DE2311073A1 - STILBEN-AZO DYES AND / OR STILBEN-AZOXY DYES CONTAINING SULPHONIC ACID GROUPS - Google Patents

Description

SANDOZ A.Gr. Case 150-5 ^ 77 BASEL CSch wel2>

Stilbene azo dyes containing sulfonic acid groups and / or Stilbene azoxy dyes

The invention relates to sulfonic acid groups Stilbene azo dyes and / or stilbene azo dyes, in which at least one -SO ^ H group is in the form of a tetraalkylaminonium salt obtained by reaction of 1 mole of a compound of the formula

(D,

wherein R is an optionally substituted alkyl radical means

and the aromatic ring A with the exception of the aforesaid ?. 3ubstituted is not further substituted,

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with an optionally substituted tetralkylammonium hydroxide, and, if the stilbene azo dye and / or stilbene azo dye obtained contains a mitro group, if appropriate, this nitro group is reduced to a primary amino group. The invention includes dyes of the formula

CH = CH

H = N

CH-CH

wherein R _{1 is} -SO ₃ H or -SO, ^Ö (OT, KN and at least one -SO, H group is in the form of the tetramethylammonium salt; or dyes of the formula

AV-N-M- (A) -CH =

OM

SO ₅ M (III),

wherein each M is hydrogen or the remainder of a tetramethylammonium cation and the dye carries at least one tetramethylammonium cation;

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or dyes of the formula

CH = CH-C Λ) N = N— (A

CH = CH

Case 150-3577

H = CH

CH = CH- / AV

(IV),

wherein R, -S0, H or -SO- (CH-KN denotes and at least one -SO-H group in the form of tetramethyl

ammonium salt is present;

or dyes of the formula

CH = CH— (A> - N = N— (A ) —CH = CH— (A> —MO

SO-M SO-M

/ "\

ζ l '. W = vscs; rstoff or the remainder of a tetramethylammonium cation and the dye

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carries at least one tetramethylammonium cation; or dyes from For.nel

N— (A V-CH = CH— (A V-N = N-C A > - CH = CH— (A V-NH,

N— (A V-CH = CH— (A) —N = N (A) —CH = CH— (A) —NH,

(VI),

where R. is -SO..H or -SO- (CHi) ₂ -N and at least one -SO, H group is in the form of the tetramethylammonium salt;

or dyes of the formula

S0, M

SO, M \ 3

CH = CH- (A) -M = N (AV-CH = CH- (AV-NH

N- (A) -CH = CH- (A) -N = N- (A> -CH = CH

SO ₃ M SO ₃ M

NH,

S0 _? M.

wherein each M is hydrogen or the remainder of a tetramethyl

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ammonium cation means and the dye at least carries a tetramethylamnonium cation. The invention also includes a method of manufacture of stilbene azo dyes containing sulfonic acid groups and / or stilbene azoxy dyes in which at least one -SO, H group is in the form of a tetraalkylammonium salt is present, characterized in that 1 mol of a compound of formula (I) with an optionally substituted tetraalkylammonium hydroxide and if the stilbene-azo dye and / or stilbene-Aζoxy dye obtained contains a nitro group, this nitro group is optionally reduced to a primary amino group. Tetramethylammonium hydroxide is advantageously used for the reaction.

The alkyl group R can mainly be a low molecular weight alkyl group and have 1 to 6 carbon atoms and preferably Contain 1 or 2 carbon atoms. Is the alkyl radical substituted so it can mainly be a hydroxyl or cyano group or a halogen atom or an aryl radical, advantageously carry a phenyl radical.

Mach the method according to the invention, dyes can Formulas (II) to (VII) are prepared. One can also

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Preparing mixtures of dyes of the formulas (II) to (VII).

The reaction of a compound of formula (I) with a tetraalkylammonium hydroxide is usually done for 15 minutes to 2 hours, and advantageously in water, and at elevated temperatures, for example between 30 ⁰ C and cooking temperature but usually at between PY ⁰ C to 7O ° C and pH values between 7 * 5 - I ^ and preferably at pH values between 11 - Ι}. The reaction usually gives mixtures of salts, but at least one -SO-H group is present in the form of a tetraalkylammonium salt,

The reduction of the nitro compounds to the corresponding primary amino compounds can be carried out by known methods carried out, e.g. in aqueous solution and in the presence of dextrose hydrate, alkali sulfite or sulfide, glycerine, hydroxyalkylamine or an aldehyde; e.g. sodium sulfite or sulfide, hydroxymethylamine or acetaldehyde.

The sulfonic acid group-containing stilbene azo dyes and / or stilbene azo dyes in which at least one -SO ^ H group in the form of a tetraalkylammonium salt available, can be used to produce the

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Speaking sulfonic acid group-containing stilbene azo dyes and / or stilbene azo dyes in the form of the corresponding alkali metal or ammonium salts can be used, with at least one -SO, H group in these dyes is in the form of a tetraalkylammonium salt. This process is characterized in that the by reacting 1 mole of a compound of formula (I) with an optionally substituted tetraalkylammonium hydroxide obtained stilbene azo dyes and / or stilbene azo dyes which have a nitro group or contain a primary amino group, with an alkali metal salt and / or ammonium salt, the corresponding sulfonic acid-containing stilbene azo dyes and / or stilbene azoxy dyes are obtained in the corresponding alkali or ammonium salt form and the obtained Dye carries at least one residue of a tetraalkylammonium cation.

The invention particularly includes dyes of the formula

0 _? N— / A V-CH = CH— ( A VN = N ( A } —CH = CH— ( A

SO Z SO Z SOZ SO Z (VIII),

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wherein Z is Li, Na, K, -NH ^ or -N (CH) ^ and the compound of the formula (VIII) is at least one N (CH,). - carries cation;

or dyes of the formula

SO Z

SO Z

ON— (A V-CH = CH— ( A

CH = CH

SO Z

N = N- ( A) -CH = CH

CH = CH

SO Z

SOZ

• NO,

NO,

SO ₅ Z (IX),

wherein Z is Li, Na, K, -NH ₂₊ or -N (CH) ^ and the compounds of the formula (IX) bears at least one -N (CH,) ^ - cation;
or dyes of the formula

N (AV-CH = CH- <A) -N = N- ( A) -CH = CH- (A) -NH

K- (AV-CH = CH- (AV-N = N (A) -CH = CH (A \ -NH

SO ₅ Z SO Z

SO ₅ Z SO Z

wherein Z is Li, Na, K, -KH ^ or -H (CH) ^ and the compound of the formula (X) is at least one -N (CH,) _; -

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Cation carries. Mixtures of dyes of the formulas (VIII) to (X) can also be prepared.

The conversion of the tetraalkylammonium salts obtained into the corresponding Li, Na, K or -NHj, salts can be carried out by methods known per se, for example with an ammonium halide or sulfate, acetate or phosphate or with a lithium halide, - sulfate, or phosphate or -aoetat a sodium halide, sulfate, acetate or phosphate or a potassium halide, sulphate, acetate or phosphate, beispielsv / else in water and at elevated temperatures, for example between 50 ° and 100 ⁰ C. , but in most cases at 70 ° - 85 ⁰ C. the halides may be mentioned the bromides, fluorides or iodides, or especially the chlorides.

The dyes of the formulas (II) to (IX) are in the form of their free sulfonic acid or in the form of the corresponding ones Lithium salts known from British patent specification 1,114; they are used for coloring paper.

It was surprising that the tetraalkylammonium salts of this Prebondings have better cold water solubility, in contrast to the conventional powder brands of

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commercially available stilbenazo dyes from said British patent. Also, the new ones Dyes significantly stronger in color in paper than the dyes in the aforementioned British patent.

The dried, i.e. completely anhydrous, dye salts from the British patent are believed to have in the Form of the pure lithium salt have good solubility in water, but they are very hygroscopic.

It is therefore not possible, or only with difficulty, to identify the dye from the British patent in transferring a granular form; the tetraalkylammonium salts can therefore be more easily converted into granulate form.

Another advantage of the tetraalkylammonium salts is there in this connection in the fact that they can very easily be subjected to atomization drying; with the This is not possible for dyes from the British patent, because they are far too hygroscopic.

The new dyes are preferably suitable for the Hers'.vlluns voii colored, sized and unsized in the mass Paper. However, you can also use it for coloring

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of paper can be used by the dipping process. The new dyes have excellent solubility properties, in particular, they are characterized by good cold water solubility the end. Furthermore, they only stain the wastewater in paper production a little, which is important for keeping it clean the water is particularly favorable. They do not blur, do not stain paper on both sides and are largely pH insensitive. The colorations are brilliant and stand out are characterized by excellent lightfastness properties. After prolonged exposure, the shade changes tone-on-tone. The colored papers are also waterproof, not only against water, but also against milk and fruit juices and sweetened mineral water, and because of their excellent alcohol resistance, they are also resistant to alcoholic beverages.

The dyes can be added to the paper pulp directly, i.e. without prior dissolving, as dry powder or granules without a reduction in the brilliance or a reduction in the color yield occurring. Through follow-up treatment With cation-active (post-) fixing agents, practically perfect wet and alcohol fastness properties are achieved. The colored papers can be bleached oxidatively as well as reductively, which means that rejects can be reused. and waste paper is important.

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The new dyes can be used in concentrated liquid preparations are transferred, which are more durable and are preferably used because of their shelf life. The manufacture of such concentrated liquid preparations is e.g. in the BeIg. Patent 7,18,007.

The use of solid dye preparations in granules or However, as stated above, powder form is also quite possible. Such preparations can also be used according to im Methods known in principle, e.g. as described in the French patent specification 1 581 900.

In the following examples, parts are parts by weight, percentages are percentages by weight; the temperatures are given in degrees Celsius.

In the examples, contain per 100 parts of the presscake used with 4-nitrotoluene-2-sulfonic acid, 80.4 Parts of 100 # 4-nitrotoluene-2-sulfonic acid and 2.55 parts Sulfuric acid.

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example 1

The dye of the formula

SO ^ X SO, X 0 SOJC SO-.X

/ Λ '/ ~ Λ / Λ

^{CH: = CH} - \ Vn = N- / VCH-CK- / Vno ₂

cH = CH / V / V / V

(-) / H I λ C-) / w

SO X SO X 0 SOX SO X

where X is a radical of the formula -N (CiO ₁ , can be prepared as follows:

11.9 parts of 4-nitrotoluene-2-sulfonic acid are in the form presented a moist press cake and to this 40 parts of a 25 # aqueous tetramethylammonium hydroxide solution added dropwise. A blue-red solution is formed; the temperature rises to about 45 °. The solution is below Stirring heated to 55 ° and kept at this temperature for 1 hour. The red-brown one obtained is then cooled Suspension and neutralized with about 4.7 parts) 0 $ hydrochloric acid. The suspension is dried in Drying cabinet and receives 17 parts of a reddish yellow dye of the formula (a).

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To neutralize the condensation product, sulfuric acid, phosphoric acid, acetic acid, formic acid or an aramonium salt can also be used instead of the 30% hydrochloric acid.

Example 2

Of the. Dye of the formula

W H

BOX SOX

^S0 3 ^X

SO ^ X SO ^ X

where X is a radical of the formula -N (CH,) ^ can be prepared as follows:

12.2 parts of 2-nitrotoluene-2-sulfonic acid are presented in the form of the moist presscake. KO parts of a 20 # -lgen tetramethylammonium hydroxide solution are added dropwise to this. The resulting blue-red solution is heated to 40 ° with stirring. This is stirred for 2 hours at this temperature. Thereupon 3.3 parts of dextrose hydrate are added

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entered and the solution stirred at 40 ° for 2 hours. The dye is in a reduced form and has precipitated out of solution. The mixture is cooled and neutralized it with 2.9 parts of 50% hydrochloric acid. Thereafter the mixture is diluted with water up to 150 parts and thus receives a clear, concentrated solution which contains the orange dye of the formula (b).

Example5

The dye of the formula

SO Y SO ^ Y. η SO Y SO Y

Θ θ ri \ - \ I 'rl V- \

ON- / VCH = CH- / Vn = N- / VcH = CK- / V ₂

Θ ^(C) '

n = N- / VcH = CH- / Vno ₂

S0, Y SO ^ Y 0 SO, Y SO ^ Y

wherein Y is a group of the formula -NC,

can be prepared with the help of (2-hydroxyethyl) trimethylarrmonium hydroxide as follows:

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27.6 parts of 4-nitrotoluene-2-sulfonic acid are placed in the form of the moist presscake with 50 parts of v / water and stirred. 60 parts of the 50% strength, abovementioned aqueous choline solution are then added dropwise over the course of 15 minutes. The mixture is then heated to 75 ° and held at this temperature for one hour. 20 parts of ice are now added. The cooled solution is neutralized with 11.7 parts of a 30 % strength hydrochloric acid. This gives a clear, concentrated solution which contains the reddish-tinged yellow dye of the formula (c).

Example 4

The dye of the formula

SO ₇ M S0J4 0 SO M SO ₃ M

0-N- / N-CH = CH- / VN = N- / N-CH = CH- / N- I *
N- / N-CH = CH- / NN = N

SO _x M SO, MO SO, M SO, M

J sc = sj 3

can be made as follows:

5 parts of the dye obtained in Example 1 offpulver

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are introduced into 35 parts of water with stirring. This creates a dark red, clear solution. Now 10 Parts of sodium chloride are added. The dye precipitates out quantitatively. The mixture is left to stir and heated for a further 30 minutes to 70 °. The suspension is then suctioned off under vacuum. A moist press cake is obtained which contains the reddish-yellow dye of the formula (d), where M is the sodium and tetramethylammonium cation in the ratio of 2.8: 1 is available.

Example 5

In Example 4, 10 parts of ammonium chloride or 10 parts of lithium or potassium chloride are used instead of 10 parts of sodium chloride used, a moist press cake is obtained which contains the dye of the formula (d), where M is present as an ammonium, lithium or potassium and tetramethylammonium cation in a ratio of 0.75 J 1.

UeberfUhrung to the tetraalkylammonium salt of the dyes (a), (b) and (c) into the corresponding alkali metal or ammonium salts by the methods in Examples 4 and 5, in place of chlorides used therein, the corresponding sulphates, acetates, phosphates, etc. of the

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speaking alkali or ammonium ions are used. In addition, instead of the dextrose hydrate mentioned in Example 2 as a reducing agent also an equivalent amount of alkali metal sulfite or sulfide, glycerol, hydroxyalkylamine or an aldehyde can be used.

To determine the cation ratio, the dye is freed from excess salt with the aid of dialysis and dried and with known analytical methods (titrimetry, Gravimetry, flatnm spectrometry, etc.) determines the percentage of cations.

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Dyeing instructions A

In a Dutch machine, 70 parts are chemically bleached Sulphite cellulose (from softwood) and 30 parts chemically bleached sulphite cellulose (from birch wood) in 2000 parts Ground water. 0.2 part of the dye described in Example 1 is sprinkled onto this mass. After 20 minutes Mixing time is made from this mass of paper. The absorbent paper obtained in this way is reddish-tinged yellow colored. The wastewater is practically colorless.

Dyeing instruction B

0.5 parts of the dye from Example 1 are in 100 plates dissolved in hot water and cooled to room temperature. This solution gives wan to 100 parts of chemically bleached sulphite cellulose, which with 2000 parts of water in a Hollander was ground. After mixing for 15 minutes, sizing takes place. Paper made from this substance has a reddish-yellow shade of medium intensity with good wet fastness properties.

Dyeing instruction C

An absorbent paper web made from unsized paper is available at 309839/1101

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40-50 ° with a dye solution of the following composition drawn:

0.5 part of the dye from Example 1

0/5 parts starch and 99.0 parts water.

The excess dye solution is passed through two rollers pressed. The dried paper web is colored reddish yellow.

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Claims (1)

- 21 - Case 150-5577 Claims 1. Stilbene azo dyes containing sulfonic acid groups and / or stilbene azo dyes in which at least one —SO ₁ —H group is in the form of a tetraalkylammonium salt, obtained by reacting 1 mol of a compound of the formula (D, where R is an optionally substituted alkyl radical and the aromatic ring A with the exception of the substituents mentioned is not further substituted with an optionally substituted tetraalkylammonium hydroxide, and, if the stilbene azo dye and / or stilbene azo dye obtained contains a nitro group, if appropriate, this nitro group is reduced to a primary amino group. 2. Stilbene azo dyes containing sulfonic acid groups according to Claim i of the formula 309839/1101 Oasis 150-3577 CH = CH N = N -CH = CH (II), wherein -SO ₃ H or -SO means and at least one -SO ^ H- group in the form of the tetramethylammonium salt is present. 3 · Stilbene azo dyes containing sulfonic acid groups according to Claims 1 and 2 of the formula CH = CH Ο, Μ SO M N = N- / αΛ — CH-CH— ( A. SO M SO ₃ M (III), wherein each M hydrogen or the remainder of a tetramethylammonium cation means and the dye means at least one tetramethylammonium cation wearing. 4. Stilbene azoxy dyes containing sulfonic acid groups according to Claim 1 of the formula 309839/1101 Case 15C-5577 CH = CH CH = CH N «N- <AV-CH = CH (IV), wherein R _{1 is} -SO ₃ H or -SO ₃ (CH ₃ ) ΛΓ *
and at least one —SO, H group is present in the form of the tetramethylammonium salt. 5 · Stilbene azoxy dyes containing sulfonic acid groups according to Claims 1 and 4 of the formula SO ₃ M CH = CH CH = CH N— (A) —CH = CH— <A> —N = N— (A \ - CH I = CH— (A) - NO, SO ₃ M SO M, _ » SO ₅ M SOjH _{(v) (} v; orin each l ·! V.'ascerstcff or the remainder of a tetramethylarrimon iumkat ions means and the dye 309839/1101 Case 150-3377 carries at least one tetramethylammonium cation. 6. Stilbene azo dyes containing sulfonic acid groups according to Claim 1 of the formula • R, N- ( A y- CH = CH N- (A) -CH = CH N = N N = N CH = CH- ( A V-NH ₂ CH = CH (VI), wherein R, -SO, H or -SO ® (CH,) 2, N and at least an -SO, H group is present in the form of the tetramethylammonium salt. 7. Stilbene azo dyes containing sulfonic acid groups according to Claims 1 and 6 of the formula SO ^ M SO _x M 5 \ O ₅ M SO ₅ M CH = CH- (A) -N = N (A) -CH = CH- (A) -NH CH-CH SO ₃ M SO ₃ M N = N- (A> -CH = CH- (A) -NH 309839/1101 - 25 - Cas3 150-5377 wherein each M is hydrogen or the remainder of a tetramethylammonium cation means and the dye carries at least one tetramethylammonium cation. 8. Mixtures of dyes according to claims 1 to 7 9. Process for the preparation of sulfonic acid groups Stüben azo dyes and / or stilbene azo dyes in which at least one -S0, H-0 group is present in the form of a tetraalkylammonium salt, characterized in that that one mole of a compound of the formula (I) with an optionally substituted tetraalkylammonium hydroxide converts and, if the stilbene azo dye and / or stilbene azo dye obtained contains a nitro group, if appropriate, this nitro group is reduced to a primary amino group. 10. The method according to claim 9, characterized in that tetraniethylammonium hydroxide is used for the reaction. 11. The method according to claim 9, characterized in that dyes of the formulas (II) to (VII) are prepared. 309839/1101 - 26 - Case 150-3577 12. The method according to claim 9, characterized in that mixtures of dyes of the formulas (II) to (VII) are prepared. 15 · The method according to claim 9, characterized in that the reaction in water and at temperatures ranging from 3O ° C to the boiling temperature, usually between 45 ° C to 70 ⁰ C and at pH values between 7 * 5 to 14 and preferably at pH -Values between 11 and IJ. 14. The method according to claim 9, characterized in that the reduction is carried out in the presence of dextrose hydrate, alkali sulfite or sulfide, glycerol, hydroxyalkylamine or an aldehyde . 15 · stilbene azo dyes containing sulfonic acid groups and / or stilbene azoxy dyes in the form of the corresponding alkali metal or ammonium salts, wherein at least one -S0 present, H-group in the form of a tetraalkylammonium salt, obtained by reacting a stilbene azo dye material and / or Stilbene azoxy dye according to claim 1, with an alkali metal salt and / or ammonium salt. 309839/1101 Case 150-5377 16. Stilbene azo dyes containing sulfonic acid groups soaked Claim 15 of the formula CiI = CH SO Z SO ₃ Z N = N CH = CH SO, Z SO Z (VIII), where Z Li, Na, K, -NH ^ or -N (CH) ^ means and the Compound of formula (VIII) at least one N (CH,). - carries cation. 17. Stiblen-azoxy dyes containing sulfonic acid groups get wet Claim 15 of the formula SO, Z SO, Z ^v ~ 'SO, Z SO, Z 0-N— (A> —CH = CH— ( A VN = N— / T) —CH = CH— <A) —NO, CH = CH SO Z CH = CH SO-Z NO 2
(IX), wherein Z is Li, Na, K, -NH ^ or -N (CH,) ^ and the compounds of the formula (IX) are at least one - !! (CH.,), - carries cation. 309839/1101 Case I3O-5377 18. Stilbene-azoxy dyes containing sulfonic acid groups according to Claim 15 of the formula SO Z CH = CH CH = CH CH = CH SO ₅ Z A) —CH = CH (A) —NH SO, Z SO Z wherein Z is Li, Na, K, -NH ^ or -N (CH) ^ and the compound of formula (X) at least one -N (CH, ) ^ - Cation carries. 19. Mixtures of dyes containing sulfonic acid groups according to Claim I5. 20. Mixtures of dyes containing sulfonic acid groups according to Claims l6 to l8 of the formulas (VIII) to (X). 21. Process for the preparation of sulfonic acid groups
Stilbene azo dyes and / or stilbene azo dyes !! according to claim I5, in which the -S0, H group in
In the form of alkali metal and / or ammonium salts, 309839/1101 - 29 - Case 150-5377 wherein at least one -SO Η group in the form of a tetraalkylammonium salt is present, characterized in that by reacting 1 mol of a compound of the formula (I) with an optionally substituted tetraalkyl arr.ir.onium hydroxide obtained stilbene azo dyes and / or stilbene azo dyes which have a nitro group or contain a primary amino group with an alkali metal salt and / or ammonium salt, the corresponding stilbene azo dyes containing sulfonic acid groups and / or stilbene azoxy dyes are obtained in the corresponding alkali and / or ammonium salt form and the dye obtained bears at least one residue of a tetraalkylammonium cation. 22. A process for dyeing paper, characterized in that ^r 'ass dyestuffs according to claims 1-8 and 15 - used twentieth 2J>. The paper colored according to claim 22. The patent attorney /IN THE 309839/1101