MXPA97006138A

MXPA97006138A - Benzoxazolilisoindoleni

Info

Publication number: MXPA97006138A
Application number: MXPA/A/1997/006138A
Authority: MX
Inventors: Lorenz Manfred
Original assignee: Bayer Aktiengesellschaft
Priority date: 1996-08-16
Filing date: 1997-08-12
Publication date: 1998-02-01

Abstract

The present invention relates to: Compounds corresponding to formula (I) or their tautomeric forms (See Formula) where R 1, R y X have the meaning indicated in the description, are especially suitable for dyeing and printing synthetic or hydrophobic materials semi-synthetic, especially such for car upholstery

Description

BENZOXAZOLILISOINDOLENINAS FIELD OF THE INVENTION The invention relates to benzoxazolyl isoindole-nines, to processes for their preparation as well as to their use for the dyeing of synthetic or semi-synthetic hydrophobic materials.

Background of the Invention It is already known from DE-A 16 70 748 isoindolenine dyes similar to those of the formula (I), but which nevertheless still have drawbacks from the point of view of the application technology.

As a disadvantage from the point of view of the application technology, for example, absorption or texturing capacities that are too low during polyester dyeing or a light fastness mass, especially hot light fastness, such as those that they are required when textiles dyed with them are used in the automotive sector.

REF: 25404 Description of the invention Benzoxazolilisoindoleninas have been found, corresponding to the formula I or tautóras eras forms wherein R x means a saturated or unsaturated aliphatic radical, optionally substituted, with 1 to 12 carbon atoms, which may be interrupted, if appropriate, by one or more oxygen atoms, a cycloaliphatic radical optionally substituted with to 12 carbon atoms or means a araliphatic radical, optionally substituted by 7 to 20 carbon atoms, x means a number from 0 to 4, preferably means 0, 1 or 2, R are the same or different and mean halogen, especially Cl or Br, alkenyl having 1 to 10 carbon atoms, especially alkyl having 1 to 4 carbon atoms, alkoxy or alkoxyalkoxy having 1 to 10 carbon atoms, especially with 1 to 4 carbon atoms, saturated or unsaturated, CN, N02, or as long as x is greater than 1, it means the remainder of a ringed benzene ring. All the formulas described in this application represent certainly only a tautomeric form, insofar as they can be imagined several of them, of the corresponding compound (s), however it is representative of all the imaginable tautomeric forms. Furthermore, the invention encompasses an E or Z isomer described by means of a formula, especially as regards the exocyclic double bond (s), and also the other isomer. It is valid, insofar as nothing else is expressly stated. As tautomeric forms of the compounds of the formula (I), there can be cited, for example, the two formulas Possible substituents of the aliphatic, cycloaliphatic as well as araliphatic moiety in R.sup.1 can be mentioned, for example CN, saturated or unsaturated oxytoste with 4 carbon atoms, such as alkoxy with 1 to 4 carbon atoms, allyloxy and / or an acyloxy moiety as 2-acetoxyethyl. Suitable radicals R are, for example: methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, 2-methoxy- ethyl, 2-ethoxy-ethyl, 2-butoxy-ethyl, 3-methoxy-propyl, 3-ethoxy-pro-pyl, 3-butoxy-proyl, 3-allyloxy-propyl, 2-ethyl-hexyl, 3- (2-ethylhexyloxy) -propyl, butoxyethoxy-ethyl, 2-phenoxy-ethyl, benzyl, cyclohexylmethyl, cycloheptyl, cyclopentyl, furfuryl. As Rx branched radicals, preference is given to those with a methyl side chain, such as, for example, iso-butyl or iso-pentyl. Alkyl radicals Rx with 4 and more carbon atoms are preferred. Preferred R resins are chlorine, methyl, methoxy and ethoxy. Dyes of the formula (I), in which R? means a straight chain aliphatic radical with 4 to 8 carbon atoms, which is interrupted, if appropriate, by an oxygen atom and R means chlorine, methyl, methoxy or ethoxy and x means 0 or 1. Very particularly preferred dyes of the formula (I) are those in which Rx means a straight chain aliphatic radical with 4 to 8 carbon atoms, which may be interrupted by an oxygen atom and x means 0. The invention also relates to a process for obtaining of the compounds of the formula (I), characterized in that either a compound of the formula (II) is condensed with an ester of the cyanoacetic acid of the formula (III) according to the reaction equation or a compound of the formula (IV) is condensed with 2-a-ino-benzooxazoles of the formula (V) according to the reaction equation where R, R1 and x have the meaning indicated above. An ammonia equivalent is released in the reactions respectively. The compounds of the formula (IV) are already known from DE-A-16 70 748. Particularly preferably, the process according to the invention is carried out by reacting compounds of the formula (II) with those of the formula (III). The reaction of (II) with (III) or of (IV) with (V), particularly preferably (II) with (III) is preferably carried out in water, in organic solvents, preferably polar organic or in mixtures thereof. As polar organic solvents there may be mentioned, for example: amides, such as dimethylformamide, formamide, dimethylacetamide, N-methylpyrrolidone, in addition diaethylsulfoxide, acetonitrile or acetic acid. In a preferred embodiment, the reaction is carried out in an alcohol based on the radical R1. These solvents can be used alone or as a mixture. The process according to the invention is preferably carried out at reaction temperatures of 50 to 150 ° C, especially of 60 to 100 ° C. Components (II) and (III) can be used in equivalent amounts or one of them in excess, an excess in esters of cyanoacetic acid being advantageous from 5 to 50%, preferably from 5 to 30%, since it has been observed, surprisingly , that this leads to especially short reaction times and very pure end products. In the configuration of the present invention it has surprisingly been found that it can be used for the reaction of the compounds of the formula (II) with compounds of the formula (III) according to the above reaction scheme, also water or an aqueous medium such as means of the reaction. In addition to water, organic solvents can be added, particularly those which are totally or partially miscible with water, such as, for example, alcohols, preferably the alcohols on which the radical R 1 # is based, such as, for example, acetone, methyl ethyl ketone, cyclohexanone, ethers such as tetrahydrofuran and dioxane, dimethylformamide, N-methylpyrrolidone and the like. However, non-miscible solvents can also be added with water, to improve, for example, the crystallinity and to obtain special crystalline forms. These solvents can be added from the beginning during the course of the reaction. In a particularly preferred embodiment of the process according to the invention, it will be worked in the presence of an organic acid. This leads, as a rule, to an acceleration of the reaction, often also achieving higher yields and a higher purity. Suitable organic acids are, for example, the aliphatic, saturated or unsaturated mono- or dicarboxylic acids, such as, for example, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, fumaric acid, maleic acid, succinic acid. , glutaric acid, adipic acid, as well as also aromatic acids such as for example benzoic acid, phthalic acid, phenylacetic acid, iso- and terephthalic acid. The acids are preferably added in amounts of 0.2 to 3 equi-valent, preferably 1 to 2 equivalents, based on components II, III, IV or V. However, higher amounts of acids can also be added, preferably when the acids serve at the same time as solvents, for example acetic acid. If water or a predominantly aqueous medium is used as the reaction medium, it will be advantageous to add surface-active substances such as, for example, surfactants, dispersants, emulsifiers and humectants. The known non-ionic, anionic and cationic auxiliary agents come into consideration. Such compounds are, for example, salts of acids to the hydrochloric acid, alkylphene-sulphonic acids, alkylnaphthalenesulphonic acids, condensation products of phenylsulphonic acids, formaldehyde and urea, lignin sulfonates, addition products of ethylene oxide and propylene oxide on alkanols, alkanediols, phenols, carboxylic acids, amines, amides of carboxylic acids and their semi-esters with sulfuric acid, mixtures of these compounds can also be used. However, lignin sulfonates such as, for example, kraft lignin of the Reax * type from the Westvaco firm or sulfur lignin of the Ufoxane * type from the Borregaard company are particularly preferred. The compounds of the formula (IV) are preferably obtained by reacting the aminoiminoisoindolenyl of the formula (VI) with esters of the cyanoacetic acid of the formula (III) (VI) (III) (IV) and the compounds of the formula (II) are preferably obtained by reaction of aminoiminoisoindolenine (VI) with 2-aminobenzoxazoles of the formula (V) where R, Rx and X have the meanings indicated above. The preparation of the monocondensates (IV) or (II) is preferably carried out by heating the components (VI) and (III) or (VI) and (V) in water, in an organic solvent or in mixtures of the solvents used are the solvents already mentioned above, in particular amides, for example formamide, dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone and, preferably, alcohols, especially lower alcohols, such as methanol, ethanol, propanol and iso-propanol. Organic acids which, in general, accelerate the reaction, are preferably added in order to obtain the monocondensates. In this case, the same acids as those which have already been described above come into consideration. In the same way, an aliphatic amine addition acts, as a rule, in an accelerating manner, the cycloaliphatic amides being particularly suitable. Such amines are, for example, piperidine, piperazine or morpholine. It is advantageous to carry out the reaction of (Vi; (III), in water or in an aqueous medium such as that which has been described, for example, for the reaction of (II) with (III), and carrying out the reaction of (VI) and (V) in organic solvents. The process for obtaining the compound of the formula (I) according to the invention, especially preferred, is characterized in that the monocondensates (II) or (IV) prepared as indicated above are not isolated in an intermediate manner and out the reaction from the aminoiminoisoindolenine of the formula (VI). The invention also relates to a process for obtaining the compounds of the formula (II), characterized in that compounds of the formula (Vlla) and / or (Vllb) are reacted are 2-amino-benzoxazoles of the formula (V ), (V) (ID where R and x have the above-indicated meaning and R2 means an aliphatic moiety, especially means alkyl with 1 to 4 carbon atoms. The compounds of the formula (Vlla) or (Vllb) are known, for example, from DE-A-16 70 748. Their preparation is preferably carried out by reaction of dinitrile of phthalic acid with aliphatic alcohols with 1 to 4. carbon atoms according to the following reaction scheme: (Vlla) (Vllb) where R2 has the meaning indicated above.

The compounds R2OH are especially constituted by alcohols such as, for example, methanol, ethanol, propanol, isopropanol, preferably methanol. The reaction of (Vlla) and / or (Vllb) with (V) is preferably carried out in-between without intermediate isolation of the compounds (Vlla) or (Vllb) with addition of the corresponding 2-amino-benzoxazoles (V ) and heating until compound (Vlla) or (Vllb) can no longer be detected. The reaction temperatures both for obtaining (Vlla) or (Vllb), and for (II), are preferably between 20 and 80 ° C. The preparation of the compounds of the formula (Vlla) or (Vllb) is preferably carried out in the presence of a base, preferably in the presence of an alcoholate, especially R20Me where Me means an alkali metal such as Na, K or Li and R2 has the meaning indicated above. Once the reaction is complete, the alcoholate, which serves as a catalyst, is neutralized, preferably with an acid, for example with acetic acid, and then the precipitated product is isolated or, after dilution with a solvent, it is immediately reacted, and the solvents already mentioned. The invention also relates to the compounds of the formula (II) where R and x have the meaning indicated above. The invention also relates to the use of the dyes of the formula (I), for the dyeing of completely synthetic or high molecular weight products. They are especially suitable for dyeing or printing synthetic fibrous materials consisting of aromatic polyesters and / or cellulose acetates. They have a high coloring strength and exhibit surprising lightfastness, especially a high hot light fastness and are therefore particularly suitable for dyeing and printing textile materials for automobiles as well as for dyeing so-called microfiber. They are also suitable for so-called heat transfer printing on textile and non-textile substrates, for example according to the D2T2 process (Dye Diffusion Thermo Transfer) for the representation of images. Furthermore, the dyes can be used for mass dyeing of synthetic materials, for example of polyethylene, polypropylene, styrene, polycarbonates as well as for mixing of plastics, for example by ABS. The dyes are partially fluorescent and are therefore also suitable as fluorescent dyes. The textile materials constituted by polyester can be dyed with the dyes according to the invention according to the type of a spin dye, but they will preferably be from an aqueous suspension. For this purpose, the colorants are prepared in known manner in general to give coloring preparations, for example by grinding in water in the presence of thickening agents and / or fillers. With the preparations, which may be dried under vacuum or by spraying, it can be dyed, padded or stamped, after addition of water, in so-called short or long baths. To obtain or to improve the degree of dispersion, a surfactant or a mixture of such auxiliary agents can be added during grinding or during the synthesis reaction. Obviously, the particle size of the dye can be influenced by means of a grinding treatment, for example wet grinding with beads, either during the synthesis or after the synthesis, and adjusting to a required value. Suitable dispersants are those of an anionic or non-anionic nature. In addition to the dispersing agents of one or the other group, they can also be used. mixtures of dispersing agents, with what is meant, first, mixtures of nonionic and anionic dispersing agents, since the anionic and cationic dispersing agents, when mixed together, have a tendency to precipitate formation. Among the anionic dispersing agents, the condensation products of aromatic sulfonic acids with formaldehyde, such as the condensation products of formaldehyde and of alkylnaphthalylsulfonic acids or of formaldehyde, naphthalenesulfonic acids and benzenesulfonic acids, condensation products of phenol, have proved to be particularly active. if necessary substituted, with formaldehyde and sodium bisulfite. Furthermore, lignin sulphonates, for example those obtained by the sulfite process or by the kraft process, are suitable. Preferably they are partly hydrolyzed, oxidized, propoxylated or desulphonated products and fractionated according to known processes, for example according to the molecular weight or according to the degree of sulfonation. Mixtures of lignin sulfites and sulphite and kraft are also perfectly effective. Especially suitable are lignin sulfates with an average molecular weight of between 1,000 and 10,000, with an active lignin sulfonate content of at least 80% and preferably with a low content of polyvalent cations. The degree of sulfonation can vary within wide limits. Nonionic dispersing agents or emulsifiers are, for example, reaction products of alkylene oxides with alkylating compounds, such as, for example, fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols, arylalkyphenols and carboxylic acid amides. This is, for example, ethylene oxide adducts of the class of reaction products of ethylene oxide with: a) saturated and / or unsaturated fatty alcohols having 6 to 20 carbon atoms, or b) alkylphenols with 4 to 12 carbon atoms in the alkyl moiety, or c) saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms, or d) saturated and / or unsaturated fatty acids with 14 to 20 carbon atoms. Suitable ethylene oxide adducts are, in particular: a) reaction products of saturated and / or unsaturated fatty alcohols having 6 to 20 carbon atoms, with 5 to 30 moles of ethylene oxide. b) Reaction products of alkylphenols with 4 to 12 carbon atoms with 5 to 20 moles of ethylene oxide. c) Reaction products of saturated and / or unsaturated fatty amines with 14 to 20 carbon atoms with 5 to 20 moles of ethylene oxide. d) Reaction products of saturated and / or unsaturated fatty acids contain 14 to 20 carbon atoms with 5 to 20 moles of ethylene oxide. Other preferred dispersing agents are alkoxylated styrene-phenol condensation products, which are optionally used in admixture with their inorganic esters, which are obtained by reacting alkoxylated styrene-phenol condensation products with inorganic acids, such as example, aminosulfonic acids. Especially for the dyeing of polyesters, mixtures of dyes of the formula (I) are also suitable, the dyeing ability of the dyes as well as their dispersibility being able to be improved under certain circumstances. The new dye mixtures can be prepared according to various methods. 1. By mixing the individual coloring components prepared and formed separately, 2. by jointly forming the individual components prepared separately, 3. by joint synthesis of dye mixtures of the formula (I) from mixtures of various starting products . The dye mixture is conveniently carried out in suitable mills, for example ball mills or sand mills. The individual dyes separately formed can, however, also be mixed by introduction under stirring into the dyebaths. Mixtures of cislorants of the formula (I), which differ only in the radical Rj, are especially preferred. The dyes are also suitable, however, in an excellent manner for obtaining mixtures with other dispersion dyes for obtaining, for example, brown, gray or green tones on fibers since they do not have a negative effect on the lightfastness of these fibers. dyes Another preferred embodiment of the present invention relates to mixtures of one or more of the dyes of the formula (I) with one or more dyes, such as those usually used for dyeing polyester fibers or textile materials. polyester for upholstery fabrics for automobiles. These colorants for dyeing fabrics for automotive upholstery can be constituted especially by azo dyes, disazo dyes, anthraquinone dyes, nitrocolouring agents, naphthalimide dyes and terephthalimide dyes. Particularly preferred dyes for such mixtures are for example Color-Yellow Yellow dyes 23, 42, 51, 59, 65, 71, 86, 108, 122, 163, 182, 211, Orange 29, 30, 32, 41, 44, 45, 61, 73, Rot 60, 82, 8691, 92, 127, 134, 138, 159, 167, 191, 202, 258, 279, 284, 302, 323, Blau 27, 54, 56, 60, 73, 77, 79, 79: 1, 87, 266, 333, 361, Víolet 27, 28, 57 and 95, the proportions by weight of the color mixtures depending on the desired color tones. Examples: Example 1: 86.1 g (0.55 mol) of industrial aminoiminoi-soindolenine (92.8%), 67 g of 2-aminobenzoxazole and 5 g of piperazine were stirred with 500 ml of methanol and the The mixture was heated to reflux for 5 hours. The mixture was then cooled to room temperature and after addition, drop by drop, of 200 ml of water, the precipitated product was separated by suction filtration and washed with water. After drying, 87.9 g of a product of the formula were obtained: The product was further purified by recrystallizations from DMF. Elemental analysis: C15H10N4O; "MW = 262.3 g / mol. c HN Calculated: 68, 7 3, 8 21, 4 Found: 69, 9 3, 6 21, 1. Element 2: They were added to a mixture, consisting of 80 ml of methanol and 80 ml of a 30% solution of sodium methylate, for 30 minutes, 54.9 g of phthalic dinitrile and in this case the temperature was maintained at 20-25 ° C by light cooling. Then, 53.6 g of 2-aminobenzoxazole were intermixed for approximately 15 minutes and the mixture was stirred for a further 5 hours at room temperature. Subsequently, it was heated for another 15 minutes at 40 ° C, 25 ml of glacial acetic acid were added dropwise and kept for a further 30 minutes at 60 ° C. The precipitated product was separated by suction filtration at room temperature and washed with water and with methanol. 84.8 g of a product were obtained with the same formula as in example 1. Example 3: 26.2 g (0.1 mol) of the substance of example 2 and 300 ml of amyl alcohol were stirred and 17 were added. g (0.11 moles) of amyl cyanoacetate, as well as 6 ml of glacial acetic acid. The mixture was heated for 3 hours at 80 ° C and then still briefly at 100 ° C. After cooling to room temperature, the precipitated substance was separated by suction filtration and washed with ice-cold methanol and with water. After drying, 29.2 g of a product of the following formula were obtained.

The dye dyes polyester fibers in yellow tones iridescent green with excellent light fastness. Example 4: 26.2 g (0.1 mole) of the substance of Example 2, 150 ml of water and 2.4 g of Lignisol "SD 60, a dispersing agent based on lignin sulfonates of the Borregaard Company were stirred. , 6 ml of glacial acetic acid was added and heated to 70 ° C. Subsequently, 17.1 g of amyl cyanoacetate were added dropwise in 30 minutes, heated to 90 ° C. and the temperature was maintained. for 5 hours The precipitated product was separated by filtration by suction at room temperature and washed with water and with methanol, 36.5 g of the same dye was obtained as in example 3. Example 5: The procedure is as in Example 4 , however, instead of the amyl cyanoacetate, the methyl glycol cyanoacetate, a dye of the formula was obtained in a comparative yield: The dye has properties similar to those of the dye of Example 4, but nevertheless it shows an even better light fastness and an even better sublimation fastness. If the procedure is as in Examples 1-5 and if the esters of cyanoacetic acid and the corresponding 2-amino-benzoxazoles are used analogously, the dyes indicated correlatively in Table 1 will be obtained. Table 1: (When not to say otherwise, always R3 and R4 mean hydrogen in the table).

FORMULATION EXAMPLE 1. 26 g of dye obtained in Example 5 (in the form of the press cake moistened with water) were combined in 200 ml of water with 55 g of lignin sulfonate, sodium salt and 5 g of a dispersing agent. nonionic (addition product constituted by abietic acid and 50 molar equivalents of ethylene oxide) and adjusted to a pH value of 7 with sulfuric acid. It was then milled for 1 hour at room temperature in the bead mill to a fine distribution (90% <μm), sieved and dried in the dryer by spraying. FORMULATION EXAMPLE 2. The procedure was as in training example 1, but the 5 g of the nonionic dispersing agent was replaced by 5 g of a surfactant mixture based on an alkoxylated styrene-phenol condensation product (fe- nol / styrene = 2.81: 1, 29 molar equivalents of ethylene oxide) and their inorganic esters (amidosulfonic acids), which additionally contained a condensation product constituted by oleic acid and, 5 molar equivalents of ethylene oxide. Application example l. 2 g of the powder obtained in the formation example 1 were dispersed in 1,000 g of water. The dispersion was combined with 0.5 to 2 g / 1 of a commercially available dispersing agent based on a condensation product of sodium salt of naphthalenesulfonic acid and formaldehyde, 0.5 to 2 g / 1 of roonosodium phosphate and g of a commercially available equalizing agent and adjusted to a pH value of 4.5 to 5.5 with acetic acid. 100 g of a textured polyester fabric based on polyethylene glycol terephthalate were introduced ithe dyeing bath obtained in this way and stained for 60 minutes at 130 ° C.

Application example 2. In a manner analogous to that of Example 1, the dye preparation obtained in dyeing example 2 was also filled. Bright yellow shades of intense color were obtained with excellent color properties and light fastnesses, the thermal stability of the dye, the dispersion and the dye evening of the application example 2 being even better. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims

RgIVlfWCM.IQ * tgg l.- Compounds, which correspond to the formula (I) or its tautomeric forms characterized by Rx means a saturated or unsaturated aliphatic residue, substituted or unsubstituted, with 1 to 12 carbon atoms, which is interrupted, if appropriate, by one or several oxygen atoms, a cycloaliphatic residue unsubstituted or substituted with 5 to 12 carbon atoms or means an araliphatic residue unsubstituted or substituted by 7 to 20 carbon atoms, x means a number from 0 to 4, preferably means 0, 1 or 2, R are the same or different and mean halogen, alkyl with 1 to 10 carbon atoms, alkoxy or alkoxyalkoxy having 1 to 10 carbon atoms, CN, N02 or, as long as x is greater than 1, means the remainder of a ringed benzene ring.
2. Compounds according to claim 1, characterized in that R are the same or different and mean Cl, Br, alkyl are 1 to 4 carbon atoms, alkoxy with alkoxyalkoxy having 1 to 4 saturated or unsaturated carbon atoms, cu, N02, or , as long as x is greater than l, it means the remainder of the ringed benzene ring.
3. Compounds according to claim 1, characterized by R1 means a straight chain aliphatic radical with 4 to 8 carbon atoms, which is interrupted if necessary by an oxygen atom and R means Cl, methyl, methoxy or ethoxy and x means 0 or 1.
4. - Compounds according to claim 1, characterized in that x means 0.
5. Process for obtaining compounds according to claim 1, characterized in that either a compound of the formula (II) is condensed. with an ester of cyanoacetic acid of the formula (III) NCC ^ COOR! (III) a compound of the formula (IV) with 2-aminobenzooxazole of the formula (V) where R, Rx and x have the meaning indicated in claim 1.
6.- Compounds of the formula (II) characterized by x means a number from 0 to 4, preferably meaning 0, 1 or 2, and R are the same or different and means halogen, alkyl with 10 carbon atoms, alkoxy or alkoxy-alkoxy with 1 to 10 carbon atoms, saturated or unsaturated, "ON, N02 or, as long as x is greater than 1, it means the remainder of the ringed benzene ring.
7. Process for obtaining compounds according to claim 6, characterized in that aminoiminoisoindolenine of the formula (VI) is reacted with 2-aminobenzoxazoles of the formula (V) where R and x have the meanings indicated in claim 6.
8. Process for obtaining compounds according to claim 6, characterized in that compounds of the formula (Vlla) and / or (Vllb) (Vlla) (Vllb) are reacted with compounds of the formula (V) where R and x have the meaning indicated in the claim 6 and R2 means an aliphatic moiety, especially means alkyl with 1 to 4 carbon atoms.
9. Use of the compounds according to claim 1, for dyeing and printing completely synthetic or semi-synthetic products of high molecular weight. R E S U M E N Compounds corresponding to formula (I) or their tautomeric forms where Rx, R and x have the meaning indicated in the description, they are especially suitable for dyeing and printing synthetic or semi-synthetic hydrophobic materials, especially fabrics for auto-movable upholstery.