DE2225248A1 - Anthraquinone dyes - Google Patents

Description

PATENT LAWYERS

DR.-ING. H. FINCKE DIPL.-INQ. H. BOHR DIPL.-ING. S. STAEGER

Fe r η r u fi «26 60 60

8 MUNICH S, MQllemraSe 31

May 24, 1972

Folder 22896 - Dr, Case Dd 239 ^ 8

Imperial Chemical Industries Ltd; London, UK

Anthraquinone dyes

Priority: May 24, 1971 - Great Britain

The invention relates to anthraquinone dyes used for coloring polymeric materials in the form of fibers, Film, Fädea. or tapes and especially of polymers Materials made from acid modified polyesters, polyamides and polymers and copolymers of acrylonitrile or dicyanoethylene can be used.

209851/1046

According to the invention, anthraquinone dyes are proposed, which are free of sulfonic or carbonic acid groups and the formula

OH

wherein X stands for a nitro or amino group, Y ^{+ stands} for an organic group containing a cationic group, and Z "stands for an anion.

As groups represented by Y ⁺ , groups of the type -AQ ⁺ should be mentioned in particular, in which Q ^{+ stands} for the cationic group and A stands for a group which connects the cationic group with the amino group.

Examples of cationic groups are quaternary ammonium, oyclammonium, hydrazinium, sulfonium, isothiouronium, etherified hydroxylammonium and phosphonium groups _? associated with an anion.

MLt the expression "quaternary ammonium groups" means: Uad groups of the formula -N ⁺ KR ¹ R, in which R >> R ¹ and R each represent a hydrogen atom or, preferably, represent an alkyl or cycloalkyl group or a substituted derivative thereof. Examples of alkyl or substituted alkyl groups which can be represented by R, R and R are ethyl, β-hydroxyethyl and benzyl and especially methyl.

209 8 51/1046

IHt the term "cyclammonium groups" are heterocyclic Meant groups that contain a quaternized nitrogen atom in the Hing, through which the ring preferably, but is not necessarily tied to the best of the molecule. Examples of such groups are N-alkyl, such as N-methylpiperidinium and morpholinium groups and especially aromatic heterocyclic groups such as pyridinium, Quinolinium and isoquinolinium groups.

The aromatic heterocyclic groups can optionally be substituted by a carbon atom of the heterocyclic ring be bound. An example of this is the N-methylpyridinium group, which is linked by the 4-position. These heterocyclic Systems can optionally be substituted, for example by alkyl groups, and they can additionally contain other heteroatoms to the quaternized nitrogen atom.

The expression "sulfonium groups" means groups of the formula -SR * R, in which Br is an alkyl or substituted alkyl radical, such as methyl or ethyl, and R is an alkyl or substituted alkyl radical, such as methyl, ethyl or β -Bydroxyäthyl, a cycloalkyl radical, such as «. Cyclohexyl, an aralkyl radical such as benzyl, or an aryl radical such as phenyl or p-tolyl.

Groups like to use the phrase "isothiouronium groups" j nt, which in one of its resonance forms by the formula

- S.

209851/1046

can be represented, where R ^ R, Ε? and R for hydrogen atoms or hydrocarbon or substituted hydrocarbon radicals, where r5 and R 'together also can form an alkylene radical.

Examples of hydrocarbon and substituted carbon

C C. IJ Q

hydrogen radicals represented by R, R, R 'and R. are alkyl radicals such as methyl and ethyl, substituted alkyl radicals, such as ß-hydroxyethyl, cycloalkyl radicals, such as cyclohexyl, aralkyl radicals such as benzyl, and aryl radicals such as phenyl and p-tolyl. A Example of an alkylene radical, which is defined by R ^ and R ' formed together is ethylene. In this case, an imidazoline ring is formed.

With the expression "Bydraziniumgruppen" are groups of the form

+ Q 10 11 12 'Q

mel -HH ⁷ R -HE B meant, where R ^{7 is} an optionally

substituted alkyl, cycloalkyl, aralkyl or phenyl

10 is radical or together with R and the neighboring

11 nitrogen atom forms a heterocyclic system, R for

a hydrogen atom or an optionally substituted one

12 is an alkyl radical or an acyl radical which can form a ring with R and N when R ⁷ and R are something else

12th
as a phenyl radical. stands, and R stands for a hydrogen atom

or an optionally substituted alkyl radical or an acyl radical.

The term "phosphonium groups" means groups of the formula -Jr ¹⁵ R ¹⁴ R ¹⁵ , in which R ¹⁵ , R ¹⁴ and R ^{15 are} organic radicals, which can be the same or different, and each bonded directly to the phosphorus atom by a carbon atom are, examples of organic radicals,

209851 / 10A8

13 14-1S
represented by R, R and R ^ are aliphatic radicals such as methyl, ethyl, propyl, butyl, allyl, chloromethyl, hydroxymethyl and ß-hydroxyethyl, aromatic radicals such as phenyl, haphthyl, p-tolyl and p ~ Chlorophenyl, aralkyl radicals such as benzyl, and heterocyclic radicals such as -2-thienyl.

Anions associated with the cationic group are, for example, inorganic anions * such as chloride, bromide, iodide, tetrachlorozincate, bisulfate, acetate, Sulfate, sulfamate, phosphate or borate, or organic anions, such as methosulfate, methyl sulfate and p-tolyl sulfonate. In the In cases where the anion is polyvalent, the water-soluble dye will be an appropriate molar proportion of the cationic (dell of the dye included.

The linking group A can be any aliphatic group, such as an alkylene group which may contain a heteroatom in the chain, or a cycloaliphatic, arylene or heterocyclic group, all of which may be optionally substituted, or a combination of such groups. Specific examples of such groups are ethylene, propylene, m-phenylene, p-phenylene, p-CgH ₄ .0.C ₂ E _4. , P-CILj.C ^ H ^., P-CgH ₄ .CH _2. , P-CgH ₄ .HH.CO.CH _2. , 6-methyl-m-CgH, .CH _2. , 6-methoxy-m-CgH ,. CH _2. , 6-methyl-m-CgH ^. CH ₂ .HH. CO. CH _2. , 6-methoxy-m-CgH ,, CH ₂ HH.CO.CH ₂

.Sp-CgH ^., P-CgH ₄ -CH ₂ -P-CgH _4. , C ₂ H ₄ -CC ₂ H ₄ . and P-CgH ₄ .KR-C ₂ H ₄ . wherein R stands for a hydrogen atom or an optionally substituted alkyl, aralkyl or aryl group.

In the above list, CgH ₄ denotes a phenylene group and CgH, a substituted phenylene group, with the letters

2 0 9 8 51/10 4 6

m- and ρ- indicate that the anthraquinoid and kafcionoids Parts of the molecule are bound by positions which are related to one another have an m or p ratio.

The preferred dyes are those of _s in which the group Y is a group of Type -AQ wherein either A is a m- or p-phenylene group, on the one hand directly to the imino group and the other by a divalent aliphatic group to a quaternary ammonium or Cyclammoniumgruppe or A is an m- or p-Ehenylengruppe, which on the one hand is directly bound to the imino group and on the other hand to a quaternary ammonium group in which the other substituents on the quaternary nitrogen atom are alkyl groups which contain 1 to 4 carbon atoms

Examples of specific dyes according to the invention are dyes in which X, X and TT have the following meanings:

X T Z

Nitro amino

m-Trimethylammonium phenyl chloride

ρ- (trimethylammonium ethy 1) phenyl

IT

p-trimethylammonium benzyl p ~ trimethylammonium benzyl ^ -trimethylammonium propyl

209851/1046

-, Π -

Nitro amino

Hitro

Amino

Mtro

Amino

Hitro

Amino NO ₂

I ^ Iifethyläthylsulfoniumpropyl

ir

p-dimethylsulfonium phenyl

p- (Pyriainiuia-N-acetylamino) phenyl chloride

Kotrachlorosin cat

ρ- (Pyridiniuni-H-ethoxy) -phenyl bromide

p- (N-ethyl-H-trimethylammonium äthylaiaino) -phenyl

ρ- (tri s-ß-oxyethyl ammonium ethoxy) -phenyl

ρ- (dimethylbenzylammoniumethyl) ■ phenyl

4- ~ methyl-3- (tetramethylisothiourontumethyl ) pheny chloride

y ^ - (pyridiniumacetylamino- '' methyl) phenyl

4-helyl-3 ~ (4'-dimethyl aminopyridine lumiaethyl ) phenyl '

p ~ (Dim © th jlhyaraziniumäthos: y) phenyl ^f

209851/1046

The dyes according to the invention can thereby be prepared that you can use a dye of the formula

(ID

OH

where T stands for an organic group which has a primary, contains secondary or tertiary amino, sulfide ether or dialkylphosphine groups, alkylated. Suitable alkylating agents are alkyl halides, such as methyl iodide, ethyl iodide or Ethyl bromide, cycloalkyl halides, aralkyl halides, e.g. Benzyl chloride, alkyl sulfates such as dimethyl sulfate, diethyl sulfate and diisopropyl sulfate, and aryl sulfenic acid esters, such as e.g. methyl, ethyl and butyl p-toluenesulfonate.

The alkylation can be carried out in an inert organic solvent such as benzene, toluene, xylene, chlorobenzene, nitrobenzene, Acetone, carbon tetrachloride, tetrachloroethane or ß-lthoxyethanol can be run, but in some cases it is also possible and it may even be preferred to use a medium which is composed of the alkylating agent or consists of water or an aqueous organic solvent. The alkylating agent is preferably in one considerable excess is used, for example about 6 moles per mole of dye are used. It is desirable also an acid-binding agent, such as ammonium oxide., or sodium carbonate, admit. Suitable temperatures for the alkylation are 20 to 150 ° C.

209851/1046

When the alkylation is carried out in organic solvents then the dye and also the excess of the acid binding agent will normally be insoluble and can be separated off by filtration. The dye can be removed from the acid-binding agent by extraction with water and salting out Or by extraction with hot ethanol and subsequent cooling for the purpose of precipitating the dye to be deposited.

Suitable dyes for use in the above alkylation process are those in which T stands for m- or p-aminophenyl, dimethylaminopropyl, p-dimethylaminomethylphenyl, p-dimethylaminobenzyl, p-bimethylaminoethoxyphenyl, p-methyl mercaptophenyl and it is ethyl mercaptopropyl and X is in each Trap is either a nitro or an amino group.

The dyes according to the invention can also thereby can be made by having an anthraquinone bond the formula

X 0

CIIO

O MH-G

wherein G is an organic group which is a reactive Contains halogen atom or a sulfate ester group, and X represents represents a nitro or amino group with a tertiary amine implements.

209851/1046

By the term "reactive halogen atom" is meant a halogen atom attached to an aliphatic carbon atom is.

Examples of halogen atoms are bromine and iodine and especially chlorine.

Examples of tertiary amines are aliphatic tertiary amines, such as trimethylamine, triethylamine and triethanolamine, N ₉ N-disubstituted hydrazines, such as sB Jf, F-dimethylhydrazine, and cyclic amines, such as pyridine, quinoline, isoquinoline and substituted derivatives thereof, such as Or, β- and ^ -picolin and 2,6-lutidine.

The last-mentioned process according to the invention can conveniently be carried out by heating the anthraquinone compound and the tertiary amine together in a solvent which may consist of an excess of the amine or a solvent, such as water, aryl halides, for example monochloroebeazole and . o-dichlorobenzene, tetrahydrofuran, acetone, N, N-dimethylformamide and dimethyl sulfoxide and mixtures thereof. Suitable Keaktionstempera are doors 20 to 150 ⁰ C ,, but it may optionally also higher temperatures are used.

If the dye is insoluble, then it can be used, for example be separated from the reaction mixture by filtration. Another separation is by diluting with one suitable power dissolver and subsequent isolation of what has fallen Dyestuff or by diluting it with water, separating water-soluble impurities and salting out, for example as double salt, e.g. with Zmkehlortd,

2 0 9 8 5 1/1046

The anthraquinone compounds used in the process according to the invention of the formula (III) can be prepared by customary processes. For example, in the case of chloromethyl compounds the corresponding arylaminoanthraehinone with formaldehyde and chlorosulfonic acid or dichloro dimethyl ether treat in a strongly acidic medium such as sulfuric acid.

Examples of anthraquinone compounds of the formula III are compounds in which X is either a nitro or amino group and G for p-chloroacetylaminophenyl 1, p-ß-bromoethoxyphenyl,. p-N-ß-chloroethyl-N-alkylaminophenyl, 4-methyl- or 4-methoxy-3-chloromethylphenyl or 4-methyl- or ^ -methoxy-i-chloroacetylaiaino-methylphenyl stands.

This method is not generally applicable to the preparation of anthraquinone dyes of the present invention: where the cationic group directly. bonded to a phenyl group is because the halogen atom or the sulfate ester group is then not sufficiently reactive.

The fiction, contemporary dyes in which X stands for a nitro group can also be obtained by reacting 5 ~ nitro-4-aminochrysazine with an amine of the formula Y - KH ₀ , Z * ", in which

i_ ■ ■ ^

and Z have the meanings given above, in the presence of boric acid or boric anhydride or a boric acid derivative getting produced.

This further process of the invention can for example be carried out in that 5-NitΓO-4-aminochrysazin, the amine and boric acid at a temperature which is preferably between 50 ⁰ C and the boiling point of the mixture, stirred for "temperatures between 50 and 100 ⁰ C. are common

209 851/1046

suitable when the amine is an aliphatic amine. There are however, temperatures of 100 ° 0 are generally required if the amine is an aromatic amine · It is preferred to use the method in an organic solvent, especially in a phenolic compound such as phenol or o-cresol.

Examples of amines used in this further process are p-ß-pyridinium ethoxyaniline bromide and p-ß-Gf ~ Picolinium) ethylaniHn chloride.

The dyes according to the invention can be used to achieve bright greenish blue shades on polymeric materials are used, which are in the form of textile materials, applying the dyes from an aqueous dye bath. The dyes are particularly useful for application to polymers and copolymers of acrylonitrile and dicyanoethylene, and on polyesters, polyamides and cellulose esters. The polymeric materials can be modified, for example they can be acid-modified.

The dyes of the invention can be made acidic, neutral or slightly alkaline dyebaths (ie, pH of 3 to 6) by! Temperatures between 40 and 120 ⁰ C and preferably between 80 and 120 ⁰ C, or polyamide, or in particular Zelluloseester- polyacrylonitrile or Polydicyanoäthylenmaterialien by printing techniques using thickened printing pastes.

In the case of polyacrylonitrile, especially if the polyacrylonitrile modifier ¹ '; has been »so that © s contains acidic groups, the textile materials are dyed in bright greenish blue shades, which are characterized by their good wet and light fastness.

2 0-9851 / 1048

The dyes are also particularly valuable for dyeing Polyamide and polyester materials modified to contain acidic groups, preferably made from neutral baths is colored.

The invention is illustrated by the following examples, in which all parts and percentages are by weight are expressed unless otherwise specified.

Example 1

2 parts of an anthraquinone compound of the formula II, in which X is a nitro group and T is a p-aminophenyl group stands, and 2 parts of magnesium oxide are suspended in 100 parts of acetone, and the resulting mixture is stirred and used for Boiling heated. 7.8 parts of dimethyl sulfate are then added, and the mixture is stirred and heated to flow for 22 hours. The mixture is filtered hot and the residue is with washed a little acetone and extracted 3 times with 100 parts of boiling water. The combined aqueous extracts are treated at tree temperature with 1 part zinc chloride and 30 parts sodium chloride. The fancy dye that made the formula (I), wherein X is a nitro group, T is a. p-Trimethylammonium pheny! group and Z "stands for a tetrachlorosine cat anion, is filtered off, washed with a little 10% sodium chloride solution and dried.

Venn the product of a neutral or weakly acidic Dye bath is applied to polyacrylonitrile fibers, then you get an attractive greenish blue shade with excellent authenticity properties

209851/1046

The anthraquinone compound used as the starting material in the above example can be prepared by reacting 4-nitro-5-aminochrysazine with p-phenylenediamine in phenol, using butyl borate as a catalyst.

The following dyes of the formula I can be prepared in a similar manner by using the corresponding aminoanthraquinones of the formula II quaternized.

209851/1046

ro CD co co cn

CD

E.g. Σ y Z " chloride Hue on
Polyacrylonitrile 2 Nitro m-Ir imethyl ammonium pheny1 Tetrachlorozincate η greenish blue η p- (4-trimethylammonium-
phenylmethyl) phenyl It Il η 4th η p- (4-trimethylammonium-
phenoxy) phenyl It fl 5 It 5-methyl diethylammonium
2-methoxyphenyl) bromide ti 6th Il methoxyphenyl chloride Il 7th η o-trimethylammonium
phenyi η Il 8th Amino p-trimethylammonium
phenyl It η 9 It m-trimethylammonium
phenyl Il 10 η p- (4-trimethylammonium-
phenoxy) phenyl Il 11 Nitro p-trimethylammonium
methylphenyl η

-Λ

ν »

ro ro

KJ O CD

E.g.
1
! J p-triethylammonium
methylphenyl ir Hue on
Polyacrylonitrile I. j 12 Fitro ^ Trimethylammonium
propyl chloride blue greenish blue] 13th Il 3-triethylainmonium ethyl Methosulfate ti ! 14th It ρ- (ß-Trimethylaiomonium-
Stho35y) phenyl chloride Il bromide

ro cn ro

7.2 parts of sodium chloride for a period of 1 st 0.5 ⁰ G to a stirred Losimg of 3 $ 7! Peilen paraformaldehyde added in 36.8 parts of sulfuric acid * 3.9 parts Anthraehinonverbindung of formula II wherein one of J. Hitro group and T stands for a p ~ tolyl group., Are then added to the mixture over 1 hour at 0-5 °, and the mixture is stirred for 48 hours at room temperature. The solution is poured into 200 parts of a mixture of ice and water, and the precipitated dye is filtered off and washed with cold water until the washing liquids are acid-free.

The chloromethylated anthraquinone obtained is dissolved as a wet paste in 10 parts of pyridine, and the solution is refluxed for 3 hours. The solution is added to 150 parts of water, and the mixture is filtered. The small amount of residue is washed free of water-soluble dye with water, and the combined aqueous washing liquid and filtrates are salted out with 5% sodium chloride. A dye of the formula I becomes obtained, in which X stands for a nitro group, Y ^{+ stands} for a 4 ~ methyl-3-pyridiniummethylphenyl group and Z ~ stands for a chloride ion.

If with the above product polyacrylonitrile from neutral or weakly acidic dyebaths are then obtained a greenish blue shade with good fastness properties,

The anthraquinone compound used as the starting material in the above example can be obtained by condensation of 4-Eiitro-5-aminochrysazine with p ^ toluidine in Phenol and in the presence of boric acid.

209861 /.1046

The following anthracite ingredients of formula I can be prepared in a similar manner. Your strategies are given below *

209851/1046

ro ο co

'Ρ = -Ό a i

i- * -. V a S

1? 18 19 20 21 22 23 24 25 26

■ Vi'iMi'fc-.ca '-

Nitro

y methylpher> y

4Μθ thyl 3dimey 25 iniuinma t hylphe nyl

2.4Dimey methylphenyl

2 ₉ i |.-Dimethyl-5-diinethylkydraz Inium-methylphenyl

4-MetliyI »'3-ispthiouronlumtlbl

y3y isothiouronium methylpheay1

ς7 methylplienyl

i | - methyl-3-t me thy! phenyl

chloride

Tetrachloro silicate

chloride

Color shade a ¹ ·?.!

greenish blue

ro ο co

3sp. X Y ⁺ Z " Hue on
Polyacrylonitrile 27 Nitro - 4-methyl thio-3-tri ( B-Ey-
droxyäthy1) ammonium methyl-
phenyl Tetrachlorozincate greenish "blue 28 Il 4-methyl-3-triethylphosphate
phonium-methylphenyl It It 29 Amino 4-methyl-3-dlmethylbenzyl-
ammonituaiBethy! phenyl It It 30th • I 4-methyl-3-quinolinium
methylphenyl It H 31 4 — Methvl — 3 — pyridiniuBHB6thyl— Il Il phenyl "

Example 32

3 parts of an Ohloroanthraquinone of the formula III, wherein X stands for a nitro group and Gr for a p-ß-chloroethoxyphenyl group stands, are dissolved in 27 parts of pyridine, and the resulting solution is refluxed for 12 hours. The mixture is then poured into 150 parts of water. The solution is then salted out with 37 * 5 parts of sodium chloride, and the precipitated dye is filtered off, washed with 150 parts of 30% sodium chloride solution and at 40 ° 0 dried in vacuum. The product has the formula I, in which X stands for a nitro group, Y for a p-ß-pyridinium ethoxyphenyl group and Z ~ stands for a chloride ion.

If the above product is applied to polyacrylonitrile fibers from a neutral or weakly acidic dye bath, then a bright greenish blue shade with good fastness properties.

The Chlqroant'araehinonverbia & ung used in the above example as starting material is obtained by a solution of the corresponding hydrosyanthraquinone in nitrobenzene treated with thionyl chloride in the presence of pyridine.

Example 33

0.8 part of a chloroanthraquinone compound of the formula III, wherein X stands for an amino group and G for a β-chloroethoxyphenyl group stands, are dissolved in 25 parts of pyridine, and the solution is stirred and refluxed for 18 hours. The reaction product is worked up in a similar manner as in Example 3, wherein a dye of the formula I is obtained in which X is an amino group, X is a p-ß-pyridinium

209851/1046

ethoxyphenyl group and Z "stands for a chloride ion Bteht.

If this product from a neutral or acidic dye bath is applied to polyacrylonitrile fibers, then © in Greenish-blue shade obtained, which, however, tends more towards green than the dye of Example 32.

The chloro used as the starting material in the above example anthraquinone is obtained by the fact that the corresponding hydroxyanthraquinone with thionyl chloride in nitrobenzene and in Treated presence of pyridine.

The hydoxyanthrachisone is produced by sodium sulfide reduction of the corresponding 4-BTitroanthraquinone obtained.

Other cationic anthraquinone dyes of the formula I, which are similar to the chloro-, bromo- or sulfatoanthraquinones of formula III can be obtained., are listed below.

209851/1046

ί
E.g* X Y ⁺ Z " Hue on
Polyacrylonitrile 34 Nitro ρ- (β-a-picolinium ethoxy) -
phenyl bromide greenish blue 35 !> ρ- (B-rs-pie olinium ethoxy) -
phenyl ti « 36 ti ' ρ- (ß-dimethylhydrazinium-
athoxy) phenyl Il It 37 I? ρ- (ß-isothiouronium ethoxy) -
phenyl ti dd 38 η p- (ß-tetramethylisottiiouroniuni) -
phenyl chloride It 39 η ρ- (ß-triethylphosphonium
ethoxy) phenyl bromide ti 40 dd p- (ß ~ dimethylsulfonium-
ethoxy) phenyl chloride ti 41 · H p ~ (ß-Hydroxy-2Tlpyridinium-
propyloxy) phenyl bromide ti 42 ti ο- (ß-pyridinium ethoxy) -
phenyl Il η

CD CO OO

J
E.g. X Y ⁺ Z " Hue on
Polyacrylonitrile 43 Amino ο- (ß- ^ Plc olinium ethoxy ) -
phenyl bromide greenish blue 44 η ο- (ß-isoquinolinium ethoxy) -
phenyl It Il 45 η m- (ß-pyridiniumethylamino) -
phenyl chloride "1 46 η m- (ß-quinoliniumethylamino) -
phenyl rf H 47 η m- (ß-dimethylhydrazinium-
ethylamino 5phenyl 11 n 48 Nitro m- (pyridinium methyl) phenyl ti n 49 H m- (ctr-picoliniixmmethyl} phenyl H It 50 η p- (ß-diethylmethylammonium-
ethoxy) phenyl dd ti 51 ti 2-methoxy-5-pyridiniuiamethyl-
phenyl Tetrachlorozincate η 52 Il 2-kethoxy-5-trimethylai «imonium-
methylphenyl Il ti

ί
E.g.
53
55 X carbonylaminophenyl
earbonylaminophsnyl
ß-pyridinium ethyl CSI Hue on
Polyacrylonitr.il Nitro
Amino
Nitro Tetrachloro zincate
It
1" greenish blue
«
blue

A mixture of 50 parts of phenol and 0.65 parts of boric acid is heated to 140 ° 0 for 2 hours in a nitrogen atmosphere :; and then cooled to 80-90 ° C. Then, 2.5 parts of 4-nitro ~ 5-aminochr5rsazin are added, and the mixture is stirred for 15 Miss at 80 to 90 ⁰ C. The mixture is then heated to 130.degree. C., and then 3.0 parts of β (4-aminophenos: y) -ethylpyridinium bromide are added over a period of approximately 30 minutes. The mixture is ^{kept at 130 °} C. for a further period, cooled to 100 ^° C. and diluted with 50 parts of water. The mixture is then steam aastilized to remove the phenol and then finally cooled to room temperature, whereupon the crude dye precipitates. The crude product is filtered off and redissolved with 750 parts of boiling water; which contains 1.7 parts of sulfaic acid. The solution is boiled for 40 minutes, stirred for 18 hours at room temperature and then filtered, and the filtrate is then salted out with 5% sodium chloride. The purified dyestuff is collected, washed with 100 parts of 5% sodium chloride solution and dried in vacuo at Haurfileanatur. It has a similar constitution to the dye from »Example 32,

Venn the product of a neutral or acidic TFACH ah ^v *. Dyebath on polyaer-jlonitri! Fibers applied to ^ v / '- ^ d, the product is bright greenish blans Fa: c ο errste mit guteiA authenticity seiye ^ sv hn ftea.

209851/1046 ^BAD ° * <®NAL

The following ionic anthraquinone dyes of the formula I can be prepared in a similar manner as in Example 55 by condensing 4-nitro-5-ai-eochrysin with a teat ionic aromatic amine compound.

209851/1046

CD CD OO

E.g. X Y ⁺ Z " Shade on poly- 5
acrylonitrile | Il 57 Nitro 0- (ß-cu-picolinium ethoxy) -
phenyl bromide ί
greenish blue j
j 58 If 0- (ß-tetramethylthiouroniuni-
ethoxy) phenyl : t ti i j .59 f! 0- (ß ~ dimethylhydraainium-
ethoxy) p} ienyl " chloride ι
60 ti ρ- (pyridiniummethylcarbonyl-
amino) phenyl · » I.
i 61 It p-CDiraethylhydsaziniummetliyl-
carbcnylamino) phenyl η 62 -
«I. m- (t '-' Dlm.e thylaminopyridinium-
methylcarbony! amino jphenyl It

A mixture of 2 _r , S parts of an anthracite mixture of the formula II _s where J Hip stands for a nitro group and T stands for a methylniereaptophil group _? and 6 _? 7 parts of dimethyl sulfate is 10 ms for 15 min at 105 to 110 ⁰ G, cooled to room temperature, diluted with 100 parts of acetone and filtered, and the residue is dissolved in 180 parts of water, wobai a greenish "blue solution. The solution is treated with 27 parts of sodium chloride and 1 part of zinc chloride are salted out After stirring for 10 minutes at room temperature, a dye is filtered off which has the formula I, in which X stands for a nitro group, Y stands for a p-dimethylsulfonium phenyl group and Z ~ for a The dye is then washed with a little 20% EochsaIsslösung and dried ^{at 40 0 G.}

If the product is from a neutral or weakly acidic Dye bath is then applied to polyacrylonitrile obtained bright greenish blue colorations.

The anthrachixron compound used in this example as the main starting material is obtained when 4-nitro-5-amyiochrysazine and p-thioanisidine are condensed in phenol in the presence of boric acid.

ispiel

Egg; ü mixture of 0.85 parts of an anthraquinone compound of formula II> wherein X is an amino group and T represents a p ~ Hethjlmercaptophenylgruppe, and 3.3 parts of dimethyl sulfate is heated for 30 min at 105 ⁰ C. The mixture · wild

209851/1046

cooled to room temperature and the solidified massa is slurried with 20 parts of Ither to remove excess dimethyl sulfate. After decanting off the ether, the remaining solid is dissolved in 100 parts of water, and the greenish blue solution obtained is filtered off and salted out with 25 parts of sodium chloride and 1 g of zinc chloride. The precipitated dye, which is filtered off and washed with a little 20% saline solution, has the formula I, in which X stands for an amino group, X stands for a p-Dimethjlsulfoniuaiphenylgruppe and Z "stands for a Tetraehloroziiikatartion"

If the above product consists of a neutral or scb.i «; oh sour Dyebath applied to polyacrylic fibers wild, then one obtains strong greenish blue shades.

The anthraquinone compound used as the starting material in the above example was lurch Hatrimsulfidredukblon of the corresponding ^ -Nitroanthraquinones obtained (vrelches in example 65 was used as output SB material).

The following dyes of the formula I can be obtained in a similar manner ornaments by quaternizing the corresponding anthraquinones with sulfate ether groups of the formula.

209851/1046

¹ 209 Bat), Nitro Y ⁺ Z " Hue on
Polyacrylonitrile It OO
cn 65 It p-methylene cyl sulfonium
phenyl Ohloria greenish blue M. O
■ Τ
Ο) 66 It m-ethyltoenzylsulfonium-
p & sayl, fl η 67 Amino p ~ (methylphenylsulfonitun-
methydplienyl η 68 Nitro p-ethylbenzylsulfonium
phenyl it 69 p-ethylmethylsulfonium
phenyl dd

Type II anthraquinone dyes can be treated with acid and use as a salt when dyeing acrylic fibers ~ be det. Examples of these dyes of the formula I are given below.

OWGINAt INSPECTED

209851/1046

E.g. • χ Y ⁺ f Hue on
Polyacrylonitrile 70 NO ₂ p-dimethylaminomethyl
phenyl, protonated chloride greenish blue 71 protonated IPe'ttT'af.'h.loro sLT ^ sraii 72 NO ₂ ß-methylaminoethyl,
protonated η blue 73 CVJ • p-diethylaminomethyl
phenyl, protonated chloride greenish blue
■. r *
¹

ro ro ro cn ro

Claims (1)

Claims 1. Anthraquinone dyes that are free from sulfonic acids and Carboxylic acid groups are and the formula \ Il Il IZ OH 0 have, in which Z stands for a nitro or amino group, Y represents an organic group containing a cationic group, and ΊΓ represents an anion. 2. Anthraquinone dyes according to claim 1, characterized in that the organic group ι stands for a group of the type -AQ ⁺ , wherein Q is the cationic group and A is a group which connects the cationic group with the amino group. 3. Anthraquinone dyes according to claim 2 _t wherein dia group -AQ ⁺ is a group in which A is a m- or p-Fhenylengruppe bonded on the one hand directly to the amino group and the other by a divalent aliphatic group to a quaternärβ Ammonium or Cyclaiamoniumgruppe is bound. 209851/1046 4- »Antlirachinon dyes. Claim 1, characterized gekennseich.net ,, that the group -AQ ^{+ is} a group in which A is an m- or p-phenylene group which, on the one hand, is bonded directly to the amino group and, on the other hand, is bonded directly to a quaternary ammonium group, in The more axial substituents on quaternary nitrogen atoms are alkyl groups that contain 1 to 4 carbon atoms. 5 « Process for the preparation of anthraquinone dyes according to claim 1, characterized in that a dye of the formula wherein T stands for an organic group which contains a primary, secondary or tertiary amino group, a sulfide ether group or a dialkylphoaphine group, and X stands for an amino or nitro group, alkylated. 6 »Method according to claim 5» characterized in that that the alkylation is carried out in the presence of an acid-binding agent. 7- A process for preparing anthraquinone dyes according to claim 1, characterized datvorch _t that an anthraquinone compound of the formula 209851/1046 wherein G represents an organic group containing a reactive halogen atom or a sulfate ester group, and Z represents a nitro or akino group, with a tertiary Ämin implements. 8. The method according to claim 7, characterized in that that G contains chlorine as the reactive ε halogen atom. 9 · Method ζ nr production of anthraquinone dyes according to claim 1, wherein X stands for a nitro group, characterized in that 5 ~ nitro-4 ~ aminochrysazine with an amine of the formula T ⁺ -HH ₂ , Z "", wherein Y ⁺ and Z ~ have the meanings given above, in the presence of boric acid, boric anhydride or a boric acid derivative. 10. The method according to claim 9, characterized in that da8 5-Hitro ^ -arainochrysazine, the amine and the boric acid or the boric anhydride or the boric acid derivative ^{are heated to a temperature between 50 0} C and the boiling point of the mixture. 11. The method according to claim 9 «characterized in that that it is in a phenolic compound as a solvent is performed. SAD ORiQiNAL 2 0 9 8 5 1/10 4 6 12c Use of the dyes according to one of the claims 1 to 4- for dyeing textile materials from aqueous Dye baths. 13 · use of the dyes according to one of claims 1 to 4 · for dyeing polyacrylonitrile or PolydlcyanoäthyXenmaterialien of an acidic, neutral or weakly alkaline Färbeb-td at a temperature between 40 and 120 ⁰ C or D ucktschniken using a thickened Druckr.aste . JI.FIfiCKL-, Oi.'L-INÖ. DlPl-JNG ä-STAEGfil » 209851/1046