DE2036505A1 - Cationic dyes - Google Patents

Description

A the remaining links of a 5- or 6-row, the

further rings can be fused, -
R is an aryl radical or a heterocyclic radical

aromatic character,

R ^ hydrogen or another non-ionic radical, R ₂ hydrogen or another non-ionic radical, R ~ hydrogen or another non-ionic radical, R ^ hydrogen or another ntc litioniseheή radical, Rc hydrogen or another nonionic radical, R ^ hydrogen or another nonionic radical, R ₇ V / water, an alkyl, cycloalkyl, aralkyl

or aryl radical,

m the numbers zero or one,
η the numbers zero or one
and X "mean an anion,

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and in which the radicals R, R ₁ , R ₉ , R ₇ , R _A , R.-, R, - and R ₇ can be connected to one another to form one or more ring systems, and R ^ with about one. existing at A fused ring can be connected, and in which the carbocyclic and heterocyclic rings contained in these formulas and the acyclic radicals in de ^ chemistry of cationic dyes can contain nonionic substituents usual,

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

Suitable, 'in the chemistry of basic dyes customary nonionic substituents are, for. B. alkyl, hydroxy, alkyloxy, Aryloxy, acyloxy, acyl, alkoxycarbonyl, amidocarbonyl, nitrile, nitro, amino, acylamino, alkylamino, dialkyl = amino, sulfonyl, mercapto, alkyl mercapto and aryl mercapto groups as well as halogen atoms.

-Suitable -alkyl radicals-are -z.B. Methyl, ethyl, n-propyl, iso-propyl, η-butyl, iso-butyl, n-amyl, iso-amyl, neo-pentyl, allyl and their substitution products such as ß-cyanoethyl, ß-chloroethyl, ß-Methoxyethyl, ß-Kthoxyäthyl, ß-A'thoxycarbonyläthyl.

Of the CyclO "alkyl radicals" the "cyclohexyl radical" stands out in particular Meaning, of the aralkyl radicals the benzyl, ß-phenylethyl, ^ -Phenylpropyl and phenylpropyl (2,2) radicals.

Suitable aryl radicals are, for example, phenyl, 2-, 3- and 4-methylphenyl, 2-, 3- and 4-ethy! Phenyl, 4-isopropylphenyl, 4-tert.-butylphenyl, 4-cyclohexylphenyl, 4-bisphenylyl, phenyl-4,5-tetramethylene, 2-, 3- and 4-chlorophenyl, 2,4-dichlorophenyl, 2-, 3- and 4-bromophenyl, 4-fluorophenyl, 4-trifluorophenyl, 4-acetylphenyl, 4-Cyanophenyl, 4-Methoxycarbonylphenyl, 4-Ä'tlioxycarbonyl-

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phenyl, .4-methylsulfonylaminophenyl, ^ - methylsulfonylphenyl, 2-, 3- and 4-methoxyphenyl / 2-,> and 4-ethoxyphenyl, 4-isopropoxyphenyl, ^ -Methyl mercaptophenyl, naphthyl-1.

Suitable heterocyclic radicals are ζ.Β * thienyl-2, furyl-2, P, yridyl-2, benzoxazolyl-2, benzthiazolyl-2.

Suitable halogen atoms are fluorine, chlorine and bromine.

The organic and inorganic anions common to basic dyes are suitable as anionic radicals χ ", for example: chloride", bromide ", CH ^ SO /", C ₂ H ₅ SO ₄ ^- J p-toluenesulfonate, HSO, ~, SO., Benzenesulfonate, p-chlorobenzenesulfonate, dihydrogen phosphate, phosphate, acetate, chloroacetate, formate, propionate, lactate, crotonate, NO, ~. Perchlorate, ZnCl-, and the anions of saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, 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 also those anions are preferred which promote the solubility of the dye in organic solvents or at least do not adversely affect it.

The dyes of the formula

f- <o-o) f

C-IT

-CR ₁ I ¹ = C

(CH = CH) -R

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wherein

A the remaining members of a 5- or β-ring, the

further rings can be fused., R is an aryl radical or a heterocyclic radical aromatic character,

R _{1 is} hydrogen or another nonionic radical, R _{2 is} hydrogen or another nonionic radical, R is hydrogen or another nonionic radical, R. is hydrogen or another nonionic radical, Rc is hydrogen or another nonionic radical, Rg is hydrogen or another nonionic radical Radical, R ₇ hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical,

m the numbers zero or one,
η the numbers zero or one and
X "mean an anion,

and in which the radicals R, R ₁ , R ₂ , R *, R ^, R ₁ -, Rg and R ₇ can be linked to one another to form one or more ring systems and R _{7 can be} linked to a ring fused to A, if present , "and in which the" carbocyclic and heterocyclic rings contained in ^ these formulas and the acyclic radicals in the chemistry of cationic dyes can contain nonionic substituents customary,

can. be produced by adding compounds of the formula

= 0

(II)

in which A, R, -, Rg, R ₇ and η have the meaning given above,

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or compounds of the formula

where A, Rc,
own and
means,

(III)

and η has the meaning given above an anionically cleavable radical

or compounds of the formula

G - "X.

(O-

^L 5 ^Ά 6

χ · C-) (IV)

in which A, Rk, Rg, R ₇ and η have the meaning given above, X _{1 is} an anionically removable radical and X 'is an anion,

or their precursors with the addition of an anion X " Condensing agent with pyrazolines of the formula

RTJ T) a XW Up

X- i- R ₁

"Η -Ί *

= C
(CH = CH) _a - R

(V)

wherein R, R ₁ , R2, R 1, R, and m are those given above

Have meaning

converts and - if R ^ is hydrogen - desired? «if it is an alkyl, cycloalkyl or aralkyl radical. introduces-. In the reaction of compounds of formulas m V and the possible introduction of alkyl, cycloalkyl or Aralkylrcsten arise dyes of the formula I ₁ v / orin 'RRJ hydrogen, an alkyl, cycloalkyl or Aralkylreßt stands.
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Compounds of the formula (II) suitable for carrying out the process according to the invention are, for example, sfaphtho = lactam- (1.8), 4-chloro-naphtholactam- (1.8), 4-bromo-naphtho = lactam- (1.8), 5-chloro-naphtholactam- (1 _? 8), 5-bromo-naphtho = lactarn- (1,8), 2,4-dichloro-naphtholactam- (1,8), 2,4-dibromonaphtholactam- (i, 8 ), 2,4,5-Trichlor ~ naphtholactain- (i, 8), 4-methoxy-naphtholactam- (1,8), 4-A "thoxy-naphtholactam- (1,8), 2-methyl-naphtholactam- (1,8), 2-ethyl-naphtholactam- (1,8) and 6-hydroxy-naphtholactam ^ 1,8), N-methyl-naphtholactam- (1,8), N-ethyl-naphtholactam- (1, 8), Nn-propyl-naphtholactam-O, 8), N-iso-propyl-naphtholactam- (1,8), Nn-butyl-naphtholactam- (1,8), N-iso-amyl-naphtholactam-C1, 8), Nn-hexyl-naphtholactam- (1,8), N-cyclohexyl-naphtholactam-O, 8), N-benzyl-naphtholactam-Ci, '8), N-β-phenylethyl-naphtholactam- (1,8 ), N- ^ f-phenyl-n-propylnaphtholactam- (1,8), N-phenyl-naphtholactam- (i, 8), N-methoxy = carbonylmethyl-naphtholactam-ii, 8), H-ß-cyanoethyl naphtholac = tam- (1,8), N-ß-chloroethyl-n aphthulactam-ii, 8), N-ß-Äthoxycar = bonylätl '^ l-iiaphtholactaiu- (1,8), H-ß-methoxyethyl-naphtho = lactam- (1,8), N-ß-dimethylamino-ethyl -naphtholactam- (1,8), N-firMorpholino-ethyl-naphtholactam-ii, 8), N-methyl-4-chloronaphtholactam- (1,8), N-ethyl-4-bromo-naphtholactam- (1,8 ) ₉ N-ithyl "4-hydroxy-naphtholactam- (i, 8), I-ethyl-4-methoxynaphtholactam- (1,8), N-ethyl-4-n-butoxy-naphtholactam- (1,8), N-ethyl-4-dimethylamino-naphtholactam- (1,8), N-ethyl-4-nitronaphtholaetam- (1,8), N-ethyl-4-acetyl-naphtholactam- (1,8), N-ethyl 4-methyl-naphtholactam- (1,8), N-methyl-5-chloronaphtholactam- (1,8), N-methyl-2-ethyl-naphtholaetam- (1,8), N-ethyl-2,4- dichloro-naphtholactam- (1,8), N-.ethyl-2,4-dibromonaphtholactam- (1,8), Nn-butyl-4-bromo-naphtholactam- (1,8), N-methyl-T-methoxy -naphtholactam-O, 8) N-ethyl-4-methoxy-ß = ethoxy-naphtholactam- (1 ₉ 8), N, 2-trimethylene-naphtholactam- (1.8), N, 2-trimethylene-4-chloro -naphtholactam- (1,8), H, 2-trimethylene-4-bromo-naphtholactani- (1,8), acridone ₉ N-methyl-acridone, N-ithylacridone , N'-n-propyl-acridone, N-iso-propyl-acridone, Nn-butylacridone, N-iao-butyl-acridone, Nn-amyl-acridone, N-iso-amyl

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ι, ifi-phenyl-

acridon, Nn-hexyl-acridon ,. N-neo-pentyl-acridone, acridone, N-benzyl-acridone, N-ß-phenylethyl-acridone, N-cyelohexyl-acridone, ΪΤ-allyl-acridone, 1-chloro-acridone, 2-chloro-acridone, 3- Chloro-acridone, 4-chloro-acridone, 1-bromaeridone, 2-bromo-acridone, 3-bromo-acridone, 4-bromo-acridone and their N-methyl and N-ethyl derivatives, 1-mexhoxy-aoridone, 2- Methoxy-acridone, 3-methoxy-acridone, ^ methoxy-acridone, 1-ethoxy-acridone, 2-ethoxy-acridone, 3-ethoxy-acridone, 4-ethoxy-acridone, 2-n-butoxy-acridone, 2-phenoxy ~ acridon _f 2-methylraercapto-acridone, 2-methylsulfonyl-acridone, 2-dimethylamino-acridone, 2-diethylamino-acridone, 2-methylacridone, 4-methyl-acridone, 2-ethyl-acridone, 4-ethyl-acridone, 4-ethyl-acridone Propyl-acridone, 3-hydroxy-acridone, 1,4-dimethoxy-acridone, 2,4-dimethoxy-acridone, 2,7-dimethoxy-acridone, 2,7-diethoxy-acridone, 2-methoxy-7-chloro-acridone , U, 4-trimethylene acridone, N-ß-gyanethyl acridone, N-ß-chloroethylacridone, N-ß ~ methoxyethyl acridone, Ίί-ß-ethoxyethyl acridone, iT-ß-Ätlic ^ j-carbonyl acridone , IT-Metlioxycaroonylmethyl-auriuuii and N-ß-D imethylaminoethyl acridone, anthrapyridone (formula VI), N-methyl-anthrapyridone, Nn-butyl-anthrapyridone, lf - ß-ethoxy = ethyl-anthrapyridone, 2-methyl-anthrapyridone, 6-methyl-anthrapyridone, 4-dimethylamino -anthrapyridon and 4-anilino-anthra = pyridon ^

(VI)

(VII)

(V-IH)

(IX)

Anthrapyrimidone (formula VII), N-methyl- and N-ethyl-annthra = pyrimidone.

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Suitable compounds of the formula (III) are, for example 2-methylmercapto-benz- (c, d) -indole, 2-chloro-benz- (c, d) -indole, 9-chloro-aoridine, 9-fluoro-acridine, py-chloro-anthrapyridine (Formula VIII) and Py-chloro-anthrapyrimidine (Formula IX) as well as the 9-chloro-acridines, which are used in treating those in Table 1. mentioned diphenylamine-2-carboxylic acids in which R ™ Is hydrogen, with phosphorus oxychloride uüd / or phosphorus = pentachloride arise »

Suitable compounds of the formula (IV) are, for example, the hydrochloric acid, sulfuric acid or acetic acid salts of abovementioned compounds' (III) or their z. B. with dimethyl sulfate, diet sulfate, toluenesulfonic acid methyl ester 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) diphenyl aminocarboxylic acids the formula

COOH

M · H

(X)

where R ^. Hydrogen, an alkyl, cycloalkyl, Represents aralkyl or aryl radical.

However, the term "precursors" is not intended to mean that the diphenylamine-carboxylic acids are initially closed in each case Acridine derivatives are cyclized and only then condensed with pyrazolines. The reaction steps can be carried out rather, also exchange them, i.e. first a compound of the formula

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where R ^, R, R .., Rg, R ~ * R. and m the given · Have meaning

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

Suitable compounds of the formula (X) are, for example, the diphenylamine-2-carboxylic acids compiled in the following table: ~~

COOH

2 »

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!Tabel

Substituents

methyl

ethyl

Benzyl

Phenyl

methyl

methyl

ß-cyanoethyl ß-cyanoethyl ß-chloroethyl ß-methoxyethyl '

ß-dimethylaminoethyl

Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen hydrogen hydrogen hydrogen hydrogen hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen Hydrogen hydrogen hydrogen 4'-methyl 4'-methoxy

4'-ethoxy 4'-ethoxy 4 ', 5'-dirnethoxy

3'-methyl 4'-methyl 6'-methyl 3 ', 4'-dimethyl 4', 6'-dimethyl 4'-ethyl 4'-iso-propyl 4'-cyclohexyl 4'-hydroxy 4 ^f- methoxy 4 ' Ethoxy 4'-n-propoxy 4'-iöo-propoxy 4'-n-butoxy 4'-iso-amyloxy 4-ethoxy 4,4'-diethoxy 3 ', 4'-diethoxy 3', 5'-diethoxy 4 ', 6'-diethoxy

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Table 1 continued

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

Substituents or fused rings

4-chloro-4 ', 6-diethoxy 4'-dimethylamine 4'-diethylamino 4-chloro-4'-diethylamino 3,4-benzo

3,4-benso-4'-ethoxy 2 ", 3'-benzo 5 ', 4'-benzo 4'-methoxycarbonyl, 3'-ethoxycarbonyl, 4'-acetyl

4-chloro-4'-acetyl 3 ', 4'-dichloro 3 ', 4', 4-trichloro 4'-bron

4'-fluoro

4'-methylsulfonylamino 4'-dimethylamidocarbonylamino 4'-methoxycarbonylamino 4'-methylsulfonyl 4'-trifluoromethyl 3-methyl-4'-methoxy 5-methoxy-4'-methyl 6-methoxy-4'-ethoxy 4,5-dichloro-4'-ethoxy

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Further suitable compounds of the formula X are, for example, the compounds of the following structure:

GOOH

O CH,

0-OHr

COOH

H N

N _ / \ y_ 0- η V = /

= O

0-CH ₂

C = O

H
COOH 'IL

C = O

= / H V = / H

COOH

0-CH ₀

CH,

COOH

CH

C = O

0OH —H "2 H ₂

COOH

and

Suitable pyrazolines of the formula V are, for example! 3-phenyl-pyrazoline- (A.2), 3 ~ (4'-methylphenyl) -pyrazoline- (A2), 3- (2'-ethylphenyl) -pyrazoline- (A2), 3- (4'-isopropylphenyl) -pyrazoline- (A2), 3- (4'-tert-butylphenyl) -pyrazoline- (A2) _f · 3- (4 · cyclohexylphenyl) -pyrazoline- (Δ2), 3- (4'-bisphenylyl) -pyrazoline - (A2), 3- (4'-chlorophenyl) -pyrazoline- (A2), 3- (3'-chlorophenyl) -pyrazoline- (Δ2), 3- (2'-chlorophenyl) -pyrazoline- (A2), 3- (2 », 4'-I) chlorophen5 ^r l) -pyrazoline- (A2), 3- (3 ^f , 4'-dichlorophenyl). pyrazoline- (Δ2), 3- (4'-bromophenyl) -pyrazoline- (A2), 3- (4'-fluoro = phenyl) -pyrazoline- (Δ2), 3- (4 ^l -trifluoromethyl) -pyrazoline- ( Δ2) _t

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_ (4'-Acetylphenyl) -pyrazoline ~ (A2), 3 ~ (4'-Cyanophenyl) -

pyrazoline - (& 2), 3- (4'-methoxycarbonylphenyl) -pyrazoline- (A2), 3 - ^ (4'-Λ'thoxy carbonylphenyl) -pyrazoline- (Δ2), 3 ^ (4'-methylsul = fonylphenyl) -pyrazoline- (A2), 3- (4'-methylsulfonylarainophenyl) -pyrazoline- (Δ2), 3- (4'-methoxyphenyl) -pyrazoline- (Δ2), 3- (4'-xthoxyphenyl) -pyrazoline- (Δ2), 3- (4'-phenoxyphenyl) -pyrazoline- (A2), 3- (4'-isopropoxyphenyl) -pyrazoline- (A2), 3-styryl-5-phenyl-pyrazoline- (£ 2), 3- (p-chlorostyryl) -5- (4'-chlorophenyl) -pyrazoline- (A2), 3- (o, p-dichlorostyryl) ~ 5- (2 ', 4'-dichlorophenyl) -pyrazoline- (A2) , 3- (2'-thienyl) -pyrazoline- (Δ2), 3- (5'-methyl = thienyl-2 ') - pyrazoline- (Δ2), 3- (2'-puryl) -pyrazoline- (Δ2), 3_ ^ 5 '- (o, p-dichlorophenyl-furyl-2j7-pyrazoline- (A2), 3- (4'-pyridyl) -pyrazoline- (A2), 3- (2'-Benzoxazolyl) -pyrazoline- (A2), 3- (2. -Benzthiazolyl) -pyrazoline- (A2), 3- (1'-naphthyl) -pyrazo = lin- (A2), 3- (2'-uaphthyl) -pyrazoline- (Δ2), 3-phenyl-4,5-tetramethylene-pyrazoline - (A2), 3,4-diphenylpyrazoline- (Δ2), 3,5-T) iphenyl-pyrazoline- (A2) and the pyrazoline derivative XII.

(XII)

Of the dyes of the general formula I, those of the formulas-XIII or XIV are preferred:

-N = G-

- CH

= c

(XIII)

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_ · > = • ^GH 2 - CH ₂
C.
\ (+) x (" 2036505 ^R 8 V ⁾ (XIV) _f " J

■ where Rr, and Σ have the meaning given above, Rg represents an aryl radical or a thienyl radical and in which the rings and acyclic radicals are common nonionic substituents in the chemistry of cationic dyes may contain »

Dyes of the formula XIII can be prepared by Connections of the formulas

-C = O

(a)

N = C-X,

R - Π = C - T

(c)

where Rr _{7 has} the meaning given above and can be bonded to the naphthalene ring, X _{2 is} an anionically removable radical, in particular a mercapto group or a halogen atom, X 'is an anion, and where R and the naphthalene ring are more cationic in chemistry Dyes can contain customary nonionic substituents,

with pyrazolines of the general formula

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H -

GE ₀ - CH ²

= C

-H-

(XVI)

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ORIGINAL

where Rg has the meaning given above, _qβ C η C

condensed and - if R is hydrogen - if desired instead introduces an alkyl, cycloalkyl or aralkyl radical. ·

Dyes of the formula XI? can be made by one Connections of the formulas

or

or

R ₇ (c)

(a). (b) (c) (XVII)

or their precursors of the formula (X),

in which R ~ 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,

- ■ with pyrazolines of the general formula - ~

- CH,

H-N

= σ

■ (XVI)

wherein R _{Q has} the meaning given above,

condensed and - if R «stands for hydrogen - if desired instead introduces an alkyl, cycloalkyl or aralkyl radical.

If a starting product of the formula (a) is used to prepare the dyes of the formulas XIII or XIV, then is • It is necessary to carry out the condensation with the addition of a condensation agent which provides an anion X ~.

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To carry out the process according to the invention, heating is carried out a compound of formula II or X with an equivalent Amount of a pyrazoline of the formula V in an inert diluent. nungsiriittel with the addition of an anion X ^ "" 'supplying. Condensing agent. One of the components can also be used in excess. Preferred diluents are those liquids which are inert towards the condensing agent and which - if appropriate under reduced Pressure - can be easily removed again by distillation like I-lethy = Lene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichlorethylene, dichloroethane, chlorobenzene, dichlorobenzene, .. Benzene or toluene. Suitable condensing agents are acid chlorides, for example phosphorus oxychloride, phosphorus oxybromide, Phosphorus tri- and pentachloride, thionyl chloride and phosgene. These condensing agents can often also be used in such an excess that they can be used at the same time as solvents or Serve diluents. This is particularly true for phosphorus oxychloride. The rate of condensation can through the additional use of other water-releasing

the JM agent. such as aluminum chloride, titanium tetrachloride ". or.

Phosphorus pentoxide can be increased.

In one process variant, a compound of the formula III or IV is condensed with a pyrazoline of the formula V or XVI. In this embodiment, the addition of a condensing agent is generally not necessary; rather, it is sufficient to heat 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 determined very easily by means of a preliminary test, since the occurrence of condensation is associated with a color effect; generally warming will lead to about 16O ⁰ C to the target. Suitable solvents are, for. B. alcohols such as methanol, ethanol, n- and iso-propanol, iso-amyl alcohol, glycol, GlykolmonOmetnyl- ether and Glyeerin, ethers such as diethylene glycol and dimethyl

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BATH ORIGINAL

diethyl ether and dioxane, also pyridine, quinoline, dimethyl = formamide, IT-methylpyrrolidone, tetrachloroethane, chlorobenzene and o-dichlorobenzene. The high-boiling ones, soluble in water Solvents are preferred because they are "particularly simple Enable way of working.

The nature of the anion X is generally determined by the manufacturing process and any purification of the raw dye that may have been carried out. In general, the dyes are as Halides (especially as chlorides or bromides) or as methosulphates, thiosulphates, sulphates, benzene or toluenesulphonates or as acetates. The anions can be used in any way against other anions such as tetrafluoroborate, phosphate, Ohloro = zincate *, nitrate, perchlorate, oxalate, propionate, formate, Citrate, tartrate, lactate or benzoate ions exchanged will.

To Iiöalinbireit in the 7.υιη coloring ens organic solvents To achieve suitable media, these anions are exchanged

from against, for example, 2-xthyloaproic acid, la uric acid, _L

Oleic acid, Lihol acid, a mixture of aliphatic carboxylic acids with Ii? - 19 carbon atoms (Versatic acid 1519 of the Pirma Shell), a mixture of aliphatic carboxylic acids with 9-11 carbon atoms (Versatic acid 911 from Shell), coconut

. Fatty acid preliminary, latiadecianic acid, undecylenic acid, .DJ.ra £ .1ihyl =:

propanoic acid, dimethyl acetic acid, carboxylic acids, their carbon chain is interrupted by heteroatoms, such as nonylph "= noltetraethylene glycol ether propionic acid, nonylphenol diethylene = glycol ether propionic acid, dodecyl tetraethylene glycol ether » propionic acid, 3- (nonyloxy) -propionic acid, 3- (isotridecyloxy) - ' propionic acid, 3- (isotridecyloxy) -diethylene glycol ether propionic acid, Ether propionic acid of the alcohol mixture with 6-10 carbon atoms, Konylphenoxyacetic acid, aromatic carboxylic acids such as tert-butylbenzoic acid, cycloaliphatic carbonic acids such as hexahydrobenzoic acid, cyolohexenecarboxylic acid,

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Abietic acid and sulfonic acids such as tetrapropylene benzene sulfonic acid and dodecylbenzenesulfonic acid.

The new products are valuable dyes that are used for dyeing and printing on materials made of leather, tanned cotton, Cellulose, synthetic super polyamides and super polyurethanes, as well as for dyeing lignocentric fibers such as coconut, jute and sisal. You are still suitable for the production of writing fluids, stamp inks, ballpoint pen pastes and can also be used in rubber printing.

In particular, however, the basic dyes of the above general formula are suitable for dyeing - from aqueous liquor ty or from organic solvents - and printing from

Threads, tapes, woven or knitted fabrics made of polyacrylonitrile or from copolymers of acrylonitrile with other vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, Vinyl acetate ι vinyl pyridine, vinyl imidazole, vinyl alcohol, acryl and methacrylic acid esters and amides, as. Dicyanäthylen, or Flakes, fibers, thread tapes, woven or knitted fabrics made of sour modified aromatic polyesters, as well as acid modified polyamide fibers. Acid modified aromatic polyesters are for example polycondensation products from sulfo = terephthalic acid and ethylene glycol, d, h. sulfonic acid groups __.-JialtigeH-polyethylene glycol terephthalates (type DACRON 64 of ^ E. I. DuPont de Nemours and Company) as described in the belgi- ™ See U.S. Patent No. 549 179 and U.S. Patent 2,893,816.

Dyeing can be carried out from weakly acidic liquor, in which case it is expedient to enter the dyebath at 40-60 ° C. and then dye at the boiling temperature. You can also dye under pressure at temperatures above 100 ° C. Furthermore, the dyes can be added to spinning solutions for the production of polyacrylonitrile-containing fibers or they can also be applied to the undrawn fiber.
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. - - - - ORIGINAL BATHROOM _r .

The dyeings and prints are characterized - especially on the last-mentioned materials - by excellent fastness properties, especially light, wet, decatur, sublimation, perspiration and rubbing fastness, and in many cases due to the extraordinary Clarity of hue. The new dyes exhibit desirable reservation effects; H. selected accompanying fibers, like wool or polyester, are not stained.

Application of the dyes to the materials to be colored can use the known methods of dyeing or printing including dyeing from organic solvents (e.g. chlorinated carbons).

■ i

The parts given in the examples are parts by weight.

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example 1

19.7 parts of N-ethyl-naphtholactam-C1.8) and 14.6 parts of 3-phenylpyrazoline- (A2) are dissolved in 60 parts of chloroform. 20 parts of phosphorus oxychloride are allowed to run in, the temperature being up to to the boiling of the solvent rises, and keeps the mixture then boil for about 1 hour. The crude dye remaining after the chloroform has been distilled off is converted into Dissolved 700 parts of boiling water and treated with activated charcoal. The bulk of the filtrate separates out when it cools of the dye of the formula

₀ H _n ² 5

- N = G ι

- CH

Cl

crystalline from; - the rest is precipitated by adding table salt. The dye is suitable for dyeing, printing and bulk dyeing of materials that are wholly or predominantly made up Polyacrylonitrile exist in extremely genuine, very clear and fluorescent yellow tones.

If, instead of 3-phenyl-A2-pyrazoline, the equivalent amount of 3-4'-methylphenyl-, 3-4'-ithylphenyl-, 3-3'-Methyiphenyl-, 3-4'-Methoxyphenyl-, 3-4'-Ethoxyphenyl-, 3-3 ', 4'-dirnethoxyphenyl-, 3-4'-chlorophenyl-, 3-4'-bromophenyl-, 3-4 «_ cyanophenyl or 3 - <* - thienyl-Ä2-pyrazoline, one obtains with otherwise unchanged procedure also very real, yellow dyes.

Example 2

169 parts of naphtholactam ^ 1,8) and 146 parts of 3-phenyl-pyrazoline- (Δ2) are in 750 parts of chlorobenzene with 150 parts of phosphorus =

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Oxychloride stirred at 80-100 ° G for 2 1/2 hours. After that it decomposes the remaining condensation agent by adding dropwise of water and removes the solvent by distillation with steam. An aqueous dye solution is obtained in this way. When it cools, the dye of the formula separates

H - IT =

- CH, = C

Cl

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

The dye can in a conventional manner, for. B. by stirring with dilute, aqueous soda solution at about 50 ° C, in the Color ^ aae ^^ r formula

^ CH ₉ - CH ₉ H = CN I.

be convicted. This compound melts after recrystallization from methylcyclohexane or from toluene at 186 ■

Example 3

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

are dissolved in 50-100 parts of dry dimethylformamide,

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BATH ORIGINAL

At about ^1ΟΟ υ G is allowed with stirring 13.0 parts of dimethyl sulfate acid-free run, stirred for 1-3 hours at about 100 ° to 0 and diluted, the cooled to about 50 ° G dye solution with 900 parts of water. The dye of the formula is separated by adding table salt

-N = G-H '

If the equivalent amount of diethyl sulfate _t ethylene chlorohydrin, ß-dimethylaminoethyl chloride, ß-diethylamino-ethyl chloride, ß-piperidinyl-ethyl chloride, ß-morpholino-ethyl chloride, ß-ethoxy-ethyl chloride, ß-ethoxy-ethyl chloride, fi-chlorine is used instead of the dimethyl sulfate -propionitrile or 1-iodobutane, very real, yellow dyes are also obtained.

Example 4

27.6 parts of H-ethyl-4-bromo-1,8-naphtholactam and 14.6 parts 3-phenyl-A2-pyrazoline are freshly distilled with 100 parts Phosphorus oxychloride stirred at 70-80 ° G for 2-4 hours. After that, most of the phosphorus oxychloride is used distilled off under reduced pressure below 80 ° C. The residue is first decomposed with 750 parts of water and then boiled. The dye of the formula separates from the filtrate

GH,

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BATHROOM OBlQiNAL

3Lb

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

Used instead of the naphtholactam derivative given above one of the following compounds in an equivalent amount, one also gets very real, coloristically similar dyes: IT-methyl-4-bromo-, IT-n-propyl-4-bromo-, N-iso-propyl-4-bromo-, N-n-butyl-4-bromo-, if-iso-amyl-4-bromo-, H-n-hexyl-4-bromo-, N-methyl-4-chloro-, N-ethyl-2,4-dichloro, N-methyl-5-chloro, N-methyl-2,4,5-trichloro, H-methyl-5-bromo-, N-ethyl-4-acetyl ~, N-ethyl-4-acetylamino-, N-ethyl-4-methylsulfonyl-amino-, ΪΓ-ethyl-4-dimethylamino-, IThyl-4-methoxy-, N-methyl-6-methoxy- and N-methyl-ö-methylamino-naphtholactam-Ci, 8).

Example 5 ■

209 parts of IT ^ -trimethyleii-naphtholactam-Ci, 8) and 146! Parts 3-phenyl-A2-pyrazoline are freshly distilled with 750 parts er ± ^ jn_ Phosphor oxy chlarld with the addition of 70-150 parts Phosphorus pentoxide stirred for 4-6 hours at about 60 ° C. Thereafter the cooled mixture will decompose the excess Poured condensing agent into 5000 parts of water. When the hydrolysis is complete, the deposited dye becomes the formula

Cl

purified by recrystallization from water with the addition of charcoal. On materials made of polyacrylonitrile, the dye gives very real, bright greenish yellow colorations and Prints.

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If instead of the N, 2 ~ trimethylene naphtholactam, the each equivalent amount of 2-methyl-, 2-ethyl-, 2-iso-propyl- or N-methyl ~ 2-ethyl-naphtholactam- (1.8) is obtained at otherwise unchanged procedure also very real, greenish yellow dyes.

Example 6

222 parts of N-β-cyanoethyl-1,8-naphtholactam and 152 parts 3_cC-Thienyl-A2 ~ pyrazoline in 750 parts of chloroform with 150-200 parts of phosphorus oxychloride as described in Example 1 condensed. The dye of the formula is obtained

STILL ₂ CH ₂ -F = C

,, CHp - CHp

Cl

that on polyacrylonitrile is very yellow in color and print -does .. · - -

If the equivalent amount of N-methoxycarbonylmethyl, IJ-ethoxycarbonyl = methyl, N-ß-methoxycarbonylethyl, M-ß-ethoxycarbonylethyl, N-ß-dimethylaminoethyl, N-ß-methylaminoethyl is used instead of cyanoethyl naphtholactam , U-ß-ethoxy = ethyl-, N-benzyl-, IT-4'-methoxybenzyl-, N-ß-phenylethyl-, N-phenyl-, N-4 ^f -hydroxyphenyl- or N-4'-ethoxyphenyl- 1,8-naphtholactam, with the otherwise unchanged procedure, very real, yellow dyes are also obtained.

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Example 7

32.5 parts of the salt of the lormel

CH ₃ -N =

- NS,

CH ₃ SO ₄

and 17.6 parts of 3-4'-methoxyphenyl-A2-pyrazoline are in 100 parts of dimethylformamide are heated to 100-110 ° C. until the elimination of methyl mercaptan has ended. After Ifer thinning with water the resulting dye becomes the formula

CH, -N = C-N

- CH

-N = C

CH ₃ SO ₄

isolated in the usual way. On polyacrylonitrile it gives brilliant, very real yellow dyeings and prints.

Example 8

22.5 parts of N-n-butyl-naphtholactam- (i, 8) and 22.2 parts 3,5-Dipheny.l-TÄ2-pyrazoline v / earth according to the information of Example 1 condensed together. The dye of the formula is obtained

CH, -

CH ₂ CH ₂ CH ₂

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2036605

which is suitable for dyeing, bulk dyeing and printing of polyacrylonitrile in very real, yellow tones, instead of 3,5-diphenyl-A2-pyrazoline, the equivalent amount of one of the following Δ-2-pyrazolines is used in each case
Formula V, you also get very real, yellow dyes:

Phenyl hydrogen hydrogen hydrogen phenyl 1

Hydrogen hydrogen phenyl hydrogen phenyl O

Methyl methyl hydrogen hydrogen phenyl O

R + R = cyclohexyl hydrogen hydrogen phenyl O

Hydrogen hydrogen Rj- + Rg = cyclohexyl phenyl O

Hydrogen R. + R ^ = cyclohexyl hydrogen phenyl O

Hydrogen hydrogen methyl methyl phenyl O

Hydrogen hydrogen hydrogen hydrogen p-methoxy = O

phenyl

Hydrogen Hydrogen Hydrogen Hydrogen OC-Thienyl O Example 9 ~ "

A solution of 18.7 parts Naphthostyryl-imide chloride "(prepared as described in German Offenlegungsschrift 1,445,624, Example 1b) in 100 - 150 parts of anhydrous
14.6 parts of 3-phenyl-A2-pyrazoline are added to chlorobenzene. The mixture is heated slowly to about 120 ° C., the mixture is kept at this temperature for about 20 minutes and then the solvent is distilled off 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-A2-pyrazoline are in 1000 parts of o-dichlorobenzene with 250 parts of phosphorus = Oxychloride heated to about 120 ° G for 5 hours. Then you let

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cool the mixture, the excess phosphorus decomposes = oxychloride by carefully adding water and driving off the o-diehlorbenzene with steam. From the thus obtained aqueous solution, the resulting dye separates out partially on cooling. The excretion is by adding completed by table salt. The dye of the formula thus obtained

GE ₀ - GE

- N ^ά Ι
"^ N = C

Oil

can be purified by recrystallization from water with the addition of charcoal. It is suitable for dyeing, printing and, Custom dyeing of materials, either entirely or predominantly Polyacrylnicril or acid modified polyesters or acid modified polyamides, in brilliantly real, yellow! hairdryers. ■

If one uses instead of the 3-Ph.enyl'-pyrazolin3 the respective equivalent amount of one of the .Pyrazolines mentioned in Example 1, last paragraph, so you also get very real, _ yellow dyes.

Example 11

239 parts of 2-ethoxy-acridone and 146 parts of 3-phenyl-A2-pyrazoline are condensed with one another as described in Example 10. The strongly reddish-tinged yellow dye is obtained formula

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BATH

H-N

Cl

very real colorations on the mentioned materials and Prints results.

If you use the equivalent in each case instead of the 2-ethoxy-acridone Amount of the acridones given in the table below, the corresponding dyes are obtained, the very real colorations and prints given in the table on polyacrylonitrile materials result in:

Acridone

Tone on ~ Pol.yacT.Ylr> j tril

2-methoxy-acridone 2-n-propoxy-acridone 2-n-butoxy-acridone 2-iso-butoxy-acridone 2-benzyloxy-acridone 3-methoxy-acridone 4-phenoxy-acridone 2,7-dimethoxy-acridone 1 , A- 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-bromine -acri don

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reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow reddish yellow yellow

reddish orange orange

reddish orange orange
orange

reddish yellow reddish yellow reddish yellow yellow
reddish yellow

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1Q988S / 1S78

Acridone

Clay on polyacrylonitrile

2 _f 7-dichloro-acridone 2 _t l ~ dibromo-acridone 2-methyl-acridone 2-ethyl-acridone 4-iso-propyl-acridone 3-phenyl-acridone 2-cyclohexyl-acridone 2-dimethylamino-acridone 2-diethylamino- acridon

Example 12

red-tinged yellow red-tinged gel red-tinged gel red-tinged yellow yellow

reddish yellow reddish yellow violet
violet

213 parts of Oiphenylamin-2-carboxylic acid are with 500 parts Phosphorus oxychloride heated to about 100 ° C for 1 1/2 hours. Then 146 parts of 3-phenylpyrazoline- (A2) are added in portions at about 50 ° G to, the mixture is stirred for a further 2 1/2 hours at about 50 ° C and then left with rapid stirring and sufficient Cooling run in about 1000 parts of water. One receives a yellow suspension. After complete hydrolysis of the Phosphorus oxychloride is suctioned off and washed with cold water. The dye of the formula obtained in very good yield

HIT

C.

Eq

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

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

= C

'CH ₂ - CH ₂

convicted. This connection can be z. B. from methylcyclo = hexane recrystallize and then melts at 158 ° C Quaternization of this color base with dimethyl sulfate in toluene at 70-100 ° C., the dye of Example 10 is obtained as methosulfate; with diethyl sulfate or another of the Quaternizing agents mentioned in Example 3 are also obtained if true, yellow dyes.

Example 13

213.5 parts of 9-chloro-acridine and 176 parts of 3- (4'-methoxyphenyl) Pyrazoline- (A2) v / earth slowly with 750 parts of chlorobenzene

120 - Ί30 C heated and 2 - 3 ^ hours at this temperature held. The solvent is then distilled off with steam. The residue is covered with excess milk of lime or caustic soda stirred, creating the color base of the formula

is vacated. This connection can be made by Umkristall-.JLisierßn from ToluoJ. clean. Orange-red crystals are obtained, which melt at 210-214 ° C.

The salts of this compound with inorganic and organic acids such as hydrochloric acid ¹ »hydrobromic acid, sulfuric acid,

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Methyl sulfuric acid, phosphoric acid, Amidοsulfonsäure, methanesulfonic acid, benzenesulfonic acid and para-toluenesulfonic acid, formic acid, acetic acid, lactic acid, chlorine, di- and tri = chloroacetic acid, propionic acid, butyric and isobutyric acid, and the quaternary salts -? ,, as 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 tones.

Example 14

257 parts of 4'-ethoxy-diphenylamine-2-carboxylic acid and 400-500 Parts of phosphorus oxychloride are heated to about 90 ° C. for 2 1/2 hours. Then 152 parts of 3 - (<* - thienyl) pyrazoline (A2) are added at 40 - 50 ° C to, the mixture is stirred for a further 2 hours at about 50 ° C. and works up according to the information in Example 1.2. Man maintains the dye of the formula

H -

OHn - CHp

of the materials mentioned in the above examples excellently delivers real, orange-red dyeings and prints. . -

If, instead of the 4 ^l -ethoxy-diphenylamine-2-carboxylic acid, the equivalent amount of 4'-methoxy, 4'-n-propoxy, 4'-iso-butoxy, 4'-phenoxy, 3 ', 4 is used '-Dimethoxy-, 2.' ^ '- Dimethoxy-, 2', 5'-Dimethoxy-, 2 ', 5'-Diethoxy-, 3', 5! -Diethoxy-, 4,4'-Diethoxy-, 4 -Chlor-4'-ethoxy-, 4,4 ^I -Dichlor-4'-methyl-,

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BATH

4'-ethyl-, 4'-phenyl-, 4'-cyclohexyl- or 4'-benzyldiphenylamine-2-carboxylic acid, very real, orange-red dyes are also obtained. -Methoxyphenyl-, 3-4'-Ä'thoxyphenyl ~, 3-4'-n-butoxyphenyl or 3-4'-iso-Amyloxyphenyl-n A2 ~ pyrazoline _i we obtain 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 ₉ 7-3 parts of 3-Phc: v * l-pyrazoline- (A2), 75 parts of o-dichlorobensol and 10 parts of phosphorus oxychloride is heated to about T20 ° 0 for 5 hours . When it cools, the dye of the formula separates

0 =

■ Έ = C-

- < r

CH ₂ - CH ₂

Cl

in crystalline form. _Is it enough for cleaning? the. Crude product with a suitable solvent, e.g. B. benzene or ethylene chloride to wash, but the dye can also be purified by recrystallization from water. It dyes polyacrylonitrile orange with good lightfastness.

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BATH ORIGINAL

If you use the equivalent in each case instead of Phenylpyrazolina Amount of 3- (oC - thienyl) -pyrazoline- (4 2), 3- (4'-methoxy = phenyl) -pyrazoline- (A2), 3 ~ (4'-Ä'thoxyphenyl) -pyrazoline- (A2) or 3- (4'-Diethylamdnoäthoxyphenyl) -pyrazolin- (A2), so obtained using the same procedure, dyes that dye polyacrylonitrile red-orange with very good lightfastness.

Example 16

A polyacrylonitrile fabric is printed with a printing paste that has been produced in the following way: 30 parts by weight of the paraffin of the formula

01

50 parts by weight of thiodiethylene glycol, 30 parts by weight of Oyclo = —Iiexanol and .JO-üewichtsteile -— 3 ^ -f * -iger- acetic acid are mixed with 330 parts by weight of hot water poured over them and the obtained - Solution to 500 parts by weight of crystal gum (gum arabic as thickener) added. Finally there are 30 parts by weight Zinc nitrate solution added. The pressure obtained we.d dried, steamed for 30 minutes and then rinsed. A yellow print with very good fastness properties is obtained. ■■ "

Example 17

Acid-modified Polyglykolterephthalatfasern are grown at 20 ⁰ C in a liquor ratio 1: introduced 40 in an aqueous bath containing, per liter, 3 g to 10 sodium sulfate, .0.1 -1g Oleylpoly = glycol ether (50 moles of ethylene oxide), 0 - 15 g Dirnethyl-benzyldodecylammoniumchlorid and 0.15 g of the dye of the formula

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BATH ORIGINAL

Cl

and was adjusted _{to P H} 4-5 with acetic acid. The mixture is heated to 100 ° C. over a period of 30 minutes and the bath is kept at this temperature for 60 minutes. The fibers are then rinsed and dried. A yellow dyeing with very good fastness properties is obtained.

Example 18

Polyacrylonitrile fibers are at 40 ° C in a liquor ratio of 1; 40 introduced into an aqueous bath containing per liter 0.75 g of 30 follow acetic acid, 0.38 g of sodium acetate and 0.15 g of the dye of the formula

CHq - CHq

Cl

contains. It is heated to the boil within 20-30 minutes and the bath is kept at this temperature for 30-60 minutes after rinsing and drying a yellow coloration is obtained very good fastness properties,

Example 1.ft

_{O 9} O55 g of the dye of the formula are placed in a 500 ml dye container, which is located in a heated water bath. . . ·

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σι

with 20 times the amount of hot water, with the addition of something. Acetic acid dough and dissolved with hot water. The dye liquor is also given an addition of 0.5 g of the action product of 50 moles of ethylene oxide to 1 mole of oleyl alcohol and
is made up to 500 ml with cold water. The Pg value of the dye liquor is adjusted to 4 »5 with acetic acid or sodium acetate
"set to 5.

In this dye liquor, 10 g of piece goods made of acid-modified polyamide are kept constantly in motion, while the temperature is increased to 100 ° C. in 1-5 minutes. At boiling temperature, dyeing is carried out for 15-20 minutes, the material is rinsed with cold water
Water and then dries it, e.g. by ironing it
in a drying cabinet at 60-70 ° C.

A yellow colored material is obtained.

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BAD ORiGHNAU

Claims (1)

Claims = C
(CH = CH) -R A the remaining links of a 5- or 6-ring, the further rings can be fused, R an aryl radical or a heterocyclic radical aromatic character, R ^ hydrogen or another nonionic radical, R ₂ hydrogen or another nonionic radical, R ~ hydrogen or another nonionic radical, Rr-hydrogen Or-another nonionic radical, -Rj- hydrogen or another nonionic radical, "Rg hydrogen or another nonionic radical, R _{7 is} hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, «. m the numbers zero or one,
η .. the numbers zero or one and
X "mean an anion, and in which the radicals R, R- *, R /, R and R can be interconnected to form one or more ring systems and R ₇ can be connected to any existing ring fused to A, and in which the carbocyclic and heterocyclic rings contained in these formulas and the acyclic radicals in the chemistry of cationic dyes can contain nonionic substituents customary in the chemistry of cationic dyes . Le A13 139 - 36 - 109885/1578 2) Cationic dyes according to claim 1 of the general Formula "· 'CHp - CHp in which A., 'Rr, Rg, R ^, η and X have the meaning given in claim 1, Rg stands for an aryl radical or a thienyl radical, and in which the radicals A _f R ₁ -, Rg, Ro and Rq in the Chemistry of cationic dyes can contain customary nonionic substituents. 3) cationic dyes according to claims 1 and 2 of the general formula N = C- Ν! , CH ₂ - CH ₂ R, wherein R, and X has the meaning given in claim 1, Rg stands for an aryl radical or a thienyl radical, wherein R ™ ra can be connected to the naphthalene ring and wherein FU, Rg and the naphthalene ring contain nonionic substituents customary in the chemistry of cationic dyes can. Le A13 139 - 37 - 10988S / 1S78 ORIGINAL INSPECTED 4) Cationic dyes according to claims 1 and 2 of the general formula ο - OH ₉ wherein R ₇ and X has the meaning given in claim 1, Ro represents an aryl radical or a thienyl radical and wherein R ₇ , Rq and the acridine. ring may contain non-ionic substituents common in the chemistry of cationic dyes. 5) dyes of the formula , CH ₂ - ^ N = I.
C. wherein R _a for methyl, ethyl or n-butyl, Ry ₃ for phenyl, 4-methoxyphenyl, 4-ethoxyphenyl or thienyl-2 and
X ~ stand for an anion. Le A13 139 1Q9S8S / 1S1S 6) dyes of the formula , GH ₂ - CH, = c wherein R _n for hydrogen, methyl or ethyl, R. for hydrogen or ethoxy, R ₀ for phenyl, 4-methoxyphenyl or thienyl-2 and X ~ stand for an anion. 7) Visrfctmtin zui · representation kaiionischer dyes of the general formula rc ^l 7 ^R 5 ^R 6 R ₉ I ¹ = C (CH = CH -) _m R where ■ A the remaining links of a 5- or 6-ring, the ' further rings can be fused, R an aryl radical or a heterocyclic radical aromatic character , R _{1 is} hydrogen or another nonionic radical, R _{2 is} hydrogen or another nonionic radical, Le A13 139 - 39 - 10988S / 1S78 ORIGINAL INSPECTED R ~ hydrogen or another nonionic rust, R hydrogen or another nonionic radical, R ₅ hydrogen or another nonionic radical, Rg hydrogen or another nonionic radical, - R ₇ hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, m the numbers Ifull or one,
η the numbers zero or one and
X "~ mean an anion, and in which the radicals R, R ₁ , Rg, R- *, R ^, Rc »Rg and R ₇
can be interconnected to form one or more ring systems and R ₇ can be connected to any fused ring present on A, and in which the carbocyclic and heterocyclic rings and the acyclic rings contained in these formulas
Residues common in the chemistry of cationic dyes
may contain nonionic substituents, daäurcn characterized that compounds of the formula C = O wherein A, R ₁ -, Rg, R ₇ and η have the meaning given above. owning or their precursors with the addition of an anion χ "
supplying condensing agent with pyrazolines of the formula ³ U h Ϋ2 ' ^ CCR ₁
HN ^ I ^Ί
^ N = C '(CH = CH) _m - R wherein R, R ₁ , R ₂ , R 1, R. and m are those given above
Have meaning Le A 13 139 - 40 - " 109885/1578 converts and - if R "stands for hydrogen - desired- - if for this introduces an alkyl, cycloalkyl or aralkyl radical. ß) Process for the preparation of cationic dyes of the general ! Formula. - C - P. R-, R "
<4/3 | 2 J ^ C - G - R ₁ C ' \ N = C (CH = CH) _m R in which. A the remaining links of a 5- or 6-ring, the further rings can be fused, R an aryl radical or a heterocyclic radical aromatic character, R _{1 is} hydrogen or another nonionic radical, Rg is hydrogen or another nonionic radical, R is hydrogen or another nonionic radical, R. is hydrogen or another nonionic rust, R _{5 is} hydrogen or another nonionic. Radical, R ^ hydrogen or another nonionic radical, R ₇ ¹ hydrogen, "an alkyl," cycloalkyl or aralkyl group, m the numbers zero or one,
η the numbers zero or one and
X "". J mean an anion, and in which the radicals R, R ₁ , Rg, R ,, R ^, R ^ and R ₆ can be linked to one another to form one or more ring systems, and in which the carbocyclic and heterocyclic rings contained in these formulas and the acyclic radicals in the Chemistry katio- Le A13 139 - 41 -109885/1578 mixer dyes common nonionic substituents may contain characterized in that compounds of the formula -A ^- C-X, ■ where A, R ₁ -, Rg and η have the meaning given above and X. is an anionically removable radical, with pyrazolines of the formula RjI Ή.-7 H - CC- R.
= C "(CH = CH -) _m -" Η wherein R, R-, Rg, R-z, R / and · m are those given above Have meaning converts and, if desired, the hydrogen connected to A. Nitrogen atom replaced by an alkyl, cycloalkyl or aralkyl radical. 9) Process for the preparation of cationic dyes of the general formula N = έ ₇ Le A13 139 Ri R-2 4/3 JC-C- R ₁ c - ϊΤ I ^Ί ^ N = C
(CH ^ CH) ₅ Η .- 42 10 9 3 3 3/1 ORIGINAL INSPECTED A the remaining links of a 5- or 6-ring, the Further rings can be fused, R an aryl radical or a heterocyclic radical aromatic character, R _{1 is} hydrogen or another nonionic radical, R _{2 is} hydrogen or another nonionic radical, R, hydrogen or another nonionic radical, R. is hydrogen or another nonionic radical, Rc is hydrogen or another nonionic radical, Rg is hydrogen or another nonionic Radical, R ₇ hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, the numbers zero or one, the numbers mean zero or one and in which stands for an anion which is formed by anionic cleavage of X ₁ , or for X ¹ , and -wherein the radicals R, R ₁ , Rg, Rz, R /, Rc »Rg and R ₇ with the formation of one or more ring systems underm
η
X " can be connected to each other and R ₇ can be connected to any existing ring fused to A, _ and in which the carbocyclic and heterocyclic rings contained in these formulas and the acyclic radicals in the chemistry of cationic dyes can contain nonionic substituents customary in the chemistry of cationic dyes, characterized in that compounds of the general formula -X, wherein A, R ^, Rg, R ₇ and η have the meaning given above,
Le A 13 139 - 43 - 109885/1578 ORIGINAL INSPECTED X ₁ denotes an anionically cleavable radical and X ¹ denotes an anion, or their precursors with pyrazolines of the formula H-H / 3? 2
CCR,
I, 'N = C (CH = CH) in where R, R ₁ , Rp> Rz., R / and m have the meaning given above, and - if R _{7 is} hydrogen - if necessary, the hydrogen on the nitrogen atom connected to A is replaced by an alkyl, cycloalkyl or aralkyl radical. 10) Process for the production of ionic dyes according to Claims 7-9 of the general formula ■ N = - CH,
I '
C. wherein R _{7 is} hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, Rg an aryl radical or a thienyl radical and X "a · Anion mean and in which R _{7 can be} linked to the naphthalene ring and in which R ₇ , R _Q and the naphthalene ring can contain nonionic substituents, ' characterized in that compounds of the general formula A 13 139 4.4 - 09885/1578 BATH ORIGINAL Vi N-G = O N = O-X. or N = G-X, wherein R _{7 has} the meaning given above, X ^ is an anionically removable radical, X ^{1 is} an .Anion, optionally with the addition of an anion X ~ Condensing agent with pyrazolines of the general formula CHo - CH, H-N N = C in R _{Q has} the meaning given in paragraphs 2-4, condensed and - if R _{7 is} hydrogen - if desired, an alkyl, cycloalkyl or aralkyl radical for this purpose. 11) Process for the preparation of cationic dyes according to claims 7-9 of the general formula I ₇ -N -CH ₂ N = O Le A13 139 - 45 - 109885/1578 wherein R ₇ Wass only off, an alkyl, cycloalkyl, aral kyl or aryl radical, Rq is an aryl radical or a thienyl radical and X is an anion and in which Jl ₇ , Rg and the acridine ring can contain nonionic substituents, characterized in that compounds of the general formula or in which R _{7 has} the meaning given above, Χ «stands for an anionically removable radical, X 'is an anion, and in which R ₇ and the acridine or acridone ring may contain nonionic substituents, optionally with the addition of a condensation agent which provides an anion X ™ with pyrazolines of the general formula II - H ' C. - CH wherein R _{Q has} the meaning given above, condensed and - if R _{7 is} hydrogen - if desired introduces an alkyl, cycloalkyl or aralkyl radical for it . Ie A 13 139 - 46 - 109885/1578 BATH ORIGINAL • ft / 12) 'Process for the production of cationic dyes of the general formula 2036505 - IT - CH wherein R _{7 is} hydrogen, an alkyl, cycloalkyl, aralkyl or aryl radical, Ro is an aryl radical or a tliienyl radical and X ~ * mean an anion "and where R ^, Rg and the Acridiiiring contain nonionic substituents can, characterized in that compounds of the general formula COOH Rr "in which R _{7 has} the meaning given above and in which the phenyl rings of the diphenylamine carboxylic acid and can contain nonionic substituents, with the addition of a condensing agent with pyrazolines of the general formula which provides an anion X ~" H-N N = CH ₂ C R Le A13 139 - 47 - 109885/157 BATH wherein Ro is given in claims 2-4 "Has meaning condensed and ~ if Rr-, is hydrogen - desired if it introduces an alkyl, cycloalkyl or araIkyireBt. 13) Method according to claim 12, characterized in that a'J.0 Diphenylanüncarbonsäure selects a compound in del ¹ Hr, is hydrogen. 14) Method according to claims 7-13, characterized in that that phos = phoroxychloride is used as a dehydrating agent » 1!>) Method according to claim 14, characterized in that one of the phosphorus oxychloride is phosphorus pentoxide or phosphorus = Pentachloride adds. 16) Wach don the method of claims 7-15 produced cationic marriage Dyes, 17) Dyeing, printing and spin dyeing processes (dyeing in der I-Iaose) of materials that are wholly or predominantly from polymerized acrylonitrile or asymmetrical dicyanethylene and / or from acid-modified polyesters and / or consist of acid-modified polyamide, characterized in that the dyes of the claims 1-6 and 16 used. 18) Materials made entirely or predominantly of polymerized Acrylonitrile or asymmetric dicyanethylene and / or made from modified polyesters and / or made from Acid modified polyamide and with dyes of claims 1 - 6 and 16 have been colored or printed oind. Le_A "JXJ.39, - 40 - ' 109885 / 1S78 BATH 19) Use of dyes of claims 1-6 and 16 for dyeing leather, tarmac cotton, - writing fluids, of printing pastes and of lignin-containing Fibers. Le A 13 159 - 49 - ■ 109885/1578 bad ORiQiNAL