WO2005005551A1

WO2005005551A1 - Water-soluble macrocyclic azacalixarenes

Info

Publication number: WO2005005551A1
Application number: PCT/EP2004/007271
Authority: WO
Inventors: Warren James Ebenezer; Michael Hutchings; Werner Russ
Original assignee: Dystar Textilfarben Gmbh & Co. Deutschland Kg
Priority date: 2003-07-09
Filing date: 2004-07-03
Publication date: 2005-01-20
Also published as: TW200508327A; GB0316109D0

Abstract

The present invention refers to azacalixarenes of the formula (I) wherein each T independently is a 1,3,5-triazine ring, optionally substituted; each A independently is an optionally substituted aromatic or heteroaromatic ring-based unit; each L independently is a direct bond or a linking atom or linking group of atoms; each R independently is an aliphatic bridging component; M ≥ 1; n = 0, 1 or 2; where m ≥ 2 if n = 0; and wherein at least one of T, A, R, L independently contains one or more water-solubilising groups, a process for their production and their use for dyeing and printing hydroxyl- and/or carboxamido-containing material.

Description

DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG 2003/C001 Dr.MY

Description

Water-soluble macrocyclic azacalixarenes

The present invention relates to water-soluble macrocyclic azacalixarenes, which contain two or more triazine rings and which can be used as dyestuffs or precursors of dyestuffs.

Macrocyclic compounds containing two or more triazine rings are already known and described for example in DE 1 96 36 337 A1 and DE 1 96 46 537 A1 . These compounds can be used in sensor technology, for the separation of organic compounds or for the manufacture of host-guest-compounds. Similar compounds which are only of scientific interest are described in several publications, for example in J.Prakt.ChβmJ 995, 337, 401 , J.Prakt.ChβmJ 998, 340, 1 65 or Chem.Eur.J., 2003, 9, 1 465-69. Synthesis of most of such compounds include difficult reaction steps which cannot be performed on an industrial scale.

The inventors of the present invention have now found that macrocyclic azacalixarenes containing two or more triazine rings can have a wide variety of industrial application, especially as dyestuffs, provided they are water-soluble and can be obtained in processes which can be performed in industry.

The present invention claims azacalixarenes of the formula (l)

- -A— L— T— L-) f-R-L— T— L- m

(I) wherein each T independently is a 1 ,3,5-triazine ring, optionally substituted; each A independently is an optionally substituted aromatic or heteroaromatic ring-based unit; each L independently is a direct bond or a linking atom or linking group of atoms; each R independently is an aliphatic bridging component; m > 1 ; n = 0, 1 or 2; where m > 2 if n = 0; and wherein at least one of T, A, R, L independently contains one or more water-solubilising groups.

T is preferably a group of the formula (2)

wherein

X is halogen, a quaternary ammonium group, sulpho, OR¹, NR¹R², SR¹ or R¹, where R¹ and R² independently are hydrogen, optionally substituted C,-C₄ alkyl, optionally substituted aryl such as phenyl and naphthyl or a dye chromophore; where, in the case X is NR¹R², R\ R² and the N atom to which they are attached optionally together with a further heteroatom may optionally comprise a ring, such as, for example a piperidine ring or a morpholine ring.

An optionally substituted aromatic or heteroaromatic ring-based unit representing A can be a single ring, a condensed ring system or two or more connected aromatic or heteroaromatic rings, wherein each single ring can carry up to four, preferably 1 , 2 or 3, substituents. Preferably, A is of the formula (3) (Y)r I (3) wherein Ar is 1 ,2-, 1 ,3- or 1 ,4-phenylene, 1 ,2-, 1 ,3-, 1 ,4-, 1 ,5-, 1 ,6-, 1 ,7-, 2,3-, 2,6- or 2,7-naphthylene or is derived from pyridine, pyrimidine, thiophene, furan, pyrrole, thiazoie, isothiazole, oxazole, isoxazole, imidazole, benzothiophene, benzofuran, indole, benzothiazole, benzoisothiazole, benzoxazole, benzisoxazole or benzimidazole; or

Ar is a condensed ring system which is intrinsically coloured, for example a ring system of the formulae (4) and (5)

or Ar is a connected aromatic system of the formulae

- A¹-K-A¹- ; or

- A¹-K-A²-; or

- A¹-K-A³-K-A¹- wherein each A¹ independently is phenylene or naphthylene or a heteroaromatic derivative of these, derived from for example pyridine or pyrimidine; each A² is derived from pyrazole or pyridone; each A³ is phenylene or naphthylene;

K is a direct bond or a connecting atom or group of atoms such as O, S, NR¹, [CH₂]_aO, [CH₂]_aNR¹ , SO, SO₂, N = N, CH = N, CH = CH, C = O, CO₂, CONR¹,

SO₂NR\ SO₃, NHCONH, CR³R⁴ or NR¹ (CH₂)_aNR\ where R¹ is defined as given above; and

R³ and R⁴ independently have one of the meanings of R\ or R³ and R⁴ together with the C atom to which they are attached form a ring, for example a cyclohexyl ring; and a = 1 -6; each Y independently is SO₃M with M being hydrogen, an alkali metal, an ammonium ion or the equivalent of an alkaline earth metal, preferably Na or K, halogen, NO₂, CN, R¹, CO₂R¹, OR¹, NR¹R², NR¹COR², NR¹CONH₂, SR¹, CONR¹R²,

N = N-R⁵ or an aromatic or heteroaromatic residue, for example phenyl; where R¹ and R² are defined as given above, R⁵ is optionally substituted aryl; and r = 0 - 1 0.

A linking atom or linking group of atoms representing L is preferably O, S, NR⁶, [CH₂]_aO, [CH₂]_aNR⁶, SO₂C₂H₄NR⁶, N(R⁶)COCH(R⁶)CH₂NR⁶, OCOCH(R⁶)CH₂NR⁶, wherein R⁶ independently is hydrogen, optionally substituted C.,-C₄-aIkyl or optionally substituted aryl and a is 1 -6.

An aliphatic bridging component representing R is preferably C₂-C₂₀-alkylene, which may be substituted by up to 5 R¹ groups, with R¹ being defined as given above and/or which may be interrupted by one or more divalent heteroatoms or heteroatom-based units such as O, S and NR¹ with R¹ being defined as given above.

R can also preferably stand, optionally together with one or both of the L units attached to it, for a ring unit or can contain a ring unit. An example of a ring unit L-R-L is the piperazine derivative of the formula (6) /— Λ — [NH(CH₂)_a]_b-N N— [(CH₂)_cNHJ_d (6) wherein a and c are independently 2 or 3 and b and d are independently 0 or 1

The above mentioned alkyl groups representing R¹ or R⁶ can be straight-chained or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. They can be substituted by one or more, for example 1 , 2 or 3, substituents preferably selected from the group consisting of hydroxyl, (C.-C^-alkoxy, halogen or carboxyl.

The above mentioned aryl groups representing R¹, R⁵ or R⁶ are preferably phenyl and naphthyl. They can carry up to four, for example 1 , 2 or three, substituents preferably selected from the group consisting of hydroxyl, (C_rC₄)-alkoxy, halogen, -COOM or SO₃M, where M is defined as given above. In addition, a substituent representing R⁵ can be -SO₂CH₂CH₂SO₃M or -SO₂CH = CH₂.

Halogen representing X or being present as substituent of alkyl or aryl representing R is preferably chlorine or fluorine. Dye chromophores which stand for R¹ can be monoazo, bisazo, polyazo, dioxazine, anthraquinone, phthalocyanine or formazan chromophores. Such chromophores are well known in the art and extensively described in the literature (see for example EP 0 478 503 B1 , EP 0 652 262 A1 , especially including the literature given on page 5 of this document, EP 0 733 680 A2, EP 0 735 107 A1 , EP 0 735 1 1 3 A1 , EP 0 755 985 A2, WO02/092697 and

Venkataraman: The Chemistry of Synthetic Dyes, Vol. VI, Chapter II, pages 21 1 - 325, New York, London, 1972).

In especially preferred compounds of the formula (1 ) each T independently is a group of the formula (2')

wherein X¹ is chlorine, fluorine, or NH-D, wherein D is a dye chromophore;

each A independently is 1 ,2-, 1 ,3- or 1 ,4-phenylene;

1 ,2-, 1 ,3- or 1 ,4-phenylene substituted by 1 , 2 or 3 substituents independently selected from the group consisting of -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM, where M is defined as given above;

-A¹ '-K'-A¹ '-, where each A¹ ' is independently 1 ,3- or 1 ,4-phenylene or 1 ,7-, 2,7- or 2,6-naphthylene and K' is N = N, O, NH, NMe, CR³R⁴, CH = CH, SO₂, CO₂,

CONR¹ , NR¹ (CH₂)_aNR¹ or SOJ lR_! , wherein both A¹' independently can carry 1 , 2 or 3 substituents Y; or

-A¹ "-K"-A³'-K"-A¹"- where each A¹ " is 1 ,3- or 1 ,4- phenylene, A³' is 2,7- naphthalene and each K" is N = N, wherein both A¹" and/or A³' independently can carry 1 , 2 or 3 three substituents Y;

each L independently is NH, NMe, O, CH₂O, CH₂NH or CH₂NMe; and each R independently is C₂-C₁₀-alkylene, C₂H₄(OC₂H₄)_y or C₃H₆(OC₂H₄)_yOC₃H₆, wherein y = 1 -5; or L-R-L is a piperazine derivative of one of the formulae

and m = 2, 3 or 4 when n = 0 and m = 1 when n = 1 .

Examples of especially preferred compounds of the formula (1 ) have one of the formulae (1 a) to (1 d)

(la) wherein

X¹ is chlorine, fluorine, or NH-D, wherein D is a dye chromophore, and

Y¹ is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM, where M is defined as given above and at least one Y¹ is -SO₃M and at least one X¹ is

NH-D.

wherein

X¹ is chlorine, fluorine, or NH-D, wherein D is a dye chromophore, and

Y¹ is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM, where

M is defined as given above and at least one Y¹ is -SO₃M and at least one X¹ is

NH-D.

wherein

X² is chlorine or fluorine , Y¹ is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM,

R⁵ is phenyl or naphthyl substituted by 1 , 2 or 3 substituents selected from the group consisting of hydroxyl, (C C₄)-alkoxy, halogen, carboxyl or SO₃M; and t is 0 or 1 ; where M is defined as given above and the compound carries at least one -SO₃M.

wherein

X² is chlorine or fluorine ,

Y is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM,

R⁵ is phenyl or naphthyl substituted by 1 , 2 or 3 substituents selected from the group consisting of hydroxyl, (C.-CJ-alkoxy, halogen, carboxyl or SO₃M; and t is 0 or 1 ; where M is defined as given above and the compound carries at least one

-SO₃M and at least one t is 1 .

The present invention further provides processes for preparing the compounds of the formula (1 ) . They are obtainable by reacting the compounds of the formulae (7), (8) and optionally (9)

Cl - T - Cl (7)

HL - A - LH (8)

HL - R - LH (9)

wherein T, A and R are defined as given above, in the desired order and in amounts which result in the desired compound in conventional condensation reactions. The synthesis can usually be carried out wholly in water as solvent and at normal concentrations. High dilution techniques appear to be unnecessary to induce macrocyclisation over polymerisation, but may be used if wanted.

A typical procedure involves condensation of a substituted phenylene diamine (for example metaphenylene diamin) with two equivalents of cyanuric chloride in water at 0°C. Addition of one equivalent of a phenylene diamine (for example (paraphenylene diamine) at ambient temperature then furnishes the required macrocycle as the major component of the reaction mixture, which can easily separated and purified using conventional methods.

A colourless compound according to the present invention, for example (1 e), can be reacted with a dyebase under aqueous basic conditions to yield the coloured inventive compound (1 p)

wherein Dye is a dye chromophore as defined above.

As far as the azacalixarenes of the present invention are coloured they can be used as dyestuffs. Colorless azacalixarenes of the present invention can be further reacted to result in coloured azacalixarenes and are thus valuable precursors of dyestuffs.

If coloured azacalixarenes of the present invention are used as dyestuffs they can be present as a preparation in solid or liquid (dissolved) form. In solid form they generally contain the electrolyte salts customary in the case of water- soluble and in particular fibre-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and also the auxiliaries customary in commercial dyes, such as buffer substances capable of establishing a pH in aqueous solution between 3 and 8, such as sodium acetate, sodium borate, sodium bicarbonate, sodium citrate, sodium dihydrogenphosphate and disodium hydrogenphosphate, small amounts of siccatives or, if they are present in liquid, aqueous solution

(including the presence of thickeners of the type customary in print pastes), substances which ensure the permanence of these preparations, for example mold preventatives.

In general, the dyestuffs of the present invention are present as dye powders containing 10 to 80% by weight, based on the dye powder or preparation, of a strength-standardizing colorless diluent electrolyte salt, such as those mentioned above. These dye powders may additionally include the aforementioned buffer substances in a total amount of up to 10%, based on the dye powder. If the dyestuffs of the present invention are present in aqueous solution, the total dye content of these aqueous solutions is up to about 50 % by weight, for example between 5 and 50% by weight, and the electrolyte salt content of these aqueous solutions will preferably be below 10% by weight, based on the aqueous solutions. The aqueous solutions (liquid preparations) may include the aforementioned buffer substances in an amount which is generally up to 10% by weight, for example 0.1 to 1 0% by weight, preference being given to up to 4% by weight, especially 2 to 4% by weight.

As far as the dyestuffs of the instant invention are reactive dyestuffs they are suitable for dyeing and printing hydroxy- and/or carboxamido-containing fibre materials by the application and fixing methods numerously described in the art for fibre-reactive dyes. They provide exceptionally strong and economic shades. Such dyes especially when used for exhaust dyeing of cellulosic materials can exhibit excellent properties including build-up, light-fastness, high levels of solubility in water or salt solution, high fixation degrees, ease of washing out the unfixed dyestuff, as well as robustness to process variables. They are also wholly compatible with similar dyes designed for high temperature (80-1 00° C) application to cellulosic textiles, and thus lead to highly reproducible application processes, with short application times.

The present invention therefore also provides for use of the inventive dyestuffs for dyeing and printing hydroxy- and/or carboxamido-containing fibre materials and processes for dyeing and printing such materials using a dyestuff according to the invention. Usually the dyestuff is applied to the substrate in dissolved form and fixed on the fibre by the action of an alkali or by heating or both.

Hydroxy-containing materials are natural or synthetic hydroxy-containing materials, for example cellulose fiber materials, including in the form of paper, or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton but also other natural vegetable fibers, such as linen, hemp, jute and ramie fibres. Regenerated cellulose fibers are for example staple viscose and filament viscose.

Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-1 1 , and nylon-4.

Application of the inventive dyestuffs is by generally known processes for dyeing and printing fiber materials by the known application techniques for fibre- reactive dyes. The dyestuffs according to the invention are highly compatible with similar dyes designed for high temperature (80-1 00°C) applications and are advantageously useful in exhaust dyeing processes.

Similarly, the conventional printing processes for cellulose fibers, which can either be carried out in single-phase, for example by printing with a print paste containing sodium bicarbonate or some other acid-binding agent and the colorant, and subsequent steaming at appropriate temperatures, or in two phases, for example by printing with a neutral or weakly acid print paste containing the colorant and subsequent fixation either by passing the printed material through a hot electrolyte-containing alkaline bath or by overpadding with an alkaline electrolyte-containing padding liquor and subsequent batching of this treated material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well defined contours and a clear white ground. Changing fixing conditions has only little effect on the outcome of the prints. Not only in dyeing but also in printing the degrees of fixation obtained with dye mixtures of the invention are very high. The hot air used in dry heat fixing by the customary thermofix processes has a temperature of from 1 20 to 200°C. In addition to the customary steam at from 1 01 to 103°C, it is also possible to use superheated steam and high pressure steam at up to 1 60°C.

The inventive dyestuffs can in addition be used to produce inks useful for printing the substrates described above, for example textiles, especially cellulosic textiles, and paper. Such inks can be used in all technologies, for example conventional printing, ink-jet printing or bubble-jet printing (for information on such printing technologies see for example Text. Chem. Color, Volume 1 9(8), pages 23 ff and Volume 21 , pages 27 ff).

Acid-binding agents responsible for fixing the dyes to cellulose fibers are for example water-soluble basic salts of alkali metals and of alkaline earth metals of inorganic or organic acids, and compounds, which release alkali when hot. Of particular suitability are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the sodium and potassium compounds. These acid-binding agents are for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium dihydrogenphosphate and disodium hydrogenphosphate.

Treating the dyestuffs according to the invention with the acid-binding agents, with or without heating, bonds the dyes chemically to the cellulose fibers. Especially the dyeings on cellulose, after they have been given the usual aftertreatment of rinsing to remove unfixed dye portions, show excellent properties.

The dyeings of polyurethane and polyamide fibers are customarily carried out from an acid medium. The dyebath may contain for example acetic acid and/or ammonium sulfate and/or acetic acid and ammonium acetate or sodium acetate to bring it to the desired pH. To obtain a dyeing of acceptable levelness it is advisable to add customary leveling auxiliaries, for example based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or based on a reaction product of for example stearylamine with ethylene oxide. In general the material to be dyed is introduced into the bath at a temperature of about 40°C and agitated therein for some time, the dyebath is then adjusted to the desired weakly acid, preferably weakly acetic acid, pH, and the actual dyeing is carried out at temperature between 60 and 98°C. However, the dyeings can also be carried out at the boil or at temperatures up to 120°C (under superatmospheric pressure) .

The examples hereinbelow serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as the kilogram relates to the liter. The compounds described in the examples in terms of a formula are indicated in the form of the free sulphonic acids, but as in general they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used for dyeing in the form of these salts. The starting compounds and components mentioned in the form of the free acid in the examples hereinbelow may be used in the synthesis as such or similarly in the form of their salts, preferably alkali metal salts. Example 1

(1^β)

Cyanuric chloride (8.1 1 g, 0.044mol) in acetone (200mls) was added dropwise to a stirred solution of the sulphonated diamine [(a), 5.48g, 0.02mol] in water d OOmls) adjusted and maintained at pH6 by the addition of sodium carbonate solution and cooled to 0°C. After allowing to stir overnight at 0°C the reaction mixture was adjusted to pH7 and the solution of the bis-dichlorotriazinyl intermediate (b) was added dropwise to a stirred solution of p-phenylenediamine (5.96g, O.055mol) in water (100mls) at room temperature and pH3.5. After 1 hour the reaction was complete. The pH was adjusted to 5 and the reaction allowed to stir over night. Subsequently, a precipitate was filtered off and dried, to yield an off white solid (1 9.3g) . HPLC analysis revealed the solid to be a single component. Analysis of the solid by ¹H and ¹³C-NMR plus mass spectrometry, confirmed it to be the macrocycle (1 e). Example 2

Cyanuric chloride (26.55g, 0.144mol) in acetone (l OOmls) was added in one portion to water (200mls) at 0°C and the pH adjusted and maintained to 6. A solution of the monoazodiamine [(c), 40g, 0.060mol] in water (400mls) was added dropwise maintaining pH 6 and 0°C. After 1 hour the reaction was complete and the pH was adjusted to 7. A portion of the bis- dichlorotriazinyl intermediate solution [(d), 1 85mls, 0.0159mol] was taken and allowed to stir at room temperature before adding a solution of the diamine [(e), 1 9.1 g, 0.01 59mol] in water (300mls) and maintaining the resulting solution at pH 6. After 6hours the reaction was complete and

5 % NaCl was added. The resulting precipitate was filtered off and dried to give an orange powder (14.3g, 45% yield). HPLC analysis revealed the solid to be a single component. Analytical data were in full agreement with the macrocyclic structure (1 f). λ_max = 406nm, ε_max = 23500.

When applied to knitted cotton from an 80°C dyebath in the presence of sodium carbonate, the cotton was dyed a golden yellow shade reaching

1 : 1 standard depth with good fastness properties including Xe light fastness(5-6), C9A(5) and UK-TO(4-5)

Examples 3-8

The macrocyclic structures (1 g), (1 h), (1 i), (1j), (1 k) and (1 1) were prepared in an analogous fashion to example 2. In each case analytical data were in full agreement with the respective macrocyclic structures.

When applied to cotton from an 80°C dyebath in the presence of sodium carbonate, each of dyes dyed the cotton a golden yellow shade.

Example 9

A solution of the bis-monochlorotriazinyl red dye [(f), 0.5g, 0.23mmol] (obtained according to GB 1 ,283,771 A) and p-phenylenediamine (0.025g, 0.23mmol) in water (50mls) was adjusted to pH6.6 and heated under reflux for 7 hours. After cooling, NaCl was added and the resulting precipitate filtered off and dried to give a dark red solid (0.4g, 71 % yield). HPLC analysis revealed the solid to be a single component. Analytical data were in full agreement with the macrocyclic structure (1 m).

Example 10

The reactive dye (1 n) was prepared in a manner analogous to Example 9, but replacing the 1 ,5-disuIpho-2-naphthylamine by 4-sulphatoethyl- sulphonyl aniline to give the dye as a single component. Analytical data were in full agreement with the macrocyclic structure (1 n) λ_max = 524nm, ^ε _ma ⁼ 74500. When applied to cotton either under cold pad-batch conditions (room temperature, pH 1 3), or at 60°C under exhaust dyeing conditions, the cotton was dyed a bluish-red shade reaching 1 : 1 standard depth with good fastness properties including C9A(4-5), UK-TO(3) and E03 (3-4) .

Example 1 1

To a solution of the bis-dichlorotriazinyl intermediate [(b), 0.034mol, prepared as described previously] in water (500mls) was added the diamine [(e), 39. Og, 0.032mol]. The resulting solution was adjusted and maintained at pH 6 and allowed to stir at room temperature for 24 hours.

On allowing to stand a precipitate formed and was filtered off and dried to give an off white powder (3.4g). HPLC analysis revealed the solid to be a single component. Analytical data were in full agreement with the macrocyclic structure (1 o) of twice the size anticipated for a 1 :1 reaction between (b) and (e) .

Claims

1 . Azacalixarene of the formula (I)

wherein each T independently is a 1 ,3,5-triazine ring, optionally substituted; each A independently is an optionally substituted aromatic or heteroaromatic ring-based unit; each L independently is a direct bond or a linking atom or linking group of atoms; each R independently is an aliphatic bridging component; m > 1 ; n = 0, 1 or 2; where m > 2 if n = 0; and wherein at least one of T, A, R, L independently contains one or more water-solubilising groups.

2. Azacalixarene according to claim 1 , wherein T is a group of the formula (2)

wherein

X is halogen, a quaternary ammonium group, sulpho, OR¹, NR¹R², SR or R¹, where R¹ and R² independently are hydrogen, optionally substituted C,-C₄ alkyl, optionally substituted aryl such as phenyl and naphthyl or a dye chromophore; where, in the case X is NR¹ R², R¹, R² and the N atom to which they are attached optionally together with a further heteroatom comprise a ring, such as, for example a piperidine ring or a morpholine ring.

3. Azacalixarene according to claim 1 and/or 2, wherein A is of the formula (3) (Y)r .Ar (3) wherein

Ar is 1 ,2-, 1 ,3- or 1 ,4-phenylene, 1 ,2-, 1 ,3-, 1 ,4-, 1 ,5-, 1 ,6-, 1 ,7-, 2,3-, 2,6- or 2,7-naphthylene or is derived from pyridine, pyrimidine, thiophene, furan, pyrrole, thiazole, isothazole, oxazole, isoxazole, imidazole, benzothiophene, benzofuran, indole, benzothiazole, benzoisothiazole, benzoxazole, benzisoxazole or benzimidazole; or

or Ar is a connected aromatic system of the formulae

- A -K-A¹- ; or

- A¹-K-A²-; or - A¹-K-A³-K-A¹- wherein each A¹ independently is phenylene or naphthylene or a heteroaromatic derivative of these, derived from for example pyridine or pyrimidine; each A² is derived from pyrazole or pyridone; each A³ is phenylene or naphthylene;

K is a direct bond or a connecting atom or group of atoms such as O, S, NR¹ ,

[CH₂]_aO, [CH₂]_aNR\ SO, SO₂, N = N, CH = N, CH = CH, C = O, CO₂, CONR¹,

SO₂NR¹ , SO₃, NHCONH, CR³R⁴ or NR¹ (CH₂)_aNR\ where R¹ is defined as given in claim 2; and R³ and R⁴ independently have one of the meanings of R\ or R³ and R⁴ together with the C atom to which they are attached form a ring, for example a cyclohexyl ring; and a = 1 -6; each Y independently is SO₃M with M being hydrogen, an alkali metal, an ammonium ion or the equivalent of an alkaline earth metal, preferably Na or K, halogen, NO₂, CN, R¹, CO₂R\ OR¹, NR¹R², NR¹COR², NR¹CONH₂, SR\ CONR¹ R²,

4. Azacalixarene according to one or more of the claims 1 to 3, wherein L is O,

5, NR⁶, [CH₂]_aO, [CH₂]_aNR⁶, SO₂C₂H₄NR⁶, N(R⁶)COCH(R⁶)CH₂NR⁶, OCOCH(R⁶)CH₂NR⁶, wherein R⁶ independently is hydrogen, optionally substituted C,-C₄-alkyl or optionally substituted aryl.

5. Azacalixarene according to one or more of the claims 1 to 4, wherein R is C₂-C₂₀-alkylen, which may be substituted by up to 5 R¹ groups, with R¹ being defined as given in claim 2 and/or which may be interrupted by one or more divalent heteroatoms or heteroatom-based units such as O, S and NR¹ with R¹ being defined as given in claim 2 or wherein

R stands, optionally together with one or both of the L units attached to it, for a ring unit or contains a ring unit of the formula (6)

/ \ — [NH(CH₂)_a]_b-N N— [(CH₂)_cNH]_d — (6) wherein a and c are independently 2 or 3 and b and d are independently 0 or 1

6. Azacalixarene according to one or more of the claims 1 to 5, wherein each T independently is a group of the formula (2')

wherein X¹ is chlorine, fluorine, or NH-D, wherein D is a dye chromophore;

each A independently is 1 ,2-, 1 ,3- or 1 ,4-phenylene;

1 ,2-, 1 ,3- or 1 ,4-phenylene substituted by 1 , 2 or 3 substituents independently selected from the group consisting of -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM, where M is defined as given in claim 3;

-A¹'-K'-A¹'-, where each A¹' is independently 1 ,3- or 1 ,4-phenylene or 1 ,7-, 2,7- or 2,6-naphthalene and K' is N = N, O, NH, NMe, CR³R⁴, CH = CH, SO₂, CO₂,

CONR¹, NR¹(CH₂)_aNR¹ or SO^R, , wherein both A¹' independently can carry 1 , 2 or 3 three substituents Y; or

-A¹"-K"-A³'-K"-A¹"- where each A¹" is 1 ,3- or 1 ,4- phenylene, A³' is

2,1- naphthalene and each K" is N = N, wherein both A¹" and/or A³' independently can carry 1 , 2 or 3 three substituents Y;

each L independently is NH, NMe, O, CH₂O, CH₂NH or CH₂NMe; and

each R independently is C₂-C₁₀-alkylen, C₂H₄(OC₂H₄)_y or C₃H₆(OC₂H₄)_vOC₃H₆, wherein y = 1 -5; or L-R-L is a piperazine derivative of one of the formulae

and m = 2, 3 or 4 when n = 0 and m = 1 when n = 1 .

7, Azacalixarene according to one or more of the claims 1 to 6, wherein it has one of the formulae (1 a) to (1 d)

wherein

X¹ is chlorine, fluorine, or NH-D, wherein D is a dye chromophore, and Y¹ is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM, where M is defined as given above and at least one Y¹ is -SO₃M and at least one X¹ is NH-D.

wherein

X¹ is chlorine, fluorine, or NH-D, wherein D is a dye chromophore, and

Y¹ is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM, where

NH-D.

wherein

X² is chlorine or fluorine ,

Y¹ is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM, R⁵ is phenyl or naphthyl substituted by 1 , 2 or 3 substituents selected from the group consisting of hydroxyl, (C.-C^-alkoxy, halogen, carboxyl or SO₃M; and t is 0 or 1 ; where M is defined as given in claim 3 and the compound carries at least one

-SO₃M.

wherein

X² is chlorine or fluorine ,

Y¹ is hydrogen, -SO₃M, methyl, methoxy, chlorine, fluorine or -COOM,

R⁵ is phenyl or naphthyl substituted by 1 , 2 or 3 substituents selected from the group consisting of hydroxyl, (C^CJ-alkoxy, halogen, carboxyl or SO₃M; and t is 0 or 1 ; where M is defined as given in claim 3 and the compound carries at least one -SO M and at least one t is 1.

8'. Process for the preparation of an azacalixarene according to one or more of claims 1 to 6 which comprises reacting the compounds of the formulae (7), (8) and optionally (9)

Cl - T - Cl (7)

HL - A - LH (8)

HL - R - LH (9)

wherein T, A and R are defined as given above, in the desired order and in amounts which result in the desired compound in conventional condensation reactions.

9. The use of a azacalixarene dye as claimed in one or more of claims 1 to 6 for dyeing and printing hydroxyl- and/or carboxamido-containing material, especially fiber material.