DE1569777C - Fluorescent cationic dyes and processes for their preparation - Google Patents

Description

It has been found that valuable fluorescent cationic dyes of the formula I

or o-phenoxy radical

(I)

in which X is a divalent radical which complements the nitrogen-containing ring A to form a five- or six-membered ring, R ₁ and R ₂ independently of one another are hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, the cyclohexyl group or the phenyl group, or R ₁ and R ₂ together with the nitrogen atom form the piperidine ring or the morpholine ring, R _{3 is} an unsubstituted or nonionic substituted straight-chain alkyl radical which has 1 to 4 carbon atoms, and Y® is the anion of a strong inorganic or organic acid, obtained by a compound of the formula II

represents, the hetero ring A is accordingly a benzimidazolium, benzthiazolium or benzoxazolium ring.

If the nitrogen-containing heterocycle A is an azinium ring, then the ring complementing this ring is divalent Radical X according to the above formula I the meaning of the butadienylene radical

of the styrylene radical bound in the o-position to the vinylene group

CH = CH-

(H)

in which X, A, R ₁ and R _{2 have} the meaning given under formula I, is reacted with the reactive ester of an unsubstituted or nonionic substituted straight-chain alkanol with 1 to 4 carbon atoms with a strong inorganic or organic acid to form a cyclammonium compound of the formula I.

In formula I, the nitrogen-containing ring A is by definition a five- or six-membered ring, i. H. either an azolium or an azinium ring, which optionally with a naphthalene ring, or preferably with a benzene ring, is condensed.

If the nitrogen-containing heterocycle A is an azolium ring, then it means according to formula I above this ring complementary divalent radical X the vinylamino radical -CH = CH-NH-, the vinylthio radical —CH = CH - S—, the vinyloxy radical

-CH = CH-O-

or the leftovers

-CH = N-NH-

-N = CH-O-,

- N = CH - S -. In these meanings, X complements a pyrazolium or imidazolium, thiazolium, 1,2- or 1,3-oxazolium, 1,2,4- or 1,2,3-triazolium, 1,3,4- or 1,2,4-oxdiazolium or 1,3,4- and 1,2,4-thiadiazolium ring, respectively. Represents the two-valued Radical X is an o-phenylimino

NH-

o-phenylthio-,

or of the propenylimino radical

- CH = CH-CH = N-.

In these meanings, X supplements a pyridinium bonded in the 3-position to the coumarinimide residue, Quinolinium or pyrimidinium ring.

The carbocyclic-aromatic rings fused onto the nitrogen-containing ring A, in particular the benzene ring, can be further substituted. Inert atoms and groups are used as ring substituents in question, namely halogen atoms, such as chlorine or bromine; low molecular weight unsubstituted or by halogens such as fluorine, chlorine or bromine, or hydroxyl and low molecular weight alkoxy groups substituted alkyl groups, low molecular weight alkoxy groups, such as the methoxy or ethoxy group; low molecular weight alkanoyl groups such as acetyl group; low molecular weight alkylsulfonyl groups, such as the methylsulfonyl or ethylsulfonyl group; Aryl sulfonate groups, such as the sulfonic acid phenyl ester group; low molecular weight carbalkoxy groups, such as the carbomethoxy or carbethoxy group, or the carbophenoxy group; the carbamoyl or sulfamoyl group or N-mono- or N, N-disubstituted Carbamoyl or sulfamoyl groups, in particular N-low molecular weight alkyl or N, N-low molecular weight dialkylsulfamoyl groups; low molecular weight alkanoylamino groups, such as the acetylamino group, or low molecular weight alkylsulfonylamino groups such as the methylsulfonylamino group.

In preferred cationic dyes of the formula I, X is a divalent radical which the nitrogen-containing ring A to form an azolium ring condensed with a benzene or naphthalene ring, in particular to a benzazolium ring. In particularly easily accessible dyes above Formula I, X denotes a divalent o-phenylimino radical, d. i.e., X supplements the nitrogen-containing one Ring A to a benzimidazolium ring. This ring is bound to the coumarinimide residue in the 3-position and can be further substituted by the ring substituents described above.

_{If the nitrogen substituents R 1} and R _{2 in the} cationic dyes of the formula I which can be used according to the invention represent an alkyl radical, the same preferably has 1 to 6 carbon atoms.

If this alkyl radical is substituted, the substituents are chlorine or bromine; the cyano group; the hydroxyl group; low molecular weight alkoxy groups; low molecular weight alkanoyloxy groups, low molecular weight carboxylic acid ester groups or the phenyl group. Examples of such substituted alkyl radicals are ß-chloroethyl or ß-bromoethyl, ß-cyanoethyl, ß-hydroxyethyl, ß- or γ-hydroxypropyl,, γ-dihydroxypropyl, ß-methoxy or p'-ethoxyethyl -, γ-methoxy or γ-ethoxypropyl, p'-acetoxy or / i-propionyloxyethyl, carbomethoxymethyl, carbethoxymethyl or benzyl group. If Rj and R _{2 represent} aryl groups, they are carbocyclic and advantageously mononuclear.

Preferably, R ₁ and R _{2 are} identical and represent a low molecular weight alkyl group, in particular the methyl or ethyl group.

The alkyl radical R _{3 contains} the cyano group, the carbamoyl group or a carbalkoxy group, such as the carbomethoxy or carbethoxy group, or the phenyl group, as nonionic substituents. Phenyl-substituted alkyl groups are Λ preferably the benzyl group.

In preferred canonical dyes of the formula I, _{however, R 3 represents} the methyl or ethyl group.

As an anion of a strong inorganic acid, Υ ^Θ ζ. B. the chlorine, bromine, iodine or sulfate ion or the anion of a metal halide acid, e.g. B. the trichlorozinc anion. As an anion of a strong organic acid, Y ^e z. B. an alkoxy sulfate, an aryl sulfonate, such as benzene or p-toluenesulfonate ion, or the oxalate ion. The dyes according to the invention differ from the prior art only in that they have the coumarinimide group instead of the coumarin group.

Most of the starting materials of the formula II are known or can be known per se Manner, for example by the method described in German Patent 1,098,125 Aldol condensation of a 2-hydroxy-4-aminobenzaldehyde of the formula III

(III)

with a cyanomethyl compound of the formula IV

X \

CN-CH ₇ -CA
\
N /

(IV)

and subsequent coumarin ring closure.

In the formulas III and IV, the symbols R ₁ , R ₂ , X and A have the meaning given under formula I.

Examples of suitable starting materials of the formula II are: 3- (Benzimidazol-2'-yl) -7-amino-, -7-monoäthylamino-, -7-phenylamino-, -7-cyclohexylamino-, -7-dimethylamino-, -7-diethylamino-, -7-dibutylamino-, -7-di - (/) '- cyanoethyl) -amino-, -7-N- / v'-hydroxyethyl-N-ethylamino-, -7-N - /) '- methoxyäthyI-N-äthylamino-, -7-N- / j'-cyanoethyl-N-methylamino-, -7-N-benzyl-N-methylamino-, -morpholino-coumarinimide; 3- (1'-methyl- or 3'-ethyl-, 3 '- / ^ - cyanoethyl-, 3' -carbamoyl-ethyl-benzimidazol-2'-yl) -7-diethylamino-coumarinimide; 3- (3'-ethoxycarbonylmethyl- or 3'-benzyl-benzimidazol-2'-yl) -7-dimethylamino - coumarinimide; 3 - (5 '- chloro- or 5'-methyl-, 5'-methylsulfonyl-benzimidazol-2'-yl) -7-diethylamino-coumarinimide; 3- (naphthimidazol-2 '- yl) - 7 - dimethyl - coumarinimide; 3 - (6 '- chlorobenzothiazole - 2 '- yl) - 7 - dimethylamino - coumarinimide; 3 - (Benzthiazol - 2 '- yl) - 7 - diethylamino - coumarinimide; 3 - (6 '- methoxybenzthiazol - 2' - yl) - 7 - diethylaminocoumarinimide; 3 - (Benzthiazol - 2 '- yl) - 7 - N -ethyl-N-ß-cyanoethyl-amino-coumarinimide; 3- (Naphthiazol-2'-yl) - 7 - N - /? - hydroxyethyl - N - ethylamino - coumarinimide ; 3 - (Pyridine-2'-yl) - 7-dimethylamino-coumarinimide or 3- (quinolin-2'-yl) -7-dimethylaminocoumarinimide.

As reactive alkanol esters, with which the dyes of the formula II to form cyclammonium compounds of formula I are implemented, come primarily the methyl, ethyl, n-propyl, n-butyl, Cyanoethyl and benzyl esters of hydrogen chloride, hydrogen bromide, hydrogen iodide, dimethyl and Diethyl sulfate, the methyl and ethyl esters of benzene or p-toluenesulfonic acid, and also the alkyl bromoacetate with a straight-chain alkyl radical of 1 to 4 carbon atoms.

Instead of certain substituted alkanol esters of the type mentioned above, one can also use them Use pre-stages, e.g. B. instead of / i-cyanoethyl or / 5-carbamoylethyl chloride or bromide acrylonitrile or acrylamide in the presence of concentrated hydrochloric or hydrobromic acid.

The reaction of a dye of the formula II with a reactive alkanol ester of the type mentioned above for Cyclammoniumverbindung of formula I is preferably carried out by heating the two compounds at a temperature of 80 to 150 ⁰ C, if appropriate in the presence of acid-binding agents, such as magnesium oxide, CaI-carbonate or Sodium acetate, expediently carried out in an organic solvent which does not participate in the reaction.

Suitable solvents are, for example, optionally halogenated or nitrated aromatic Hydrocarbons, such as toluene, xylene, halogen or nitrobenzenes, or optionally halogenated aliphatic ones Hydrocarbons, e.g. B. trichlorethylene or trichloroethane.

The new cyclammonium compounds of the formula I fall as salts of the acids for their preparation used alkanol esters or aralkanol esters according to the definition, i.e. stronger than color salts inorganic or organic acids. It is therefore primarily a matter of chlorides, bromides, Iodides, methosulfates, ethosulfates, bisulfates, benzenesulfonates, or p-toluenesulfonates. If so desired Salts of other acids, for example oxalates, can also be produced by double conversion by adding oxalic acid. Double salts can also be produced, for example by reaction of the dye halides with the corresponding zinc or cadmium salts.

The new compounds of the formula I are, especially when they are used as salts of a strong inorganic

see acid or organic sulfonic acid, mostly soluble in water. You're in a big one pH range (2 to 8) applicable and draw from aqueous, neutral or weakly acidic solution, optionally in the presence of dispersing wetting agents, such as in the presence of condensation products of alkylene oxides with higher alkanols, on fiber material made of polymeric or copolymeric acrylonitrile when heated open or closed Dyebath under pressure to a large extent to completely and result in this material being wet-fast, such as washable and, in particular, decatural and lightfast, fluorescent greenish yellow, yellow, reddish yellow and orange colors.

Compared to known dyes of a similar constitution, the cationic dyes according to the invention have Dyes have the advantage that they are stable in the dyebath over a very large pH range (2 to 8) and above all that they do not lose their fluorescence, even if at pH values between 6 and 8 is colored.

The following examples illustrate the invention. The temperatures are in degrees Celsius specified.

example 1

A suspension of 5 g of 3- (benzimidazol-2'-yl) -7-diethylamino-coumarinimide in 20 g of dimethyl sulfate is heated to 120 ° for 10 minutes. The still hot reaction mass is heated to 500 ml at 60 ° Poured water and brought the solution to a pH of 4 to 5 by adding sodium acetate. The yellow color salt is made from the clarified solution with the help of zinc and sodium chloride precipitated as zinc chloride double salt, filtered, washed with aqueous sodium chloride solution and dried. The resulting color salt of the formula

Table I.

ZnCL

40

45

dissolves in water with an intense green fluorescence and colors fibers made of polyacrylonitrile from acetic acid Bath in bright yellow tones of excellent purity and excellent fastness properties.

The 3- (benzimidazol-2'-yl) -7-diethylaminocoumarin-imide used is obtained by condensation of benzimidazol-2-yl-acetonitrile with 4-diethylamino-2-hydroxybenzaldehyde in dimethylformamide in the presence of basic catalysts such as pyrrolidine or piperidine.

Is used instead of 3- (benzimidazol-2'-yl) -7-diethylamino-coumarinimide equivalent amounts of the 3 - (benzimidazol - 2 '- yl) - 7 - amino - coumarinimide derivatives listed in Table I below, in this way, with otherwise the same procedure, one arrives at basic colored salts with similar coloring properties Properties which polyacrylonitrile fibers with those given in the last column of Table I. Color shades.

example R ₁ CH ₃ R ₂ C ₆ H ₁₁ H Staining on poly
acrylonitrile fiber 2 C ₂ H ₅ CH ₃ C ₆ H ₅ H Greenish yellow 3 C ₄ H ₉ H Greenish yellow 4th H C ₄ H ₉ Greenish yellow 5 CH ₂ -C ₆ H ₅ H Greenish yellow 6th C ₂ H ₄ CH CH ₃ Greenish yellow 7th C ₂ H ₄ OH CH ₃ Greenish yellow 8th C ₂ H ₄ OCH ₃ C ₂ H ₅ Greenish yellow 9 C ₂ H ₄ CN C ₂ H ₅ Greenish yellow 10 C ₂ H ₄ CN Greenish yellow 11th Morpholino Greenish yellow 12th Greenish yellow 13th Greenish yellow

If, instead of dimethyl sulfate, equivalent amounts of methyl p-toluenesulfonate are used as the alkylating agent, in this way one arrives at the same colored salts.

0.5 g of the basic dye obtained in accordance with paragraph 1 are made into a paste with 0.5 ml of 80% acetic acid and then doused with 4000 parts of warm water. To the solution obtained are still 2 g of sodium acetate, 1 ml of 80% acetic acid and 4 g of a condensation product of oleic alcohol and 15 moles of ethylene oxide were added. 100 g of polyacrylonitrile fibers are added at 50 ° and the bath temperature is increased to boiling point within 15 minutes and colors 1 hour at boiling temperature. After this Time the dye liquor is practically completely exhausted. The dyed material is then during 15 minutes at 80 ° in 5000 ml of water with the addition of 6 g of the sodium salt of oleic acid-N-methyl-N - /? - sulfonic acid-ethylamide soaped, washed and dried. A bright greenish yellow color is obtained Polyacrylonitrile fiber, which is extremely washable.

Example 14

The solution of 6.7 g of 3- (l'-methyl-benzimidazol-2'-yl) -7-diethylamino-coumarinimide in 200 ml of chlorobenzene, a solution of 2.5 g of dimethyl sulfate in 20 ml of chlorobenzene is added at 110 °. Man holds the reaction mixture for one hour at 110 to 120 °, the yellow color salt forming begins to precipitate, the reaction mixture is cooled to room temperature and then filtered the precipitated basic dye from. The resulting color cation is identical to that in Example 1 described identical.

The 3- (l'-methyl-benzimidazol-2'-yl) -7-diethylamino-coumarinimide used is made by condensation of l-methylbenzimidazol-2-yl-acetonitrile with 4-Diethylamino-2-hydroxybenzaldehyde produced in dimethyl sulfoxide in the presence of pyrrolidine.

Basic dyes with similar coloring properties can be obtained by adding equivalents Amounts of the 3- (3'-alkyl-benzimidazol-2'-yl) -7-dialkylamino-coumarinimide compounds listed in Table II below alkylated as described in the example.

The color tones of the colorations of the corresponding color salts obtained on polyacrylonitrile fibers can be seen from the last column in Table II.

Table II

example R ₁ R ₂ R3 Coloring on
Polyacrylonitrile fiber 15th
16
17th
18th
19th QH ₅
QH ₅
QH ₅
CH ₃
CH ₃ QH ₅
QH ₅
QH ₅
CH ₃
CH ₃ QH ₅
QH ₅ CN
C ₂ H ₄ CONH ₂
CH ₂ COOC ₂ H ₅
CH ₂ -QH ₅ Greenish yellow
Greenish yellow
Greenish yellow
Greenish yellow
Greenish yellow

Example 20

7.4 g of 3- (5'-chlorobenzimidazol-2'-yl) -7-diethylamino-coumarinimide and 0.8 g of magnesium oxide are suspended in 250 ml of tetrachloroethane. The mixture is heated to 120 ° while stirring a solution of 5 g of dimethyl sulfate in 20 ml of tetrachloroethane and then added during a Held at 120 ° for hour. After adding 400 ml of water to the cooled reaction mixture, is the organic solvent is distilled off in vacuo. The basic dye formed is from the clarified aqueous solution precipitated by salting out with zinc chloride and sodium chloride Filtration isolated and dried.

The color salt corresponds to the formula

CH,

Melt is extracted with 500 ml of hot water and the solution with sodium acetate to a pH value from 4 to 5 blunted and then clarified warm. By adding zinc and sodium chloride the orange basic dye formed can be precipitated.

The basic dye corresponds to the formula

QH ₅

CH,

ZnCL ⁹

dissolves in water with a bright yellow color and stains fibers made of polyacrylonitrile from acetic acid Bath in greenish yellow tones of high purity and excellent wet fastness properties.

The starting material is obtained by condensation of 5-chlorobenzimidazol-2-yl-acetonitrile with 4-Diethylamino-2-hydroxy-benzaldehyde in dimethylformamide in the presence of pyrrolidine.

Cationic dyes with similar properties are obtained if, in the methylation described above, instead of 3- (5-chlorobenzimidazol-2'-yl) -7-diethylamino-coumarinimide, equivalent amounts of 3 - (5 '- methylbenzimidazol -T- yl) - , 3 - (5 '- methylsulfonylbenzimidazol - 2' - yl) - or 3 - (naphthimidazol - 2 '- yl) - 7 - dimethyl - coumarinimide is used.

Example 21

5 g of 3 - (6 '- chlorobenzothiazol - 2' - yl) - 7 - dimethylamino-coumarinimide are heated to 120 ° in 25 g of diethyl sulfate for 30 minutes. The red-brown one

ZnCl ₃ Q

and dissolves easily in water with a bright orange color. He dyes fibers from an acetic acid bath Polyacrylonitrile in red-orange tones of excellent purity and excellent wet fastness.

The starting material is obtained by condensation of 6-chlorobenzothiazol-2-yl-acetonitrile with 4-dimethylamino-2-hydroxy-benzaldehyde in dimethylformamide in the presence of pyrrolidine.
Dyes with similar properties are obtained if the above reaction conditions are observed if equivalent amounts of 3- (benzthiazol-2'-yl) -7-diethylaminocoumarinimide, 3 - (6 '- methoxybenzthiazol -T- yl) -7 - diethylamino are used as starting materials - Coumarinimide, 3 - (Benzthiazol - T - y I) -7-N-ethyl-N- / i-cyanoethyl-aminocoumarinimide or 3- (Naphthiazol-2'-yl) -7-N - /? - hydroxyethyl-N -äthylamino - coumarinimide used in place of 3- (6'-chlorobenzthiazol-2'-yl) -7-dimethylamino-coumarinimide.

Example 22

3- (Pyridin-2'-yl) -7-dimethylaminocoumarinimide is alkylated by adding a solution of 5.3 g of this Compound in 200 ml of chlorobenzene at 120 ° with 2.5 g of dimethyl sulfate and the reaction mixture for 30 minutes at this temperature holds. 500 ml of water are then allowed to flow into the cooled reaction mixture and removed the organic solvent in vacuo with continuous replenishment of the distilled water. After the aqueous solution of the yellow color salt formed has been cleared, the colorant is precipitated with zinc and sodium chloride as zinc chloride double salts.

109 527/350

From an acetic acid bath, this color salt dyes polyacrylonitrile fibers in bright yellow shades of excellent purity.
It corresponds to the following formula:

ZnCl ₃ ⁹

IO

A similar, somewhat reddish-tinged yellow color salt is obtained starting from equivalent amounts - (quinolin - 2 '- yl) - 7 - dimethylamine - coumarinimide, the alkylation taking place under the conditions described.

The starting materials mentioned are obtained by condensation of pyridin-2-yl- or quinolin-2-yl-acetonitrile with 4-dimethylamino-2-hydroxy-benzaldehyde in dimethylformamide in the presence of catalytic Amounts of pyrrolidine.

Claims (6)

Patent claims: 1. Fluorescent cationic dyes of the formula 1 Λ / R. N
/ 2 R. ^ o ^/ = NH γ _θ 30th in which X is a divalent radical which complements the nitrogen-containing ring A to form a five- or six-membered ring, R ₁ and R ₂ independently of one another are hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, the cyclohexyl group or the phenyl group, or R ₁ and R ₂ together with the nitrogen atom form the piperidine ring or the morpholine ring, R _{3 is} an unsubstituted or nonionic substituted straight-chain alkyl radical which has 1 to 4 carbon atoms, and Υ ^{θ is} the anion of a strong inorganic acid. 2. Process for the preparation of fluorescent cationic dyes of the formula _Y e 55 in which X is a divalent radical which complements the nitrogen-containing ring A to form a five- or six-membered ring, R, and Rf independently of one another are hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, the cyclohexyl group or the phenyl group, or R ₁ and R ₂ together with the nitrogen atom form the piperidine ring or the morpholine ring, R _{3 is} an unsubstituted or nonionogenically substituted straight-chain alkyl radical which has 1 to 4 carbon atoms, and Y® is the anion of a strong inorganic or organic acid, characterized in that a compound of the formula in which X, A, R ₁ and R _{2 have} the meaning given under formula I, is reacted with the reactive ester of an unsubstituted or nonionogenically substituted straight-chain alkanol having 1 to 4 carbon atoms with a strong inorganic or organic acid to form a cyclammonium compound of the formula I. 3. The method according to claim 2, characterized in that a compound of the im Claim 2 given formula used in which X is a divalent radical, which the nitrogen-containing ring A to form an azole ring condensed with a benzene or naphthalene ring added. 4. Process according to Claims 2 and 3, characterized in that there is a connection the formula given in claim 2 is used, in which X is a divalent radical means which complements the nitrogen-containing ring A to form a benzazole ring. 5. Process according to claims 2 to 4, characterized in that there is a connection the formula given in claim 2 is used, in which X is a divalent radical, which complements the nitrogen-containing ring A to form a benzimidazole ring. 6. Process according to claims 2 to 5, characterized in that a compound of the formula given in claim 2 is used, in which R ₁ and R ₂ each represent a low molecular weight alkyl group.