DE2300591A1 - Nitro-anthraquinone dispersion dyes - contg. 1-phenyl-amino substit. grps., for synthetic fibres, esp. polyesters and cellulose esters - Google Patents

Abstract

The dyes are of formula: (in which R is opt. substd. phenyl, one X is nitro and the other is hydrogen). R pref. contains up to 2 substits., consisting of 1-4C alkyl, halogen, hydroxy, or 1-4C alkoxy or 2-5C alkyl carbonyl opt. further substds. with hydroxy or 1-4C alkoxy. The dyes or their mixts. are suitable for dyeing and printing synthetic fibres in fast brown, navy blue, dark blue and black shades.

Description

Nitroanthraquinones The invention relates to the use of compounds of the general formula which are free from sulfonic acid groups in which R is an optionally substituted phenyl radical, one X is a nitro group, the other X is hydrogen, or mixtures thereof for dyeing and printing synthetic fiber materials.

Suitable substituents on R are alkyl, cycloalkyl, aralkyl, aryl, Cycloalkoxy, aralkoxy, aryloxy, alkoxy, alkoxycarbonyl, alkoxycarbonyloxy, acylamino, in particular alkylcarbonylamino, alkylsulfonyl, arylsulfonyl, alkylaminocarbonyloxy, Acylaminocarbonyloxy, alkylaminocarbonylamino, acylaminocarbonylamino, altylaminothiocarbonylamino, Alkylaminosulfonyloxy, acylaminosulfonyloxy, amino, mono- and dialkylamino, arylcarbonyloxy, Alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, amino, alkylsulfonyloxy, arylsulfonyloxy, Alkoxysulfonyl, aryloxysulfonyl, Alkoxycarbonyl, alkylaminosulfonyl, Aralkylaminosulfonyl, dialkylaminosulfonyl, halogen such as F, Cl, Br, carboxy, cyano, Nitro, hydroxy and cycloalkylamino.

Alkyl as a substituent on R preferably has 1-12 C atoms and can include others Contain substituents of the group mentioned above.

The other alkyl and alkoxy groups preferably contain 1 - 4 G atoms, Cycloalkyl and Oycloalkoxygruppen and especially those with 5 - 7 carbon atoms. at the aryl radicals are preferably phenyl radicals. The groups mentioned can further substituted by amino, hydroxy, carboxy, cyano, halogen or C1-C4-alkoxy be.

Examples of I are 1-anilino-6- or -7-nitro-anthraquinone, 1-gmethyl-, 2 ', 6'-dimethyl-, 2', 4 ', 6'-trimethyl-, ethyl-, 4'-tert-butyl-, 4'-dodecyl-, 2'-methyl-6'-ethyl, 2 ', 4'-dimethyl-6'-ethyl, chlorine, bromine, fluorine, cyano, methoxy, Ethoxy, ß-hydroxyethoxy, ß-cyanoethoxy, 3'-chloro-4'-methoxy, 2'-methyl-4'-methoxy, 2 ', 5'-dietoxy, 4'-methylaminomethyl, 4'-phenyl, 4'-cyclohexyl, 2', 5'-dimethoxy, 2'-, 3'- or 4'-dimethylaminomethyl-, 4'-phenoxy-, 4'-methylthio-, 4'-phenylthio-, 3 '- (ß-Hydroxyäthylsulfonyl) -, 3'-Phenylsulfonyl-, 2'-, 3'- or 4'-Amino-, Acetylamino-, N-methylacetylamino-, N-cyclohexyl-acetylamino-, hydroxyacetylamino-, methoxyacetylamino-, Phenylsulfonyloxy-, methylsulfonyloxy-, phenoxysulfonyl-, ethoxysulfonyl-, 4'-acetylamino-2 ' -carboxy-, methoxycarbonyl-, acetyl-, phenylcarbcinyl-, diethylaminosulfonyl-, N- (ß-hydroxyethyl) -N- (ß-cyanoethyl) -aminosulfonyl-, N, N-Di (B-cyanäthylamino) -sulfonyl-, ß-Phenyläthylaminosulfonyl-, ß-Hydroxyäthoxy-ethoxy, γ-Hydroxypropoxy-, ß-Hydroxyäthylmercapto-, N- (ß-Hydroxyäthylamino) -carbonyl -, ß-γ-dihydroxypropoxyphenyl, also methoxy, cyclohexyloxy, benzyloxy and phenoxycarbonylamino, o-p-propyloxy-; o-p-tert. Butyloxy-; o-, p-methoxyethoxy-; 4'- or 5'-chloro-2'-methoxy-; 4 ', 5' .- dichloro-2'-methoxy-; 2'-, 3'- or 4'-hydroxy-; 3 ', 5'-dichloro-4'-hydroxy-; 4'-chloro-3'-hydroxy-; 2- or 3'-methoxy-4'-acetylamino] -anilino-6- or 7-nitro-anthraquinones. Furthermore, alkyl, hydroxy, alkoxy, amino subst. 1-anilino-6, (7) -nitro-anthraquinones, which in the aniline residue by one or more phthalimino-N-methylene, Caprolactam-N-methylene, propionylaminomethylene, succinimidomethylene, benzoylaminomethylene, Carbamoylaminomethylene or carbethoxyaminomethylene radicals are substituted.

Binds preferred group of dyes within Formula I. corresponds to the formula > R2 (II) O where R1 and R2 are independently hydrogen, hydroxy, C1-C4-alkyl, halogen, C1-C4-alkoxy, amino or C1-C5-alkylcarbonylamino and X has the meaning given above. The alkoxy groups can be further substituted by hydroxy or C1-C4-alkoxy.

Particularly preferred are compounds of the formula II in which R1 is hydrogen, Chlorine, bromine, hydroxy, C1-C4-alkyl or C1-C4-alkoxy, with the alkoxy radical through Hydroxy or C1-C4-alkoxy can be further substituted, and R2 is hydrogen, while X has the meaning given above.

You can make these compounds by reacting 1,6 or 1,7-Dinitro-anthraquinone with amines of the general formula H2N-R (III) where R is the in formula I has the meaning given. Technically and economically particularly advantageous it is, however, to implement mixtures of 1,6- and 1,7-dinitro-anthraquinone.

Mixtures of this kind can easily be separated off from 1,5- and 1,8-dinitro-anthraquinone win from the anthraquinone dinitration.

The reaction takes place in organic solvents at temperatures from 60-2000C, preferably at 80-1500C.-The ß-nitro groups not attacked. High-boiling halogenated or nitrated solvents are used Hydrocarbons, such as dichloroethane and tetrachloroethane, chlorobenzene, o-dichlorobenzene, Trichlorobenzene and especially nitrobenzene, or those of a hydrophilic type, such as riethanolamine, Pyridine, dioxane, dimethyl sulfoxide, sulfolane and especially dimethylformamide are possible. It is also advantageous to use the bases of the formula III in excess as solvents to use.

One can thereby neutralize the primarily split off nitrous Acid acid-binding agents, such as salts of weak inorganic or organic acids, for example the Na, K, Mg salts of carbonic acid or acetic acid, or else organic or inorganic bases such as triethanolamine, pyridine, quinoline or magnesium oxide to add.

The conversion times depend on the type of amine to be converted, on the chosen reaction temperature and the concentration of the reactants. The reaction times can vary within wide limits, depending on the choice of conditions; they are usually between 4 and 10 hours. The isolation of the reaction products can in a manner known per se by diluting with low molecular weight alcohols or by evaporating the reaction mixture, preferably in Venuleth. If compounds of the formula III are used as solvents, the reaction products can also by dilution with optionally aqueous mineral acids or organic Acids are deposited.

Of course, after the reaction at R, further chemical Carry out conversions, e.g. acylate existing amino groups or existing acylamino groups saponify or hydroxyl groups by alkylation into alkoxy groups or by acylation convert into ester groups. Exposure to halogens such as chlorine or bromine halogen-releasing agents, such as S02C12 or SOC12, HN03 or HN03-H2S04 mixtures you can prepare compounds of the formula I in which R is one or more C1, Br or contains N02 groups. The reaction with methylene-active compounds, e.g. N-methylolcaprolactam, allows the introduction of residues that are linked via a methylene bridge. Sulfonyl residues can be removed by sulfochlorination and subsequent replacement of the Introduce chlorine against residues containing amino or hydroxyl groups.

The compounds of the formula I are particularly suitable for dyeing and Printing on synthetic fibers such as cellulose triacetate, polyamide and above all Polyester fibers. They can also be used in solvent coloring.

Polyester fibers can be used in a known manner after the carrier, High temperature or thermosol processes can be colored.

Also as basic products for brown, navy blue, dark blue and black They are eminently suitable for dye settings. For example, by combining with commercial blue (green) a dye real navy blue polyester dye produce.

The dyeings and prints obtained have good fastness properties the end.

Example 1 a) 1Q g of strand material made of polyethylene terephthalate in a liquor of 400 ml of water, Q, 4 g of a mixture of 1-anilino-6- and -7-nitro-anthraquinone in finely divided form, 3.4 g of a mixture of o-, m-, p-cresotinic acid methyl.

ester and 0.6 g of a mixture of equal parts of an anionic Dispersing agent and a non-ionic polyglycol ether after adding sulfuric acid Colored until a pH value of 4.5 has been set for 2 hours at 96-980C, then is rinsed and dried. A deep reddish purple color is obtained, which is very lightfast.

b) The dye mixture used in a) can be obtained as follows are: 298 g of a mixture of 1,6- and 1,7-dinitro-anthraquinone (80.4 ig) become stirred into 900 ml of aniline and stirred at 100 - t050C until a sample no more input material can be detected (approx. 8 hours required), one dilutes at 50-60 ° C. within 2 hours with 900 ml of methanol, stirred for 2 hours, sucks the crystalline precipitated reaction product, washes it with a solution of 150 g of aniline in 300 ml of methanol, finally with 300 ml of methanol and hot water and dries at 80 ° C. 277 g of a mixture of 1-anilino-6- and -7-nitro-anthraquinone.

c) The dinitro-anthraquinone used in b) can be obtained as follows are: 10 kg of anthraquinone are dissolved in 40 kg of 20% oleum, in 2 hours below 50 ° C with 20.6 kg of a mixture consisting of 33% HNO3 and 67% H2S04, added, heated to 90 ° C. in 2 hours and held at this temperature until no anthraquinone and monoitration product are more detectable. One stirs cold, sucks the separated 1,5- and 1,8-iinitro-anthraquinone and washes the filter material in portions 37 kg of anhydrous sulfuric acid. The effluent broths (approx. 91 kg) are at 1000C filtered, stirred cold up to 700C, cut into approx.

1 hour with 7.8 ltr. Water is added, which increases the temperature 80 - 85 ° C increases. After a further 50 minutes, it is suctioned off at 80 ° C. and washed with 20 kg of 88% H 2 SO 4 after. After washing neutral and drying, 3.3 kg of one is obtained Product which is composed as follows: 1,6-dinitro-anthraquinone 41.8 ffi 1.7 38.6 ffi 1.8- "" 12.0% 1.5- "" 1.6% 2.6- + 2.7-dinitro- "<1.0% hydroxy-dinitro- "1.2 ffi Example 2 au 1 g of a rag made of polyethylene terephthalate are in a liquor with a pH of 4.5 from 400 ml of water and 0.4 g of the finely divided water Dye mixture of 1-m-toluidino-6- and -7-nitro-anthraquinone and 0.3 g of one Mixture of equal parts of an anionic dispersant and a nonionic one Polyglycol ether dyed for 2 hours at 120 - 130 ° C. After rinsing and drying a deep purple color is obtained.

b) If cellulose triacetate is treated according to one of the examples in la) and 2a) given instructions with the same dye mixture, one also obtains purple tints.

c) The dye mixture used in a) and b) can be reacted of 1,6- and 1,7-dinitro-anthraquinone with m-toluidine analogous to that in Example Ib) given prescription.

Example 3 a) A fabric made of polyethylene glycol terephthalate fibers is impregnated on the padder with a liquor containing in 1000 g 20 g of the finely divided present dye 1- (p-tert-butyl-anilino) -6-nitro-anthraquinone and 10 g of a polyether described in Belgian patent 615 102 as a thermosol auxiliary contains.

The tissue is then squeezed off to a weight gain of 70% and dried in a floating nozzle dryer or in a drying cabinet at 80 - 1200C. Then the fabric is placed in a stenter or in a DUsenhot-flue approx. Treated with hot air for 45 seconds at 190 - 20000, then rinsed, possibly reductively aftertreated and dried. The reductive aftertreatment for removal of dye components adhering to the surface of the fibers can take place in such a way that one with the tissue at 2500 in a 3 - 5 cm3 / ltr. Caustic soda from 380 Be and @ - 2 g / ltr. Hydrosulfite (concentrated) containing liquor enters, within approx. Heated to 700C for 15 minutes and left at 700C for a further 10 minutes. Afterward is rinsed hot, with 2 - 3 cm3 / ltr. 85% formic acid acidified at 5000, rinsed and dried. You get a clear purple tint that is reflected characterized by good fastness to light, heat setting, rubbing and washing.

A very similar color is obtained if the polyethylene terephthalate fibers are used instead Polyester fibers made from 1,4-bis-hydroxymethylcyclohexane and terephthalic acid are used.

b) The product used in a) can be obtained as follows: 15 g 1,6-dinitro-anthraquinone and 30 ml p-tert.

Butyl aniline are stirred at 125 ° C. until no dinitro anthraquinone more is detectable (approx. 6 hours required). One dilutes in the warmth with 30 ml of ethylene glycol monomethyl ether, stirs cold, sucks off and washes successively with ethylene glycol monomethyl ether and water.

13.9 g of 1- (p-tert-butyl-anilino) -6-nitroanthraquinone are obtained.

Example 4 a) A pre-cleaned and heat-set fabric made of polyethylene terephthalate fibers is printed with a printing paste consisting of the following components: 40 g a mixture of 1- [m (p) -acetylamino-anilino] -6 (7) nitro-anthraquinone, 475g water, 465g crystal gum (1: 2) and 20g sulfated castor oil.

An alginate thickening can also be used instead of crystal rubber Find. The printed and dried goods are used for dye fixation at 190 - 2000C through a high-performance stenter frame or through a condensation apparatus drove. The exposure time is 30 - 60 seconds.

The fixed print obtained is then rinsed with cold water 1 - 2 g / ltr. soaped with anionic detergent at 70 - 800C for approx. 10 minutes, first rinsed hot and then cold and dried. A violet print is obtained, the is characterized by good fastness properties.

b) The components used in a) can be found in the technical Mixture of 1,6- and 1,7-dinitro-anthraquinone (see Example 1c) either through Conversion with m- or p-acetylamino-aniline with the addition of dimethylformamide at 130 - 140 ° C or by conversion in excess m- or p-phenylenediamine and subsequent Acetylation obtained in pyridine as a solvent.

Example 5 a) A fabric made of cellulose triacetate is, as in Example 3a), but with 15 g each of 1-m-anisidino-6 (7) -nitroanthraquinone and 1-p-anisidino-6 (7) -nitro-anthraquinone padded and then as described there, but Treated with hot supply air at 21000. A deep bluish purple is obtained Very good color fastness to light and sublimation.

b) The dyes used in a) are obtained by reacting 1,6- and 1,7-dinitro-anthraquinone with m- or p-anisidine either analogously to that in Example 1a) given instructions, the reaction with m-anisidine longer reaction time requires than the one with p-anisidine, or one puts dinitroanthraquinone in the 2-3 times the amount of nitrobenzene at 150-1600C with the addition of 2 mol anisidine / mol Dinitroanthraquinone.

Example 6 a) 100 g of a fabric made of textured polyethylene terephthalate fibers are placed in a dye bath at room temperature without pre-cleaning 1 g 1- (p-hydroxy-anilino) -6- and -7-nitro-anthraquinone and 1000 g tetrachlorethylene is prepared. The bath is under vigorous liquor circulation within 10 minutes heated to 1150C and held at this temperature for 30 minutes. Then the fleet separated and the dyed material rinsed with fresh solvent for 5 minutes at about 400C. After the rinsing fleece has been separated off, the material to be dyed is centrifuged and dried in a stream of air. A blue-tinged, ruby-colored dyeing with very good sublimation fastness is obtained as well as good wash and rub fastness properties.

An equivalent staining was done in the same way on one Obtained fabric from polycyclohexane-dimethylene-terephthalate fibers.

If the tetrachlorethylene is decomposed by the same amount of 1,1,2-lrichloroethane, in this way an equivalent color is obtained.

b) 100 g of yarn made of acetate threads are put in a dye bath at approx. 220C introduced, that of 1.0 g of the dye used in Example 6a), 1000.0 g Tetrachlorethylene, 1.5 g oleic acid ethanolamide, 1.5 g oleyl alcohol heptaethylene glycol ether and 6.0 g of water is prepared. One warms the bath within 20 minutes to 78 ° C and keep it at this temperature for 45 minutes.

After separating the dye liquor and rinsing with fresh tetrachlorethylene the dyed material is removed from the solvent by suction and drying in a stream of air freed.

A blue-tinged ruby coloration is obtained.

c) The dye mixture used in and b) can be composed of 1 -p-anisidino-6 ( 7) -nitro-anthraquinone by ether cleavage in 10 g of 78 - 80% H2S04 at 4oO "(approx. 6 hours required) can be obtained in quantitative yield.

Polyethylene terephthalate or cellulose triacetate fibers are dyed or printed according to one of the instructions described in Examples 1-6 with the dyes of the formula listed in the table in this way, violet dyeings or prints are obtained with a strong reddish - slightly bluish tint. The indication 6 or 7 in the second column means that dyeing was carried out with a pure dye whose nitro group is in the position indicated, while the indication 6.7 indicates the use of a dye mixture.

Table of substituents in the example position 2 3 4 5 6 NO2 7 6 HHHHH 8 6.7 CH3 HHHH 9 7 H CH3 HHH 10 6 HH CH3 HH 11 6.7 HH CH3 HH 12 6 CH3 HHH OH3 13 6.7 H3 H CH3 11 0113 14 7 C- (CH3) 3 H CH3 HH 15 6.7 H Cl HHH 16 6.7 HH Cl HH 17 6.7 H Cl Cl HH 18 6.7 HH N-CQ-CH3 HH CH3 19 11 K -NH-C0-GHD HHH 20 6.7 HH <HH 21 6.7 E Br HKH 22 6 H NH2 XHH 23 6 CH3 H -CH2-N ß HH 0 24 6 CH3 SO2NH2 C2H5 H OH3 25 7 SO2-NH-CH3 H OH HH 26 6.7 HH 11 <XH 27 6.7 HHHH -So 28 6 HH NH-CQ-CHX H 11 C2Hs Substituent in e.g. position 2 3 4 5 6 NO2 29 7 HH S-CH2-CH2-OH HH 30 6 H CN HHH 31 6 H oH 11 11 11 NH-CO-CH, 32 6 CH3 HH N-OO-O113 H 02H5 33 7 HH -S-CHD HH 7 7 S02-0-CH3 H CH3 11 H 35 6.7 U OH3 O1 HH 36 7 H OF'3 HHH 37 6.7 HH 02115 HH 38 6.7 H 0113 H CH3 H 39 6 H 11 C12H25 11 H. 40 6 HH NH-CH3 HH 41 6.7 HHH o CH3I- \ 11H 42 6.7 H NH-CO-CH3 OH3 KH 43 6.7 11 H 4 HH 44 6.7 00113 HHHH 45 7 00113 HHHH 46 6.7 H OCH3 HHH 47 6.7 H 11 OX HH 48 7 H OH 11 EH 49 6.7 -O-CH, -0-CH2-C-OH HHHH 50 6.7 11 - H OC2H5 HH 51 6 H 3 7 HH 52 6.7 STILL, H 11 OCH3 H 53 6 H OH Ol 11 H 54 7 H Cl OH Ol 11 Substituent in e.g. position 2 3 4 5 6 NO2 55 6.7 CH3 H OCH3 HH 56 6.7 OC2H5 HH CH3 H 57 6 OCH3 H Cl OCH3 H 58 6.7 OCH3 H Cl CH3 H 59 6.7 OCH3 H NH -COCH3 HH 60 6.7 OC2H5 HH OC2H5 H 61 7 O- (C2H4O) 2CH3 HHHH

Claims (7)

Claims: 1. Use of compounds of the formula in which R is an optionally substituted phenyl radical, one X is a nitro group, the other X is hydrogen, or mixtures thereof for dyeing and printing synthetic fiber materials. 2. Use of compounds according to claim 1, characterized in that R where R1 and R2 are independently hydrogen, C1-C4-alkyl, halogen, hydroxy, C1-C4-alkoxy or C2-C5-alkylcarbonylamino optionally further substituted by hydroxy or C1-C4-alkoxy. 3. Use of compounds according to claim 2, characterized in that that R1 is hydrogen, Cl, Br, hydroxy, C1-C4-alkyl or C1-C4-alkoxy, where the Alkoxy radical can be further substituted by hydroxy or C1-C4-alkoxy, and R2 stand for hydrogen. 4. Use of compounds according to claims 1 - 3 for dyeing and printing on polyester and cellulose ester fiber materials. 5. Use of compounds according to claims 1-3 for dyeing of polyester fiber materials. 6. Synthetic fiber materials, dyed or printed with dyes of claims 1 - 3. 7. Polyester fiber materials, colored with dyes of the claims 1 - 3.