DE1917051A1 - Anthraquinone compounds - Google Patents

Description

Pafenfanwälfe

Dr. W. Schalk, Dipl.-Jng. P. Wirtb Dipl.-Inn. G. Darnenberg Dr. V. Sc'imi-d K-,., V-rzik

Dr. P. Woinh'Jj. , ·. · .. .0. GuJeI .i.iHEiii ^: ^Gl '· «-h; - ..' ie.tner Str. 39

S A N D O SS Basel / Sobw # ls

Case 2868

Anthra.chinonverOindu: i.7en

The investigation concerns new anthraquinone compounds, the production of which is carried out and their use. These anthraquinone compounds correspond to the formula

-H ³

\ - f-CH ^

.-. ιοί · in ... one of the remains

009822/1291 sad

19170

NH,

O MH-R.

(IT) or HO ₃ S

one H ₃ one hydrogen -

ass other R ₁ a lämzs ^ simi or teslde R, Cfaloratorae »

or -

-Aikylen-CO-N

* "\ A '-R ₉ -O-SO ₃ H

S0_H

- ^R io- ⁷ "

Ri. Secondary aliyl with 3 to 6 carbon atoms- cyclohexyl or 3,5,5-trimethyleyclohe ^ rl ^ or ~ \ /

I _n hydrogen, alkyl or alkoxy with 1 to 9 carbon atoms or halogen,

6— ViI ₀ , - 1 »η _Λ -,» «» ΐ, -, - υπΛ-ν / ί.Λ- ,, -ViI ₀ -OJi-, -Vn- ^ n ₀ -, —V / Jv » —On, —vjU _o · dd ti ddd χ \ dd \ d

CH-CH OH

R ₇ V hydrogen or lower alkyl,

Ro is hydrogen, lower r-alkyl or alkoxy, halogen or

low acylamino,
R -CHp-CzI ₀ -, -CiI ₀ -CK ₀ -CfI ₀ -, -CK ₀ -CK-, -CH ₀ -CH-CHp-, -CK-

OH

or -CK- (CH ₂ ) _r ,
CrL.

CK-. CH .. t P t j>

R._ -CK ₀ -, -CK-CH ₀ -C-, -CH-CH ₀ -CH ₀ - or

CH CH

R, - hydrogen or alkyl with 1 to 8 carbon atoms,

R ^ _o -CHp-, -CKp-CK ₂ - or -CIi-,

CK,

X -O- or -S-,

Alkylene -CK -, -CH ₀ -CK ₀ -, -CH-, -CHp-CH- or -CH-CM ₀ -,

O <-. G. χ CX Jt.

CH_ CH, CH,

xn 1 or 2,
η 1 to 3,
£ 1 to 9,

r 1 to »S mean

0 0 98 2 2/1298 ßAD ORIGINAL

the SO-.H group in the formula (V) is in the 6- or 7-position, the nucleus B is a chlorine atom or an SO, H group in the 6- or 7-position or awei hydroxyl or amino groups or one each Hydroxy and oline amino groups in positions 5 ^and 8 can carry, the nucleus can carry C 1 to 3 low molecular weight alkyl or alkoxy groups and, if η stands for 2 or 2, each substituent Rn can have its own meaning.

The preferred compounds correspond to the formulas

SO H

CH-

O NH,

(VI)

(VII)

0 NH-R

(VIII)

Of the compounds of formulas (VII) and (VIII) are those

particularly valuable in which

R ₂ denotes the radical of a sulfonated phenol, optionally bearing an alkyl group in the para position, or a sulfated 2-hydroxyethyl or 2- or 3-hydroxypropyl or 2,3-dihydroxypropyl radical.

009822/1298

and R, a sulfonated optionally 1 to J lower alkyl group, a lower alkoxy or acylamino group-bearing benzene radical, a sulfonated benzyl or phenylalkyl radical, the alkyl radical being bonded to the amino group through a secondary carbon atom, or a radical

Ro

SO H

means,
where m is 1 or 2,

R "for hydrogen, methyl or ethyl
and Rg for hydrogen, methyl, ethyl, chlorine, methoxy, ethoxy

or acetylamino.

One method of making the new dyes is that 1 mole of 3,5,5-trimethylcyclohexylamine is mixed with 1 mole of an anthraquinone compound the formula

0 NH,

O NH-R.

(IX)

Shark

CS »

Shark

NH-R ₁

or

(χι)

003822/1293

in which shark
Y

and R

_15th

Chlorine, bromine or fluorine, bromine or -30, H,

- ^R 10 <D

-Alkylene-CO-1

R,

-r -o-so η, -R ₁₀

9 3 10

or -alkylene-CO-N

mean"

reacts, and if Y is bromine, with a water-soluble neutral Sulphite treated and, if R., does not have a -SO, H group, with SO, or a SO, -delivering agent treated "

A first modification of the procedure is that one mole an anthraquinone compound of the formula

Shark

O NH

(XII)

! H ₃

«3

with 1 mol of an amine of the formula R ,, - NHg and, if the remainder R, -2 does not contain a -30, H group, with S0_ or a SO, -releasing

009822/1298

ORIGINALINSPECTED

Means treated.

A second modification of the procedure is that you get 1 mole an anthraquinone compound of the formula

O NH ₂

(XIII)

with a compound of the formula

Hal

Hal-R ₉ -OH,

or HO-CH,

implements and treated with SO, or a SO, -releasing Miveel, or with 1 mole of a double bond in the α-position Alkylenecarboxylic acid with 3 or 4 carbon atoms or a haloacetic acid or their functional derivatives are reacted, then in the presence of an 'inorganic acid halide with an amine •Formula

(XIV)

amidated and with SO, or an SO, -releasing smock.

009822/1299

An ancestor for the production of the * anthraquinone dyes formula

(XV)

insists that 1 KoI l ^ -Dihydroxyanthraehinon-ö- or -7-sulionic acid with 1 mole 5i5i5- ^T i "i ^rn ethylcyclohexylarriin and 1 mole of an amine of the formula R ^ -AHg, or that 1 mole of a ver

bond of the formula (XII), in which the core B bears a sulfonic acid group, _{reacts with 1 mol of an amine R 2.} -NHp »A process for the preparation of the anthraquinone dyes of the formula

(XVI)

consists in that 1 mole of an anthraquinone compound of the formula (IX) with 1 mole of 3.5 _I , 5-trimethylcyclohexylamine and the reaction product obtained with 1 mole of a compound of the formula

, HX-R ₆ -OrI or HX- (CHg) _n

implements and treated with SO, or a SO., - donating agent.

009822/1299

8AD

Suitable compounds of the formula (IX) are, for example, l-amino-2,4-dibromo-anthraehinone, l-amino-4-bromo-, l-amino-4,6- or -4,7-dibromo, l-amino - ^ - bromo-o-chloro- or -7-chloro-, l-amino - ^ - bromine-o- or -7-fluorine-, l-amino-4-bromo-6,7-diohloranthraquinone-2-sulfonic acid, 1-amino-4-bromoanthraohinone-2,6- or -2,7-disulfonic acid.

Examples of suitable compounds of the formula (X) are the following: 1-phenylamino-4-bromo- or -4-chloroanthraquinones -4,6 (7) -dichloro-, -4-bromo-6- or 'r7-ohloranthraquinone , -4-chloro-5,8-diamino-, ^, S-dihydroxj-j, ^ -amino-e-hydroxy- or; -g-hydroxy-S-amino-anthraquinone and ^ -bromoanthraquinone-o- or -7-sulfonic acid and their derivatives, which are alkyl or alkoxy radicals with 1 to 5 carbon atoms (methyl, ethyl, isopropyl, n-propyl, n- Butyl, n-amyl, tert-amyl, tert-butyl, isobutyl, methoxy, ethoxy, n-butoxy, dimethyl, trimethyl, methylethyl, methyl-methoxy, dimethoxy, diethoxy, diethyl), halogen atoms (chlorine, bromine, fluorine) or lower Eylamino radicals (acetylamino, propionylamino, n-butyrylamino, methoxycarbonylamino, ethoxycarbonylamino), as well as the compounds 5 l- (2'-hydroxy-ethylamino) -, l- (2 ^f -hydroxypropylamino) -, propylamino in the substituted or unsubstituted phenyl nucleus. 1- (3'-hydroxypropyl-2 ^f -amino) -, 1- (2'-3'-dihydroxypropylamino) -, 1- (4'-hydroxybutyl-5 ^f -amino) -, 1- (4'-hydroxybutyl -2'-amino) -4-chloro- or -4-bromo-anthraquinone, -4,6 (7) dichloro-, -4-bromo-6- or -7-chloro-anthraquinone, -4-chloro-5 , 8-diamino-, -5,8-dihydroxy-, -5-amino-8-hydroxy-, ^ -hydroxy-e-aminoanthraquinone, -4-chloro or er .4-bromoanthraquinone-6- or -7-sulfonic acid and the compounds sulfated on the hydroxyalkyl group } 1-benzylamino-,

009822/1299

1- (4'-phenyl-4'-methyl-pentyl-2'-amino); 1- (4'-Phenylbutyl-2 ¹ -amino) - or 1- (6'-Phenyl-2'-methyl-hexyl-4'-amino) -4-chloro- or -4-bromo-anthraquinone, -4 , 6- or -4,7-dichloro- or -4-bromo-e- or ^ -chloro-anthraquinone, -4-OhIOr ^, 8-diamino-, -5,8-dihydroxy-, -5-amino- 8-hydroxy-> -S-hydroxy-S-araino-anthraquinone, -4-chloro- or ^ -bromo-anthraquinone-o- or -7-sulfonic acid j l- (2'-Benzylcyclohexylamino) -, l- (2 '-ß-Phenylethyl-cyclohexylamino) -, 1- / 2' - (2 "- or -4" -Methylbenzyl) - or -Aethylbenzyl- or -n-Propylbenzyl) -cyclohexylamino / -, 1- / 2 '- ( 2 "-4" - or - (2 ", 6" -Dimethylbenzyl) - or -Diethylbenzyl) -cyclohexylamino / -, 1- / 2 '- (2 ", 4", 6 "-Trimethylbenzyl) -cyclohexylamino / -, l- / 2 '- (2 "- or -4" -methoxybenzyl) - or -ethoxybenzyl) - or -n-propoxybenzyl) -cyclohexylamino / -, l- / 2' - (2 ", 4" -dimethoxybenzyl) - or -Diethoxybenzyl) -cyclohexylamino / -, 1- (2'-benzyl-4'-methyl-, -4'-ethyl-, -4'-tert. butyl-, -4'-tert «amyl- or ^ ' -isooctylcyclohexylaminoj ^ -chlor- or -4-bromoanthraquinone, -4,6- or-4,7-dichloro- or -4-bromo-6- or -7-chlorine -anthra-ghinone, -4-chloro-5,8-diamino-, -5,8-dihydroxy-, -S-amino-S-hydroxy-, ^ -hydroxy-S-amino-anthraquinone or -4-chloro- or ^ -bromo-anthraquinone-o- or -7-sulfonic acid j 1- (2'-phenylaminocarbonyl-ethylamino) -, 1- (2'-phenylaminocarbonylpropylamino) -,! - (l'-phenylaminocarbonyl-propyl ^ ¹ -amino) - , 1-phenylaminocarbonylmethylamino-, 1- (2'-N-Methy1-N-phenylaminocarbonyl-

ethylamino) -, 1- (2'-N-ethyl-N-phenylaminocarbonyl-ethylamino) -, 1-N-methyl-N-phenylamino-carbonylmethylamino-, 1-N-ethyl-N-phenylaraino-carbonylmethylamino-4-chloro - or -4-bromo-, -4,6- or-4,7-diohlor-, -4-bromo-6/7-chloro-anthraquinone, ^ -chlor-SiS-diamino-, -5 # 8- dihydroxy-, -5-anlino-8-hydroxy- _# -5-hydroxy-8-a! nino-anthraquinone,

009822 / 129Ö

or - ^ - chloi "- or - ^ - bror.-Eiithrachinon-o- or -7-sulfonic acid and their derivatives which have alkyl or alkoxy radicals in the phenyl nucleus 1 to 5 carbon atoms (! '. Ethyl, ethyl, isopropyl, n-propyl, η-butyl, n-amyl, tert-amyl, tert-butyl, isobutyl, kethoxy, ethoxy, n-butoxy, dimethyl, trimethyl, methyl-ethyl, methyl-methoxy, dimethoxy, Diethoxy, diethyl) calogen atoms (chlorine, bromine, fluorine) or low acylamine residues (acetylamino, propionylamino, n-butyryl, amino, methoxycarbonylamino, ethoxycarbonylamino) carry, as well as those sulfonated in the substituted or unsubstituted phenyl nucleus Links.

The compounds of the formula (X) can be prepared, for example, by reacting 1 mole of a compound of the formula

(XVII) shark

with 1 mole of an amine R., - NH ₂ or by halogenation of a compound of the formula

(XVIII) i

OH
has been manufactured.

C09822- / 129Ö

The compounds of the formula (X) «in which R- is a radical

-Alkylene-CO-N · /> respectively*

«7

-Alkylene-CO-N · / ^) means.

can also be achieved by reacting 1 mole of a compound of the formula (XVIi). with 1 mol of an amino carboxylic acid HgN-alkylene-COQH, amidation of the carboxylic acid group in the presence of an inorganic ■ '· Acid halide with an amine of the formula (XIV) or amidation with an amine of the formula (XIV) and subsequent sulfonation, or by reaction with 1 mol of a compound of the formula

(XIX)

^ rV

0 shark

with 1 mole of a double bond in the α position Alkylenecarboxylic acid with 3 or 4 carbon atoms or a haloacetic acid or their functional derivatives, amidation in The presence of an inorganic acid chloride with an amine of the formula (XIV) or amidation with an amine of the formula (XIV) and sulfonation can be prepared.

Suitable compounds of the formula (XI) are, for example, 1-isopropyl-, 1-sec. Butyl, 1 sec. Arayl, 1 sec. Hexyl-, l-cyclohexylamino- or 1- (3 '# 5 ^f # 5'-trimethylcyolohexylamino) -4-chloro- or -4-bromoanthra-

009822/1290

Quinone-6- or ^ -sulfonic acids You can react 1 mole of 1,4-dihaloanthraquinone-6- or -7-sulfonic acid with 1 mole of an amine R ₂ I-NH ₂ or by halogenation, preferably bromination, a 1-Ii _i -NH-aiathraohinon-6- odor -7-sulfonic acid are produced.

The reaction of the jJ ^^ - Trimethylcyclohexylamins with the compounds of the formulas (IX), (X) or (XI) may be carried out at temperatures of 40 ° to 220 ⁰ C. The water-soluble anthraquinone compounds are advantageously, for example at temperatures from 45 ° to 100 ⁰ C, wherein Y is in aqueous or aqueous-organic medium, preferably at 45 ° to 85 ⁰ C for the compounds of formula (IX), SO-H, the insoluble in organic medium, eg at temperatures of 80 ° to 200 ⁰ C, preferably at temperatures of 100 ° to 150 ⁰ C, in particular in HO-IPO ^0, for compounds of formula (IX) wherein Y is a bromine atom for The aqueous-organic media used are mixtures of water and one or more at least partially water-soluble solvents that are indifferent to the reactants, e.g. lower alcohols (methanol, ethanol, isopropanol, butanol, ethylene glycol), ethers (dioxane, 1,2-dimethoxy- or 1,2-diethoxyethane), ether alcohols (2-methoxy- or 2-ethoxyethahol, 2- (2'-methoxyethoxy) or 2- (2 ^l -ethoxyethoxy) -ethanol), ketones (methyl ethyl ketone), Amides (dimethylformamide, dimeth ylacetamide), sulfoxides and sulfones (dimethyl sulfoxide, sulfolane = tetramethylene sulfoxide). The amount of these solvents is advantageously up to 25% _s preferably 5 to 15% ₃ of the mixture.

000822/1298

1917Q51

It is advisable to work in the presence of acid-binding agents, which result in a pH value of at least 11 (pH value of the saturated aqueous solution of 3> 5> 5-trimethyleyclohexylamine), preferably of alkali metal hydroxides (sodium or potassium hydroxide) and from a copper coffee analyzer (copper powder, copper-I-oxide,

Copper-I-chloride, copper-II-oxide). To speed up implementation too it is advantageous to use an excess of 3,5,5-trimethylcyclohexylamine, z "B. 1.3 to 3 moles, preferably 1.5 to 2 moles, each To use moles of the halogenanthraquinone compound.

For the reaction in an organic medium, the 3.5 * 5 "trimethylcyclohexylamine itself is used as a solvent and optionally as an acid-binding agent or a high-boiling solvent which is ^{indifferent to the 3> 5 * 5 ~ trimethylcyclohexylamine, for example boiling at temperatures from 130 °} to 220 ^{° C.} , e.g. mono- and dichlorobenzene, dimethylformamide, dimethyl-acetamide, dimethyl sulfoxide, glycol ether and especially nitrobenzene; as acid-binding agents, for example, an excess of the amine, a tertiary, less volatile amine, which is more basic than 3,5,5 ^ trimethylcyclohexylamine carbonate, potassium, a basic metal salt, eg sodium or or an alkali metal hydroxide, if necessary using the above-mentioned copper catalysts the reaction products can be used in customary manner, "B _e by evaporation, preferably egg under reduced pressure, steam distillation or dilution ^with;.. - nem suitable means (e.g. with water in the case of water-soluble solvents ^ with a lower alcohol such as methanol, ethanol, isopropanol or with a hydrocarbon such as petroleum ether, Llgroin) deposited, filtered off with suction, washed if necessary,

0Ö9822 / 129Ö

and be dried.

After the condensation of 3,5,5-trimethylcyelohexylamine with a compound of the formula (IX), in which Y stands for a bromine atom, the reaction product with a neutral water-soluble sulfite in aqueous-organic, e.g. in aqueous-alcoholic or aqueous phenolic (phenol itself , a cresol or cresol mixture), whereby a concentrated sulphite solution represents the aqueous portion, at temperatures of 100 ° to I50 ^0, preferably 120-130 ⁰ C, reacted under pressure "

If the compounds of the formula (X) wherein R._ an aralkyl group (- ^R Tf) "V ~ /) ^{or e} * ^NEN cyclohexyl / ^R ->2" means \ ^c ^ \,

acylated with 3,5,5-trimethylcyclohexylamine before the condensation,

so the reaction is greatly accelerated, so that the temperature decreased, for example at 60 ° to 130 ⁰ C, preferably 80 ° to 100 ⁰ C, if carried out in an excess of amine and shortened / or the duration or the formation are greatly reduced by-products can. Acylating agents include, for example, lower alkanesulphonic acid chlorides (methane or ethanesulphonic acid chlorides), arenesulphonic acid chlorides (benzene or ^ -methylbenzenesulphonic acid chlorides), and also chlorocarbonic acid alkyl esters (chlorocarbonic acid methyl or ethyl esters) and, in particular, low carboxylic acid chlorides or anhydride and preferably anhydride). To form the acetyl compound, for example, the anthraquinone compound can be increased 5 to 10 times

009822/129 9

191705Ί

Heat the amount of acetic anhydride in the presence of 2 to 5 % zinc chloride (based on the amount of the anthraquinone compound) to temperatures of 60 ° to about Γ55-ΐ4θ ° Ο, preferably at 80-100 ° C, until the starting compound has disappeared, whereupon the Ge . -mixed cools, poured into water, carefully saponified the excess acetic anhydride and syphoned off the deposited product, washed with water, dried and, if necessary, crystallized from 100% acetic acid or from an alcohol.

k * After the condensation with 3,5,5-trimethylcyclohexylamine is the acyl group again cleaved for example by heating in acetic 55 ^to 80 #, preferably 60 to 65 ^ hydrochloric acid, sulfuric acid at temperatures of 5O ⁰ to 8O ⁰ C, preferably at 60 -70 ° C.

The reaction of the anthraquinone compounds of the formula (XII) with an amine R _, - NHp can be accomplished under the abovementioned reaction conditions. The acylation of the trimethylcyclohexylamino group brings about a more rapid reaction if moil works in a large excess of the non-sulfonated amine.

If ».an carries out the reaction in an organic solvent,

depending on the strength of the amine used, you can use an alkali metal acetate, carbonate or hydroxide, e.g. in the case of an aromatic amine, or an alkali metal carbonate or hydroxide in the case of a use another amine.

If the anthraquinone compound (XII) has a 6- or 7-position -SO, H group, it is advisable to work in an aqueous one

009822/129 β

or aqueous-organic medium in the presence of an acid-binding medium By means of, for example, an alkali metal acetate, bicarbonate, -C6 roonate or hydroxide when using an aromatic amine or an alkali metal hydroxide when using an aromatic-aliphatic Amines.

Suitable amines R ,, - NHp are z.3. Aminobenzenes l-amino-2-, -3- or -4-methyl-, -ethyl- οάζ? -isopropylbenzene, 1-amino-2,4-, -2,5- or -2,6-dimethyl- or -diethylbenzene, 1-amino-2,4,6- or-2,4,5-trimethylbenzene, l -Amino-2-rr _i eth.vl-4 "6-.dxäthvlberizol ₍ . L-Amino-4-isobutyl-, -4-tert-butyl-, -4-tert-amyl-, -4-n-amyl -, -4-isooctyl-, -4-tert-octylbenzene, 1-amino-2-, -J- or -4-chloro- or -bromobenzene, 1-amino-2,4-dichlorobenzene, i-amino-2 -, -3- or -4-methoxy- or -.ethoxybenzene, l-amino-2,5-dimethoxy- or diethoxybenzene, l-amino-2-methoxy-5-methyl-oenzene, l-amino-4-acetylamino , propionylamino, butyrylamino, methoxycarbonylamino or ethoxycarbonylaminobenzene or the monosulfonic acids of these aminobenzenes according to the formulas

H _p N- <'y or E

2-hydroxyethylamine, 2-hydroxypropylamine-1; J-hydroxypropylamine-1; l-hydroxypropylamine-2-, l-hydroxybutylamine-5, - l-hydroxybutylamine-2, 2, j5-dihydroxypropylamine-1 or its sulfuric acid ester accordingly the formulas

or

Benzylamine, 2-amino-4-methyl-4-phenylpentane,

009822 / 129Ö

2-Amino-4-phenylbutane, 4-amino-2-methyl-6-phenylhexane and their Monosulfonic acids according to the formulas

or

2-benzyl- or 2-phenylethyl-oyclohexylamine, 2- (2'-methyl-, or -Aethylbenzyl) -cyclohexylamine, 2- (4'-methyl-, -Aethyl- or -h-propylbenzyl) -cyclohexylamine, 2- (2 ', 4'- or 2- (2', 6'-dimethyl-- or -Diethylbenzyl) -cyolohexylamine, 2- (2 ', 4', 6 '-Tr imethylbenzyl) -cyclohexylamine, 2- (2'- or 2- (4'-methoxy-, -ethoxy- or -n-propoxybe »azyl) -cyolohexylamine, 2- (2 ', 4'-dimethoxy- or -diethoxybenzyl) -cyclohexylamine, 2-Benzyl-4-methyl-cyclohexylamine and their Sulphonic acids according to the formulas

^R 12

^h 2 ^iJ \ / ^R ll ^Or

Amino-acetic acid, a-amino and ß-amino-propionic acid, a-aminomethyl-propionic acid and ß-amino-butyric acid-phenylamide, -N-methyl- or -N-ethyl-fl-phenylamide, - (2 '-, -3'- or -4'-methyl-, -methoxy-, ethoxy- or -chlorophenylamide) -, - (2', 4'-, -2 ', 5'- or -2 ^f , 6 ^f dimethylphenylamide), - (2 ', 4', 6'- or - (2 ', 4', 5 ^l -trimethylphenylamide), - (4'-ethyl-, - (4'-isopropyl-, - (4'- n-butyl-, - (4'-isobutyl-, - (4'-tert-butyl-, - (4'-n-amyl-, - (4'-isoamyl-, - (4'-tert-amyl- , - (4'-isooctyl- or - (4'-tert-octylphenylamide), - (4'-bromophenylamide), 42 ', 5'-dichloro-, - (2', 5'-dimethoxy- or - (2 ', 5'-diethoxyphenylamide), - (2'-methoxy-5'-methylpnenylamide), "(4'-acetylamino-, - (4'-propionylamino-, - (4 * -butyrylainino-, - (4'- methoxy-carbonyl

009822 / 129Ö

amino- or - (^ '- ethoxycarbonylaminophenylamide) or their monosulfonic acids according to the formulas

HgN-alkylene-CO-N- / Λ R

or R ₇

HoN-alkylene-CO-N

R ₇

The implementation of the anthraquinone compound of the formula (XIII) with a

A compound Kal-γ-* Hal-R ₉ -OH or Hal-CH ₃ - <\ can in a large excess of the halogen compound or in a polar solvent such as dimethyl formamide, dimethyl sulfoxide or preferably nitrobenzene at temperatures of 90 ° to 200 ⁰ C, preferably 130-l80 ^o C, and especially 135-150 ⁰ C for aryl halides, and preferably 80-130 ° _C; especially 100-110 ° C, for the benzyl halides and 80-120 ° C for the hydroxyalkyl halides, in the presence of an acid-binding agent such as alkali metal acetate, bicarbonate, carbonate or hydroxide and a copper catalyst (copper powder, copper I oxide or I chloride).

The compounds of the formula (ΧΣΣΣ) can by condensation of Bromarr.insäure and its derivatives with ^ jSjS- ^ ri ^ e ^ hylcyclohexylamine and desulfonation or by. Implementation of 1 Γ · '.ο1 of a dihalogen compound of formula (XVII) in any order with 1 KoI ^ jSjS- ^ rir.ethylcyclohexyianiin and 1 mol of ammonia or one aliphatic or aromatic sulfonic acid amide (CH -.- SG_-I "I ^,

^{in the}

Cleavage of the sulfonic acid crest: ^ _-- be established.

C09822 / 1298

SAO

^ 19 17 0S1 * S

• 20 1317051 SAHDoa AG '■.

For implementation with the aminoanthraquinone compounds of the formula (XIII) Suitable halogen compounds are, for example, bromobenzene, 1,2-, 1,3- or 1,4-dibromobenzene, 1-bromo-2-, -JJ- or -4-methyl- or

ethylbenzene, l-bromo-2-, -J _T or -4-chlorobenzene, l-bromo-2-, -Ji. . or -4-methojcy- or ethoxybenzene, .l-bromo-2,4,6-trlmethylbenzene, l-bromo-2-methoxy-5-methylbenzene, l-bromo-4-isopropyl-, -4-n-butyl, -4-tert-butylbenzene, l-bromo-4-aoetylamino, -4-propionylamino or -4-butyrylaminobenzene, according to the formula Hal- / "^ y ; 2-chloro- or 2-bromoethanol, 2-chloro- or 2-bromopropanol-l, 1-chloro- or l-bromo-2-propanol, 3- Chloro- or 3-bromopropanol, 1-chloro- or 1-bromo-2, ^ - propanediol, corresponding to the formula Hal-R _g -OH j

Benzyl chloride or bromide corresponding to the formula Hal-CH ₂

The implementation of the aminoanthraquinone compounds of the formula (XIII) with benzyl alcohol; is advantageous in a large

sen excess of the alcohol at temperatures of 80 ° to 1 ^ 0 ° C, preferably 100-11O ⁰ C, in the presence of iodine as a catalyst, the amount of iodine being about 3 to 15 %, preferably 8-12 % of the aminoanthraquinone compound.

The reaction of the aminoanthraquinone compounds of the formula (XIII) with the alkylenecarboxylic acids having a double bond in the α-position and having 3 or 4 carbon atoms and their functional derivatives, for example acrylic acid, acrylic acid ester, acrylic acid amide, acrylic acid nitrile. Methacrylic acid, methacrylic acid ester, crotonic acid, is expediently carried out in a sulfuric acid solution, the concentration of the sulfuric acid preferably being between 50 and 96 % .

009822/1298

The reaction takes place at temperatures between 4o ° C and 10O ⁰ instead, * preferably between 6o ° and 8o ° C. The amount of used

Alkylene carboxylic acid must be at least 1 mol. To achieve

In good yields, it is often advantageous to use an excess of the alkylenecarboxylic acid to use. The addition of another acid, e.g. concentrated phosphoric acid, can accelerate the reaction. During the reaction, the functional derivatives are often hydrolyzed to the free acids. If this is not the case, so hydrolysis is carried out afterwards. The reaction products can be found in the British patent specification No. 841 927 are isolated in the manner described.

The reaction of the aminoanthraquinone of formula (XIII) with a haloacetic acid can, for example in molten bromo- or chloroacetic acid, optionally in the presence of an alkali metal acetate, it and a copper compound, at temperatures from 60 ° to 120 ⁰ C, preferably at 8o-90 ° C, or in an organic inert solvent such as phenol, cresol or a cresol mixture or a naphtha Alkalimetallacetates and a copper compound at from ⁰ to 150 LOCP C, preferably at 100-120 ⁰ C is performed in the presence of. For isolation, the solvent is removed twice by distillation, for example with steam or under reduced pressure, and the reaction product is separated off by salting out and / or acidification, filtered off with suction and further purified in the usual way.

, 1

00 9822/129 8

ORIGINAL INSPECTED

For amidation, the dry carboxylic acids obtained in this way are in the presence of an inorganic acid halide (thionyl chloride, phosphorus oxychloride or id, phosphorus pentachloride or pentabromide, preferably phosphorus triochloride or tribromide) in an inert organic solvent (e.g. in an optionally halogenated hydrocarbon such as chloroform, carbon tetrachloride, benzene , Toluene, xylene, 'chlorobenzene, dichlorobenzene or in an ether such as dioxane, 1,2-dirnethoxy- or 1,2-diethoxyethane, di-isopropyl, di-n-propyl ether or in a tertiary amine (pyridine, a pyridine base mixture, quinoline, dimethylamino or Diäthylaminobenzol) is reacted with an amine of formula (XIV). Instead of an inert organic solvent can also be the amine of formula (XIV) is itself used as solvent. the reaction is carried out at temperatures between 0 ° and 50 ⁰ C in the presence of one of the above-mentioned acid halides and leads the .asetzt at temperatures from 0 ° to 100 ⁰ C, preferably b at 40 ° to 80 ° C, to the end. The isolation of the phenyl amides obtained can be carried out in the manner described in the examples of British Patent Specification No. 1,061,424.

The reaction of the, ^ - dihydroxyanthraquinone-e-sulfonic acid with 1 mole of 3,5,5-trimethylcyclohexylamine and 1 mole of an amine R ^ _-NH2 may for example at temperatures from 50 ⁰ to 150 ⁰ C, preferably at 80-120 ° C, are carried out, by adding boron compounds ^ (boric acid, boron trifluoride) and / or by inserting the 1, ² I - dihydroxy-anthraquinone-6-sulfonic acid partially or entirely in the form of the leuco compound, the introduction, in particular a second 3, 5,5-trimethylcyclohexylamino group accelerated considerably

0 0 9822/1298

will. You can use a large excess of 3,5,5-trimethylcyclohexylamine or, especially in the case of condensation with 2 different amines, in an organic inert solvent, for example in an alcohol, for example ethanol, n-propanol, n- or iso-butanol, n- or iso-arnyl alcohol, in a glycol, e.g. ethylene glycol, 1; 2-propylene glycol, diethylene glycol, dipropylene glycol, in an ether alcohol 2.B. 2-methoxy-, 2-ethoxy- or. 2-n-butoxyethanol, 2- ( 2 ^! -IVIethoxy-, -aethoxy- or -n-butoxy-ethoxy) -ethanol, in an ether such as dioxane, etc., optionally with the addition of up to 30 % water, after the condensation, preferably in the absence of air, for example in a nitrogen - Or luminous gas atmosphere takes place, the leuco compound is re-oxidized, for example by introducing air.

The implementation of the reaction product of the formula

(made from 3,5,5-trimethylcyclohexylamine and the compounds of formula (DC)) with the hydroxy or thiol compounds

⁵ , HX-R ₆ -OH or HX- (CH ₂ ) _m \)

Only at elevated temperature, for example from 50 ⁰ to 200 ⁰ C, preferably from 50 ⁰ to 10 ⁰ C, in particular from 60 to 120 ° C, for the thiol compounds and from 100 to 200 ° C, in particular at 110 ° to 180 ⁰ C, for the hydroxy compounds, in the presence of

00982271298

acid-binding agents such as the alkali metal carbonates and hydroxides. It is advantageous to work in an inert solvent, for example in an AllcchoL ^T .. ^r ie ethanol, butanol, cyclohexanol, or in an ether alcohol such as 2-methoxy, 2-ethoxy or 2-butoxyethanol, 2- (2 ^T - Methoxy, 2- (2'-ethoxy or 2- (2'-butoxyethoxy) ethanol, or in an ether such as dioxane, or in a hydrocarbon such as cyclohexyl., Toluene, chlorobenzene or, if the compounds of the formula (IX ) carry a sulfonic acid group, even in water in the case of the thiol compounds. Of course, an excess of the thiol compounds can also be used as solvent. Suitable solvents for the reaction with the hydroxy compounds are, for example, pyridine, a pyridine base mixture, quinoline, nitrobenzene, 2,6-di -tert.butyl-4-methylphenol or an excess of the hydroxy compounds themselves. Any water present or formed is removed before or during the reaction. For the reaction of the 2-position bromine atom, the addition of a copper catalyst, for example Kup fer-I chloride, especially in the case of the thiol compounds, may be advantageous. The reaction products are deposited in a known manner, for example by diluting with a lower alcohol or, if water-soluble or alkali-soluble hydroxy or thio compounds have been used, with water or with alkali metal hydroxide solutions, filtered off with suction, washed and dried.

3 The treatment with SO, (as a gas e.g. 3. Diluted with air or as a Addition compound to pyridine or to dioxane) or with chlorosulfonic acid can in an inert solvent such as chloroform, 1,2-

AD

Dichloroethane, nitrobenzene at temperatures of 0 ° to 50 ⁰ C, preferably at 15-50 ⁰ C are carried out. Usually, however, one works with concentrated, about 96 to 100% sulfuric acid or with oleum with up to about 15 % SO content at the temperatures given above. The benzene nuclei are sulfonated or the aliphatic hydroxyl groups are sulfated. For the sulfamido · kann.man concentrated sulfuric acid at 10-20 ⁰ C animals apply, while for the sulfonation at the same temperature, it is expedient oleum with eg 5 to 10% SO to use content. To convert the hydroxyalkyl groups into sulfatoalkyl groups, it is also advantageous to use aminosulfonic acid, e.g. use at 100-150 ⁰ C. The sulfonated or sulfated dyes can be isolated, for example, by pouring them into water or into a salt solution and optionally salting out.

The water-soluble dyes obtained contain at least one —SO, H group and are used for dyeing, padding or printing of wool, silk, hair, synthetic polyamide and polyurethane fibers and leather. The dyeings and prints obtained are brilliant and have good to very good wet fastness properties (washing, fulling, perspiration, water, sea water) as well as good rub and dry cleaning properties. The lightfastness on synthetic polyamide fibers is very good and better than on wool.

09 8-22 / 1? 9 8

The parts mentioned in the examples are parts by weight and the Percentages by weight.

The temperatures are given in degrees Celsius.

example 1

A mixture of 400 parts of water, 40.4 parts of 1-amino - ^ - bromoanthraquinone-2-sulfonic acids! Sodium, 20 parts of l-amino-2,5,5-trimethyl-cyclohexane, I5 parts of a ^ JJO sodium hydroxide solution, 50 parts of ethanol and 1 part of copper powder is stirred for 5 hours at 65 ^0th The blue dye formed is isolated and dried in the usual way. It corresponds to the formula (VI). With its aqueous solution, fibers made of synthetic polyamides are dyed a brilliant reddish-blue. The dyeings have very good wet fastness properties and excellent light fastness.

Compared to the well-known commercial dye, which is in the ^ position carries an unsubstituted cyclohexylamino group, stands out the new dye is characterized by the much better wet fastness of its dyeings on synthetic polyamide fibers.

The same dye can be obtained in the following way:

A mixture of 38.1 parts of l-Airiino-2,4-dibromo-anthrachioone _i 160 parts of 3 * 5 * 5-trimethylcyclohexylamine, 25 parts of anhydrous potassium acetate and 0.5 part of copper (I) chloride is kept at 110-120 ° heated until the starting substance has disappeared. The reaction mass is diluted with methanol, the precipitate is filtered off with suction while cold, washed with methanol, then with water and dried

; 0 9 δ 2 2 / i 2 ö 9

10 parts of the product are heated, optionally uinlcristallisierten 50 $ strength Kaliurnsulfitlösung during l6 hours I50 ⁰ in a Antoklaven with 50 parts of phenol and 20 parts. The phenol is distilled off with steam and the dye is salted out, filtered off with suction, washed with a salt solution, if necessary freed of any water-insoluble impurities by dissolving in hot water, filtering in the heat and salting out and then kneaded dry.

Color regulation :

2 parts of the dye prepared according to Example 1 are dissolved in 60000 parts of v / water of hO ° and 4 parts of ammonium sulfate are added. 100 parts of synthetic polyamide (nylon 66) yarn are placed in this dyebath, heated to the boil within 50 minutes and held at boiling temperature for another hour. Finally the yarn is rinsed and dried. The facarns are brilliantly reddish-ble.u and real colored.

The following table contains further dyes of the formula

0 KH ,,

(XXI),

by the substituents R. in positions 6 and 7 sov.'ie by the color of the dyeings on full or synthetic poly amide fibers are marked

: O9822 / 1290

Table 1

example
No. R ₁ in position 6 R, in position 7 Hue of
Colorations 2 Cl H reddish blue H Cl do. 4th Br H do. 5 F. H do. 6th -SO H H blue 7th Cl Cl reddish blue

Example 8

46.4 parts of the sodium salt of that prepared according to Example 1 are dissolved Dyestuff in 600 parts V / water at 60 °, added 46.5 parts of a sodium hydroxide solution and sprinkled in the course one hour 19 parts of sodium dithionite. After another

t -

The desulfonation reaction has ended in about 1 hour. One filters the If the compound is insoluble in water, it washes it with hot water V / ater neutral and dries them.

A dark purple powder is obtained which, after recrystallization from toluene melts at 204 to 205 °. The connection received has the formula

CH,

(XXII)

j} 6.2 parts of the l-amino-4- (5 ^l , 5 ^l , 5 ^l -trimethylcyclohexylamino) anthraquinones, 75 parts bromobenzene, 15 parts water

309822/1290

Free sodium carbonate and 2 parts of cuprous chloride are during 4 Heated to 135-140 ° for hours. The reaction mixture is then cooled to 100 ° and diluted it with 150 parts of ethyl alcohol. The so Precipitated blue dye is filtered off, washed with ethyl alcohol and water and dried. It has the following structure

CH.

(XXIII)

and a melting point of 183-184 ° (from toluene and ethyl alcohol). The water-insoluble dye can be added by the usual methods, e.g. by treatment with five times the amount of 10% oleum 5-10 °, are sulfonated in the benzene nucleus. How to get a blue one water-soluble dye that dyes wool or polyamide fibers in beautiful shades of blue. The dyeings have excellent hate fastness properties and excellent lightfastness.

If the corresponding amount of 4-ethoxy-1-bromobenzene is used instead of bromobenzene, a dye base with a melting point of 191-192 ^{0 is obtained} , the sulfonated derivative of which is synthetic polyamide fibers in brilliant greenish blue shades of excellent lightfastness and very good wet fastness properties (washing , Milled, white, water and sea water fastness properties) and very good rub and dry cleaning fastness properties. Compared to the corresponding dye with a cyclohexylamino group, the dye according to the invention is characterized by greater brilliance and better

009822/1288

- 3Q-

Fastness to washing and perspiration.

If other bromobenzenes are used, the following results are obtained

Table 2

inserted
Bromobenzene 12th • Hue of the watery
gene solution of the sul
called derivatives example
No. l-bromo-4-me-
ethylbenzene Melting point of
Dye base blue 9 1-Br oin-2, ^ -di
methyl benzene 17 ^ -5 ° reddish blue 10 l-bromo-2,4,6-
trimethylbenzo: 178-9 ° do· 11th 176-7 ° example

8 parts of iodine are dissolved in 150 parts of benzyl alcohol at 60 °. Is then added 72.4 parts of l-amino-4- (3 x, 5 ^r, 5 'trimethylcyclohexylamino) anthraquinone to, v / hile the temperature is raised to 100 °. The mixture is stirred at 100 ° for 6 hours, then cooled to 80 ° and diluted with 300 parts of isopropyl alcohol. The crystallized l-benzylamino-4- (3 ^f * 5 ^f # 5 '-trimethylcyclohexylamino) anthraquinone is filtered off, washed first with isopropyl alcohol and then with water and dried at 100 °. It conforms to the formula

(XXIV) -

45.2 parts of the dye base obtained are in I35 parts 100% acid and 80 parts of 25% oleum dissolved at 5-8 °. The sulfonation is complete after 6 hours. The mass is then in a mixture consisting of 150 parts of water, 400 parts of a Poured 28 # aqueous sodium chloride solution and 250 parts of ice. The dye precipitates. It is filtered off, washed with a 10 ^ iger sodium chloride solution and dried at 100 °. The so The dye produced dyes the synthetic polyamide fibers in brilliant, blue, lightfast and wetfast shades. The colorations are more wetfast than corresponding dyeings with the dye that carries an unsubstituted cyclohexylamino group.

Example 13

72.4 parts of 1-amino-4- (2 ^f , 5 ¹ , 5 * -trimethylcyclohexylamino) anthraquinone are dissolved in 160 parts of benzyl chloride at room temperature. 18 parts of NatriumbiearlKmat are added and the mixture is heated to 100 °. The condensation lasts 10 hours. After this * time, the mass is cooled to 60 ° and the dye base is precipitated with 300 parts of isopropyl alcohol. The sulfonation gives the same dye as in Example 12.

Example 14

36.2 parts of l-amino-4- (5 ^f , 5 ', 5 * -trimethylcyclohexylamino) -anthraquinone are dissolved at 70 ° in a mixture consisting of 90 parts of 55 # strength sulfuric acid and 14 parts of acrylic acid, and for 4 hours stirred further at this temperature. The hot Masoe is then poured into 50 parts water of 60 °. The crystal broi is filtered off and washed with hot Viassar until it runs out

309822/1298

is practically colorless and almost neutral, and dried at 100 °. 4 ^, 4 parts of ^{1- (2 l} -carboxy-ethylamino) -4- (3 ^tl , 5 ", 5" -trimethylcyclo- 'hexylamino) -anthraquinone are dissolved in 150 parts of aniline at room temperature »Then it is added dropwise at 40 ° 14 parts of phosphorus trichloride. The temperature of the reaction mass is then to 60 °

brought and held ^{at 60-65 0 for 4 hours.} 160 parts of methyl alcohol are then added, the dye base crystallizing out. It is filtered off, washed first with methyl alcohol, then with water and dried at 100 °. The blue crystallized product corresponds to the formula

(XXV) "

NH - CH _n -CH ^ -CO-

At 16 °, -50.9 parts of the dye base obtained are in 100 parts 100% sulfuric acid and 60 parts of 25% oleum dissolved The sulfonation is over after 5 hours.

The mass is then divided into a mixture consisting of 150 parts V / ater, 400 parts of a 28% aqueous sodium chloride solution and poured 250 parts of ice. The dye precipitates. It is filtered off washed with a 10 ^ igen sodium chloride solution and with 100 ° dried. A brilliant blue dye is obtained which gives light- and wet-fast dyeing on synthetic polyamide fibers.

009822/1291

- 33 - - ■

If the acrylic acid used here is replaced by the equivalent amount of 2-methylacrylic acid, then it is advantageous to work in a 90% solution Sulfuric acid at 95-100 ° and in the presence of 100% phosphoric acid in an amount of 3-5 ^

Example 15

A mixture of 23.1 parts of 1- (4'-methyl-4'-phenylpentyl-2 ¹ -amino) - - ^ - bromoanthraquinone, 0.1 part of copper powder and 42 parts of 3,3,5-trimethylcyclohexylamine is for 48 hours heated with stirring to 80-85 ^0th The mixture is allowed to cool to 60 ° and 120 parts of methanol are added dropwise. The precipitate formed is filtered off with suction at 20-25 °, washed with methanol and dried. He corresponds to the formula

1 3 t 3 _/ r- \ NH - CH - CH ₂ - C - ^ \

CH ₃

(XXVI)

10 parts of this dye base are dissolved in 40 parts of 100% sulfuric acid dissolved at 25 ° and stirred until no more starting material is present. The mass is then poured onto ice and the resulting The precipitate is filtered off “The residue is extracted with a 10 ^ igen Washed sodium chloride solution and dried. A blue powder is obtained, the wool and nylon in greenish blue, brilliant colors Dyes shades with good light fastness and good wet fastness properties.

009822/1208

Example 16

42.7 parts of 1- (3 ', 3 *, 5 ^L Trimethyleyclohexylamino) -anthracliinon-6-sulfonic acid are dissolved in 220 parts of lOO ^ sulfuric acid and treated at 20-25 ° ^mi ^ ¹ ^ parts of bromine. The temperature is now slowly increased to 75 ° and held at this temperature for around 16 hours. After cooling, the reaction mixture is poured onto 650 parts of ice, the precipitated 1- (3 ', 3' ¹ ^ - ^1- trimethylcyclohexylamino) "~ 4-bromoanthraquinone-6-sulphonic acid is filtered off, washed neutral with water and dried she.

25.3 parts of 1-CJ ^ SS'-trimethyleyclohexylaminoJ - ^ - bromoanthraquinone-6-sulfonic acid are suspended in 300 parts of water / water and mixed with 15 parts of sodium hydroxide solution, 1 part of copper chloride, 20 parts of isopropyl alcohol and I5 parts of 3,5,5-trimethylcyelohexylamine are added. The mixture is heated to 65-7Ο ⁰ until the starting compound has disappeared. The reaction mixture is poured into a mixture of 100 parts of v / ater and 15 parts of Oioiger hydrochloric acid, the suspension is heated to 80 °, filtered off and washed with acidified v / ater. The filter residue is taken up in 5 ° 0 parts of water, heated to 80 °, neutralized with sodium carbonate, then salted out and isolated.

If the 15 parts of 3,5,5-trimethylcyclohexylamine are replaced by 10 parts of cyclohexylamine or 6 parts of isopropylamine, the reaction can be carried out without isopropyl alcohol. The obtained Parfo · _f = materials result in brilliant synthetic polyamide fibers, and wet lieht- fast dyeings.
If an aromatic amine is used for the condensation, for example 9 parts

Aminobenzene or 1h part of l-amino-4-acetylaminobenzene, sodium carbonate (9 parts) can be used as an acid-binding agent and work without isopropyl alcohol.

If the same condensation is carried out with 18 parts of sodium l-aminobenzene-3-sulfonic acid, a leveling dye for wool is obtained.

The used here as starting materials - {^ '^' ^ '- Trimethylcyclohexylamino) anthraquinone-6-sulfonic acid i * ird how does herger- follows!:

108 parts of sodium anthraquinone-ljo-disulphonic acid are kept at 160 ° with 50 parts of 3,5,5-trimethylcyelohexylamine, 40 parts of sodium nitrobenzenesulphonic acid and 1.5 parts of copper sulphate in 360 parts of water in an autoclave for 36 hours. After cooling, the product is salted the sodium salt of l- (3 ^{f »f} 3, 5 ^I - ^T rimethylcyclohexylamir

no) -anthraquinone-6-sulfonsätire, sucks it off and washes it with sodium chloride solution until the filtrate is colorless. The residue is then taken up in 3600 parts of water at 70 °, acidified with hydrochloric acid (Congo red), filtered off, washed with acidified water until the filtrate is colorless, and dried. 1- (3 ^I , 3 ', 5 ^I -trimethylcyclohexylamino) -anthraquinone-6-sulfonic acid is obtained as red crystals.

Example 17

173.5 parts (1/2 koi) l- (3 ^l, 5 ^l, 5 ^I -Trimethylcyclohexylamino) anthraquinone be in the ar given in Example 16 V / else in position ^

009822/1209

brominated.

42.7 parts of 1- (3 ', 5' * 5'-trimethylcyclohexylamino) -4-bromoanthraquinone are introduced into 250 parts of acetic anhydride. After addition of 2 parts of anhydrous zinc chloride the mixture is heated to 90-100 ° C and holding it at that temperature until the starting product disappeared. After cooling, the reaction mixture is slowly poured into 1000 parts of water with vigorous stirring. External cooling ensures that the temperature does not rise above 30 °. and let stir until the acetic anhydride is completely saponified to acetic acid. The suspension is then filtered off with suction, washed with water and dried.

23.5 parts of the 1- (N-acetyl-N-3 ^I , 5 ¹ , 5'-trimethylcyclohexylamino) -4 -bromanthraquinone thus obtained are mixed with 19 parts of 1-phenyl-3-aminobutane at 110 ° for 20 hours touched. The melt is poured onto a mixture of 200 parts of ice, 170 parts of water and 30 parts of 30% hydrochloric acid. The precipitated resin is separated and recorded 65 ^ sulfuric acid in portions into 175 parts and heated at 60-70 ⁰ until the red acyl compound is no longer detectable. The hydrolysis mixture is poured onto ice, the blue dyestuff base is crystallized from n-butanol and sulfonated with 5-10% oleum at 20.degree.-30.degree. The dye obtained in this way dyes the synthetic polyamide fibers in blue, lightfast and wetfast shades.

L- (3 ', 5 ^l 5 * ^f - ^Tr i ⁿⁱ Gthylcyclohexylamino) used as a starting material can be prepared, for example, anthraquinone as follows: Heat a mixture of 242.5 parts (1 mole) of 1-chloroanthraquinone and 1000 parts 3 > 5 »5-trimethylcyclohexylamine as long as 100 °,"

009922/1 * 90

8AD ORIGINAL

until 1-chloroanthraquinone is no longer detectable. The surplus! - ' ge 'amine is driven off with V / ater vapor and the residue in 1000 Share water and so much concentrated hydrochloric acid that the solution is strongly acidic, stirred at 80 °, then suction filtered, neutral with water washed and dried.

Example 18

A mixture of 21.4 parts of 1- (3 ^t , 5 ^l , 5 ⁱ -trimethylcyclohexylamino) -4-bromo-anthraquinone, 20 parts of 1-phenyl-2-aminobutane, 5 parts of anhydrous potassium acetate, 0.1 Parts of copper (I) chloride, 0.1 part of water and 3 parts of 2-ethoxy-ethanol are stirred for 48 hours at 110 °. After adding 60 parts of n-butanol, the whole is allowed to cool, the dye base is filtered off with suction, washed with butanol and then with methanol, crystallized from n-butanol and dried. The sulfonated product is identical to the dye from Example 17.

If the l- (3 ^l , 5 ^l , 5 ^t -trimethylcyclohexylamine) -4-bromanthraquinone by the l- (5 ', 5 ¹ , 5 ^l -trimethylcyclohexylamino) -4-chloranthraquinone (obtained by chlorinating 1- (3 ', 5' * 5'-trimethylcyclohexylamino) anthraquinone replaced with sulfuryl chloride in nitrobenzene), the same dye is obtained. "

Example 19

10 parts of l-cyclohexylamino-4-bromo-anthraquinone-6-sulfonic acid are used in a mixture of 200 parts of water, 20 parts of ethyl alcohol, 20 Parts of 3,5,5-trimethyleyclohexylamine, 0.5 parts of copper bronze and 7 parts of ^ O ^ iger sodium hydroxide solution entered and while on 60-70 ° heated until there are no more raw materials. The up

009822/1 ^ 08

The process is carried out in the manner specified in Example 16. The dye is the same as the dye from the third paragraph of the example 16 isomer and has very similar properties. If one uses l-phenylamino - ^ - bromoranthraquinone-o-sulfonic acid instead the l-Cyclohexylamino - ^ - bromo-anthraquinone-6-sulfonic acid, so a similar dye is obtained.

Example 20

23.5 parts! - (N-Acetyl-N - ^ '^' ^ '- trimethylcyclohexylamino) - ^ - bromoanthraquinone, 0.01 part cupric oxide, 5 parts potassium acetate, 17.8 parts 2-amino-1 butanol and 50 parts of n-butanol are stirred for 24 hours at II5 ^0th After adding 75 parts of methanol at 60 °, the mixture is allowed to cool to 20-25 °. The product which has crystallized out is filtered off, washed with methanol and dried. 20 parts of the product obtained are dissolved in 100 parts of 80% sulfuric acid and stirred for 8 hours at 60 °. The solution is then poured onto ice. The precipitated dye base is filtered off, washed neutral with water and dried at 60 °. 10 parts of the dye base prepared in this way are sulfated in 40 parts of 100% sulfuric acid at room temperature. The mass is poured onto ice and the precipitate is filtered off, washed with 10 ^ iger sodium chloride solution and dried. A powder is obtained which dyes wool and nylon in brilliant blue shades and with light fastness and good wet fastness properties.

Example 21

The method given in Example 20 is used

but instead of 2-amino-1-butanol 37 parts of 2-benzylcyclohexylamine and sulfonated the dye base obtained with 5 to 10% oleum. Man receives a blue dye, the dyeings of which on synthetic polyamide fibers have good light and wet fastness properties.

Example 22 .

45 parts of l- (2 ^L -Phenylaminocarbonyl-ethylamino) -4-bromoanthraquinone be rimethylcyclohexylamin in a mixture of I50 parts of 3,5 # 5- ^T, 7 parts of anhydrous sodium carbonate and 0.5 parts of copper-I-oxide as long as at 120- 135 ° heated until no more starting goods can be purchased. The reaction mixture is worked up in the usual way and the dye base is sulfonated with seven times the amount of 3 ^ strength oleum at 18-20 °. The dye obtained is identical to the dye from Example 1h .

Example 23

23 # 4 parts! ^ - ^ dihydroxy -fcyäpoxyäthylainino-e-chloroanthraquinone are heated to I50 ⁰ to 20 parts of anhydrous sodium carbonate in 100 parts of nitrobenzene. You are I50 parts of 3,5,5-Trirnethylcyclohexylamin in the course of 1 hour and stops at I5O-I55 ⁰ until no initialvalues / ire longer be detected. The reaction mixture is mixed with methanol at 60 °, cooled to 0 °, filtered off with suction, washed with methanol and then with water and dried.

The product which has been sulphated according to the information in Example 20 is colored Wool and synthetic polyamide fibers in blue-green lightfast and wetfast tones.

009822/1298

Example 24

A blue-green dye is also obtained if the l ^ -dihydroxy ^ -hydroxyäthylamino-S-chloroanthraquinone is replaced by 1,4-dihydroxy-5- (4'-methylphenylaminoJ-S-chloranthraquinone and the sulfonation in 5 # oleum is used 20-25 ° executes. you can also get the same dye when l JO parts, 4-dihydroxy-5,8-dichloroanthraquinone with 25 parts of 3.5., 5-trimethylcyclohexylamine heated and 240 parts of nitrobenzene to I50 ⁰ until the starting material has disappeared, the reaction mixture worked up in the usual way and 12 parts of the resulting ^{1,4-dihydroxy-5- (3 ', 5', 5 l} -trimethylcyclohexylamino) -8-chloranthraquinone with 6 parts of anhydrous sodium acetate and 75 parts of 4 is heated -methyl-1-aminobenzene-I75 on I7O ⁰ until the reaction is complete, and the sulfonated dye base.

Example 25

A mixture see 10 parts 1,4-dihydroxyarithraquinone-6-sulfonic acid, 40 parts of 5,5,5-trimethylcyclohexylamine, 70 parts of 95 # strength ethanol, 0.8 parts of zinc dust and 1.1 parts of 100% acetic acid are used in a Stic4: fabric atmosphere heated to So °, until after about 4 to 6 Hours no more starting material is detectable. A stream of air is then passed through the mixture until the leuco form is still present Dye portion is reoxidized. The reaction mixture is worked up and purified in the usual way. You get one blue dye, the full and synthetic polyamide! 'asern l · nn, blue, very good lightfast and wetfast tones.

009822/1298

BAP ORIGINAL

Instead of d-le leuco compound of 1,4-dihydroxyanthraehinone-6-sulfonic acid To generate in the reaction mixture, one can also use the pure leuco-1,4-dihydroxyanthraquinone-6-sulfonic acid or a Mixture of 1,4-dihydroxyanthraquinone-6-sulfonic acid and its leuco compound go out.

Instead of the 95% ethanol you can use another alcohol e.g. n-propanol or n-butanol or an alcohol-water mixture e.g. 80 Share sec. Use butanol and 20 parts water with equal success.

Example 26

5.5 parts of potassium hydroxide are dissolved in 200 parts of glycerol at 100-110 ° and bring 2 ^, 2 parts of sodium 1-amino-4- (2 ', 5', 5'-trimethylcyclohexylamino) anthraquinone-2-sulfonate into the well-stirred solution and 12 parts of j5-nitrobenzene-1-sulfonic acid sodium. The whole is stirred for 8 hours at 120-125 °, poured into 800 parts V / ater, acidified with hydrochloric acid, filtered off the precipitated product, washed neutral with water and dried. 10 parts of the paraffin base are dissolved in 40 parts of 100% sulfuric acid Stirred at 15-20 ° until a sample is completely soluble in water and isolates the dye in the usual way. It dyes solid and the synthetic polyamic fibers in brilliant purple light- and wet-fast tones.

By replacing the 23.2 parts of sodium-l-amino ^ -O ^ '^' - ^ trimethylcyclohexylaminoj-anthraquinone sulfonate by 28.3 parts of the corresponding 2,6-disulfonate _/ one obtains a violet dye for V / olle .

009822/121 «

Example 27 ·.

7.5 parts potassium hydroxide are dissolved in 100 parts of phenol at 100-110 °. 18 parts of sodium l-amino-4- (5 ^l , 5 ^l , 5 ¹ -trimethylcyclohexylaminoj-anthraquinone-sulfonate are introduced into this melt, and the mixture is heated to 170 ° until a sample is insoluble in water 100 °

cool, mixed with 150 parts of methanol and left to 20 ° cooling down. The dye base is suctioned off, with methanol, then with Water washed and dried.

For the sulfonation of 10 parts was dissolved in Parbstoffbase h ^ parts 5 to lO ^ oleum and stirred at 15-25 ° until all of the water soluble. The dye, worked up in the usual way, dyes full and synthetic polyamide fibers in brilliant violet, lightfast and wetfast shades.

The same dye is obtained if 16 parts of l-amino-2-bromo-4- (5 ', 5 ¹ , 5 ^l- t ^r i ^rne ^ ⁿ yl ^c y ^c l ° hexylamino) -anthraquinone are mixed from 16 parts of phenol, 50 parts of nitrobenzene and 7.5 parts Kai iumhydr oxide as long as at ⁰ I50 heated until the Ausgangsv / are disappeared.

Example 28

A mixture of 2j5,2 parts of sodium-l-amino-Jf-C ^ ^1, 5 ', 5'-trimetlTylcyclohexylamino) anthraquinone-2-sulfonate, 15.5 parts;? 50 cent sodium hydroxide solution, Ί00 parts of water and 22 parts of 4-methyl-lmercaptobenzol is heated under reflux for 2k hours to 95-IOO ^0th 120 parts of ethanol are then added, the mixture is allowed to cool, the precipitated reaction product is filtered off, washed with ethanol, then with water and dried.

009822/1 ^ 98

\ D ORIGINAL

10 parts of the dye base thus obtained are dissolved in 50 parts of 100% sulfuric acid at 15-20 °. Then 15 parts of 25% oleum are instilled and the whole is stirred until a sample is completely soluble in water, poured onto ice, the precipitate is filtered off with suction, taken up again in 200 parts of water, neutralized and salted out. After filtering off with suction, washing, drying and grinding, a dark powder is obtained which dyes full and synthetic polyamide fibers in greenish blue, lightfast and wetfast shades. The same dye can also be prepared as follows: 11.1 parts of 1-amino ^ -bromo - *! - (j5 ', 5 ^f * 5' -trimethylcyclohexylamino) anthraquinone, 50 parts of 2- (2'-metho; sty -ethoxy) ethanol, 2 parts of anhydrous sodium carbonate and 5 parts of 4-methyl-l-mercaptobenzene be heated at 80-85 ⁰ until no starting material is detectable. The precipitate separated out with 40 parts of ethanol is filtered off with suction, washed with ethanol and with water and dried. The sulfonation is carried out in the manner described above.

The following table 3 contains further dyes of the formula

(XXVII),

which full and synthetic polyamide fibers in green-blue to red-tinged Coloring blue tones and using the substituents R.j, to R.g are marked.

009822/1298

- 44 - Table 3

example
No. ^R l4 ^R 15 ^R 16 R ₁₇ ^R l8 29 Sulfo-3-methylphenyl H H H H ■ 30th Sulfo-4-chlorophenyl H H H H 51 Sulfo-4-methoxyphenyl H H H H 32 SuIfO-2,5-dimethylphenyl H H H H 33 SuIfο-2-methoxyphenyl H H H H 34 Sulfo-2-methoxy-5-methylphenyl H H H- H 35 Sulfophenyl OH H H OH 36 do. OH H H NH ₂ 37 Sulfo - ^ - methylphenyl NH ₂ H H OH 38 do. NH ₂ H H NH ₂ 39 Sulfo-4-acetylaminophenyl H Cl H H 40 Sulfo-4-propionylaminophenyl H H H H 41 SuIfo-4-bromophenyl H S0-, H H H 42 SuIfo-4-n-butylphenyl H SO, H H ' H 43 do. H H H H 44 Sulfo-4-isopropylphenyl H H H H 45 Sulfo-4-ethylphenyl H H H H 46 SuIfO-4-tert-amylphenyl H H H H 47 Sulfo-4-ethoxycarbonylarnino- H H H H phenyl - 48 4-methylpheny1 H SHOE H H 49 4-kethoxyphenyl * H SO ₇ H H H 50 2-sulfato-ethyl H H H H 51 2-sulfato-propyl-l H H H H 52 l-sulfato-propyl-2 H H H H 53 l-sulfato-butyl-2 H H H H 54 4-sulfato-butyl-2 H H H H 55 3-sulfato-2-hydroxypropyl-1 H H . H H 56 do. OH H H * OH 57 2 -S ulf? ·: ■ ο »propyl -1 NH ₂ H H ; NH ₂ 58 2-sul- .o-ethyl NK ₂ H H OH 59 QO. H Cl H H 60 do. H H Cl H

009822/1298

BAD ORIGJNAl.

^R l: 4 ^R 15 ^R l6 191 ¹ 7051 example
No. 4- ( sulfophenyl) -4-methyl-
pentyl-2 H H R ₁₇ ^R l8 61 do. OH H H H 62 do. H SO H H OH 63 4- (SuIfophenyl) -butyl-2- H P.
H H H 64 6- (sulfophenyl) -2-methyl-
hexyl-4 H H H H- 6 ₅ do. H S 0, Ii H H 66 do. H H H H 67 do. OH H SO H
^ H '68 do. NH ₂ H H OH 69 4- (sulfophenyl) butyl-2 NH ₂ H H NH ₂ 70 do. H Cl H ■ OH 71 Sulfobenzyl H Cl H H 72 do. OH H H H ΊΊ> do.
2- (sulfophenylethyl) cyclohexyl NH ₂
H H
H H OH 74
75 2- (SuIf0-4'-methylbenzyl) -
cyclohexyl H H H
H NH ₂
H 76 2- (SuIfO-2 ', 4'-dimethylbenzyl) -
cyclohexyl H H H H 77 2- (J -SuIfO-2 ', 4', 6'-trimethyl-
benzyl) cyclohexyl H H H H 78 2 ~ (sulfo ~ 4'-methoxybenzyl) -
cyclohexyl H H H H 79 2- (SuIfO-4'-ethoxybenzyl) -
cyclohexyl H H H H · 8ο 2- (SuIfο-2 ', 4'-dimethoxybenzyl) -
cyclohexyl H H H H 81 2- (sulfobenzyl) -4-methyl-oyclo-
hoxyl .H H H H 82 do. H SO ^ H H H 85 2- (SuIfobenzyl) -4-ethyl-cyclo-
hexyl H H H H 84 2- (SuIfobenzyl) -4-tert-butyl-
cyclohexyl Η · SO ^ H H H 85 2- (SuIfobenzyl) -4-tert-amyl-
cyclohexyl H SO-, Η
P. H H 86 H II

Q09822 / 128Ö

example
No. ^R l4 ^R i5 ^R 16 ^r iy ^R l8 87 2- (SuIfobenzyl) -4-isooctyl- H SO-.H H H cyclohexyl ■ 88 2-methylphenyl H SO H H H 89 3-ctilophenyl H SO ^ H H H 90 4-methoxyphenyl H H SO H
^ H 91 4-acetylaminophenyl H SO H H H 92 3-acetylaminophenyl H SO ₃ H H H 95 2,4-dimethylphenyl H SO ₃ H H H 94 2,4,6-trimethylphenyl H SO ^ H H H 95 2-methoxy-5-methylphenyl H S 0, H
3 H H

The following table 4 contains further dyes of the formula

^R i8 °

NH-alkylene-CO-N-RjQ

^R 7

CH.

(XXVIII),

which wool and synthetic polyamide fibers dye green-tinged blue to red-tinged blue tones and are identified by the symbols alkylon, -R "and R ₁ , _ to R ₁₀ .

7 15 19

009822/1288

Tabel

example
No. Alkylene * 7 ^R 19 ^R 15 ^R 16 ^R 17 ^R l8 96 -CH ₂ - H Sulfophenyl H H H H 97 do. CH ₃ do. H H H H 98 do. C ₂ H do. H H' H H 99 do. H do. H Cl H H 100 do. H do. OH H H OH 101 do.· H do. NH ₂ H H NH ₂ 102 do. H do. NH ₂ H H OH 103 do. H Sulfo- * l-methylphenyl H H H H 104 do. H Sulfo-4-tert «butyl
phenyl H SO _a H
3 H H 105 do. H SuIf0-4-isopropylphenyl H H H H 106 do. H SuIf o-4-tert. amyl.phenyl H S0, H H H 107 do. H Sulfo-2,4-dimethyl-
phenyl H H H H 108 do. H 3-sulfo-2,4,6-trim-
thylphenyl H H 30 H. H 109 do. H Sulfo-U-methoxyphenyl H H H H 110 do. H Sulfo-2-methoxy-5-
methylphsnyl H H H H 111 do. Ή Sulfo-3-chlorophGnyl H H H H 112 do. H SuIf o- ² * -ace tylamino-
phenyl H H H H 113 do. H Sulfo- ^J i-ethoxycarbo ~
nylaminophenyl H H H H in the .CH ₂ -CH ₂ - CH Sulfophenyl H H H H 115 do. C ₂ H ₅ do. H H H H 116 do. H do. H Cl H H 117 do. H do. H H Cl H 118 do. H do. H SO ₃ H H H 119 do. H SuIf O-2 -me thyolphenyl H H H H 120 do. H Sulfo-3-methylphenyl H H H H 121 do. H Sulfo-4-methylphenyl H H H H 122 do. H Sulfo-4-ethylphenyl. H H H H

009822/1290

example
No. Alkylene ^R 7 ^R 19 ^R 15 ^R 16 ^R 17 ^R l8 125 -CH ₂ -CH ₂ • H Sulfo-2,4-dimethyl-
phenyl H H H Ή 124 do. H SuIf0-2,5-dimethyl-
phenyl H H H H- 125 do. H SuIf0-2,6-dimethyl-
phenyl H H H H 126 do. H Sulfo-2,4,6-trimethyl-
phenyl H H H H 127 do. H PuIfO-2,4,5-trimethyl-
phenyl H H H H 128. do. C ₂ H ₅ Sulfo-5-methylphenyl H H H H 129 do. C ₂ H SuIf 0 - ^l \ -me thoxyphenyl H H H H 150 do. H do. H H H H 131 do. H SuIfo-2-methoxyphenyl H H. H H 152 do. H Sulfo-4-chlorophenyl H H H H 133 do. H Sulfo-2-chlorophenyl H H .H H 1354 ' do. H Sulfo-4-ethoxyphenyl H H H H 135 do. H Sulfo-4-n-butoxyphenyl H SO, H H H 156 do. H SuIf o-k -n-amylphenyl H H SO ^ H H 137 do. H Sulfo-4-n-butylphenyl H SO H H H 138 do. H SuIfO-4-tert-butyl-
phenyl H 3 H- H 139 do. H Sulfo-4-isopropyl-
phenyl, H SO ₃ H H H 140 do. H Sulfo-2-methoxy-5-
methylphenyl H H H H 141 do. H SuIfO-2,5-dimethoxy
phenyl H H H H 142 do. H SuIfO-2,4-diethoxy-
phenyl H H H H 143 do. H Sulfo-4-ethyl-2-methyl-
phenyl H II H H 144 do. H Sulfo-2-methyl-4,6-di-
ethylphenyl H H H H 1 * 5 do. H SuIfO-2,4-dimethyl-6-
ethylphenyl H H H H 146 do. H SuIfo-4-acetylamino-
phenyl H H H >
H

009822 / 123d

example
No. Alkylene H ₇ ^R 19 ^R i5 ^R l6 ^R 17 ^R l8 147 -CH ₂ -CH ₂ - OH ₅ SuIfo-4-acetylamino-
phenyl H H H H 148 do. H Sulfo-4-propionylamino
phenyl H H H H 149 do. H Sulfo-4-butyrylamino
phenyl H SO ₃ H H H 150 do. H Sulfo-4-ethoxycarbonyl-
aminophenyl H H H H 151 do. H Sulfo-4-methoxycarbonyl
aminophenyl - H H H H 152 -CH-CH ₀ - H Sulfophenyl H H H H 153 do. CH ₅ do. H H H H 15 * -CH ₂ -CH- CH do. H H H H 155 CH ₃
do. H Sulfo-4-methylphenyl H H H H 156 do. H Sulfophenyl H Cl H H 157 do. H do. H H Cl H 158 -CH ₂ -CH ₂ - H do. OH H H OH 159 do. H do. NH ₂ H H OH 160 do. H do. NH ₂ H H NH ₂ 161 do. CH do. OH H H OH 162 do. H Sulfo-4-methylphenyl. OH H H OH 165 do. H Sulfo-4-chlorophenyl OH H H OH 164 do. H Sulfo-4-acetylamino
phenyl OH H H OH I65 do. H Sulfo-4-methoxyphenyl OH H H OH

The following Table 5 contains broader dyes of the formula

(XXIX),

L-CE-.

009 * 22/1298

which produce violet (if X stands for -0-) or greenish blue (if X stands for -S-) dyeings on wool and synthetic polyamide fibers and are identified by the symbols R ₁ ^ w ^ \ (· γ)> ^{x and R} p , are.

Tabe'lle «5

example ^R l (6) ^R K7) γ R. No. H H K ₂ 166 H H -Q- Sulfo-4-methylphenyl I67 H H -S- Sulfophenyl 168 H H -0- Sulfo-2-methylphenyl 169 H H -0- Sulfo-4-methoxyphenyl 170 H H -0- Sulfo - ^ - ethoxyphenyl 171 Cl H -0- Sulfo-4-n «butoxyphenyl 172 H Cl -0- Sulfophenyl 173 P. H -0- do. 174 Br H -0- do. 175 Cl Cl -0- do. 176 H H -0- do. 177 SO H H -0- Sulfo-4-isopropylphenyl 178 SO H H -0- Sulfo-4-tert-butylphenyl 179 SO ₃ H H -Q- SuIfo-4-tert-amylphenyl 180 SO ₇ H H "O ~ Sulfo-4-tert-octylphenyl 181 H H -0- Sulfo-'f-tert-nonylphenyl 182 H SO H "0- SuIfo-4-tert, butylphenyl 183 H H ■ "0- Sulfo »4-tertobutylphenyl 184 H H -0- Sulfo-4 »chlorophenyl 185 H H Sulfo-4-fluorophenyl 186 H H -0- Sulfo-4-bromophenyl 187 H H »0- Sulfofoenzyl 188 H H -S- do 0 I89 H H _O- 2- (sulfophenyl) ethyl 190 H H «0— 2-sulfato-ethyl-l 191 do 0

009822 / 1298-

example
No. ^R l (6) ^R K7) X R ₂ 192 H H -0- 2-sulfatopropyl-l 195 H H -0- j5-sulfatopropyl-l 194 • H H -0- 5-sulfatopropyl-2 195 H H -0- 2- (2'-sulfato-ethoxy) -
ethyl-1 196 . H H -0- 2- / 2 '- (2 "-SuIfato-ethoxy) -
ethoxy7-ethyl-l 197 Cl H -0- ^ -Sulfato ^ -hydroxy-
propyl-1

009822/1290

Claims (1)

Claims / Iy Anthraquinone compounds of the formula A ₁ - NH where A, one of the radicals (II) X - R, (III) O NH-R. (IV) or HO, S 0 NH-R, an R, a hydrogen, fluorine, chlorine or bromine atom or a -SO ₅ H group and the other R, a hydrogen atom or both R, chlorine atoms, -R ₆ -O-SO H or - AAkylene-CO-N R, , -R ₉ -O-SO ₃ H, 009822/1298 - ^R io <y SO-H FU secondary alkyl with 2 to 6 carbon atoms, cyclohexyl / OC ^ ^R 8 ^ n or J5,5,5-Trime thy 1 cyclohexyl, or · / y R ₁ - hydrogen, alkyl or alkoxy with 1 to 9 carbon-P atoms or halogen, R ₆ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH-, -CH-CH ₂ -, - ( CH, CH, OH or -CH ₂ -CH ₂ - (O-CH ₂ -CH ₂ ) P-, R "hydrogen or lower alkyl, Rg hydrogen, lower alkyl or alkoxy, halogen or low acylamino,
R_ —CHp-CHp-, —CHp-CHp-CHp-, —CHp-CH-, —CHp-CH-CHp-, -CH-CHp- OH C ₂ H or -CH- (CH ₂ ) _r , R- _A -CH ₀ -,, -CH-CH ₀ -C-, -CH-CH ₀ -CH ₀ - or JU d. 1 tL 1 dc -CH-CHp-CHp-, NlH ₅
Hydrogen or alkyl with 1 to 8 carbon atoms, -CH ₂ -, -CH ₂ -CH ₂ - or -CH-, CH ₃ -O- or -S-, Alkylene -CH -, -CH ₀ -CH ₀ -, -CH-, -CH ₀ -CH- or -CH-CH ₀ -, CH, CH, CH ,? 3 2 jn 1 or 2, η "1 to J,
p_ 1 to 9, r_ mean 1 to 6,
the SO, H group in the formula (V) is in the 6- or 7-position, the nucleus B is a chlorine atom or an S0, H group in the 6- or 7-position or two hydroxyl or amino groups or one hydroxyl each - and can carry an amino group in positions 5 ^and 8, the nucleus can carry C 1 to 3 low molecular weight alkyl or alkoxy groups and, if η stands for 2 or 2, each substituent Rg can have its own meaning. 2. The anthraquinone compound of the formula «F2 / ^ S ^ S ^ - ^S ° ' ^H IIIJ ' (VI) Ö NH U H 00932 2 / Anthraquinone compounds of the formula O NH __O - R, CH. (VII) O NH CH, CH. wherein R _{2 has} the meaning given above. k, anthraquinone compounds of the formula (VII), in which R ₂ denotes the radical of a sulfonated phenol, optionally bearing an alkyl group in the para position, or a sulfated 2-hydroxyethyl or 2- or 3-hydroxypropyl or 2,3-dihydroxypropyl radical. 5. Anthraquinone compounds of the formula O NH-R (VIII) wherein R, has the abovementioned meaning. 6. Anthraquinone compounds of the formula (VIII),. wherein R, a sulfonated optionally 1 to 3 lower alkyl 009822/1298 groups, a lower alkoxy or acylamino group-bearing benzene radical, a sulfonated benzyl or phenylalkyl radical, the alkyl radical being bonded to the amino group through a secondary carbon atom, or a rest R ₇ ^ SO ₅ H fc. means, where m is 1 or 2, R ₇ for hydrogen, methyl or ethyl and Rg for hydrogen, methyl, ethyl, chlorine, methoxy, ethoxy , or acetylamino. 7. Process for the preparation of the anthraquinone compounds of the formula I, characterized in that 1 mol of J5,5,5-trimethylcyclohexylamine is mixed with 1 mol of an anthraquinone compound of the formula O NH, (X)
Hal O. NH-R ^ or H0, S— (I ^ f T Ί · (Xl) 009822/1298 in which Hal and R ,, Chlorine, bromine or fluorine, bromine or -SO, H, -Alkylene-CO «F SO, H or -alkylene-CO-N K- mean, reacts, and if Y stands for bromine, treated with a water-soluble neutral sulfite and, if R ₁ - does not have a -SO, H group, treated with SO, or an SO ^ -releasing agent « 8. Modification of the method according to claim 7, characterized in that that 1 mol of an anthraquinone compound of the por- 0 shark (XII) with 1 mole of an amine of the formula R - ^ - NHg and, if the remainder does not contain a -So.H group, with SO, or a SO ^ -abhabenclen 009822/1298 Means treated. 9. Modification of the method according to claim 7, characterized in that that one mole of an anthraquinone compound of the formula O NH ₂ (XIII) with a compound of the formula Hal- / \, Hal-R _g -OH, Hal-CH ₂ - / ~~ \ or H0-CH ₂ - / ~~ \ implements and treated with S0_ or a SO, -releasing agent, or with 1 mole of a double bond in the α-position Alkylenedarboxylic acid with J5 or 4 carbon atoms or a haloacetic acid or their functional derivatives, then in the presence of an inorganic acid halide with an amine of •Formula HN- / Λ (XIV) amidated and treated with SO, or an S Q- releasing agent, 00 9822/119 10. Process for the preparation of anthraquinone compounds of 0 ,, "- Η, (XV) characterized in that 1 mol!, ^ - Dihydroxyanthraehinon-ro · or -7-sulfonic acid is reacted with 1 mol of 3,5,5-trimethylcyclohexylamine and 1 mol of an amine of the formula Ru-NH ₂ , or that 1 mol of a compound is reacted of the formula (XII), vrorin the core B carries a sulfonic acid group, with 1 mol of a compound of the formula R ^ -NHp. 11. Process for the preparation of anthraquinone compounds of the formula 0 NH _(XVI) characterized in that one mole of an anthraquinone compound of formula (IX) with 1 mol of 2,5,5-triniethylgyclohexylamine and the reaction product obtained with 1 hol of a compound of the formula HX HX-R ₆ -OH or implements and treated with SO or a SO ^ -releasing agent. 009822/1298 - 6ö - 12. Use of the anthraquinone dyes of the formula (1) for dyeing, padding and Bedructea yon MoIIe ₃ 5- @ tde, - Haaren ^ s sohen Polyamid- and Polyurethanf ομ & ρά as well as leather » IJ. The materials printed according to claim 12 Gefäffefeen ^. 009822/1298