DE2246495A1 - SUBSTANTIVE DISAZO DYES FOR PAPER - Google Patents

Description

DR. BERQ DIPL-INGL

8 MÜttCHüN βΖ, MAU-IRKlRCHEiRSTR. 49

TOMS RIVER CHEMICAL CORPORATION, Toms River, N.J. (UNITED STATES)

case 1-7750 / TRc 4o '22nd Sep. 1972

Germany

Nouns disazo dyes for paper

The invention relates to new disazo dyes which are used as Pigments, as dyes for acid-modified acrylic, cationically dyeable polyamide and polyester fibers

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as are useful for cellulose fibers. In particular the invention relates to novel substantive cationic disazo dyes, compositions of pulp and paper colored with a particular group of disazo dyes.

The use of cationic (basic) dyes do »dyeing voti paper is known. However, since the dyes currently in use have little or no affinity for bleached cellulose, theirs is Use essentially limited to the dyeing of unbleached paper pulp and such paper the remaining lignosulfonic acids provide places for the attachment of the cationic substances.

A group of basic (kationicchcn) Disazo dyes found that not only have an excellent affinity for unbleached paper and pulp, but also for bleached paper and pulp, which is especially true when in Absence of resin glue and alum colored tdrd. With the help of the dyes according to the invention, the Kachteile dor previously used basic (cationic) dyes for the paper industry essentially eliminated.

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The dyes according to the invention also have the valuable property of bleaching ability with fastness to discoloration. For the paper industry are A colored pulp and a paper especially important, for example lightly chlorine or chlorine-containing Connections can be colored so that they can be reprocessed or immediately for other types of paper can be used. Dyes should be resistant to "bleeding", if that's the case with the dyes impregnated paper when wet with damp,,; .. White paper is brought into contact. This property is particularly desirable for dyes that for dyeing tissue paper for household purposes and the like where it is foreseeable that the colored paper will come into contact with when wet other surfaces, such as textiles, paper and the like, which must be protected against contamination.

The present invention therefore relates to new substantive dyes, pulp compositions and paper containing a specific group of dyes is colored ..

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The general dyes of the present invention are as follows Formula on:.

N «N-Ar-N = N

in Ar is a group of the general formula

(2)

or

(3)

means in the A amido (-CONH-), thiourea,

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-NH-CQ-R ₅ -CO-NH-, wherein R _{5 is} C ^ -alkylene or phenyl; -SS- (disulfide), -N = N-, -NH-, -CO- or -SOg- is? B is - CH ₂ -, -0-, -S-, -SO ₂ - or -NH-; X ₁ =, X _g and Y can be identical or different and can in each case _{denote hydrogen, C 1 #} _, - lower alkyl, C.j_-lower alkoxy., Hydroxy, C "g-carbo-lower alkoxy or halogen (Cl, Br); R is alkylene of 1 to 5 carbon atoms; R ₁ , R ₂ , R, and Rj. Can be identical or different and each mean C ^ ^ -lower alkyl and Cj ^ -hydroxy-lower alkyl »R- and R ₂ or R, and R can also simultaneously form morpholinyl, piperidyl or pipirazinyl, and the inorganic or organic salts thereof. The salts can be of an inorganic monauric, di- or tribasic acid such as, for example, hydrochloric acid, sulfuric acid and phosphoric acid or a mono- »di- or trialkahic acid with up to 10 carbon atoms, such as acetic acid, succinic acid, lactic acid or adipic acid be derived. By definition, these salts also include those salts which are generally referred to as all zinc halide (chloride) complexes.

In preferred new compounds according to the invention.

means Ar.

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where A is azo, sulfonyl or amido in i eta or para positions to the azo groups. In particularly preferred new compounds, Ar has the meaning given above and Y is hydrogen or halogen * In the most preferred compounds _{according to the invention, A is amido, Y and X. both are hydrogen or chlorine and X is 2} V / aasersto'ff, C ^ g-lower alkyl, C 1-4 lower alkoxy or chlorine in the ortho, meta or parallel positions to the azo group. -R is ethylene or trimethylene, R., R ₅ and Rp, R ₁ . have the same meaning in each ring and each R ₁ , R ₂ or R ,, R ₄ . means C ₁ J η "lower alkyl, or R ₁ + R ₂ and R, ♦ R ^ together form morpholinyl and their acidic salts.

Dyes that contain the amido bridge are given before given because they are more easily accessible than, for example, dyes that contain a urea or thiourea bridge

exhibit. In addition, these and such dyes show

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22A6495

who have an azo bridge, very good discoloration authenticity In this respect they are, for example, superior to those dyes "which -CH ^ -a -0- or -S- as Pontic contains «,

The dyestuffs used for dyeing paper or paper pulp can be in the form of their acid salt or the free base, preferably used as an acid salt. »The dyes have the formula given above (1). '".

The acidic salts can be inorganic or organic salts be. The salts can be of an inorganic mono-, di- or tribasic acid such as hydrochloric acid, sulfuric acid and phosphoric acid or a mono-, Bi- or trialkaxic acid with up to 10 carbon atoms, such as acetic acid, succinic acid, lactic acid or adipic acid.

The preferred compounds for coloring paper are the same as those given above as preferred.

The dyes according to the application can expediently by Tetrazotization of a diaminoaryl compound of the general

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my formula

by well-known methods and then coupling the tetrazo compound thus obtained with a naphthalene of the general formula

ONHRN

(5)

can be obtained. In the event that R ₁ and R _{2 have} the same meaning as R 1 and R j., About 2 equivalents of naphthalene compound are. used per 1 equivalent of tetrazo compound. Are on the other hand IL. R ₂ and R _{1, R 11 are} different, first 1 mol of a naphthalene _{compound containing R 1} and R 2 is coupled and then 1 mol of a naphthalene compound containing R 1 and R 1 is coupled.

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The diaihinoaryl compounds can be produced, depending on the nature of the Α group, with the aid of numerous known methods. If A is an amido group, the diaminoaryl compounds can be obtained by condensation of an optionally substituted nitrobenzoyl chloride or a diacid dichloride with an optionally substituted nitroan compound and subsequent reduction of the nitro compound zn amino groups can be produced with the aid of known processes. If A is thiourea, the corresponding aryldlamine can be prepared, for example, by damming p-phenylenediarain with carbon disulfide in alcohol, as described in DT-PS 58 2σΊ and 60 152 ·

Typical Aryldiaraine for the production of the dye « sin «!

. * .3 ^f -diaminobenaanilide,. ■

3 · 3 * -dlaninobensanilide » - I <V-Dlaminobensaniiidt

i.'l'-diaminoben etnilide,

l, 1 ^f ^ Dianlnodiphenyl8ulfoii and

H, H * -Slauinoasobensol.

- Io -

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The coupling component can be used with the help of known Process such as the reaction of esters of 2-hydroxy-3-naphthoic acid directly with the appropriate primary Amiη with formation of the amide or by Ucsetung of 2-Hydroxy-3-naphthoic acid chloride with dea suitable Anin can be obtained. Optionally, 2-acetoxy-3-naphthoic acid chloride can also be used with an anin uneaset * and then removing the aoetyl group by known methods. Typical coupling components • indj

2-Hydroxy-3-N- (ß-dimethylaminoethyl) naphthanide, 2-hydroxy-3-N- (ß-diethylaminoethyl) naphthamide> 2-hydroxy-3-N (7-dynehylaninopropyl) naphthamide, 2-hydroxy 3 ~ N (? -Diäthylaainopropyl) naphtha »ld, 2-Hydroxy-3-N (7-morpholinylpropyl) naphtha» id, 2-Hydroxy-3-N (r-pip * ridylpropyl) naphtha »id, 2-Hydroxy- 3-N (ß-piperasinylathy1) naphtha · id and 2-hydroxy-3-N- (7-dinethylanlno-i-hfdroxypropy %) napb-

thasdd.

Numerous of the prinStrin anin · the alIgeneine fora ·!

dl · sur manufacture of the Naphthaaid coupling components

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are used, well-known compounds «Those Ver '-' * ■ · bonds that are not expressly described according to the prior art can be analogous to the process for the preparation of known compounds.

Three general methods of making primary Amines of formula (6) are the following:

a) An amine of the formula

HN (7)

is condensed with a chloroalkylnit; ril of the formula Cl (CH ₂ ) _ft CH and the product obtained with sodium alcoholate or with hydrogen via Raney nickel to form the desired product

(8th)

reduced·

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b) A secondary amine is added to an unsaturated nitrile, e.g. methacrylonitrile, and the product BU the desired primary arain is hydrated.

CH

- CN 3

- CH

gCHCN CH,

Hydrogenation

CH

(9)

c) Subsequent to the known Gebriel synthesis, potassium phthalimide is condensed with a dibromoalkyl compound of the formula Br (CHp) Br to form CgH ₁ ^ (CO) ₂ N (CH ₂ ) Br, which is condensed with an amine of the formula (7) to form from

(CO) ₂ N (CH ₂ ) _X H

(lo)

is reacted, which with dilute mineral acid to form the desired product

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R ₁
(E) H ₂ N (CH ₂ J _x N _x (11)

is hydrolyzed, in which R ^ and R _{2 have} the meaning given above, _s η 1 to 6 and χ 2 to 7 mean.

In a typical production process, a diaminoaryl compound is mixed with an aqueous mineral acid solution and cooled to ^{0 ° C. The reaction mixture is then tetrazotized at 0} ° C. by adding an aqueous solution of sodium nitrite. The reaction mixture is then stirred for a certain time at about ⁰ ° C. and then the excess nitrous acid is destroyed by adding sulfamic acid. The Tetrazoreaktionsgemisch thus obtained is then slowly added at 0 ⁰ C a solution of a naphthalene compound in aqueous acetic acid. The reaction mixture is then stirred for a certain time at the same temperature, then neutralized to a pH of 5 to 5> 5 by adding a base, then the reaction table is allowed to cool to room temperature. A salt such as zinc chloride and / or sodium chloride is then added to the reaction mixture and the mixture is heated. The dye precipitates, is washed and thus obtained.

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The high affinity of these dyes makes them especially suitable for dyeing paper with and especially without Resin glue and alum in clear yellowish-red to blue Color shades with good fastness properties can be used »

The dyes are free from sulfonic acid and carboxylic acid groups and therefore also for dyeing modified Acry1 ^ cationically dyeable nylon, polyester fibers and similar textiles are suitable.

In a preferred embodiment of this invention, the dyeing of generally known processes for dyeing paper or pulp paper is carried out by using, for example, using o, o5 to Gew.Si H, preferably. 0.1 to 2 wt other time may be added during the production of the substance. the mass coloration for dyeing paper lit known in the art. A detailed description of the mass coloration

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can be found, for example, in "Pulp and Paper Manufacture", Volume 2, "Preparation of Stock for Paper Making" _t McGraw-Hill, 1951, ß. * <92 - 509 * The dye can also be used for coating paper in the usual aqueous coating solutions which contain clay-casein, clay-starch or clay-casein-starch.

example 1

22.7 parts of lJ.3'-diaminobenzanilide are dissolved in a solution of * 100 parts of water and * J2 parts of Io η hydrochloric acid. The reaction mixture is cooled to ⁰ C and tetrasotiert by adding an aqueous solution containing 13.8 parts of sodium nitrite at ⁰ ° C. The resulting solution is stirred for 5 minutes at 0 to 2 ° C and then the excess nitrous acid is destroyed by adding sulfamic acid.

The Tetrazolösung- is slowly over a period of 3o minutes with stirring at 0 ⁰ C to a solution of 56.0 parts of 2-hydroxy-3-N- (y-dimethylaminopropyl) -naphthamid in I600 parts 25 to-acetic acid

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given. The reaction mixture is stirred for one hour at 0 to 2 ° C., then neutralized to a pH of 5-5 »5 by adding sodium carbonate and cooled to room temperature. The gel formed is broken by the addition of a mixture of zinc chloride / Natriurachlorid and heated to 5o to 55 ⁰ C. The precipitated dye is collected by filtration, thoroughly washed with 5oo parts of a 5i £ saline solution and at 65-70 ⁰ C dried. The red dye obtained dyes paper with and without the use of Harsleim and alum in light yellowish-red shades with excellent fastness properties in terms of bleeding in water, alcohol, milk and soap solutions. The compound is the zinc chloride complex of the free base of the following formula.

) ₃ HNC0 _k OH

(12)

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The above vea? Wenc! Ete S
naphthaiiiifl is obtained by one of the following processes

ä) Ea be 3o "25 parts of a-hydroxy-J-naphfcoesau ^ emethyJ ester au 17» 8 parts of 3-Diroethylauiinopropylaünin added and the ReaktionsgeKiisefo for 2 hours at 95 ⁰ C bit 100 erwSrmt. During this time, methanol is distilled off. The reaction gel is then cooled to 60 ° C. and 80 parts of asetone are added to ensure complete precipitation. The mixture is then cooled to room temperature »filtered and washed with 60 parts of acetone. This gives the © AmiuB 53 part schmilsst in the temperature range of 153 BIB 155 ⁰ C.

b) 3 ~ 35 parts of 2 * -hydroxy-3 ~ naphthoic acid ethyl ester in 50 parts of methanol with 17.8 parts of 3 ~ dimethylaminopropylamine at 65 to 70 ⁰ C to urceetsung. After completion of the reaction, the resulting product is filtered off and washed with 100 parts · methanol are obtained 32 parts Aiaid, which has a melting point of 153-155 ⁰ C.

The azo dye of Example 1 is used as the free base. isolated, being to the point after the method of the

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Examples 1 is carried out, on which the coupling reaction is allowed to cool to room temperature. The product is then completely precipitated by adding 6 parts of sodium hydroxide to a pH of 9-10. The filled in dye is recovered by filtration, washed thoroughly with cold water and dried - the insoluble product is dissolved in dilute acetic acid solution and used directly to dye paper in red shades with and without the use of ilar glue and alum.

The azo dye of Example 1 is used as an acidic salt obtained by an aqueous suspension of 1.0 part of dye, isolated as the free base as above, to 25 parts of water and 32 parts of Io η hydrochloric acid are added. The solution obtained in this way is tird evaporated to form the hydrochloride salt · The product obtained is water-soluble and stains paper in yellowish-red shades with and without iJars and alum.

Instead of hydrochloric acid, you can also use Sulfuric acid, phosphoric acid, acetic acid, formic acid, adipic acid, tartaric acid, citric acid, oxalaflur and Succinic acid with formation of the corresponding sulfate,

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Phosphates, Acetates »Porraiafce ©" A "3ipaSes _a Ta & ⁵ fefate © _a ZSfcra ^ eo, Oxalates and Sneeiaafees used ^ @ 3? <Äesi _o "

The acidic Sal "kan & also beiupisieffgise be © h nlsdas, 'that part WaT% zt & i £ & .1 & - fs ei @ o, 25 parts of tartaric acid gyflsßlieto ^ © rraahlto Des Oeßisch iet soluble in water and karsn directly from pulp? mistakenly

Example 2

If the implementation is carried out according to the example 1. rails in the amount of 3 »3 '~ Di & Biinobenz & nilid ansfeell © atuinobenxanilid, a ShRiU © hex ³ fabric is obtained, the paper string-undl without harslela alum in light Bcharlach-colored shades has good fastness properties colors «,

Example 3

SSEI using an equivalent amount of 3 ^»J · l ⁸ -Dianjinobene anilide in Example I A dye is obtained which

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Paper rait and without Harulei »and alum in bluish-red Dyes shades with good fastness properties.

Example Il

If the conversion of example 1 with an equivalent Amount of Ί.V-diaminobeneanilide carried out "so is" in Obtained dye which has very good substantive properties to paper pulp with and without Harslein and alum and provides brown shades with good fastness properties.

Example 5

5.7 parts of 3 · V ~ DianinobenBanilid are teirasotiert and the tetrazo solution obtained is coupled with 17 parts of 2-hydroxy-3-N- (7-morpholinylpropyl) naphthamide. The tetrasotation, the coupling and the extraction of the educated Dye are carried out according to the procedure described in Example 1. The resulting dye compound rubs paper pulp in light ocher shades

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tings with and without resin glue and alum with good fastness properties, the compound is the zinc chloride complex of the free base of the following formula

CH ₂ -CH ₂

Cf N (CH ₀ ) I ₄ HNCO

\ S

CHCH

H ₂ -CH,

N = N

■ OH

The coupling component used in the above example is made by reacting methyl 2-hydroxy-3-napthoate with -y-morpholinylpropylamine according to the example 1 method described. 2-Hydroxy-3-N- (7'-morpholinylpropyl) naphthamide is obtained, which has a melting point of iMO to 1 ^ 2 ° C.

The following table shows disazo compounds according to the invention together with the color they give paper pulp

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with and without the use of resin glue and alum. The listed disazo compounds are tetrazotized the diamines listed under the heading "diamine" and coupling of those obtained in this way Tetrazo compounds obtained with the compounds listed in the "Coupling component" column. Tetrazotization, coupling and recovery are carried out according to the procedures described in example 1

example Diamine Clutch
component Hue on
paper 6th Ί, ΐΓ-diaminodi-
phenyl sulfone 2-hydroxy-3-N (r-di-
methylaminopropyl)
naphthamide Scarlet fever 7th 4, iJ'-diaminodi-
phenyl disulfide Il bluish
Red 8th M'-diaminodi-
phenylamine N reddish-
blue 9 i |, V-diamino
azobenzene N blue Io H, k '-Diamino- -
? -methyl-benz-
anilide 2-hydroxy-r 3-N- (T-
diethylaminopro-
pyl) naphthamide Red 11 J), '! ¹ -Diamino- '
2 ¹ -methoxy-benz-
anilide 2-hydroxy-3-N- (7-
dihydroxyethyl
aminopropylOnaph-
thamid Red

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9 ε ^

example Diamine Clutch
component color aui
paper 12th M "-Diamino" ^ ¹ -
chlorobenaanilide 2-HyHpOXy- 3N » {γ-
di "-it ^M i3 uty! amino«
propyl) naphtha ^
mid .; '■ 13th bromobenäaniXide di-sie thy Xamino =
Mfchyl) uaphtliaraicl 6'-diehlor-bena-
anilide '2 ^ HyOrOXy * - 3N- ty * *
di! aefchylaminopro.7_. Red 15th ethoxy-benssani-.
lid 2-Hyfiroxy ^ 3N ° Cy ^
idimefehy laminopro- E ³ Ot 16 beneanilid || g || Ä - '«Λ 17th l \ _t 3'-pi amino -
benzanilide ■ 2-hydroxy-3N- (ß-
Haorpfeoliny läthy X}
äiaphfchamicl Red 18th methylbenzanilide dimethylaminopro-
pyl) naphthamide Red 19th ^, V-Diamino-e ¹ -
methoxy-benaani "
lid η Red- 2ο iJ, 3 '-Diamino- *} · -
chloro-benzani-
lid et Red 21 3,3'-diamino-6 ^! -
methylbenzanilide u Red 22nd 3, ¹ l ¹ -Diamino-2 «-
methylbenzanilide Il Red

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example Diamine Clutch
component Hue on
paper 23
24 3,3'-diamino- H-
chlorobenzani-
lid
l \, V-diamino-
benzophenone 2-hydroxy-3N- (7 ^ -
dimethylamino
propy1) naphthamic
2 ~ hydroxy-3N- (7'-
dimethylaminopro-
pyl) naphthamide Red
Red

Example 25

Follow the procedure of Example 1 using a mixture of 28.0 parts of 2-hydroxy-3-N- (7'-dimethylarainopropyDnaphthamide and 3 ^ »ο parts of 2-hydroxy-3-N - (^ - dihydro xyäthylaminopropyDnaphthamid instead of 56 parts of 2-hydroxy-3-N- (7 "-dimethylaminopropyDnaphthamide carried out, a similar dye is obtained, the paper with and without resin and Alum stains in red shades.

Example 26

If the procedure of Example 5 is followed using a mixture of 8.5 parts of 2-hydroxy-3N - (^ "- morpholinylpro-

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• *

pyl) naphthamide and 9.6 parts of 2-hydroxy-3N- ('} ^/: -di-n-butylaminopropyl) naphthamide instead of 17 parts of 2-hydroxy-3N - (^ - morpholinylpropyl) naphthamide, a similar dye is used that dyes paper with and without resin and alum in red shades.

Example 27

If the process of Example 1 is carried out using 62.5 parts of 2-hydroxy-3N- (7 ^/ * -hydroxyethylmethylaminopropyl) naphthamide instead of 2-hydroxy-3N-ty-dimethylaminopropyl) naphthamide, a similar dye is obtained, ' that dyes paper with and without resin and alum in red shades.

Example 28 '

Dyeing process

o, o2 parts of the dye prepared in Example 1 become an aqueous slurry vorr 5 parts,

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based on the dry weight, of bleached sulphite pulp add in 2oo parts of water at 20 to 25 ° C. That Cnisch v / ird thoroughly for 15 to 20 minutes

Paper sheets are then produced on known V / eise, which are colored with a light yellowish-red hue.

The men ;; c of the dye used can be within wide limits can be varied. For example, 0.1 parts result in deeply colored pots. The dye can also be used in Dissolved in water or a little acetic acid Paste overnight and then with the formation of a stock axin of the dye are dissolved. An aliquot of this solution «according to the desired Amount of dry dye is then added directly to the aqueous slurry of the bleached sulphite pulp.

Harsleim and alum can optionally be added in quantities of 0.05 or 0.15 parts. Since the inventive ice-cream dyes show a high degree of substantive property in relation to paper pulp, the use of HarsleiiQ and alum for coloring paper, which is used as tissue paper and the like, is dispensed with.

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Claims (1)

Claims he 1. Compounds of the general formula ¹ X OH, - OH COHHBlT N = N _ Ar-: H «W wherein Ar is a group of the general formula H." or - 28 - 309813/1 1 - 26 - 1st, in A amido, thiourea, -NH-CO-R ₅ -CO-NH-, in which R _{5 is} C ^^ - alkylene or phenyl j -SS-, -NsN-, -NH-, -CO- or Means SO _3; B is -CH ₂ -, -0-, -S-, -SO ₂ - or -NH-; X ₁ , X ₂ and Y each independently represent hydrogen, C 1-4 lower alkyl, C 1-6 lower alkoxy-hydroxy, C ₂ -C carbon-lower alkoxy or halogen; R is alkylene of 1 to 5 carbon atoms; R ₁ , R ₂ , R- and Rj. Each independently of one another Cjh-lower alkyl or C _1- ^ -hydroxy _{-lower alkyl, R 1} and R ₂ or R ₅ and Rj. Together can also form morpholinyl, piperidyl or piperazinyl; and the inorganic or organic salts thereof. 2. A compound according to claim 1, in which Ar is a group of general formula is wherein A is -SO ₂ -, -CpNH- or -N = N- lh of the meta or fpara position to the azo groups. - 29, - 309813/1110 3. A compound according to claim 2, in which Y is hydrogen or Means halogen. '' 4 ". Compound according to claim 2, in which A is amido; Y and X ^ are each independently hydrogen or chlorine and X is hydrogen, C ^ -Cg-lower alkyl, Cj-Cg-lower alkoxy or chlorine in the ortho-, metha- or para position to the azo groups; R is ethylene or trimethylene, R ₁ , R ₂ , R, and Rj ₁ each independently of one another C * j. rigalkylj or R ₁ and R ₀ or R and R ,. together Mor-.1 2 ₃ i} pholinyl as well as their acidic salts. 5. A method for dyeing paper or paper pulp, characterized in that a Compound of the general formula ft
• • • / . · R Oh - < • N = N _ "Ar. CONIffiN V · '· \ * _N = N. in the ar - 3b -309813 / 111Q where A is amido, thiourea, -NH-CO-R ₅ -CO-NH-, where R _{5 is} C ^ -alkylene or phenyl j -SS-, -SOg, -N = N-, -NH-, -CO- means; B is -CH ₃ -, -0-, -S-, -SO ₂ - or -NH- ; X-, Xp and Y each independently represent hydrogen, lower alkyl, lower alkoxy * C ₂ * -carboalkoxy, hydroxy or halogen; R alkylene of 1 to 5 carbon atoms; R ₁ , R ₂ , R, and R ^ independently of one another C _1- I ₁ -lower alkyl and C ₁ _ iJ -hydroxy- _{lower alkyl} , R ₁ and R ₂ or R, and R ^ together also form morpholyl »piperidyl or piperazinyl can; and the inorganic or organic salts thereof can be used. 309813/11 10 6 »\ ^r out for dyeing paper or pulp, characterized in that a compound according to claim 2 is used. 7. A method for dyeing paper or paper pulp, characterized in that a compound according to claim 3 is used. 8. Method of coloring paper or paper pulp. according to claim 5 »characterized in that A amido; Y and X _{1 are} each independently hydrogen or chlorine and X ~ is hydrogen, Cj-Cg-lower alkyl, C ^ -Cg koxy or chlorine in the ortho, meta or para position to the azo groups; R ethylene or tri · methylene, R ₁ , R ₂ , R- * and R ₁₁ each independently of one another C _1-1 J-lower alkyl, or R ₁ and R ₂ or R, ■ and R ₁ . together form morpholinyl; and mean the .zinc chloride complex thereof. 309813/1 110