H ₅ - NCN

CH, -CH,

N - C

Cl ¹

contains. The mixture is heated to the boil over the course of 20 30 minutes and the bath is kept for 30 60 minutes this temperature. After rinsing and drying, you get a yellow color with very good blemishes. idiosyncratic.

Example 19

In a staining beaker of 500 ml, which is in a heated water bath, 0.055 g of the dye of the formula

CH ₁ -CH ₂

CHc-N = C-N

N =

with 20 times the amount of hot water, with the addition of a little acetic acid, and with hot water

31 32

Dissolved water. The dye liquor is kept in motion with an acid modified polyamide

rate of 0.5 g of the action product of 50 moles kept while the temperature in 15 minutes

Ethylene oxide increases to 1 mole of oleyl alcohol and with 100 ⁰ C. At boiling temperature you dye

cold water made up to 500 ml. The pH 15-20 minutes, rinses the material with cold water

the dye liquor is treated with acetic acid or sodium 5 and then dried, e.g. B. by ironing or

acetal adjusted to 4.5-5. in the drying oven at 60-70 ⁰ C.

In this dye liquor, 10 g of piece goods are obtained from A yellow-dyed material.

809 640/154

Claims (1)

Claims: I. Cationic dyes of the general formula X ¹ A the remaining links to complete a Bcnz- (c, d) -indole, acridine or anthrapyridine ring, R is an aryl radical or a heterocyclic radical of aromatic character in the Description mentioned type, R _{1 is} hydrogen or another non-ionic radical, R _{2 is} hydrogen or another nonionic radical, R, hydrogen or another nonionic radical, R _{4 is} hydrogen or another nonionic radical, R _{5 is} hydrogen or another nonionic radical, R _{6 is} hydrogen or another nonionic radical. R _{7 is} hydrogen, an AIyI, cyclohexyl, aralkyl or aryl radical of the type mentioned in the description, m the numbers zero or one,
η the numbers zero or one and X "means an anion and in which the radicals R, R ₁ , R ₂ . Ri and R ₄ can be connected to one another to form one or more ring systems, and R _{7 can be} connected to a ring anellic to A and in which the carbocyclic and heterocyclic rings contained in these formulas and the acyclic radicals can contain non-ionic substituents customary in the chemistry of cationic dyes.
2. Kationischc dyes according to claim I of the general formula X ¹ ' wherein A. R ₅ . R ₆ , R ₇ . η and X have the meaning given in claim I. R _{s stands} for an aryl radical of the type mentioned in the description or for a thienyl radical which can contain nonionic substituents customary in the chemistry of cationic dyes. 3. Cationic dyes according to Claims J »1 and 2 of the general formula CH ₂ -CH, R, - N = C N ι ι \ in which R ₇ , R ₈ and X have the meaning given in claim 2 and in which R _{7 can be} connected to the naphthalene ring and in which the naphthalene ring can contain nonionic substituents customary in the chemistry of cationic dyes.
4. Cationic dyes according to claims and 2 of the general formula R- N CII, C \ wherein R ₇ . R ₈ and X have the meaning given in claim 2 and in which the acridine ring can contain nonionic substituents customary in chemistry of cationic dyes.
Dyes of the formula (II, CII, R ₁ NC wherein R _{1 is} methyl. Ethyl or n-butyl.
R ₁ . for phenyl.4-methoxyphenyl.4-athoxyphenyl or thienyl-2 and
X represents an anion. 6, dyes of the formula CH, - CH, N = C R .. X ¹ III R _c for hydrogen, methyl or ethyl, r. R ₁ , for hydrogen or ethoxy, R _c for phenyl, 4-methoxyphenyl or thienyl-2 and
X "stands for an anion. 7. Process ? Ατ production of cationic dyes according to claim I, characterized in that compounds of the formula C O wherein A, R ₅ ,, R ₆ , R ₇ u-iid »i dL in claim 1 given meaning Les'.tzen. or their preliminary stages with the addition of a Anion X "forming condensing agent with pyrazolines of the formula R ₄ R, R, ^x ! I. CCR ₁ II N N C I CW) ,,, R wherein R. R ₁ , R ₂ , R. ,, R ₄ and »ι those in claim I. have given meaning, and if R _{7 represents} hydrogen, if desired, it introduces an alkyl, cyclohexyl or aralkyl radical of the type mentioned in the description. N. Process for the preparation of cationic dyes according to Claim I, characterized in that that one compounds of the formula C C I ι
Rs R ₁ , where A. R «. R ». and η have the meaning given in claim ι and X | means a residue that can be split off as an anion,
with pyruzolines of shapes! R ₄ R., R ₃ H-N C- CR ₁ N = C (CH-CH-) ,, wherein R, R ₁ , R ₂ , R "R ₄ and m have the meaning given in claim 1,
and, if desired, the hydrogen on the nitrogen atom connected to A is replaced by an alkyl, cycloalkyl or aralkyl radical of the type mentioned in the description. 9. Process for the preparation of kaiionic dyes according to claim 1, characterized in that compounds of the general formula C X, wherein A ₁ R ₅ . R _ft . R ₇ , X "and« have the meaning given in claim I and X ₁ denotes a radical which can be split off as an anion,
or their precursors with pyrazolines of the formula R ₄ R ₁ R ₂ C C- R,
Il N N C I CW) _n , R wherein R. R ₁ , R ₂ -Ri-R ₄ and / n those in claim I. have given meaning,
converts and if R _{7 is} hydrogen
If desired, the hydrogen on the nitrogen atom connected to A is replaced by an alkyl, cycloalkyl or aralkyl radical of the type mentioned in the description. K). Process for the preparation of cationic dyes according to claims 7 9 of the general formula NCN CH, CH, N = C wherein R _{1 is} hydrogen, an alkyl, C'yclo- Hexyl, Arulkylader Arylresl of the type mentioned in the description, R _H an aryl radical of the type mentioned in the description or a Thicnylresl and X ~ an anion and in which R _{7 can be} connected to the naphthalene ring and in which R ₇ , R _H and the naphthalene ring may contain nonionic substituents, characterized by duö one connections the general formula R, -N-C = O N = C-X, λ λ ' ! R-- N = C-X, H-N CH ₅ -CH, N = C R ₁ - N CH, -Cl in X ¹ in which R ₇ and X have the meaning given above and X _{2 is} a radical which can be removed anionically. optionally with the addition of a condensation agent with pyrazoline n r, which provides an anion X " the general formula wherein R _{8 has} the meaning given in claims 2-4. condensed and - if R ₇ stands for hydrogen - if desired introduces an alkyl, cyclohexyl or aralkyl radical of the type mentioned in the description. 11. Process for the preparation of cationic dyes according to claims 7 9 of the general formula X denotes an anion and in which R ₇ , R _H and the acridine ring can contain nonionic Si substituents, characterized in that one compounds of the general formula or or J ' l ¹ R- in which R ₇ and X "have the meaning given above and X _{1 is} a radical which can be removed anionically, optionally with the addition of a condensation agent with pyrazolines which provides an anion X ″ the general formula CH ₂ -CH ₂ H-N in which R _{8 has} the meaning given above, condenses and, if R _{7 represents} hydrogen, if desired introduces an alkyl, cyclohexyl or aralkyl radical of the type mentioned in the description. 12. Process for the preparation of cationic dyes of the general formula > —N CH, -CH, N = C wherein R _{7 is} hydrogen, an alkyl, cyclohexyl. Aralkyl or aryl radical of the type mentioned in the description, R ₈ an aryl radical of the type mentioned in the description od'jr a Thienjircst and wherein R _{7 is} hydrogen, an alkyl, cyclohexyl, aralkyl or aryl radical in the
Description mentioned type,
R _{8 is} an aryl radical of the type mentioned in the description or a thienyl radical and Y "pin Äninn hr-Hpntrt and where R,. U" and the acridine ring is nonionic may contain. characterized in that one compounds the general formula COOM N
K