DE2150482C3 - Anthraquinone dyes and their use - Google Patents

Description

5 6

The invention relates to anthraquinone dyes in the acid form of the formula

O NH- R ₂ - (SO ₃ H) _1n

- (OSO ₃ H) _n

correspond in the

η and m Y

stand for the numbers 0-3,

Means hydrogen or SO ₃ H, if

η + τπφΟ, or for SO ₃ H, if n + m-0, where the remainder -OSO ₃ H to a C-Aiom of

Radicals R ₂ , R ₄ or R _{5 is} bonded,

for an optionally substituted one

R ₂ =? == - CH-R ₄ R _{5 is an} alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radical of the type customary in the field of acidic anthraquinone dyes and

fQr optionally substituted Ci-C ₃ -alkyl, wherein

The radicals R ₄ and R ₅ can have substituents in which n = O, / n = 1 and R ₂ for a given, for example, OH and Ci-CU-alkoxy groups or, if substituted, phenyl or phenyl-Ci-C ₂ -alkyl -Sulfatoreste, and halogen atoms such as fluorine, chlorine 30 rest

bii Another group of color according to the invention

substances are those in the acid form of the general

or bromine and optionally substituted amino groups.

Preferred dyes within this group are

a formula

HO O NH-CH

Y I Il I \

O NH

- (A-SO ₃ HL

correspond in the

m and ρ stand for numbers 0-3,

R ₄ and R5 for optionally substituted Ci-C ₃ -alkyl,

Y stands for hydrogen or SO ₃ H, where for

Y = hydrogen at least one of the radicals R ₄ , Rs or Z contains or must represent a group -A-SO _{3 H,}

Z is hydrogen or a substituent of

in the field of acidic anthraquinone dyes common type,

A represents a direct bond or —O—,

where -A-SO ₃ H must be bonded to a carbon atom of the radicals R ₄ , R5 or Z or represents a Z substituent.

Suitable radicals Z are, for example, optionally substituted Af-.yl, alkoxy, alkylmercapto or alkylsulfonyl radicals, in particular those having 1-4 carbon atoms, halogen, such as F, Cl ₁ Br, optionally mono- or disubstituted amino groups, in particular by Ci - G-alkyl groups, optionally substituted phenyl groups, acyl groups, such as optionally substituted ie.-th alkylcarbonyl, arylcarbonyl, in particular optionally substituted phenylcarbonyl, arylsulfonyl, especially optionally substituted phenyl

ss sulfonyl groups, substituted amino groups, optionally substituted phenylsulfonyl, phenylmercapto-, Phenyloxy radicals, optionally mono * or disubstituted carbo.ic acid amide or sulfonic acid amide radicals, for example sulfonic acid mono-sulfophenylamide, SuI- Fonsäure- and carboxylic acid ester residues, in particular -alkylesterresie: CN, aralkyl radicals, in particular optionally substituted benzyl radicals.

The radicals R ₄ and R ₅ can have substituents, for example UiI and Ci-C ₄ alkoxy groups or Sulphate radicals and halogen atoms, such as fluorine, chlorine or bromine and optionally substituted amino groups. Preferred dyes (II) are those with

m - O and ρ = I - J. where at least one radical Z is preferably SO) H.

Another group of substances according to the invention are those in the acid form of general Shape!

HO O

- (A-SO ₁ II) ,,,

(III)

correspond in the

in and η for door / ahlrn fl - "i stehrn

Rj and R-, optionally substituted Ci-d-Alkvl represent.

Y stands for hydrogen or SO] H, where for

Y = hydrogen at least one of the radicals Rj. R-, and Z contains a group - A-SO) H or must represent.

O stands for Ci-Cr-alkylene.

Z is hydrogen or a substituent of

in the field of acidic anthraquinone dyes common type.

A is a direct bond or —O—,

where the radical -A-SO ₁ H is bonded to a carbon atom of the radicals Rj. R ^ or Z or represents the radical Z.

The radicals Z. Rj and R- have the formula (II)

Preferred dyes (II) are those with / ;; = 0 JIi and; i = 1-3. where at least one radical Z is SO ₁ II.

The remainders O are, for example:

Methylene. 1.2-ethylene-, I,! - ethylene-.
y ,! .3-propylene-. !.! - propylene, 1,2-propylene,

2.1-propylene-. 2.4-liutvlen-,
3-hobutyl-3. ' propylene residues.

Another group according to the invention of color) ii substances are those in the acid form of the general formula

HO O NH-CH

(A — SO ₅ H) ,,,

(IV)

correspond in the

ρ stands for the numbers 0 - 3.

m stands for the numbers 0 - 2,

Z is hydrogen or a substituent of the; o

is the usual type in the field of acidic anthraquinone dyes,

Y stands for hydrogen or SO ₃ H, where for

Y = hydrogen at least one of the radicals Rs, R5 and Z contains or must represent a group —A — SO3H.

A is a direct bond or —O—,

where —A —SO3H must be bonded to a carbon atom of the radicals Rj, R5 or Z or Z represents.

Rj and R5 for optionally substituted Ci-Cj-alkyl stand and

Z has the meaning given in formula (II).

Another group of dyes according to the invention are those which are in the acid form of the general formula

HO

O NH-CH

O NH — B - (A-SO ₃ H) ,,,

(V)

L-ntsp-cchen. in the

in ^r for the numbers 0— j stone.

. ι

Alkyl darsiclll. However
CII Ri

is,

stands for a direct bond or —O—, where - A-SOiH is bonded to a carbon atom of the radicals Rj. R-, or B.

and R-, for optionally substituted Ci-CV Alkyl,

stands for hydrogen or SO ₁ H if /; i * 0 or for SO ₁ H if m = 0 .

\ is residues B are e.g. B. to name:

Unsubstituted alkyl radicals such as

Methyl, ethyl, η or i-propyl,

n-, i- or tert-butyl, η- or i-pentyl,

n- or i-hexyl radicals,

unsaturated alkyl radicals, such as. B. the allyl radical.

substituted alkyl radicals, such as. B. the

Hydroxyethyl, methoxyethyl. Amino-ethyl-,

Methylamino-ethyl-.

oj-carboxy-propyl-, cyanoethyl-,

Sulfatoethyl, sulfophenylalkylreste. wie der

Sulfophenylisobutyl radical.

The radicals Rj and R, can have substituents, such as OH and Ci-O-alkoxy groups or sulfate radicals. as well as halogen atoms such as fluorine, chlorine or bromine and optionally substituted amino groups.

For the production of anthraquinone dyes. those in the acid form of the formula

OH O NH-CFI -L (OSO ₃ H) ,,

(VI)

O NH-R ₂ - (SO ₃ H), "

correspond in the

η and m stand for the numbers 0-3,

Y is hydrogen or SOjH if

η + ιηφϋ or SO ₃ H, if n + m = 0, where the radical -OSC ₃ H is bonded to a carbon atom of the radicals R ₄ and R ₅ ,

Ri for an optionally substituted one

Alkyl, cycloalkyl, aralkyl, aryl or heterocyclic radicals of those in the art of the acidic anthraquinone dyes usual type and

R ₄ and R5 represent optionally substituted Ci-C ₃ -alkyl, where

R ₁ ^ -CH-R,
\

R ₅

is.

one puts compounds of the formula

R *

R "OO N-CH - | - (OSO ₁ H)

(VII)

Hill

ii where

R ₄ . R-,

iinrl η dip in formula (VI) given meaning

own and OSO) H to a carbon atom of

Radicals R ₄ or R; is bound, and

for H or acyl and

for halogen in particular Cl or Br,

replacing the halogen atom with amines of the formula

R *
Shark

HjN-Ri- (SO ₃ H) ,,,

(VIII)

um, in the

R> and m have the meaning given for formula (Vl),

where compounds of the formula

R ₆ -O

J- (OSO ₃ H) ,,

R.J

CX)

O NH-R ₂ - (SO ₃ H) ,,,

4 ", in the

R ₂ . Rj, R5,

m and η which have to formula (VI) and R6 is as defined for formula (VII) and OSO ₃ H to a carbon atom of the radicals R ₄ or R ₅ is ^{bound> 0} to arise.

Compounds obtained in this way are optionally sulfated and / or optionally in any order existing OH groups in the sulfuric acid half esters transferred or with water-containing or optionally SOj-containing sulfuric acid if necessary existing O-acyl or N-acyl groups and / or saponified sulfuric acid half-ester groups

The compounds (VII) can be prepared in the following way: 1,8-Dinitro-anthraquinone is added Amines of the formula

R ₄ "

H ₂ N-CH
\

- (OSO ₃ H) _n

(X)

to compounds of the formula

the formula

R ₁

/
NO ₂ O NII-CH - (- (0-SO ₃ II) ,,

R ₅ !

(XI)

U ₈ -OH

(XIl)

in the

R ₈ -O

R,
NH-CH -L (OSO ₃ H) ,,

(XIII)

wherein

R ₄₁ R ₅
and η

HO ₁ S

wherein

around. In the formulas (X) and (Xl), R ₄ , R5 and η have the meanings given for formula (VI); OSO) H is bonded to a carbon atom of the radicals R ₄ or R ^.

The compounds thus obtained are at elevated temperature with alkali hydroxides, preferably sodium or potassium hydroxide and alcohols of the formula

R _{8 is} an optionally substituted lower one

Represents an alkyl radical,

to compounds of the formula

denotes an optionally substituted lower alkyl radical and

have the meaning given in formula (VI) and OSOjH to a carbon atom of R ₄ and R? is bound, implemented.

The compounds of the formula (VII) are obtained from the compounds of the formula (XIII) thus obtained, by saponifying the alkoxy ORs with aqueous mineral acid!?, preferably aqueous Sulfuric acid, replaced by the hydroxy radical at an elevated temperature, by subsequent treatment with halogen in aqueous mineral acid solution or suspension, e.g. B. in dilute sulfuric acid or in organic solvents, e.g. B. nitrobenzene, halogenated and optionally acylated with acylating agents

One process variant for the preparation of compounds of the formula (VI) consists in this. links

R ₆ R

I /

R ₆ -OO N-CH - (- (OSO ₃ H) ,,
Rs

(XIV)

O shark

R ₄ , R- ,, Rh.

Hal and π have the meaning given in formula (VII)

inrj

OSOjH

to a carbon atom of the radicals R ₄ or R? is bound

exchanging the halogen atom with amines (VIII) implement and, if necessary, sulfate the compounds obtained in this way in any order and / or to convert any OH groups that may be present into the sulfuric acid half-esters or with water-containing ones or optionally SOj-containing sulfuric acid, optionally present O-acyl or N-acyl groups and / or saponify sulfuric acid half-ester groups.

The compounds (XIV) can be prepared by treating compounds of the formula (VII) with S0 ₍ -containing sulfuric acid at, if appropriate, elevated temperature.

Suitable leftovers

R ₄

-CH

\
^{4 (1} R ₅

are for example:

i-propyl, i-butyl, i-pentyl, i-hexyl.
Suitable radicals R ₈ are, for example:

Methyl, ethyl, 0-hydroxyethyl,
18-methoxy-ethyl-, 0-ethoxyethyl-,
j3- (j3'-methoxyethoxy) -ethyl-,
ß- (ß ' ethoxy-ethoxy) -ethyl-,
n- or iso-propyl,
n- or iso-butyl radicals.

Suitable acyl radicals R6 are, for example:

Alkylcarbonyl, like the acetyl radical,

Aroyl radicals such as optionally substituted
Benzoyl residues, alkylsulfonyl residues,
Arylsulfonyl radicals, such as optionally
substituted phenylsulfonyl radicals, where alkyl

preferred Ci-CU-Aiky! means.

Examples of amines of the general formula (VIII) are listed:

aromatic amines, such as aniline,
α- or 0-naphthylamine, o-, m-, p-toluidine,
2,6-dimethylaniline, 2,4,6-trimethylaniline,
2-methyl-6-ethyl-aniline,
2,4-dimethyl-6-ethyl-aniline,

2,6-Diethyi-4-methyl-aniline, p-tert-butylaniline, p-dodecyaniline, p-cyclohexylaniline, o-, m-, p-chloroaniline, m-bromoaniline, p-fluoroaniline, 3-chloro-4-methyl-aniline, m-Amino-benzonitrile, o-, m-, p-anisidine, 3-ethoxy-aniline,

2-, 3- or 4- (j3-Hydroxy) -ethoxy-aniline, 4 - (^ - Cyano) -eih.Gxy aniline, 2-, 3- or 4- (j9-sulfato) -ethoxy-aniline, 3-amino-aniline-2-, 4- or 5-sulfonic acid, 4-methoxy-3-chloro-aniline, 2-methyl-4-methoxy-aniline, 2,5-diethoxy-aniline.

(4-amino) -benzyl-methylamine.

4-aniinobenzdioxane,

4-Amino-phc'iyl - /? - (N, N-diethylamino) ethyl ether.

Aminohydroquinone dimethyl ether, [(o-, m-, p -) - amino] -N, N-dimethyl-benzylamine,

H-Aiiiti'iD-uipnciiylcii'iti ',

(ο-, m-, p-) rhioanisidine,

4-amino- <jiphenylthioether, 3 - (, 9-Hydroxyethyl) sulfonyl aniline, 3-phenylsulfonyl aniline.

(m-, p-) - phenylenediamine, 3- or 4-amino-acetanilide, N-methyl-N-acetyl-p-phenylene-diamine, N-Cyclohexyl-N-acetyl-p-phenylene-diamine, Glycolic acid (3- or -4-amino) anilide, N- (4-A mino) -pheny! Pyrrolidone, Glycolic acid (4-amino) phenylenes.

3-aminobenzenesilfonic acid phenyl ester, Anthranilic acid, 4-acetylamino-anthranilic acid, 3-aminobenzoic acid.

2,3,4-aminobenzoic acid methyl ester, S-amino ^ -methyl-benzoic acid, p-acetylaniline,

S-Amino ^ -methoxy-benzenesulfonic acid diethylamide,

3-aminobenzenesulfonic acid-N- (jS-hydroxy) -ethyl-N - (/? - cyan) -ethylamide, 4-aminobenzenesulfonic acid di - (/? - cyano) -ethylamide, 3-aminobenzenesulfonic acid-di (| 3-hydroxy) -ethylamide and also derivatives of the compounds mentioned containing sulfonic acid groups.

Furthermore, suitable cycloaliphatic amines of the formula (VIII) z. B. named:

Cyclohexylamine, hexahydro-p-phenylenediamine, N-acetyl-hexahydro-p-phenylenediamine, Hexahydro-o-, -m- and -p-toluidine, hexahydroaminophenyl, 2- or 4-benzyl-cyclohexylamine, 4-tert-butylcyclohexylamine, 3-cyancyclohexylaiTiin,

halogenated cyclohexylamines, 2- or 4-nitrobenzylcyclohexylamine.

Suitable aliphatic amines of the formula (VIII) are, for example:

Methylamine, ethylamine, (n-, iso) -propylene, (n-, iso-, sea-, tert-) butylamine, jS-hydroxy-ethylamine, 3-amino-pentane, 3-methoxypropylene, 0-sulfatoethylamine, y- suifatopropyiarr.in.

Examples of araliphatic amines of the formula (VIII) are

Benzylamine, 1-phenyl-2-amino-ethane, 1-phenyl-3-amino-butane,

I-phenyl-2-aminopropane.
l-phenyl-5-methyl-hexylamine- (3),
l-phenyl-3-cyclohexyl-propylamine- (3),
2-phenyl-2-methyl-penty-amine- (4)

and sulfonic acid group derivatives of the compounds mentioned.

The reaction of the compounds of the general formula (VII) with amines of the general formula (VIII) can in organic or aqueous organic medium, optionally in the presence of copper or copper salts as a catalyst and optionally with the addition of acid-binding agents in a manner known per se be performed.

The saponification of the acyl groups, if R _h for Acy. stands, or optionally present sulfuric acid half-ester can with alkaline agents, z. B. with wäßri

A \ ll \ .HMIiyUI UÄIUdl,

uegeiiwai ι

organic solvent, e.g. B. in pyridine / methanol or preferably with acidic agents, preferably with hydrous mineral acids.

The following compounds of the formula (IX) may be mentioned as examples:

l-isopropylamino-e-hydroxy ^ -anilino-

anthraquinone, l-isopropylamino-8-hydroxy-4- (o-,

m-, p-methylanilino) anthraquinone,

l-isopropylamino-8-hydroxy-4- (o-, m-,

p-methoxyanilino) -,

-4- (o-, m-, p-ethoxyanilino) -,

-4- (o-, m-, p-chloroanilino) -,

-4- (o-, m-, p-bromanilino) -,

-4- (m-, p-fluoroanilino) -,

-4- (m-, p-aminoanilino) -,

-4- (o-, m-, p-acetylaminoanilino) -,

-4- (o-, m-, p-propionylaminoanilino) -,

-4- (m-, p-benzoylaminoanilino) -,

-4- (o-, m-, p-N-methylacetylamine-anilino) -,

-4- (m-, p-glycolaminoanilino) -,

-4- (m-, p-butylanilino) -,

-4- (2'.3'-. 2'.4'-. 2.5'-. 2'.6'-dimethylanilinoK

-4- (2 ', 4', 6'-trimethylanilino) -,

-4- (2 ', 6'-diethyl-4'-methy! -Anilino) -,

-4- (o-, m-, p-carboxyanilino) -,

-4- (m-, p-N-methyl-aminoethyl-anilino) -,

-4- (m-, p-aminocarbonylanilino) -,

-4-fo-, m-, p-phenoxyanilino) -,

-4- (m-, p-phenylsulfonylanilino) -,

-4- (p-phenylmercaptoanilino) -,

-4- (o-, m-, p-phenylaminoanilino) -,

-4- (m-, p-phenylanilino) -, -4- (m-cyananilino) -,

-4- (o-, m-, p-methylmercaptoanilino) -,

-4- (m-, p-ethylmercaptoanilino) -,

^^ '- methoxy-S'-methyl-anilinoJ-anthraquinone;

l-isopropy! amino-8-hydroxy-4-beπzy! am! no-,

-4- (j? -Phenylethylamino) -,

-4 - ()> - phenylpropylamino) -,

-4- [4'-phenylbutylamino- (1 ')] -,

-4- 4'-phenylbutylamino- (2 ')] -,

-4-6'-phenyl-2'-methyl-hexylamino- (4 ')] -,

^ -p'-phenyl-S '^ M' -trimethyl-propylamino- (l ')] -,

-4- (1'-piperazinyl-N-Ji-ethylamino) -,

-4- (j3-phenoxyethylamino) -,

-4-cyclohexylamino-anthraquinone;

1 -Isopropylamino-8-hydroxy-4-7 (o-, m-, p-methyl) -, (o-, m-, p-hydroxy) -, (o-, m-, p-amino) -,

(o-, m-, p-acetylamino) -, (o-, p-benzylamino) -,

(m-, p-glycolamino) -, (m-, p-tert-butyl) -cyclohexylamino] -anthraquinone;

l-isopropylamino-8-hydroxy-4- [methylamino-, -ethylamino-, -propylainino-, -butylamino-, -pentylamino-, - / J-nydroxyathvIamino-, -j'-methoxypropylamino-, - ^ - aminoäthylamino-, -y-acetylaminopropylamino-, -pyridyl- (2 ') - or - {4 ') - amino] anthraquinone:

l-isopropylamino-8-hydroxy-4- (aminosulfonylanilino) -anthraquinone,

l-! sopropylamino-8-hydroxy-4 - [(o-, m-, p-methyl-, O-. n.-, p-methoxy-, 2 ', 4', 6'-trimethyl-, 2 '.6-diethyl-4'-methyl-,2'.6'-dimethyl-,4'-butyl-,3'- or 4'-amino-, 3 ^: - or 4'-acetylamino) -phenylaminoj-anthraquinones, which are additionally substituted in the phenyl radical by an aminosulfonyl radical.

Furthermore, the compounds mentioned in the previous section, which are used in place of the aminosulfonyl residue

[Ethyl, propyl, 0-hydroxyethyl, / I-sulfatoethyl, jS-phenylethyl-, y-phenyl-a-methyl-propyl-. y-phenylpropyl-, 0-methoxyethyl-, / S-ethoxyethyl-, 0 - (/ T-hydroxyethoxy) -äthyIaminosulfonyl-] residues wear;

1 -isopropylamino-8-hydroxy-4- [o-, m-, p- (morpholino-, -thiomorpholino-, piperidino-N-sulfonylJ-phenylaminoJ-anthraquinone and the corresponding compounds which are additionally substituted in the phenyl radical by a methyl, methoxy or acetylamino group;

1 -isopropylamino-8-hydroxy-4- [2'- or 4 '- (dimethyl, diethyl, di-ß-hydroxyethyl, / J-phenyläthyl-aminosulfonyl) -phenylamino] -anthraquinone and the corresponding compounds, which are additionally in the phenyl radical in the 3'-position are substituted by methyl, methoxy or amino groups;

1-Isopropylamino-8-hydroxy-4- [4 '(2') - phenyl- or 4 '(2') - phenylamino- or 4 '(2') - phetiylmercapto or 4 '(2') - phenoxy-pheny! Amino ] -anthraquinones, one or two (dimethyl-, ethyl-, / I-Hydroxyälhyl- or ^ -phenylethyl) -aminosulfonylreste in X-, 3'-, (3'-, 4'-) or in one or both phenyl residues Wear 2 ", 3" or 4 "positions;

l-isopropylamino-8-hydroxy-4- [2'-, 3 '* or 4 '- (methoxy- or methyl- or ethoxy- or amino or acetylamino *) or 2 ', 6'-dimethyl- or 2 ', 4 \ 6'-trimethyl or 2', 6'-diethyl-4'-methyl phenylamino] anthraquinone,

whose phenyl radical is replaced by a phthalimidomethyl,

N-hexahydro-2 "-azepinonylmethyl, N-heptahydro * 2 "-azocinonylmethyl-, N-octahydro-2 "-azoninony! Methyl-, N-nonahydro-azecinonylmethyl-, N-2 "-pyrrolidonylmethyl-, Propionylaminomethyl, Benzoylaminomethyl,

o-carboxybenzoylaminomethyl-,

Succinimidomethyl, Carbamoylaminomethyl,

Carbethoxyaminomethyl,

Chloracelylaminomethyl radical is substituted .

Further compounds of this type are those with 1-isobutylamino- (2 ') -, 1-isopentylamino- (2') - or a l- [r-hydroxy-isobutylamino- (2 ') - or - (3')] - group instead of the l-isopropylamino group or the corresponding compounds with an acylated isopropylamino group in the 1-position and / or an acylated hydroxyl group in the 8-position, the acyl radicals being in particular Acetyl, propionyl, benzoyl and p-toluenesulfonyl radicals come into question.

Further compounds are the sulfuric acid half esters from

1 -isopropylamino-8-hydroxy-4- (o-, m-,
p-glycclaminoanilino) -, -4 - /} - hydroxyäthyIamino-, -4-0-hydroxypropylamino-,
-4-ß, y-dihydroxypropyl-amino-,
^ -tu-hydroxyäthylamino- or
^ -co-hydroxypropylamino-sulfonyl-anilino- or -acetamino-anilino-, -anisidino-, -toluidino- or
-rnesidino-anthraquinone.

Further examples of (IX) are the phenyl-containing compounds of the type mentioned, in which the Phenyl radical is also sulfonated.

The sulphonation can be carried out with sulfuric acid, SO ₃ -containing sulfuric acid, chlorosulphonic acid or mixtures thereof at room temperature or elevated temperature, optionally in the presence of boric acid, or inorganic salts such as Na ₂ SO ₄ .

Represents in formula (IX)

-CH \

R ₅

M -ΜΜηηαέ * ^. '

a radical which cannot be sulphurized, but R2 is an easily sulphurable radical and if n + m = 0, then generally only this radical is sulphated under mild sulphonation conditions, only under more severe sulphonation conditions In addition, a sulphonic acid group occurs in the o-position to the OR ₆ group. If Rj is a residue that is difficult to sulfate, e.g. If, for example, the methylsulfonylphenyl group is present, a sulfonic acid group occurs first in the o-position to the OR ₆ group in the nucleus one, and only under very severe reaction conditions, if necessary, a further sulfonic acid group in the radical R ₂ . Finally, if R _{2 is} an alkyl or cycloalkyl radical, that is to say a group which cannot be sulphurized, then only one sulphonic acid group occurs in the o-position

core ORe group. Contain the leftovers

-CH "\

or R ₂ hydroxyl groups, so that, for. If, for example, a 3-hydroxyethyl group is present, esterification with H ₂ SO ₄ can optionally also take place. Provides

-CH

a sulphurizable residue

030 267/77

be sulfated in addition or as an easily sulfonatable residue. If the leftovers

/ -CH

and / or Ri is another primary or secondary Contain amine group, the compounds of the formula (IX) obtained according to the process can be post-acylated. Acylating agents are used for this i.a. Consideration: benzoyl chlorides substituted by lower alkyl, lower alkoxy or halogen groups, Sulphochlorides, such as methyl, p-toluene, benzene or «-naphthylsulphochloride, and also phenyl or alkyl chloroformate. Receives in the last two cases one urethane, which by further reaction with lower aliphatic amines, such as oxethylamine or 3-methoxypropylamine, converted into urea derivatives can be. The sulfonation of the compounds obtained in this way can be carried out by methods known per se take place. By optionally partial conversion of the sulfonic acids obtained in 'sulfochlorides, eg. B. by means of thionyl chloride, and subsequent reaction with lower, optionally substituted aliphatic amines, such as / Ϊ-hydroxyethylamine, diethanolamine, 3-methoxypropylamine and, if necessary, subsequent sulfonation of the products obtained in this way can be used win dyes of the formula (VI) which contain sulfonamide groups.

Another method of making dyes of the formula

R /

HO O NH-CH

Y I Il I \

^ (OSO ₃ H) _n

R ₅

R ₂ - (SO ₃ H) ,,

(XV)

in the

Rj. R4, R ?,

Y. π and m have the meaning given for formula (VI), and

OSG) H is bonded to a carbon atom of the radicals R4 and R5,

is characterized in that one compounds of the formula

wherein

R), Rs, Y and π have the meaning given for formula (XV), the

5 OSOjH group is bonded to a carbon atom of R ₁ or R ₅ and

Hai for halogen and R _{6 represents} H or acyl;

converting the halogen atoms with amines of the formula (VIII) to give compounds of the formula

(OSO ₃ H) _n

(XVII)

O NH-R ₂ - (SO ₃ H) _1n

in the

R ₂ , R4, Rs, Y and π

have the meaning given for formula (XVI) and m stands for a number from 0 to 3

and the compounds thus obtained are optionally sulfated in any order and / or any OH groups present are converted into the sulfuric acid half-esters or O-acyl or N-acyl groups and / or O-acyl or N-acyl groups that may be present with hydrous or optionally SOr-containing sulfuric acid and / or saponified sulfuric acid half-ester groups.

The compounds of the formula (XVI) are obtained analogously to the above-described preparation of the compounds (VII) via compounds of the formula (XIfI), by saponifying the alkoxy radical O — Rg with aqueous mineral acids replaced by the hydroxy radical, halogenated by subsequent treatment with halogen and optionally in any order with Acylating agents acylated and / or in the o-position next to the (acylated) OH group cylfiert.

The dyes according to the invention are valuable products which are particularly suitable for dyeing and printing natural and synthetic polyamide fiber materials, such as wool, silk and synthetic polyamide fibers, on which dyeings are very good Fastness properties are achievedi.

Surprisingly, the dyes according to the invention have the formulas

OH O N-CH

(OSO ₁ H) ,,

(XVI)

O shark

HO O NH- GHiCHih

O NH-CH-CH ₂ -CH ₂ ^ f> -SO ₃ H CH,

example 1

HO O NH-CH (CHj) ₃

O NH

OCH ₂ CH ₂ -OSO ₃ H

IO

compared to the closest comparable dyes from DE-OS 19 32 647 improved water solubility on.

Surprisingly, the dye according to the invention shows the formula

15th

HO ₃ S

OH O NH-CH (CH ₃ ),

SO ₃ H

20th

25th

OCH ₃

compared to that known from DE-OS? 9 32 647 next comparable dye higher water drop fastness of dyeing on wool.

Surprisingly, the dye according to the invention shows the formula

g of isopropylamino ^ -bromo-e-hydroxy-anthraquinone, 40 g of o - (/ I-hydroxy) -ethoxy-anuine, 3.5 g of potassium acetate and 0.05 g of Cu ₂ Cli are kept at 100-110 ° for 2-3 hours The melt is diluted with 40 ml of ethylene glycol monomethyl ether, filtered off with suction while cold, washed with glycol monomethyl ether and water. The 1-isopropyl-amino-4- [o - (/? - hydroxy) ethoxy] -aniIino-8-hydroxy-anthraquinone obtained can be converted into the sulfuric acid half-ester and / or sulfated as follows

Λ) 25 g are dissolved in 15OmI 93% sulfuric acid Stirred at room temperature until only traces are left in a chromatographed sample Input material is verifiable (approx. 30 Mir., Required). The melt is stirred into half-concentrated cold saline solution, suctioned off, with ! 0-5% saline solution washed neutral and dried. The dye obtained is the sodium salt of the compound

CH ₃

CH ₃

30th

HO ₃ S

OH O NH-CH (CHj) ₂

O NH

40

45

compared to the next comparable dye known from DE-OS 19 32 647 higher authenticity of the Dyeings on polyamide during mechanical washing at 60 ° C.

Surprisingly, the dye according to the invention has the formula

HO O NH-CH (CH ₃ ) J.

55

O NU -CHi-CHj

SO ₃ H

compared to the next comparable dye known from DE-OS 19 32 647 a better structure hi ability on polyamide.

The temperatures given in the examples are degrees Celsius.

CH ₂ -Ci-J ₂ -OSO ₃ H

represents and dyes wool and synthetic polyamide fibers in clear greenish blue tones.
B) 23 g are stirred in 20 ml of 96% strength sulfuric acid and 16 ml of anhydrous sulfuric acid for 7 hours at room temperature. The melt, which only contains traces of the product obtained according to A), is poured into a mixture of 270 ml of saturated sodium chloride solution and 60 g of ice, filtered off with suction and washed neutral with saturated sodium chloride solution. The product, which is present in small blue needles, is dried at 60 ° in vacuo. The dye obtained is an Na salt of the compound

CH ₃

OH O

CH ₃

SO ₃ H

O-CH ₂ -CHj-OSO., H.

and dyes the wool in a clear greenish blue tone.

C) 6.5 g of the product obtained according to B are concentrated in 65 ml. Hydrochloric acid heated to 95-100 °, after Starting material is no longer detectable for about 20 minutes. Dilute slowly with water to 10 per cent. hydrochloric acid, it sucks in large needles deposited product and washes it neutral with dilute sodium chloride solution. The received Dye of the formula

CH ₃

OH O

SO ₃ H

0-CH ₂ -CH ₂ -OH

CH ₃

OH O

OCH,

and is isolated as follows: One carries to 200 ml half-saturated ^ Saline solution, sucks off the precipitate, washes it with 5% saline solution and neutral dries in vacuum. Wool is dyed lightfast in a strong greenish blue tone.

in

dyes polyamide fibers according to the instructions given in Example 2 in clear blue-green shades very real.

Example 2

15 g of i-isopropylamino ^ -bromo-e-hydroxy-anthraquinone, 70 g p-anisidine and 3.2 g ground. Soda is stirred at 175-180 ° until there is no feedstock more is detectable (approx. 1 hour required). It is diluted with 70 ml of alcohol, filtered off with suction and washed one after the other with alcohol and hot water. The 1 -isopropylamino ^ -p-anisidino-e-hydroxyanthraquinone obtained can be sulfated as follows:

A) Monosulfation

3 g are in a mixture of 17 ml of monohydrate and 1 ml of 20% oleum for so long at room temperature stirred until no more feed material can be detected (approx. 45 minutes required). The uniform sulfonation product corresponds to the formula

50

55

B) disulfurization

3 g become anhydrous in a mixture of 17 ml Sulfuric acid and 7 ml of 20% oleum treated at room temperature until only traces of that according to A) obtained sulphonation product can be detected (approx. 2-3 hours required). One applies 200 ml of saturated saline solution, siphoned off, washed with a little 20% saline solution, dough the filter material in a little water, neutralized with soda and dried the paste in a vacuum. The dye obtained is uniform and represents the Na salt of the connection.

15th

2ü CH,

OH O

HO ₃ S

25th

OCH ₃

It dyes wool in accordance with the dyeing methods given in Example 2 in blue-green tones.

30th

Example 3

30 g of l-isopropylamino-'t-bromo-e-hydroxy-anthraquinone-7-sulfonic acid Sodium, 150 g of p-anisidine, 12 g of potassium acetate are added to 0.15 g while stirring at 100 ° Copper-I-chloride added and so long at 115—! 20 ° stirred until only a small amount of input material can be detected in a sample that has been removed and chromatographed (approx. 1 - 1 '/ 2 hours required).

The melt is poured into an ice-cold mixture of 1500 ml of 15% saline solution and 200 ml of conc. Hydrochloric acid, sucks off the precipitate, washes with half-concentrated saline solution, which initially contains a little hydrochloric acid was added, neutral and presses off sharply.

The suction filter is suspended in 800 ml of water and adjusted to pH 8 by adding a little sodium hydroxide solution and heated to 90-95 °. The resulting solution is clarified with the addition of charcoal. When it cools down, it separates the dye gradually disappears in the form of beautiful blue-green needles. One now gives so much concentrated cautiously Saline solution so that the spout is only slightly blue-green in color, sucks off, washes with it 5% saline solution neutral and dries. 27.8 g of the compound are obtained in pure form formula

CH ₃

b0 OH O

65

OCH ₃

Example 4

4.6 g! -Isopropylamino ^ -brorn-S-hydroxy-anihrach! Sodium non-6-sulfonic acid and 4.6 g of ni-phenylenediamine-4-sulfonic acid sodium are stirred in a mixture of 40 parts of water and 15 parts of ethanol at 85.87. To this mixture, 1.2 g of soda and a solution of 0.05 g of copper-1-chloride in 0.5 ml of saturated sodium chloride solution are now added and the mixture is stirred at the same temperature with the addition of a solution of 0.05 g of copper-1-chloride in 0.5 ml in portions saturated saline solution until chromatographically no progress in the I ^; MseI is invalid and recognize more / / Filter and wash the remaining Rückstanc 3 "to / niger saline. The filtrate (about 80 ml mixed it with"> g solid sodium chloride, filtered and translated the F'iltrat so much solid sodium chloride admit that just a small amount of common salt remains, leave to stand in the hot bath for several hours, filter, wash the blue product with saturated sodium chloride solution and dry at 60 ". This gives the compound, which is easily soluble with a clear greenish blue color the formula

CM,

O N H - C H

CII.

no, s

It dyes wool and polyamide in clear greenish blue tones.

From 1-alkylamino-4-bromo-8-hydroxy-anthraquinone or 1-alkylamino ^ -bromo-S-hvdroxv-anthraquinone-S O. It

7-sulfonic acids are obtained by reaction with amines or sulfated amines as shown in the table below Listed dyes of the general formula he keep.

Tabel

Dyes of the formula

Y O NH-R

Y ₁ O NH-X

R,

R. CHj
/ X /
CH
CH ₃ the same - the same - the same - CHj
CH
CH ₂ -CHj - CH ₂ -CH ₃
CH
\
CH ₂ -CH ₃ - CH ₃
/ - /
CH
CH ₃

Y Y, Z

OH H H

OH H H

OH H H

Z, R-

H CH ₃ (4)

OH H H H CH ₃ (3) OH H H H OCH ₃ (2) OH H H H OCH ₃ O) OH H SO, H H OCH, (4)

H OC ₂ H ₅ (4)

H Cl (4)

R.,

R ,, Kirbtun on

SO ₃ H greenish blue - ^{n / a}

H SO j H SO 3 H greenish blue OO H H SO 3 H Blue green N) H SO 3 H SO 3 H Blue green

SOjH blue-green

SO ₃ H blue-green

SO ₁ HH greenish blue

continuation Y Y, Z Z, R. R, R., Rlu Shade on wool K) oc R X OH H SO ₃ H H Cl (4) H SO ₃ H H Blue green 50 482 CH ₃
CH -
CH,
the same - OH H H H NH ₂ (4) H H SO ₃ H blue the same - OH H SO ₃ H H NH ₂ (4) H H SO ₃ H greenish blue the same - OH H H H NH- CH ₁ (4) H H SO ₃ H greenish blue the same - OH H H H NH-CO-CHj (4) H H SOjH Blue green the same - OH H SO ₃ H H NH-CO - CH, (4) H H SO ₁ H bluish green the same - OH H H H CHj (4) H H SO ₁ H greenish blue the same - OH H SO ₃ H H (
1" H H SOjH strong
greenish blue the same - OH H H H > J-CO-CH ₃
: h ₃ (4)
J-CO-CH ₃ H SO ₃ H SO ₃ H greenish blue CHj (3) the same - OH H H H N —CO —CHj H SO ₃ H H greenish blue the same - OH H SO ₃ H H H H H SO ₃ H Blue green the same - OH H H H H CH ₃ (4) CH ₃ (O) SO ₃ H clear blue the same - OH H SO ₃ H H CH ₃ (2) CH ₃ (4) CH ₃ (6) SO ₃ H greenish blue CHj CH ₃ (2) CH - OH H H H H CH ₃ (6) SOjH clear blue CH ₂ -CH ₃ CH ₃ (2) the same - OH H H H H H SO ₁ H greenish blue the same - OH H SO ₃ H H Br (3) H H SO ₁ H Blue green Br (3)

continuation

CH ₃ CH

CH ₃

the same

like. like. like. like. like. like.

CH ₂ -OH

CH ₂ -CH ₃

OH H H

OH H H

NH-CO-CH ₂ -OHO)

SO ₃ H NH

(4)

R ₁₁ Rirblon; iul 'WoIl

SO ₃ H blue-green

SO ₃ H blue-green

OH H H H OH H H H OH H H H OH H SO ₃ H H OH H SO ₃ H H OH H H H OH H H

OH H H

CO-CH ₂ -OH

NH-CO —CH ₂ -CSO, H (4)

NH-CO —CH ₂ -0SO, H (4)

CH, (2)

COOH (4)

CO- NH, (4)

O - CH ₂ -CH ₂ -OH (4)

0-CH ₂ -CH ₂ -OSO ₃ H (4)

NH-CO-CHj (4)

H H

HH NH ₂ O) H

H H

H H

H H

H H

H Blue green cn SO ₅ H Blue green SO ₁ H greenish blue 00 H greenish blue K) H greenish blue SO ₁ H Blue green SO ₁ H greenish blue

SO ₃ H blue-green

CH -
CH ₂ -CH ₃ OH H H H NH- CO- CHj (4) H H SO ₃ H Blue-green uj
0 CH ₃
CH - \
CH ₃
the same - OH H SO ₃ H H H H H H greenish blue OH H SO ₁ H H CHjO) H H H strong
greenish blue

ι continuation Y Yl Z Z, - SOjH R * K " K ₁₁₁ Kiirhton iiul 'Wolk J ro ro R X - ° - ^< w ^> CH, OH H SOjH H R ₁ S-CH ₃ (4) H H H strong
greenish blue O CH -
CH, OH H SOjH H FO) H H 11th strong
greenish blue 482 the same - OH H SOjH H CH ₃ (4) —S —- / "" V-CHj H H H Green Blue the same - H OH SOjH H CH ₃
- C —CH ₃ (4)
CHj SOjH H H H Green Blue the same - OH H SOjH H OCHj (2) -O H H II bluish green the same - OH H SOjH H OCHjO) CNO) H H II bluish green the same - OH H SO ₃ H H NH-CO-CHj (4) H H H greenish bluu the same - OH H SOjH H N - CO- CH ₃ (4)
I. CH ₃ (4) CH ₃ (O) H greenish bluu the same - I.
CHj
NH ₂ O) OH H H H CH ₃ (2) H H SO ₁ H greenish blue the same - OH H H H H SOjH H greenish blue the same - OH H SOjH H H H SO ₃ H Bluu the same - OH H SOjH H H H SO ₃ H greenish bluu the same - OH H SOjH H H SO ₃ H H Bluegreen § the same -
K) OH H SOjH H H H H greenish blue S.
3 the same -

CH., CH
\ X Y V ₁ Z No. ₁ R, Rb R, R ₁₁ , Coloring on wool Ul
ui NJ
1-* Ul continuation \
CH, Oi
O R. CH ₃ - OH H H H OSO ₃ H (3) H H H greenish blue OO -CH NJ CH, the same - OH H H H - SO ₂ - 0— <\ /> H H SO ₃ H Blue green the same the same - OH H H H SO ₃ H H SO ₃ H H greenish blue the same - OH H H H -CH ₂ -SO ₃ H H H H greenish blue the same - CH ₂ -CH ₂ - OH H H H H H SO ₃ H H blue -CH ₂ -CH ₂ - OH H SO ₃ H H CHj (4) H H SO ₃ H greenish blue the same - CH- CH:
I. OH H H H H H H SO ₃ H blue CH ₃ CH ₃ - the same -CH-CH ₃ -CH ₂ -
I. OH H H H H H SO ₃ H H blue CH ₂ -CH-CH ₃
\
CH ₃ -CH-CH ₂ -CH ₂
ό OH H SO ₃ H H H H PO ₃ H H greenish blue

PQ W. m CQ op X ω OO 2 O 2 2 U U ο * -ί3 X '^ * -r3 E / l O Vi CA B. V) C. C. ^: Ξ ^: S. : 3 OO OO 00 X O X V) X X δ δ V) V)

Example 5

18 g of l-isopropylamino ^ -bromo-e-hydroxy-anthraquinone, 36 ml of cyclohexylamine, 6.5 g of potassium acetate, catalytic amounts of copper-1-chloride are used for so long 80-SO "stirred until there was only a little bit of material left is detectable It is now diluted with 36 g of methanol, the precipitated reaction product is sucked at 60 °, washed with boiling hot methanol and finally stirred with dilute hydrochloric acid

The l-isopropylamino-4-cyclohexylamino-8-hydroxy-anthraquinone thus obtained is sulfated as follows:
3 g are dissolved in a mixture of 7 ml of 96% sulfuric acid and 10 ml of 20% oleum and stirred for 15 hours at room temperature. Then another 2 ml of 20% oleum are added over 5 hours at room temperature ° and holds at this temperature until only a trace of the base can be detected by chromatography. 30 g of a mixture of equal parts of ice and water are added, the temperature rises to about 60 °. So much ice and water are now added that an acid concentration of 37-39% is reached. The mixture is stirred for some time, the precipitated dye is filtered off at 30 °, washed with 30% H ₂ SO ₄ , then with 15-20% sodium chloride solution until it runs neutral and dried
The dye conforms to the formula

X X
U U X X X SO ₃ H SO ₃ H X X X X X
O X
O X
O

CH ₃

HO ₃ S

/
OH O NH-CH

CH ₃

O NH

and dyes natural and synthetic polyamide fibers vigorously according to the instructions given in Example 2 and really in bright blue tones.

Dyes of the general formula are obtained from 1-alkylamino-4-bromo- (8) -hydroxy-anthraquinone or their 7-sulfonic acids

X υ χ / OO t / 5 υ υ υ
X) • S

NH-R

X, O NH-R ₁₁

or their Na salts.

Tabel

2ί 50 38

Y, R Hue of the wool dye

OH

OH

OH

OH

OH

OH

SO ₃ H

SO ₃ H

SO ₃ H

SO ₃ H

SO ₃ H

CH \

CH ₃ CH ₃

blue

CH

CH ₃ CH ₃ -OH

CH \

CH \

CH ₂ -CH ₃ CH ₂ -OSO ₃ H

^ CH ₂ -CH ₃ CH ₂ -OSO ₃ H blue

blue

CH \

CH ₂ -CH ₃ CH ₃

CH \

CH ₃ CH ₃ NH ₂

sth. rotst. blue

blue

NH-CO-CH ₃ blue

CH ₃

Example 6

10 g of l-isopropylamino - ^ - bromo-e-hydroxy-anthrachi- so non, 50 g isobutylamine, 0.1 g each of copper-1-chloride and basic copper sulphate are refluxed (approx. 70 °) until only a small amount of feedstock is left is verifiable (approx. 2 hours required). It is diluted with 50 ml of methanol, the needle-like suction separation in the cold, washes them with methanol and hot water. You can also suction directly without prior dilution with methanol. The thus obtained l-Isopropylamino-8-hydroxy-4-isobutylamino-anthraquinone is sulfated as follows:

10 g are so long in 10% oleum at 25-30 ° Stirred until only traces of input material can be detected. It is poured onto half-concentrated saline solution, the precipitate is filtered off and washed with it Saline solution neutral. To remove some of the red by-product formed in the sulphonation, falls the sulfonic acid is converted as the sodium salt in the pH range 9-10 from hot water by adding saline solution. The dye conforms to the formula

HOjS

CH ₃

CH ₃

NH-CH ₂ -CH \

CH ₃

CH ₃

and dyes polyamide fibers in clear blue tones.

In the same way, from 1-alkylamino-4-bromo- (8) -hydr (> xy-anthr; ichim> n "der their 7-silfonic acid derivatives the dyes of the general formula

XO NH-R ₁

Tabel
X \ Y

X ₁ O NH-U ₁

l - '. irhtnn iler \\ Ί> ΙΙΙί "ι! Ϊ́ιιηΐ!

CII,

SO, H

Steal

Il SO ₃ H H CH, CH, CjH, Bhiu OH Il SOjH H the same - CJI ,, (n) blue OH II SOjH H the same CHj CH ₂ -CH ₃ -OSOjH blue OH Il SOjH H the same (CH,), - OCH, blue OH H SOjH II the same CH ₂ -CH ₂ -NH ₂ ßlau OH H SOjH H the same -CH ₂ -CH ₂ -NH-CO- -CH, blue OH the same CH,
/ H SO ₃ H H CH ₂ -
/ /
CH
\ blue OH /
CH
\ \
CH ₃ \
CH ₂ -

Example 7

10g l-isopropylamino ^ -ni-amino-anilino-e-hydroxyanthraquinone. obtained from l-isopropylamino-4-bromo- S-IivuiuA jr-diiuiiduiiiiuii um in - FHeHy ieniiia in ι π analogous example 1. but at a reaction temperature of 140-145 '. 5 ml of acetic anhydride are added in 30 ml of pyridine at 55-60 ". After a short time the free amino group is acetylated. It is diluted at 50 ⁼ with 40 ml of methanol, and the 1-isopropylamino-4-m-acetamino-anilino- 8-hydroxy-anthraquinone, washes it with methanol and water and dries.

A) Monculfation

3 g are dissolved in 17 ml of anhydrous sulfuric acid and 2 ml of 20% oleum for 1 hour at room temperature stirred. After the usual work-up, a dye of the formula is obtained

CHj

OH O NH-CH

CH ₃
NH-CO-CH ₃

B) disulfurization

If one takes place under the same conditions as in A) 2 ml now 5 ml 20% oleum to. in this way, after 5 hours of work-up at room temperature, uiiii uiiuiiei a mixture of different disulfonic acids. dyes the wool in a blue-green tone.

SO ₃ H

obtained that dyes wool in a real blue-green tone.

C) trisulfation

If, under the same conditions as in A), 10 ml of 20% oleum are now added instead of 2 ml. so after 4 Hours at room temperature and the usual work-up, a chromatographically almost uniform appearance trisulfated product, the wool has a much greener tinge colors as the dyes obtained according to A and B.

Example 8

A) 30 g of 2-aminopyridine, 103 g of 1-isopropylamino-4-bromo-8-hydroxy-anthraquinone. 3.8 g of potassium acetate and 0.1 g of copper (I) chloride are so long with Stirred 125-130 ° until only traces of input material can be detected in a sample (approx Hours required).

It is now diluted with 50 ml of methanol and suctioned 70 °, washed with hot methanol and hot water and dried. 43 g of one are obtained

Product of the formula

OH

(II,

CH,

H) 2.7 fj of the product obtained according to A) are in 17 ml of sulfuric acid monohydrate dissolved, little by little

ϋ:! ί '! ι ü !!! !! ! i ;! Oleüüi 20%! "At 20 25 verses !: ^7. !

and stir until there is less than i "/ o used material (approx. 5 hours necessary). You work up in cold, half-con / entrapped saline solution as usual. Of the nculrule Niitschkuchen is in 150 ml of water, the some pyridine / ugcset / t was dissolved, and cleared by filtration.

The ritrat becomes the color of the formula

CfI ₃

IK) O NU-CH

no, s I Il I \

CH ₃

precipitated by adding 10 ml of saturated saline solution, suctioned off in the cold, with 5% saline solution washed and dried. 2.1g are obtained.

Wool and linear polyamide are tinged with green following the procedure described in Example 2 colored blue tones.

Example 9

A) 10 g of i-isopropylamino-'t-o-anisidino-e-hydroxy-anihraquinone are introduced into 80 ml of chlorosulfonic acid at 0-10 °, after 20 minutes it is chromatographically no more input material detectable. This solution is added dropwise to 800 ml below 20 ° ice-cold semi-concentrated saline solution. The resulting precipitate is sucked off with cold Washed neutral sodium chloride solution, washed anhydrous with methanol or acetone and dried. The product is gradually stirred into 50 ml of methylamine solution and then so Stirred for a long time at 50-55 ° until no progress of Sullamia formation according to chromatography can be seen more. After a similar work-up

as described in Example 27A, 11.4 g are obtained a compound that corresponds to the formula !:

CH,

OH O Nil-CH

CH,

O HN

H ₁ CO

X> ^süi

- NU —CH.,

B) 5 g of the product obtained according to A) are dissolved in 27 ml of J'Voigem oleum below 20 ", this 2 ml of 20% oleum are added to the solution and the mixture is stirred until there is no starting material according to chromatography more is detectable (approx. 2 hours required). It is poured into 15% strength while stirring cold saline solution, sucks off the resulting precipitate. washes with dilute saline solution neutral and dries. 6.9 g of a saline product of the formula are obtained

OH O

HO ₃ S

CH ₃

CH ₃

T -JfSO ₂ -NH-CH ₃

/ S /

H-.CO

This dye dyes wool and polyamide fibers in ίο real, green-blue tones.

In one of the ways described above, from 1-alkylamino- (8) -hydroxy-anthraquinone by sulfochlorination, the dyes of the general formula listed in the table below

YO NH-R ₁

Y, O NH-X -

or their alkali salts are obtained.

43

s ε

■ ζ - ■

OQ

XU X

X O

X X

I U

.X U

44

3 3 lukewarm 3 3 lukewarm rün lukewarm C. C. rün 73 03 J2 SQ 03 O 03 : 3 : 3 O 03 5 03 äö 50 ί / 1 ■ j \ 3 3
73 '.Λ tst C.
: 3 tst C.
: 3 UU: C.
: 3 E. 03 3
_73 O ο SO ε so X) SO JO

X X

X X

(O X)

co

χ u

XO

OO

XXX

XXX

X O XX
OO

X
O

NH

SO

OCH

SO

X Z

SO,

X O

υ ο

X X S. d I. d X I. ό O O d OO 6th O in CO CO CO CO

^ x, υ

so X cn υ BO a cn -α -a

χ QO
cn X X \ χ / U Τ3 O U U

as ο

X X U U O O

X U O

X X O O

X O

Example 10

Λ) In 50 ml of 93% sulfuric acid you add 10 " 4.85 g of N-methylolcaprolactam and stir long after, until a clear solution has formed; 12.05 g of l-isopropylamino ^ -o-anisidino-e-hydroxy-anthraquinone are carried into this solution at 15-20 ° and stir at room temperature for so long. until in a chromatographed sample less than 3% input material can be detected (approx. 2-3 hours required). One pours in Ice water, filter the resulting precipitate, wash it neutral and dry. Obtain becomes a compound of the formula

CII,

H ₃ CO

The product is quite pure, with small amounts of salting material, a biscondensation product and sulphurized base (together 5 - 7%) can, for example, by dissolving from pyridine getting cleaned.

B) 4 g of the product obtained according to A) are dissolved in 20 ml of sulfuric acid monohydrate, with 2 m! 2% oleum is added and the mixture is stirred at 20-30 ° until only traces of the feed material are left available. The solution is stirred on 300 g of a mixture of saturated sodium chloride solution / ice 2: 1, sucks off the precipitated product, washes it with 5% saline solution

neutral and dries. The product obtained is a monosulfonic acid derivative of the compound obtained in A) and dyes wool and fibers made of linear polyamide with excellent wet-fastness in green-blue Tones.

Following the procedure described in Example 10, one can. starting from connections of the j) Formula A, by reaction with the corresponding N-methylol lactams or N-methylol dicarbonamides and subsequent sulfonation compounds of the formula B are obtained.

Tabel

γ o nh: —R »

Y ₁ O HN

R.

R, R ₈

OCH ₃ (4) H

H CH \

CH ₃

CH ₃

CH ₃ (2) CH ₃ (O)

H CH \

CH ₃

CHj

Y ₂ 0 NH-R,

- (SOjH).

CHj-R ₇

YY ₁ R ₄

OH H OCHj (4) H

H -N

OH H CH ₃ (2) CH ₃ (O) H -N

CH ₃ (2) CjH, (6) H

-CH

CHj-OH

OH H CH ₃ (2) C ₂ H ₅ (6) H -N

CH ₂ -CH ₃

R, Y ₁ Y, X coloring
Wool IO OD CH ₃
CH
CH ₃ cn
O CH ₃
CH
\ OH H 1 Green Blue OO
ro CH ₃ CH ₂ -OSO ₃ H
-CH
CH ₂ -CH ₃ OH H 1 Green Blue OH H 1 Green Blue

continuation

A. Ri R $ Y Y ₁ B. Rs R (j R7 R, Y ₂ Y ₃ X coloring R | R ₂ R. Wool

OCH, (2) H.

H CH
\

CH ₃

OH H OCH ₃ (2) H

CH ₃

CHj

OCH ₃ (4) H H CH
CH ₃ OCH ₃ (2) H H CH ₃
CH
CH ₂ -CH ₃ CH ₃
CH
CH ₃ OCH ₃ (4) H H CHj
-CH
\ OCH ₃ (4) H H

H —Ν

/ ^c \

OH H OCH ₃ (4) HH -N (CHj) ₆

OH H OCH ₃ (2) HH -NH-COCH ₃ OH H OCH ₃ (4) HH -NH-CO

—NH - CCt - P \

CH \

CH \

CH

CH \

CH ₃

^ CH ₃ CH ₃

^ CH ₃ CH ₃

^ CH ₂ -CH ₃ CH ₃

OH H 1 green blue

OH H 1 green blue Ü1

OH H 1 green blue

OH H 1 green blue

OH H OCH ₃ (4) HH -NH-CO-CH ₂ Cl

CH ₃ CH ₃ CH ₃

-CH OH H 1 green blue

CH ₃

Claims (6)

Claims: I. Anthraquinone dyes in the acid form of the formula O NH-R ₂ - (SO ₃ H) _n , - (OSO ₃ H) ,, correspond in the π and m stand for the numbers 0-3, Y is hydrogen or SO ₃ H, if n + miO, or for SO ₃ H, if π + m = O, where the radical -OSO ₃ H is bonded to a carbon atom of the radicals R ?, Ra or R5, R _{2 represents} an optionally substituted one Alky! -, cycloalkyl, aralkyl, aryl or heterocyclic radicals in the field of the acidic anthraquinone dyes usual type and R4 and Rs represent optionally substituted Ci - C ₃ alkyl, where R ₅ 2. Anthraquinone dyes, which are in the acid form of the formula R4 O NH correspond in the m and ρ stand for the numbers from 0-3, R ₄ and FMUr optionally substituted Ci-C ₁ - Alkyl, Y represents hydrogen or SO ₃ H, where for Y = hydrogen at least one of the radicals R4, R; or Z is a group -A-SO) H contain or represent got to, - (A - SO ₃ H) _1n Z represents hydrogen or a substituent of the type customary in the field of t .uric anthraquinone dyes, A is a direct bond or - O - represents, where - A — SO3H must be bonded to a carbon atom of the radicals R ₄ , Rs or Z or represents a Z substituent. 3. Anthraquinone dyes, which are in the acid form of the formula CH O NH-Q- - SO ₃ H) _n , correspond in the m and ρ stand for the numbers 0-3, R) and Rs represent optionally substituted Ci-C ₃ -alkyl, Y represents hydrogen or SO ₃ H, where for Y = hydrogen at least one of the radicals R * Rs and Z must contain or represent _{a group -A-SO 3 H,} Q is Ci-C7-alkylene. 10 Z is hydrogen or a substituent of on the subject of the acidic anthraquinone dyes common type, A for a direct tie or - O- stands, where the radical -A-SO ₃ H is bonded to a carbon atom of the radicals R ₄ , R5 or Z, or represents the radical Z. 4. Anthraquinone dyes, which are in the acid form of the formula O NH - - (A-SO ₃ H) _n , correspond in the ρ stands for the numbers 0-3, m stands for the numbers 0-2, Z is hydrogen or a substituent of is the usual type in the field of acidic anthraquinone dyes, Y represents hydrogen or SO ₃ H, where for Y = hydrogen at least one of the radicals R ₄ , Rs and Z is a group 30th 35 -A-SO ₃ H contain or represent got to, A for a direct tie or —O— stands, where —A — SO ₃ H on a carbon atom the radicals R ₄ , Rs or Z be bonded must or Z represents, R * and Rs for optionally substituted Ci-C ₃ - Alkyl stand. 5. Anthraquinone dyes, which are in the acid form of the formula O NH-B - (A-S0 ₃ H) _w correspond in the m stands for the numbers 0-3, B represents Ci-C ₇ -alkyl, however ^ CH-R ₄ R ₅ is. A for a direct tie or —O— stands, where -A-SO ₃ H is bonded to a carbon atom of the radicals FU, Rs or B, R ₄ and Rs stand for optionally substituted Ci-C ₃ -alkyl, MY stands for hydrogen or SO ₃ H, if ΠΊΦ0 or for SO ₃ H, if m = 0. 6. Use of the dyestuffs according to Claims 1-5 for dyeing and printing natural and synthetic polyamide fiber materials.