MXPA00000697A - Isoxindigos useful as colorants and preparation thereof - Google Patents

Abstract

The present invention relates to a process for coloration of a high molecular weight material by admixing said high molecular weight organic or inorganic material, preferably high molecular weight organic material, prior to processing with at least one compound of formula (I), where A1 and A2 are independently unsubstituted, monosubstituted, disubstituted, trisubstituted or tetrasubstituted o-C6-C18arylene. The invention further relates to compositions of matter comprising isoxindigo compounds and high molecular weight organic material. The invention also relates to processes for preparing the compound of said formula and also to novel isoxindigo compounds which can be symmetrical or asymmetrical or else have a bisisoxindigo structure.

Description

USEFUL ISOXÍNDES AS COLORANTS AND ITS PREPARATION This invention relates to the use of (E) - [3,3 '] -bibenzofuranylidene-2,2' -diones ("isoxyndigos") as dyes for the mass coloration of high molecular weight organic materials, the novel compositions of material that includes isoxindigos, to novel isoxindigos and also to a novel process to prepare isoxindigos. Isoxindigos are closely related to Pechmann dyes and are sometimes even referred to as such. Pechmann dyes, as described in Chem. Reviews 54, 59 (1954), are known to color wool and silk but the results are unsatisfactory, since light stability in particular proves to be inadequate. Like the Pechmann dyes, the isoxindigos are relatively unstable from a chemical point of view and are converted for example by base catalysis or even thermally in the thermodynamically more stable naphthirone isomers, of different color: Isoxindigos have a wide range of colors that vary with the substitution pattern and extend from yellow for red and blue to black [J. Org. Chem. 4716, 1095 (1982); J. Chem. Soc. Perkin 1, 2479 (1992)]. The color results mainly from a charge transfer absorption that is enhanced by methoxy substituents, although it is said that part of the twisting and length of the central double bond plays additionally due to steric hindrances [Aust. J. Chem. 38, 85 (1985)]. It has now been found that surprisingly, isoxydants are excellent dyes for dyeing polymers, producing non-migrating colors that are very firm to light and firm to heat. Unlike conventional dyes having comparable color properties, the dyes of this invention advantageously do not contain heavy metals. The solubility of the isoxindigos of this invention in organic solvents is highly dependent on the structure, making them easily adaptable to the desired specifications, which is an advantage. The isoxindigos of this invention are highly useful as dyes for bulk coloration of a high molecular weight organic material, and may be present in the substrate to be colored in a dissolved state (such as dyes) and / or in a finely dispersed state (like the pigments). The present invention accordingly provides a method for coloring a high molecular weight material, in particular in the dough, which comprises mixing the high molecular weight organic or inorganic material, preferably high molecular weight organic material, preferably before processing, with at least one compound of the formula wherein x and A2 are independently o-arylene with 6 to 18 carbon atoms, unsubstituted, monosubstituted, disubstituted, trisubstituted or tetrasubstituted. 0-arylene with 6 to 18 carbon atoms, for example is 1,2-phenylene, 1,2-naphthylene, 2,3-naphylene, 1,2-phenanthylene, 2,3-phenanthylene, 3,4-phenanthrylene or 9, 10-phenanthylene. In the case of o-arylene with 6 to 18 carbon atoms substituted, the substituents can be independently of one another or of each other, any desired atoms, groups of atoms or radicals which, depending on their valence, can be connected in a simple manner or multiple ao A2. Bivalent radicals, for example, 1,3-butadiene-1, 4-ylene or -CH = CH-NH-, can form an additional ring of 5- or 6-members fused on Ax and A2. The compounds of the formula (I) are, for example, symmetric or asymmetric isoxindigos. In the case of o-arylene with 6 to 18 carbon atoms substituted, the substituent for example may be a bridge leading to an additional isoxyndigo. In this bisisoxyindigo structure, two isoxyinds can be joined together, for example, by an alkylene, cycloalkylene, polycyclo, aryl or heteroaryl bridge. Preference is given to using an isoxyndigo of the formula a bisisoxindigo of the formula wherein A3 is a single bond or is alkylene with 1 to 24 carbon atoms or cycloalkylene with 5 to 12 carbon atoms monosubstituted or polysubstituted with halogen-, hydroxyl-, oxo-, cyano-, R600C-, X + 0 ~ 0C -, R503S-, X + 03 ~ S- or a polycycle that can be interrupted by heteroatoms such as O, N, S or P, or aryl with 6 to 24 carbon atoms and heteroaryl with 5 to 18 carbon atoms which can be be without interrupting or interrupting a 0 multiple times times 0, S or NR6, R-ioo / -R-ioi 'R? O2f Rioo' K-ioi 'R-02'Í And also R103 / Rio R? O5 YR? O6 each independently have the same meanings that for Rl7 Rj., R3, R3, R4 and also R28, R29, R30 or R31 are independently H, halogen, cyano, N02, R5, NR5R6, NR7COR5, NR7C00R5, N = CR5R6, CONR7R8, 0R5, C00R5, ( I rent with 1 to 12 carbon atoms) -COOR, COO "X +, SR5, S0R5, S02R5, S02NR7R8, S03R5 or S03 ~ X +, and optionally ^ and R3, R2 and R3, R3 and R4 or R5 and R6 and also R28 and R29 , R29 and R30 or R30 and R31 each can be additionally linked by a direct bond (with extraction of one hydrogen in each of the two atoms connected by the bond) to form a 5- or 6-membered ring, R5 is hydrogen, alkyl with 1 to 25 carbon atoms, cycloalkyl with 5 to 12 carbon atoms or alkenyl with 2 to 24 carbon atoms unsubstituted or monosubstituted or polysubstituted by halogen or hydroxyl, oxo-, cyano-, R6OOC- or X + 0"0C , which may be uninterrupted or interrupted simply or multiply by O, S or NR6, or is aryl with 6 to 18 carbon atoms, aralkyl with 7 to 18 carbon atoms or heteroaryl with 5 to 18 carbon atoms, unsubstituted or mono-substituted or polysubstituted with halogen-, nitro-, cyano-, R60-, R6S-, R8R7N-, R8R7NOC-, R600C-, X + 0"0C-, R602S-, R8R7N02S-, R603S-, X + 03"S-, R6OCR7N- or R6OOCR7N-, R6 is hydrogen or alkyl with 1 to 25 carbon atoms or alkenyl with 2 to 24 carbon atoms unsubstituted or mono-substituted or polysubstituted by halogen or hydroxyl-, oxo- or cyano-, which may be uninterrupted or interrupted once or multiple times by O, S or NR7, or is aryl with 6 to 18 carbon atoms, aralkyl with 7 to 18 carbon atoms or heteroaryl with 5 to 18 unsubstituted or monosubstituted carbon atoms, polysubstituted by halogen-, nitro-, cyano-, hydroxyl-, R70-, R7S-, R8R7N-, R8R7NOC-, R7OOC-, HOOC- or X + 0"OC-, R7 and R8 are individually H, aryl with 6 to 18 carbon atoms, aralkyl with 7 to 18 carbon atoms, alkyl with 1 to 25 carbon atoms or alkenyl with 2 to 24 carbon atoms, unsubstituted or monosubstituted or polysubstituted by halogen-, hydroxyl- or alkoxy with 1 to 12 carbon atoms, or R7 and R8 are combined with the common N to form pyrrolidine, piperidine, piperazine or unsubstituted or monosubstituted morpholine, disubstituted, trisubstituted, or tetrasubstituted with 1 to 4 carbon atoms or to form carbazole, phenoxazine or phenothiazine, X + is a cation Li +, Na +, K +, Mg ++ 1/2, Ca ++ 1/2, Sr ++ 1/2, Ba ++ 1/2, Cu +, Cu ++ 1/2, Zn ++ 1/2, Al +++ 1/3 or ^ R ^ R ^ R ^] +, and R? Oyn are individually H, alkyl with 1 to 25 carbon atoms, aryl with 6 to 18 carbon atoms or aralkyl with 7 to 18 carbon atoms. In the case of a polysubstituted group, various substituents can be combined. In a further embodiment of the process of this invention, the high molecular weight organic or inorganic material can also optionally be mixed with a plurality of compounds, preferably 2 to 10, particularly preferably 2 or 3 compounds of the formula (I). Alkyl, alkenyl or alkylene can be straight chain, branched, monocyclic or polycyclic. Preference is given to alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkylene having 2 to 24 carbon atoms. Alkyl with 1 to 12 carbon atoms therefore for example is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tertbutyl, cyclobutyl, n-pentyl, 2-pentyl, 3 -pentyl, 2,2-dimethylpropyl, cyclopentyl, cyclohexyl, n-hexyl, n-octyl, 1, 1,3, 3-tetramethylbutyl, 2-ethylhexyl , nonyl, trimethylcyclohexyl, decyl, menthyl, tujyl, bornyl, 1-adamayl, 2 -adamantyl or dodecyl. Alkylene with 1 to 24 carbon atoms is therefore, for example, methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, -cyclobutylene, n-pentylene, 2-pentylene, -pentylene, 2, 2 -dimethylpropylene, cyclopentylene, cyclohexylene, n-hexylene, n-octylene, 1,1,3,3-tetramethylbutylene, 2-ethexylene, nonylene, trimethylcyclohexylene, decylene, mentylene, tujylene, bornylene, 1- adamantylene, 2-adamantylene, dodecylene, tetradecylene, hexadecylene, heptadecylene, octadecylene, eicosylene, heneicosylene, docosylene or tetracosylene. C 2 -C 12 alkenyl is C 2 -C 12 -alkyl having single or multiple unsaturation, two or more double bonds that are optionally isolated or conjugated, for example vinyl, allyl, 2-propen-2-yl , 2-buten-l-yl, 3-buten-l-yl, 1,3-butadien-2-yl, 2-cyclobuten-l-yl, 2-penten-l-yl, 3-penten-2-yl , 2-methyl-l-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-l-yl, 1,4-pentadien-3-yl, 2-cyclopenten -1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2,4-cyclohexadien-1-yl, 2,5-hexadien-2-yl, 1, -p-ment-8- ilo, 4 (10) -tir-10-yl, 2-norbornene-1-yl, 2, 5-norbornadien-1-yl, 7,7-dimethyl-2, 4-norcaradien-3-yl or the various hexenyl isomers , octenyl, nonenyl, decenyl or dodecenyl. Alkoxy with 1 to 12 carbon atoms is O-alkyl with 1 to 12 carbon atoms, preferably O-alkyl with 1 to 4 carbon atoms. O-alkyl having 1 to 12 interrupted carbon atoms, for example is C 4 -alkyl, such as in particular -CH 2 -CH 2-0-CH 2 -CH 3. O-alkyl having 1 to 12 carbon atoms double-interrupted is, for example, C 6 -alkyl, such as in particular -CH 2 -CH 2-0-CH 2 -CH 2 -0-CH 2 -CH 3. Alkyl with 1 to 12 substituted oxo carbon atoms for example is C 2 -alkyl such as in particular -C (= 0) -CH 3. Alkyl with 1 to 12 oxo-substituted and 0-interrupted carbon atoms, for example is C 8 alkyl such as in particular - (CH 2) 3 C (= 0) -C (CH 3) 3, -C (= 0 ) - (CH2) 6-OCH3 or -C (CH3) 2-C00- (CH2) 3-CH3. C 1 -C 24 -alkylene which is interrupted, for example, is C 4 -C 4 -alkylene, such as, in particular, -CH 2 -CH 2 -0-CH 2 -CH 2 -. 0-alkylene with 1 to 24 carbon atoms double-interrupted is for example C 6 -C 6 alkylene, such as in particular -CH 2 -CH 2-0-CH 2 -CH 2 -0-CH 2 -CH 3. Oxo-substituted carbon atom with 1 to 24, for example, is alkylene with 2 carbon atoms, such as in particular -C (= 0) -CH 2 -. O-Substituted and O-interrupted C 1 -C 24 alkylene is for example C 1 -C 8 -alkylene, such as in particular - (CH 2) 3-0-C (= 0) -C (CH 3) 3 , -C (= 0) - (CH2) 6-OCH2- or -C (CH3) 2 -COO- (CH2) 3 -CH2-. The single or multiple substitution with halogen, hydroxyl, oxo or cyano and the simple or multiple interruption by O, S or N, in general the chemical reactivity of an alkyl, alkenyl or alkylenyl group only in minimal form. The person with skill in the specialty will therefore have no problem identifying larger possible variations.

Cycloalkylene with 5 to 12 carbon atoms for example is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl, preferably cyclopentyl, cyclohexyl and cycloheptyl. A polycycle which may be interrupted by hetero atoms for example by O, N, S or P, for example is an aliphatic or aromatic and aliphatic aromatic polycycle such as polyether, for example a crown or polyamine or polythio ether ether, or octahydroquinolizine or tetradecahydroacridine . Preferred aralkyl and aryl are aralkyl with 7 to 12 carbon atoms and aryl with 6 to 12 carbon atoms, respectively. Aralkyl with 7 to 12 carbon atoms for example is benzyl, 2-benzyl-2-propyl, β-phenylethyl, 9-fluorenyl, α, α-dimethylbenzyl, α-phenylbutyl or β, β-dimethyl-β-phenylbutyl. Aryl with 6 to 24 carbon atoms for example is phenyl, 1-naphthyl, 2-naphthyl, 4-biphenylyl, 2-fluorenyl, phenanthrene, anthracene, naphthacene or pentacene. Aryl with 6 to 12 carbon atoms for example is phenyl, 1-naphthyl, 2-naphthyl, 4-biphenylyl or 2-fluorenyl. Heteroaryl with 5 to 18 carbon atoms is a polyunsaturated heterocyclic structure of 5 to 18 atoms selected from C, N, O and S containing at least 6 p-electrons conjugated. Examples of heteroaryl with A5-A18 are thienyl, benzo [b] thienyl, bibenzo [b, d] thienyl, thiantrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, bibenzofuranyl, phenoxythinyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, preferably mono and bicyclic heteroaromatic radicals. Halogen is chlorine, bromine, fluorine or iodine, preferably fluorine or chlorine. Alkyl with 1 to 12 carbon atoms or alkenyl with 2 to 12 carbon atoms mono-substituted or polysubstituted with halogen-, hydroxyl-, alkoxy with 1 to 12 carbon atoms or cyano, for example is 2-chloroethyl, trifluoromethyl, pentafluoroethyl, β, β, β-trifluoroethyl, trichlorovinyl, β-chloropropyl, β-bromobutyl, perfluorohexyl, perfluorododecyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2,3-dihydroxypropyl, 2,3-dimethoxypropyl , 2,3-dimethoxypropyl or 2-cyanoethyl, preferably trifluoromethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl or 2-cyanoethyl. Preference is given to using an isoxyndigo of the formula a bisisoxindigo of the formula wherein R12, R13, R32 and R33 independently are H, halogen, N02, R14, (alkyl having 1 to 12 carbon atoms) -COOR5, OR14, SR14, O-alkyl having 9 to 18 carbon atoms or S-alkyl with 9 to 18 carbon atoms and R34 is a single bond, alkylene with 1 to 24 carbon atoms or cycloalkylene with 5 to 12 carbon atoms, wherein R14 is alkyl with 1 to 25 carbon atoms unsubstituted or monosubstituted or polysubstituted with oxo-, cyano- or X1 + 0"0C, which may be uninterrupted or interrupted in single or multiple times by 0, or is aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms unsubstituted or mono substituted or polysubstituted with halogen-, nitro-, cyano-, R160-, R17R16N-, R17R16NOC-, R16OCR18N- or R16OOCR18N-monosubstituted or polysubstituted, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms , X1 + is a cation Na +, K +, Mg ++ 1/2, Ca ++ 1/2, Zn ++ 1/2, Al +++ 1/3, or [NR16R17R18R19] +, and R16 and R17 indepente They are usually H, aryl with 6 a carbon atoms, aralkyl with 7 to 10 carbon atoms. unsubstituted or mono-substituted alkyl or polysubstituted with halogen-, hydroxyl- or alkoxy with 1 to 4 carbon atoms, or R16 and R17 combine with the common N to form pyrrolidine, piperidine, piperazine or morpholine unsubstituted or monosubstituted, disubstituted, trisubstituted or tetrasubstituted with alkyl of 1 to 4 carbon atoms, and R18 and R19 independently are H, alkyl with 1 to 8 carbon atoms, aryl with 6 to 10 carbon atoms, or aralkyl with 7 to 10 carbon atoms. Particular preference is given to using an isoxyndigo of the formula a bisisoxindigo of the formula wherein R20, R21, R34 and R35 are independently H, chloro, R22, C2H5-COOH, C2H5-COO (alkyl having 1 to 12 carbon atoms), OR32, SR22, O-alkyl with 9 to 18 carbon atoms or S-alkyl with 9 to 18 carbon atoms and R37 is a single bond, C 1 -C 8 -alkylene or C 5 -C 6 -cycloalkylene, or R 22 is unsubstituted or unsubstituted C 1-8 alkyl or polysubstituted with oxo-, cyano- or X 2 + 0"OC- , which may be uninterrupted or interrupted simply or multiply by 0, or is aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms, X2 + is a Na +, K +, Mg ++ 1/2 cation, Ca ++ 1/2, Zn ++ 1/2, Al +++ 1/3, O [NR24R25R26R27] +, R24 R25 YR? E are independently H, alkyl with 1 to 4 carbon atoms or phenyl, and R27 is H, alkyl with 1 to 8 carbon atoms, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms More particular preference is given to using an isoxyndigo of the formula wherein R50 is tert-butyl, 0-CH3, CH2CH2COOH or CH2CH2COO (alkyl having 1 to 12 carbon atoms).

Some compounds of the formula (I), (lía), (Ilb), (III), (IV), (V) or (VI) are new. The invention therefore also relates to a compound of the formula (VII), or a compound of the bisisoxindigo structure (IIb) wherein Ax and A2 are independently arylene with 6 to 18 carbon atoms unsubstituted or monosubstituted, disubstituted, trisubstituted or tetrasubstituted, with the conditions that Ai and A2 are not both phen-1,2-ylene, 6-methylphen-1, 2-ylene, 6-isopropyl-phenyl-1,2-ylene, 6-tert-butyl-phenyl-1,2-ylene, 4-methyl-6-tert-butylphen-l, 2-ylene, 4-tert-butyl-6- methylphen-1, 2-ylene, 4,6-di-tert-butylphen-1,2-ene, 4-methoxy-6-tert-butylphen-1,2-ylene, 5-methoxyphen-1,2-ylene; 3-carboxy-5-methylphen-1,2-ylene, 3-methoxycarbonyl-5-methylphen-1,2-ylene, anthraquinone-1, 2-ylene, phenanthren-9, 10-ylene or l-oxa-2, 2-dimethyl-3-acetoxy-5-methylaceneften-6, 7-ylene, and that when Ax is phen-1, 2-ylene, A2 is not 5-methoxyphen-1,2-ylene, 4,6-dihydroxyphen 1, 2-ylene, naft-1, 2-ylene or naft-2, 1-ylene and when Ax is 3-methoxycarbonyl-5-methylphen-1,2-ylene A2 is not 3, 5-dimethylphen-1, 2 -ethylene, and o-arylene with 6 to 18 carbon atoms is connected to oxygen lactone with the first site indicated by the diradical. For some compounds of the formula (I), (lia), (III), (IV) or (V), the crystal structure is known from the crystal analysis with x-rays and polymorphism was found for at least one compound [Aust. J. Chem. 38, 85 (1985)]. In the case of polymorphism, each polymorphic form is in principle useful as a dye. Preference is given to compounds of the formula (VII) that comply with the formulas (lia), (IIb). Particular preference is given to compounds of the formula (VII) which comply with the formula (III) or (IV). Particular preference is given to compounds of the formula (VII) which comply with the formula (V) or (VI). The present invention furthermore relates to compositions comprising 2 to 10, preferably 2 or 3 compounds of formulas (I) or (VII) and / or (Ilb). The molar ratio of the composition comprising two compounds of the formula (I) or (VII) and / or (Ilb) is usual within the range of 99: 1 to 1:99. If three compounds of the formula (I) are used, they can be, in particular, compounds of the formulas where Ax and A2 differ. The molar ratio of the compositions of this invention comprising the three above compounds is usually within the range of 98: 1: 1 to 1: 98: 1 or 1: 1: 98, preferably within the range of 25:50:25, based on (VIII): (X): (IX). Compositions comprising 2 to 10 compounds can be prepared by conventional methods of mixing individual compounds or otherwise, in the case of mixtures of the three components, by direct synthesis which will be described more particularly below. The compounds of the formula (I) can be prepared from known starting materials by known methods or in close similarity thereto. A 3-methylenefuranonyl compound of the formula (XIII) and a 3-oxofuranonyl compound of the formula (XIV) wherein X is O or N-aryl, can be reacted in equimolar amounts with a dehydrating reagent, for example with acetic anhydride or with phosphorus tribromide [Bull. Soc. Chim. Fr. 9./5, 826 (1942); Chem. Reviews 54, 59 (1954); J. lndian Chem. Soc. 45/1, 35 (1968)]. The condensation of 3-oxobenzofuranone with 3-methylenebenzofuranone is described by J.N. Chaterjea in J. lndian Chem. Soc., 3_6, 70 (1959). However, the dehydrating reagent employed in this reference is phosphorus tribromide which is ecologically problematic. The invention therefore also provides a more ecological process for condensing 3-oxofuranonyl compounds with 3-methylene-furanonyl compounds, which comprises reacting differently substituted 3-methylene-furanonyl compounds of the formula (XIII) with 3-oxofuranonyl compounds of the formula (XIV) using hydrochloric acid, sulfuric acid, acids or organic bases, to form isoxyindigos (lia) or bisixoindigos (Ilb) asymmetric, where Ax and A2 are different and independently comply with the meaning given above. The reaction is generally initiated by contacting a 3-methylenurafuranonyl compound with a 3-oxofuranonyl compound and with the dehydrating reagent in a conventional manner, for example by mixing the starting materials or by dropwise addition of one starting material to the other. The dehydrating reagent employed can be an acid or a base. For example, inorganic acids such as hydrochloric acid or sulfuric acid, organic acids such as arylsulfonic acids, especially p-toluenesulfonic acid or alkyl acids such as formic acid or acetic acid, especially trifluoroacetic acid, may be employed. Examples of useful bases are organic nitrogen bases such as triethylamine, piperidine, pyridine, morpholine, or aliphatic alkoxides, for example methoxide, ethoxide, propoxide or butoxide, or aromatic alkoxides, for example phenoxide. The solvent used can be an organic acid, for example acetic acid. In general, the molar ratio of the 3-methylene-furanonyl compound to the 3-oxofuranonyl compound will be within the range of 1: 1 to 3: 1, and preferably the molar ratio is 1: 1. In general, the molar ratio of dehydrating agent to compound 3 -oxofuranonyl will be within the range of 0.001: 1 to 5: 1, preferably within the range of 0.001: 1 to 1: 1. Preferably, the reaction temperature employed will be a temperature at which the reaction mixture boils, the reaction temperature is within the range of the boiling temperature of the solvent used. The reaction mixture can be processed in a conventional method, for example by addition of water and subsequent repeated extraction of the crude product with an organic solvent, such as toluene. The organic phase comprising the crude product can be washed with water and then evaporated. If desired, the product is mixed with methanol and then filtered, the product is obtained as filter residue.

The starting materials for this process are prepared in a similar manner to known processes. 3-Methylene-furanonyl compounds can be prepared, for example, from phenols by reaction with glyoxal similarly to the method of H.-D. Becker,. Gustafsson, J. Org. Chem. 42, 2966 (1977). 3 -Oxofuranonyl compounds can be prepared by oxidation of 3-hydroxyfuranonyl compounds by commonly known methods to oxidize hydroxy compounds to keto. These are described, for example, in Houben-yyl, Methoden der Organischen Chemie, 4th Edition, Volume 4 / la & 4 / lb. Z-Ma, J.M. Bobbitt in J. Org. Chem., 56, 6110 (1991), which describes oxidation with nitroxides. 3-Hydroxyfuranonyl compounds can be prepared similarly to the process involving 3-hydroxybenzofuranones which is described in U.S. Pat. No. 5,614,572. Preferably, the bisisoxindigos (Ilb) are prepared from bis-3-oxofuranonyl compounds of the formula (XXXII) or bis-3-methylenefuranonyl compounds of the formula (XXXIII).

Synthesis from bis-3-oxofuranonyl compounds (XXXII) preferably takes the form of a reaction with a 3-methylene-furanonyl compound (XXXIII) or, if desired with a mixture of two differently substituted 3-methylene-furanonyl compounds (XXXIII) . For example, it is also possible to react a compound of the formula (XIII) with an oxidizing agent, for example with thionyl chloride, sulfur dichloride or bromine in nitrobenzene, with iron (III) anhydrous chloride or chromic acid (VI) in glacial acetic acid, with potassium permanganate in acetone, with selenium dioxide in acetic anhydride, with perbromide pyridinium hydrobromide in acetic acid or with selenium in a sealed tube [Bum. Soc. Chem. Fr. 9/5, 826 (1942); Acta Chem. Scand. 3,1117 (1949); J. Amer. Chem. Soc. 83, 3808 (1961); J. Chem. Soc. Perkin 1, 2479 (1992)]. The disadvantage of this oxidative method is that it proceeds reasonably satisfactorily only in the absence of substituents sensitive to oxidation. In addition, phenols can be reacted first with aluminum trichloride, then with chloral and the resulting product dehydrochlorinated with aluminum oxide in decalin [Tetrahedron 29/13, 2147 (1983)]. Disadvantages of this method are: unsatisfactorily low yield and the production of a major amount of solid chemical waste that is difficult to discard. In addition, it was found that the orthoalkyl groups with respect to the phenol group are partially detached, so that the desired product is not obtained in the desired purity. In individual cases, it is also possible to use other methods, for example the self-condensation of phenanthrenquinone in the presence of pyridine and acetic anhydride in the dark at room temperature, the pyrolysis of bis-2-keto-3-acetyl-4,5: 6 , 7-bibenzocoumar-3-yl, the oxidation of ethyl- (10-acetoxifenantren-9-yl) acetate with perhydromide pyridinium hydrobromide, the oxidative re-arrangement of benzofuranilidenonas with DDQ and water in dioxane [J. Amer. Chem. Soc. 83, 3808 (1961); J. Org. Chem. 47, 1095 (1982); J. Chem. Soc. Perkin 1, 2479 (1992)], the hydrolysis of the corresponding bishoesters obtained from oxaphosphetanes [Chem. Ber. 113, 2950 (1980)] or the condensation of dehydrooxoperezinone with acetic anhydride [Rev. Latinoam. Quim 22 / 1-2.7 (1991)].

However, these methods can not be generalized and the chemicals to be used are expensive or harmful on an industrial scale. Of course, many isoxindigos can also be prepared from other isoxindigos, by chemically modifying their substituents as functional groups without changing the basic isoxyndigo structure. The person of ordinary skill in the art knows numerous methods with which substituents can be converted to other substituents, for example those described in the series "Compendium of Organic Synthetic Methods" (Wiley & amp; amp;; Sons, New York, ab 1971). Advantageous reaction conditions are those in which the known reactivity of the isoxynd makes it unlikely that its lactone bonds will break down or their double bonds will be reduced. Depending on the nature of their substituents, the compounds of the formula (I) can be used to prepare novel isoxindigos of the formula (I). For example, novel ester or amide derivatives can be prepared by synthetic methods commonly known for the manufacture of esters- or amines as described for example in Organic Syntheses, Collective Vol. I-VII. Preference is especially given to esters prepared by esterification or transesterification of compounds of the formula (1) for example, with various alcohols under commonly known catalysis and synthesis conditions, for example at temperatures of 0 ° C to 200 ° C, in amounts of alcohol of 2 to 200 equivalents based on an equivalent of the compound of the formula (I), in the presence or absence of a solvent. It has now been found that surprisingly the compounds of the formula (I) are obtained with particular good yield and purity from 3-hydroxybenzofuranone. This method is moderate and economical, and the product can be directly useful as a colorant. The invention therefore also provides a method for preparing a compound of the formula or a mixture consisting of the compounds of the formulas wherein R1 and A2 independently are arylene with 6 to 18 carbon atoms, unsubstituted or monosubstituted, disubstituted, trisubstituted, or tetrasubstituted, when dehydrating a compound of the formula or a mixture of compounds of the formulas or its tautomers. The compounds of the formulas (XI) and (XII) and their tautomers are known from the US patent. No. 5,614,572. It is not necessary to isolate the compound of formulas (XI) and (XII); on the contrary, the reaction mixture as obtained in the U.S. patent. No. 5,614,572 can be advantageously reacted more directly. 1 mol of (XI) or of the mixture comprising (XI) and (XII) theoretically is converted into 1/2 mol of (VIII) or 1/2 mol of the mixture comprising (IX) and (X). The dehydration can be carried out thermally, for example from 80 to 350 ° C, preferably from 100 to 200 ° C, in an inert solvent, optionally in the presence of an organic acid or protic mineral, a Lewis acid or an acidic earth. , for example fulcato, montmorillonite, ion exchanger. The amount of acid is not critical, since it only acts as a catalyst to accelerate the elimination of water. In general, a sufficient amount of acid is within the range of 0.01 to 250 mol%, preferably 1 to 10 mol%, based on the compound of the formula (XI) or the total moles of (XI) or (XII). The dehydration is preferably carried out by removing water azeotropically from the reaction mixture in a water separator with vigorous stirring and refluxing optionally under reduced or superatmospheric pressure. The dehydration can also be carried out chemically, in which case the compound of the formula (XI) is reacted with an equimolar amount of an electrophilic reagent and then an acid is removed from the resulting product, for example from -20 to 250 ° C, preferably from 50 to 200 ° C, in an inert solvent, optionally in the presence of an organic base (for example triethylamine, dialkylaniline, for example dimethylaniline, diethylaniline or 1,8-diazabicyclo [5.4.0] undec-7-ene, DBU , 1,4-diazabicyclo [2.2.2] octane, DABCO, pyridine, alkylpyridines, for example methylpyridine, ethylpyridine or 4-dimethylaminopyridine, DMAP or quinoline). The amount of base is not critical, if an acid is to be removed it is volatile under the conditions of elimination (for example hydrogen chloride). In general, an amount of 0.01 to 250 mol%, preferably 0.1 to 50 mol% based on the compound of the formula (XI), will then be sufficient. If, by contrast, the acid to be removed is not volatile under the conditions of elimination, it is advantageous to use not less than 100% in mol of base, based on the compound of the formula (XI). This makes it possible to remove the acid even at a lower temperature. Suitable electrophilic reagents are for example methyl and ethyl esters of mineral acids such as dimethyl sulfate or dimethyl phosphonate, or organic or inorganic acid chlorides such as thionyl chloride, phosgene, methanesulfochloride, mesyl chlorine, tosyl chloride or acetyl chlorine, or anhydrides such as acetic anhydride. The person of ordinary skill in the art will effortlessly identify additional convenient electrophilic reagents. If a stable ester is formed or, for example in the case of thionyl chloride, the immediately continuous reaction is immaterial to the process described above, provided that as an acid it can be removed from the product that is formed. Thionyl chloride is the preferred electrophilic reagent. The present invention relates generally to a process for preparing the compounds of the formula or a mixture consisting of the compounds of the formulas wherein Ax and A2 are independently o-arylene with 6 to 18 carbon atoms unsubstituted or monosubstituted, disubstituted, trisubstituted or tetrasubstituted, by a) reacting a compound of the formula (XIII), or b) a mixture of the compounds of the formulas with c) a halogenating agent to form a compound of the formula (XLI) I wherein X3 is halogen, such as iodine, bromine or chlorine, preferably bromine or chlorine, and d) simultaneously or subsequently, preferably subsequently, dimerizing at a temperature in the range of -20 to 250 ° C, preferably 50 to 200 ° C, to form a compound of the formula (VIII), (IX) and / or (X). The reaction with the halogenating agent is generally carried out by commonly known methods, for example by the direct halogenation method described in US Pat. No. 5,614,572. According to the process of the invention, it is initially possible to isolate the halogenated compound of the formula (XII) or (XIII) and then dimerize it at a temperature within the range of -20 to 250 ° C, preferably 50 to 200 °. C, to form a compound of the formula (VIII), (IX), or (X), or dimerize directly without isolating the halogenated compound of the formula (XII) or (XIII) or mixtures thereof. Preference is given to dimerize without isolating the halogenated compound (XII) or (XIII). Suitable halogenating agents are, for example, iodine, bromine, chlorine, N-chlorosuccinimide, N-bromosuccinimide, with preference given to Br2. The molar ratio of the compound of the formula (XIII) and (XI) is usually within the range of 1: 100 to 100: 1. In general, the halogenation can be carried out in an inert solvent at a temperature within the range of -20 ° C to 150 ° C, preferably 20 to 80 ° C, in the course of 5 minutes to 20 hours . The weight ratio of the compound of the formula (XIII) and (XI) or of the halogenated compounds of the formulas (XII) and (XIII) to the solvent, is generally within the range of 1: 100 to 100: 1. The inert solvent generally employed is for example an ether such as tetrahydrofuran, dioxane, diethyl ether or an alkane with 5 to 12 carbon atoms such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane or a cycloalkane with 5 to 12 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane or cyclododecane or especially a halogenated alkane such as dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, dichloroethane, trichloroethane or tetrachloroethane or an aryl which is benzene, ortho -dichlorobenzene or toluene. The preferred dimerization is carried out in an inert solvent which generally conforms to the above-specified definition. If desired, the halogenation, synthesis step c) and / or dimerization, synthesis step d), can be carried out in the presence of an organic base such as for example triethylamine, dialkylaniline such as for example dimethylaniline, diethylaniline or 1,8-diazabicyclo [5.4.0-1-undec-7-ene, DBU, 1,4-diazabicyclo [2.2.2] octane, DABCO, pyridine, alkylpyridines such as, for example, methylpyridine, ethylpyridine or 4-dimethylaminopyridine, DMAP or quinoline. The amount of base is not critical. In general, an amount of 0.01% to 250% by mole, preferably 0.1 to 50% by mole, based on the compound of the formula (XIII) or (XI) or (XII) or (XIII), will suffice . If desired, in case low temperatures are used for the dimerization, it is advantageous to use not less than 100 mol% of the base, based on the compound of the formula (XIII) or (XI) or (XII) or (XIII). The isolation of the halogenated compound (XII) or (XIII) or of the dimers (VIII), (IX) or (X) or their mixtures, is carried out by methods that are of general knowledge common to the person skilled in the art. It is usual for example to wash the organic phase comprising the reaction product with water and then to concentrate the organic phase, preferably to dryness. In a further variant of the processing, the organic reaction product can also be directly evaporated and subsequently purified, for example by re-crystallization or column chromatography. For a re-crystallization, the isolation is usually done by filtration and subsequent washing of the filter residue, preferably with a solvent in which the reaction product is only slightly soluble. The organic phase, column chromatography comprising the reaction product can be directly evaporated. If desired, the reaction products can be dried after isolation. Drying is generally achieved using a commonly known drying apparatus such as drying cabinets or paddle dryers. A particular embodiment of the process of the present invention relates to the controlled preparation of the asymmetric compounds of the formula (X) by reacting a compound of the formula (XIII) with a halogenating agent to form a compound of the formula (XII) and dimerizing this product at a temperature in the range of -20 to 250 ° C, preferably 50 to 200 ° C, with a compound of the formula Depending on the nature of their substituents and the polymer to be colored, the compounds of formula (I), (VII) or (Ilb) or the compositions of the invention can be employed as polymer-soluble dyes or as pigments. In the latter case, it is advantageous to convert the products as they were synthesized in a finely divided form. This can be achieved in a conventional manner. Depending on the compound and the intended purpose, it is advantageous to use the dyes as organic pigments or in the form of preparations. The compound of formula (I), (VII) or (Ilb) is advantageously employed in an amount of 0.01 to 70% by weight, usually 0.01 to 30% by weight, preferably 0.01 to 10% by weight, based on the high molecular weight organic material to be colored. The invention accordingly provides a composition of matter comprising an organic material of high molecular weight and at least one compound of the formula (I), (VII) or (IIb) or a composition consisting of a compound of the formula (I) or (VII) and / or (IIb) in an effective coloring amount in general within the range of 0.01 to 70% by weight, especially 0.01 to 30% by weight, preferably 0.01 to 10% by weight , based on the high molecular weight organic material. The present invention also relates to the individual use of the compounds of the formula (I), (VII) or (Ilb) as dyes, especially for coloring or pigmenting high molecular weight organic or inorganic material. However, it is probably possible to use the compositions of the invention comprising compounds of the formula (I), (VII) or (Ilb) as mixtures, solid solutions or mixed crystals. Compounds of the formula (I), (VII) or (IIb) can also be combined with dyes of another chemical class, for example with dyes or pigments, for example selected from the group of diketopyrrolopyrroles, quinacridones, perylenes, dioxazines, anthraquinones, indatrones, flavantrones, indigos, thioindigos, quinophthalones, isoindolinones, isoindolinas, phthalocyanines, metal complexes, azo pigments and azo dyes. Depending on the nature of their substitution and that of the polymer to be colored, the compounds of the formula (I), (VII) or (Ilb) can be used as polymer-soluble dyes or as pigments. In the latter case, it is advantageous to convert the products as they were synthesized in a finely divided form. This can be achieved in a conventional manner. Depending on the compound and the intended purpose, it is advantageous to use the dyes as pigments or in the form of preparations. The high molecular weight materials can be organic or inorganic and can be synthetic and / or natural substances. They can, for example, be natural resins or drying oils, rubber or casein or modified natural substances such as chlorine, rubber, alkyd resins modified with oil, viscose, ethers or cellulosic esters such as ethyl cellulose, acetate, propionate or cellulose butyrate, acetate or cellulose butyrate and nitrocellulose, but special fully synthetic organic polymers (thermosetting and thermoplastics) as can be obtained by polymerization, for example by polycondensation or polyaddition. The class of polymers includes for example polyolefins such as polyethylene, polypropylene, polysilobutylene, substituted polyolefins such as polymers of monomers such as vinyl chloride, vinyl acetate, styrene, acrylonitrile, acrylic esters, methacrylic esters, fluorine polymers, for example polyfluoroethylene, hexafluoropropylene / tetrafluoroethylene or polytrifluorochloroethylene interpolymer and also copolymers of the aforementioned monomers, especially ABS (acrylonitrile / butadiene / styrene) or EVA (ethylene / vinyl acetate). Exemplary polycondensation and polyaddition resins which can be used are condensation products of formaldehyde with phenols, known as phenolic and condensation products of formaldehyde and urea or thiourea also melamine, known as aminoplasts, also polyesters used as surface coating resins, either saturated such as alkyd or unsaturated resins such as maleic resins, also linear polyesters, polyamides , polyurethanes, polycarbonates, polyphenylene oxides, silicones or silicone resins. The aforementioned high molecular weight compounds may be present individually or in mixtures as plastically deformable materials or fusions or in the form of centrifugation solutions. They may also be present in the form of their monomers or in the polymerized state in dissolved form as film formers or binders for paints or printing inks, for example linseed oil varnish, nitrocellulose, alkyd resins, melamine resins, and resins of urea-formaldehyde or acrylic resins. The present invention according to this, further allows the use of the compositions of the invention consisting of compounds of the formula (I) or (VII) and / or (Ilb) or compounds of the formula (I), (VII) or (IIb), for preparing inks, for printing inks in printing processes, for flexographic printing, stencil printing, packaging printing, security color printing, intaglio printing or offset printing, for printing precursors and also for printing textile, for office applications, domestic applications or graphics applications such as for example paper articles, for pens, felt-tipped pens, fiber-tip pens, cardboard, wood (wood dyes), metal, stamp cushions or inks for impact printing process (involving color ribbons for impact printing) to prepare dyes, for coatings for industrial or commercial use, for textile decoration and for industrial marking, for roller coatings or powder coatings or for automotive coating, for coatings of high solids content (low solvent), aqueous or metallic or for pigmented formulations for aqueous paints, for mineral oils, fats or waxes, to prepare colored plastics for coatings, fibers, plates or carriers of molds, to prepare print material without impact, for digital printing, for the thermal wax transfer printing process, the ink jet printing process or for the thermal transfer printing process, also for preparing color filters, especially for visible light within the range of 400 to 700 nm, for liquid crystal displays (LCDS = Liquid Crystal displays) or charge coupled devices (CCDs = charge coupled devices) or for preparing cosmetics or to prepare polymeric color particles, pigments, dry copying pigments, liquid copying pigments or electrophotographic pigments. The present invention furthermore relates to inks comprising an organic material of high molecular weight and a coloristically effective amount of the compound (I), (VII) or (IIb) or of the composition consisting of compounds of the formula (I) or (VII) and / or (Ilb). Processes for preparing inks, especially for inkjet printing, are part of common general knowledge and are described, for example, in U.S. Pat. No. 5,106,412.

The inks can be prepared, for example, by mixing the compounds of the invention with polymeric dispersants. The mixing of the compounds of the invention with the polymeric dispersant is preferably carried out by commonly known methods of mixing such as stirring or mixing, the use of high intensity mixers such as ultraturax, are preferably recommended. In order to mix the compounds of the invention with polymeric dispersants, it is advantageous to use an organic solvent which can be thinned with water. It is advantageous to choose a weight ratio for the compounds of the invention to the ink which is within the range of 0.0001 to 75% by weight, preferably in the range of 0.001 to 50% by weight, based on the total weight of the ink. The present invention thus also provides a process for preparing inks by mixing a high molecular weight organic material with a coloristically effective amount of compound (I), (VII) or (Ilb) or compositions consisting of compounds of the formula (I) or (VII) and / or (IIb). The present invention further provides colorants comprising organic material of high molecular weight and a coloristically effective amount of a compound (I), (VII) or (IIb) according to the invention or of a composition according to the invention. The present invention further provides a process for preparing dyes by mixing a high molecular weight organic material and a coloristically effective amount of the compound (I) according to the invention or the composition of the invention consisting of the compound of the formula (I) ) or (VIII) and / or (Ilb). The present invention further provides colored plastics or polymeric colored particles comprising organic material of high molecular weight and a compound (I), (VII) or (Ilb) or a composition consisting of the compounds of the formula (I) or ( VII) and / or (Ilb) in a coloristically effective amount. The present invention further provides a method for preparing colored plastics or polymer colored particles by mixing a high molecular weight organic material and a coloristically effective amount of compound (I), (VII) or (Ilb) or a composition consisting of the compounds of the formula (I) or (VII) and / or (Ilb). The organic substances of high molecular weight are colored with dyes of the formula (I), (VII) or (IIb), or compositions comprising compounds of (I) or (VII) and / or (Ilb), for example by mixing said dye, optionally in the form of master batches, in these substrates using roller mills, mixing or milling apparatus, to dissolve or finely disperse the dye in the high molecular weight material. The high molecular weight organic material with the mixed dye is subsequently processed in a conventional manner, for example by calendering, pressing, extruding, coating, spinning, casting or injection molding, whereby the colored material acquires its ultimate shape. The mixing of the dye can also be carried out directly before the current processing stage, for example by continuously dosing a pulverulent dye of this invention and an organic material of high granulated molecular weight and also optionally additional substances such as for example additives, in simultaneous form direct in the entrance area of an extruder where the mixing is carried out just before processing. In general however, prior blending of the colorant into the high molecular weight organic material is preferable, since more uniform results can be obtained. It is often desired to incorporate plasticizers in the high molecular weight compounds before shaping to produce non-rigid molded parts or reduce their brittleness. Examples of useful plasticizers are esters of phosphoric acid, phthalic acid or sebasic acid. In the process of the present invention, plasticizers can be incorporated into the polymers before or after the dye is incorporated. It is also possible for the purpose of achieving different shades to add to the organic substances of high molecular weight, not only the compounds of the formula (I), (VII) or (Ilb), or the compositions of the invention but also constituents such as white, colored or black pigments in any desired quantities. For color paints and printing inks, the high molecular weight organic materials and the compounds of the formula (I), (VII) or (Ilb), or the compositions of the invention optionally together with additional substances such as fillers, dyes , pigments, driers or plasticizers are finely dispersed or dissolved in a solvent or mixture of common organic solvents. This can be achieved by dispersing or dissolving the individual components by themselves or otherwise more than one as a whole and only then combining all the components. The processing is carried out in a conventional manner, for example by spraying, pouring by molding or one of the many printing methods whereby the paint or the printing ink, if necessary after drying, is cured by radiation or thermally advantageous way. If the high molecular weight material to be colored is a paint, it can be a standard paint or otherwise a specialty paint, for example an automotive paint, preferably a metallic effect paint comprising for example mica or metal particles. - Preference is given to the coloration of the thermoplastic materials, including in particular in the form of fibers, and also printing inks. Preferred high molecular weight organic materials useful for coloration in accordance with this invention are generally polymers having a dielectric constant >; 2.5, especially polyester, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene / acrylonitrile (SAN) or acrylonitrile / butadiene / styrene (ABS). Particular preference is given to polyester, polycarbonate, polystyrene and PMMA. Particular preference is given to polyester, polycarbonate or PMMA, especially to aromatic polyesters which are obtained by polycondensation of terephthalic acid, for example polyethylene terephthalate (PET) or polybutylene terephthalate (PBTP).

Particular preference is also given to the correlation of mineral oils, fats and waxes with the compounds of the invention. The present invention also provides a non-impact or non-impact printing material, comprising high molecular weight organic material and a compound (I), (VII) or (Ilb) or composition consisting of the compounds of the formula (I) ) or (VII) and / or (Ilb) in a coloristically effective amount. The present invention also provides a method for preparing non-impact printing material by mixing an organic and high molecular weight material and a coloristically effective amount of the compound (I), (VII) or (Ilb) or composition consisting of the formula (I) or (Vil) and / or (11b). The present invention further provides a method for preparing color filters comprising a transparent substrate and applying thereto a layer of red, blue and green in any desired order, when preparing the red, blue and green layers using in each case a compound of appropriate color (1), (VII) or (Ilb) or composition consisting of compounds of the formula (I) or (VII) and / or (Ilb). Layers of different color of preference include patterns such that they do not overlap in not less than 5% of their respective areas and more preferably do not actually overlap. Color filters, for example, can be coated using inks, especially printing inks, which comprise the compounds or compositions of the invention or can be prepared, for example, by mixing a compound or compositions according to the invention with high molecular weight, chemical, structure, structure material or photolytically (protective layer). Further preparation can be carried out for example similar to EP-A 654 71 1 per application to a substrate, such as an LCD, subsequently photo-structured and developed. The invention further encompasses a transparent substrate coated with a red layer, a blue layer and a green layer, each comprising an appropriate colored compound (I), or a composition comprising? compounds of the formulas (I) or (VII) and / or (IIb), which comprise organic material of high pigmented molecular weight. The order in which the layers are applied is generally immaterial. The layers of different color, preferably have patterns such that they do not overlap in not less than 5% of their respective areas and more preferably do not overlap in fact. The present invention also encompasses color filters that comprise a transparent substrate and are applied a red layer, a blue layer and a green layer, each one obtained from an appropriate color compound (I), (VII) or (Ilb), or a composition consisting of compounds of the formula (I) or (VII) and / or (IIb). The present invention further provides organic pigments comprising high molecular weight organic material and a compound (I), (VII) or (IIb) or composition consisting of compound of the formula (I) or (VII) and / or (Ilb) in a coloristically effective amount. The present invention also provides methods for preparing pigments by mixing high molecular weight organic material and a coloristically effective amount of compound (I), (Vil) or (Ilb) or composition consisting of compounds of formula (I) or (VII) ) and / or (Ilb). In a particular embodiment of the process of the invention, pigments, coatings, inks or colored plastics are prepared by processing master batches of organic pigments, coatings, inks or colored plastics in roller mills, mixing or milling apparatus. For the purposes of the present invention, a coloristically effective amount of the compound (I), (VII) or (Ilb) or composition consisting of compounds of the formula (I) or (VII) and / or (11b) is generally within from the range of 0.0001 to 99.99% by weight, preferably in the range of 0.001 to 50% by weight, particularly preferably in the range of 0.01 to 50% by weight, based on the total weight of the colored or pigmented material there. When the compounds of the formula (I), (Vil) or (Ilb), or the compositions of the invention are present in a dissolved state in the polymers employed, they are remarkable for clean tone, high color intensity, high resistance to light and resistance to the weather, especially for PET, PMMA, PS and PC, and also for high fluorescence. The colors obtained for example in thermoplastic or thermosetting materials, fibers, paints or coatings, are remarkable for a clean tint, high color intensity, high saturation, high transparency, good firmness to overrooting, migration, rubbing, light, weathering, and especially heat and good brightness. The dyes have good dispersibility and generally good solubilities in organic solvents. They are useful in collectors of solar energy and to generate laser beams. Mixtures comprising the compounds of this invention have attractive dyes. Particularly advantageously, asymmetric isoxindigos and also bisisoxyndigos offer more dyes and make it possible to vary their solubility by the selection of substituents. The examples below elucidate the invention without restricting it in any way: Example IA; A multi-necked flask with 1.5 liters capacity, equipped with stirrer, addition funnel, water separator, condenser and thermometer is charged with 300 ml of toluene, 212 g of 2, 4-di-tert-butylphenol 97%, 121.9 ml of 50% aqueous glyoxylic acid and 0.5 g of p-toluenesulfonic acid monohydrate which are added in succession with agitation. The reaction mixture is then vigorously refluxed with complete agitation. The water present in the glyoxylic acid and the reaction water formed in the first stage are collected in the water separator. After a reflux time of approximately 3 hours, the water removal ceases, leaving a slightly yellow, homogeneous solution of hydroxybenzofuranone. The reaction mixture is then diluted with 40 ml of a linear C 9 to 13 alkylbenzene (MRMarilcan, Hüls) boiling at 275-312 ° C. Subsequently, approximately 200 ml of toluene are distilled off at atmospheric pressure and a heating bath temperature of up to 142 ° C. At the end of the distillation, the internal temperature is approximately 121 ° C. The pale yellow oil mixture is cooled to an internal temperature of about 60 ° C and mixed with 13.9 ml of triethylamine. Subsequently 79.8 ml of thionyl chloride are added dropwise from the addition funnel at a rate such that the evolution of HCl and S02 remains active but still controllable. The addition takes approximately 35 minutes and the internal temperature is 60 to 67 ° C. After the gas formation has virtually ceased, the reaction mixture is stirred at 100 ° C for one more hour. The heating controller of the heating bath is adjusted to 200 ° C. The temperature of the reaction mixture increases to 186 ° C in the course of about 35 minutes, while an additional 105 ml of toluene are removed by distillation. At the same time, again there is an active stream of escaping HCl gas. If the evolution of the gas is too vigorous, the heating rate is appropriately reduced. The mixture, which is already intense red, is subsequently stirred from 180 to L90 ° C for two more hours. The dark red to black, thick glass suspension is cooled to approximately 150 ° C; 200 ml of N-butanol are then added via the condenser followed by 400 ml of ethanol. The crystal suspension is stirred under reflux for about 1 more hour, then cooled to 0 to 5 ° C and filtered. The crystal cake is washed with sufficient cold ethanol (approximately 600 ml) until the filtrate is clear and is no longer brown but slightly red. The crystalline dye is subsequently dried at 80 ° C / 50 mbar to obtain 186.2 g (76.2% theory, based on 2, 4-di-tert-butylphenol) of bright, intense, bright red crystals of 5, 7, 5 ', 7 '-tetra-tert-butyl [3,3'] bibenzofuranylidene-2,2 '-dione of the formula Melting point: 254-256 ° C; Elementary Analysis:% C% H calculated 78.65 8.25 obs. 78.40 8.39 Example IB: 10 g of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (prepared as described in Example 1 of US Patent No. 5,614,572), enter 25 ml of 1,2-dichlorobenzene as initial charge and mix with 0.5 g of 4-dimethylaminopyridine and 3 ml of thionyl chloride. The solution is then gradually heated to 100 ° C so that the evolution of HCl and S02 remains active but still controllable. Subsequently, the reaction mixture is stirred at 100 ° C for a further half hour. The temperature subsequently rises to the reflux point. After 75 minutes, the 1,2-dichlorobenzene is distilled off at the end under reduced pressure. The isoxindigo is separated by crystallization by the addition of 30 ml of acetonitrile to the residue, separated by filtration, washed with acetonitrinyl and dried to leave 6.8 g (73% theory) of 5,7, 5 ', 7'-tetra-terbutyl. [3,3 '] bibenzofuranylidene-2,2' -dione of the formula (XV). Example 1C: 78.7 g of 5,7-di-tert-butyl-3-hydroxy-3H-benzofuran-2-one (prepared as in Example IB) are introduced into 150 ml of toluene as initial charge and mixed with 3 drops of dimethylformamide (DMF) and 45 ml of thionyl chloride. The solution is then gradually heated to 100 ° C, so that the release of HCl and S02 remains alive but still controllable. Subsequently, the reaction mixture is stirred at this temperature for an additional hour. Approximately 150 ml liquid is subsequently removed by distillation to remove excess thionyl chloride. The residue is diluted with 480 ml of toluene and mixed at room temperature with 42 ml of triethylamine which is added dropwise. The thick red reaction mixture is then refluxed for 15 minutes. The precipitated triethylamine hydrochloride is filtered off after cooling to room temperature, the filtrate is washed with water and concentrated NaCl solution and concentrated in a rotary evaporator to an oily consistency. The isoxindigo is separated by crystallization by the addition of 225 ml of acetonitrile, separated by filtration, washed with acetonitrile and dried to leave 57.7 g (78.7% theory) of 5, 7, 5 ', 7'-tetra-tert-butyl [ 3, 3 '] bibenzofuranylidene-2, 2'-dione of the formula (XV). Example ID: 12.9 g of 5, 7-di-tert-butylbenzofuran-2-one (prepared similar to H.-D. Becker, K. Gustaffson, J. Org. Chem. 42, 2966 (1977), are introduced in 50 ml of 1,2-dichlorobenzene as initial charge and mix with 1 ml of triethylamine and subsequently with 2.83 ml of bromine The solution is then heated to 60 ° C, and HBr is released after 2.5 hours and the addition by drops of 1 ml of triethylamine, the temperature gradually rises to 165 ° C. After 2.5 hours, the reaction mixture is cooled and washed with water, dried and concentrated in a rotary evaporator to an oily consistency.The isoxindigo crystallizes upon addition of 150 ml of methanol, and it is separated by filtration, washed and dried and obtained in an amount of 7.96 g (62% theory) Example 2A: 22 g of 7-tert-butyl-3-hydroxy-5-methyl- 3H-benzofuran-2-one (prepared as described in Example 2 of U.S. Patent No. 5,614,572) is introduced into 50 ml of toluene as initial charge and mixed with 3 drops of DM F and 15 ml of thionyl chloride. The solution is then gradually heated to 100 ° C so that the evolution of HCl and S02 remains active but still controllable. Subsequently, the reaction mixture is stirred at 100 ° C for one more hour. Approximately 50 ml of liquid are subsequently removed by distillation to remove excess thionyl chloride. The residue is diluted with 160 ml of toluene and mixed at room temperature with 14 ml of triethylamine which are added per drops. The thick red reaction mixture is then refluxed for 30 min. The precipitated triethylamine hydrochloride is filtered off after cooling to room temperature and the residue is concentrated in a rotary evaporator to an oily consistency. Isoxindigo is separated by crystallization by addition of 200 ml of acetonitrile, separated by filtration, washed with acetonitrile and dried to leave 11.6 g (57% theory) of 7,7'-di-tert-butyl-5, 5'- dimethyl [3,3 '] bibenzofuranylidene-2,2' -dione of the formula Melting point: 253-255 ° C; > H NMR (CDC13, 300 MHz), d [rmn]: 1.43 s / 9H, 2.41 s / 3H, 7.26 s / lH, 8.72 s / lH. Example 2B: 2.2 g of 7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2 -one (prepared as in Example 2A) are refluxed for 17 hours with 0.23 g of camphor-10-sulfonic acid in 10 ml of 1,2-dichlorobenzene. The red reaction mixture is subsequently diluted with 20 ml of dichloromethane, washed with water and evaporated on a rotary evaporator. The isoxyindium is separated by crystallization by addition of 15 ml of methanol to the residue, separated by filtration, washed with methanol and dried to give 0.77 g (38% theory) of 7, 7'-di-t er-bu ti 1 - 5, 5'-dime ti 1 - [3, 3 'Ibibenzofuraniliden-2, 2' -dione of the formula (XVI). Example 2C: 2.2 g of 7-tert-butyl-3-hydroxy-5-methyl-3H-benzofuran-2-one (prepared as in Example 2A) are heated for 3 hours at 235 ° C in a flask equipped with a descending capacitor. The red reaction mixture is subsequently cooled to about 150 ° C and the isoxynd is crystallized by the addition of 10 ml of methanol, filtered off, washed with methanol and dried and leaves 0.55 g (27% theory) of 7.7 g. '-di-tert-butyl-5,5' -dimethyl- [3, 3 '] bibenzofuranylidene-2,2' -dione of the formula (XVI). Example 3: 7.1 g of 3-hydroxy-5-methyl-7- (1,1,3,3-tetramethylbutyl) -3H-benzofuran-2-one (U.S. Pat.

No. 5,614,572, Column 35, Compound No. 111) are introduced into 12.5 ml of toluene as initial charge and mixed with 3 drops of DMF and 2.7 ml of thionyl chloride. The solution is then heated gradually to 100 ° C so that the evolution of HCl and S02 remains active but is still controllable. Subsequently, the reaction mixture is stirred at 100 ° C for one more hour. Approximately 12 ml of liquid are subsequently removed by distillation to remove excess thionyl chloride. The residue is diluted with 37.5 ml of toluene and mixed at room temperature with 3.5 ml of triethylamine which is added per drop. The thick red reaction mixture is then refluxed for 30 minutes. The precipitated triethylamine hydrochloride is filtered off after cooling to room temperature and the filtrate is concentrated in a rotary evaporator to an oily consistency. The isoxindigo is separated by crystallization by the addition of 25 ml of acetonitrile, separated by filtration, washed with acetonitrile and dried to leave 3.45 g (53% theory) of 5, 5'-dimethi, 7,7,7-bis ( 1, 1, 3, 3-tetramethylbutyl) [3, 3 'Ibibenzofuranylidene-2, 2'-dione of the formula Melting point: 187-190 ° C; ! HRMN (CDC13, 300 MHz), d [ppm]: 0.75 s / 9H, 1.52 s / 6H, 1.94 s / 2H, 2.41 s / 3H, 7.27 s / lH, 8.75 s / lH. Example 4: 42.7 g of 3-tert-butyl-4-hydroxyanisole are evaporated together with 38.5 g of 50% aqueous glyoxylic acid and 0.2 g of p-toluenesulfonic acid in 75 ml of toluene under a water trap for 90 minutes. The reaction mixture is subsequently mixed at 100 ° C with 19 ml of thionyl chloride which is added dropwise at a rate such that the evolution of HCl and S02 remains active but still controllable. The reaction mixture is subsequently stirred at 100 ° C for one more hour. 10 ml of MRMarlican and 3.3 ml of triethylamine are then added. The temperature is then raised to 180 ° C for 30 minutes, while 71 ml of toluene are distilled off. After a further 1.5 hours of stirring at 180 ° C, the reaction mixture is cooled to 150 ° C, mixed with 50 ml of n-butanol and subsequently with 100 ml of ethanol, refluxed for 1 hour and then stirred at 5 ° C. C to precipitate the isoxindigo, and then the precipitated isoxindigo is filtered off, washed with ethanol and dried to leave 17.2 g (33% theory) of 7,7'-di-tert-butyl-5,5'-dimethoxy [ 3,3 '] bibenzofuraniliden-2, 2'-dione of the formula (XVIII) Melting point: 244-248 ° C; Elementary analysis:% C% H calculated 71.54 6.47 obs. 71.44 6.51 Example 5: 5: 2.8 g of 2-tert-butyl-4-chlorophenol [J. Amer. Chem. Soc. 78, 4604 (1956)] are refluxed for 3 1/4 hours, with 2.45 g of 50% aqueous glyoxylic acid and 50 mg of p-toluenesulfonic acid in 20 ml of 1,2-dichloroethane. Subsequently 2.45 g of 50% aqueous glyoxylic acid are added to continue the reflux for 18 hours. The reaction mixture is then washed with water, dried over MgSO 4 and evaporated in a rotary evaporator. Crystallization of the residue from hexane leaves 1.15 g of 7-tert-butyl-5-chloro-3-hydroxy-3H-benzofuran-2-one (melting point: 150-154 ° C). 1.1 g of this compound are introduced into 5 ml of toluene with 1 ml of thionyl chloride as initial charge and then gradually heated to 100 ° C in such a way that the evolution of HCl and S02 remains active but still controllable. The reaction mixture is subsequently stirred at 100 ° C for an additional 1 hour. Approximately 5 ml of liquid are subsequently removed by distillation, to remove excess thionyl chloride. The residue is diluted with 13 ml of toluene and mixed at room temperature with 0.6 ml of triethylamine which is added dropwise. The thick red reaction mixture is then heated to reflux and refluxed for 45 minutes. The precipitated isoxindigo is filtered off after cooling to room temperature, frees triethylamine hydrochloride by washing with water and methanol and dried to leave 0.47 g (46% theory) of 7, 7'-di-tert-butyl-5, 5'-dichloro [3, 3 '] bibenzo-furanylidene-2, 2'-dione of the formula Melting point: above 300 ° C; Elementary analysis:% C% H calculated 64.73 4.98 obs. 64.59 4.96 Example 6: 32.5 g of 2,6-di-tert-butyl-4-phenylsulfonylphenol [Org. Chem. 38, 687 (1973)] are melted at 120 ° C together with 1.2 g of camphor-2-sulfonic acid. A slow stream of nitrogen (approximately 1 ml / min) is subsequently passed through the stirred portion for 29 h. The reaction mixture is subsequently diluted with toluene, washed with water and evaporated in a rotary evaporator. The residue is column chromatographed on silica gel (hexane: ethyl acetate 19: 1) to recover 10.8 g of oily 2-tert-butyl-4-phenylsulfanylphenol. This oil is refluxed for 24 hours with 6.84 g of 50% aqueous glyoxylic acid and 50 mg of p-toluenesulfonic acid in 40 ml of 1,2-dichloroethane. Subsequently, an additional 4 g of 50% aqueous glyoxylic acid are added to continue the reflux for a further 5 hours. The reaction mixture is then washed with water, dried over MgSO 4 and evaporated in a rotary evaporator. 20 ml of hexane are added to the residue to remove 7-tert-butyl-3-hydroxy-5-phenylsulfanyl-3H-benzofuran-2-one as a viscous oil which is removed and dried under reduced pressure (9.3 g). 2.45 g of this viscous oil are introduced into 10 ml of toluene with 1.1 ml of thionyl chloride and 3 drops of DMF as initial ch and then gradually heated to 100 ° C, so that the evolution of HCl and S02 remains active but still controllable. The reaction mixture is subsequently stirred at 100 ° C for 1 hour. Approximately 10 ml of liquid are subsequently removed by distillation to remove excess thionyl chlorine. The residue is diluted with 15 ml of toluene and mixed at room temperature with 1.1 ml of triethylamine added per drop. The thick red reaction mixture is then heated to reflux and refluxed for 45 minutes. After cooling, 20 ml of water are added. Isoxindigo is isolated by chromatography of the concentrated organic phase over silica gel (hexane: toluene 2: 1) to leave 0.53 g (23% theory) of 7, 7'-di-tert-butyl-5,5'-bisphenyl sulfañil [3, 3 '] bibenzofuraniliden-2, 2' -dione of the formula Melting point: 206-212 C; Elementary analysis:% C% H cale. 72.95 5.44 obs. 72.99 5.34 Example 7: 23.6 g of methyl 3- (3-tert-butyl-4-hydroxyphenyl) propionate, 10.1 g of glyoxylic acid monohydrate and 0.08 g of p-toluenesulfonic acid are boiled in 80 ml of 1,2-dichloroethane under a water separator, for 7 hours. The reaction solution is then cooled, washed three times with 50 ml of water each time and the solvent is freed in a rotary evaporator to leave 29.2 g of methyl 3- (7-tert-butyl-3-hydroxy-2-oxo-2). , 3-dihydrobenzofuran-5-yl) propionate in the form of a yellowish oil. This yellowish oil is introduced into 50 ml of toluene as initial ch together with 15 ml of thionyl chloride and 3 drops of DMF and then heated gradually to 100 ° C so that the evolution of HCl and S02 remains active but still controllable . The reaction mixture is then stirred at 100 ° C for one more hour. Approximately 50 ml of liquid are subsequently removed by distillation to remove excess thionyl chloride. The residue is diluted with 160 ml of toluene and mixed at room temperature with 14 ml of triethylamine which is added dropwise. The thick red reaction mixture is then refluxed for 30 min. The precipitated triethylamine hydrochloride is filtered off after cooling to room temperature and the filtrate is concentrated to an oily consistency in a rotary evaporator. The isoxyindium is separated by crystallization by the addition of 100 ml of acetonitrile, separated by filtration, washed with acetonitrile and dried to leave 7.4 g (27% theory) of methyl 3 - [7,7'-di-er-butyl-5 '- (2-methoxycarbonylethyl) -2,2' -dioxo [3,3 '] bibenzofuranylidene-5] yl-propionate of the formula (XXI). Melting point: 224-226 ° C; ! H NMR (CDC13, 300MHz), d [ppm]: 1.43s / 9H, 2.6t / 2H, 3. 01t / 2H, 3.70 s / 3H, 7.30 d / lH, 8.77 d / lH, J = l .8Hz. Thermal stability, light fastness and migration in engineering plastics (EPL = engineering plastics) such as ABS, PC, PMMA or PS. %% Stability Migration thermal firmness to light Pigment Ti02 (XXI) * GS4 ** DE3 24 hr scale 200 500 1000/80 ° C Blue hr hr hr PS 0.20% 300 300 2 8 5 5 5 PET 0.02% 300 300 5 8 5 5 5 * GS denotes gray scale and is used for the visual quantification of color differences, the gray scale has 5 levels. GS4 denotes level 4. ** DE denotes a colorimetric evaluation of color differences. DE is the sum of all divergences. Wet firmness: The wet firmness is determined in a yarn produced in a spin machine. For this purpose, 1.00% (percent by weight) of the compound (XXI) is mixed with 99.0% (percent by weight) of polyester in an extruder (Collin kneader 25 laboratory extruder) and centrifuged in a laboratory centrifuge machine. (Labspin II, ESL, UK) at 280 ° C to a 24 filament wire 110 dtex. Pigment (XXI) Grayscale concentration 1.00% Test method changes * degree of spots * WO CO PES Washing 4-5 (ISO 105-C06) Firmness in Hypochlorite 4 hypochlorite (ISO 105-N01) Bleached with peroxide 4-5 (ISO-105 / N02) Alkaline perspiration 4-5 5 5 5 (ISO 105-E04) acid 4 -5 5 5 5 Dry rub 4-5 4-5 4-5 76. 2 cm (30") dry 80 ° C after heating 4-5 Steam treatment 4-5 4-5 (ISO 105-P02) Example 8: 7.4 g of the compound of the formula (XXI) according to the example 7 are refluxed for 56 hours with 3 ml of methanesulfonic acid in 300 ml of acetic acid, then 100 ml of acetic acid are distilled off and the residue is poured into 120 ml of water.The red precipitate is filtered off, washed with water and dried to leave 7.05 g (approximately 100% theory) of 3- [7,7'-di-tert-butyl-5 '- (2-carboxyethyl) -2,2'-dioxo [3, 3] 'Ibibenzofuraniliden-5-yl] propionic of the formula Melting point: 289-291 ° C; Elementary analysis% C% H cale, 69.22 6.20 obs. 69.23 6.22 Example 18.7 of 4-tert-butyl-2- (1-methylpentadecyl) phenol, 5.06 g of glyoxylic acid monohydrate and 0.05 g of p-toluenesulfonic acid are heated for 7 hours under a water separator in 40 ml of 1, 2-dichloroethane. The reaction solution is then cooled, washed 3 times with 80 ml of water each time and freed of solvent in a rotary evaporator, to leave 21.4 g of 5-tert-butyl-3-hydroxy-7- (1-methylpentadecyl) - 3H-benzofuran-2 -one as a yellowish oil. This yellowish oil is introduced into 25 ml of toluene as initial charge together with 8 ml of thionyl chloride and 3 drops of DMF and then heated gradually to 100 ° C so that the evolution of HCl and S02 remains active but still controllable . The reaction mixture is then stirred at 100 ° C for one more hour. Approximately 25 ml of liquid are subsequently removed by distillation to remove excess thionyl chloride. The residue is diluted with 80 ml of toluene and mixed at room temperature with 7 ml of triethylamine added per drop. The thick red reaction mixture is then refluxed for 30 minutes. The precipitated triethylamine hydrochloride is filtered off after cooling to room temperature and the filtrate is concentrated to an oily consistency and in a rotary evaporator. The residue is chromatographed on silica gel (hexane: ethyl acetate 99: 1) to isolate the isoxyndigo as a red waxy material to obtain 4.1 g. (20% theory, based on 4-tert-butyl-2- (1-methylpentadecyl) phenol) of 5,5'-di-tert-butyl-7,7 '-bis (1-methylpentadecyl) [3, 3 '] bibenzofuraniliden-2, 2'-dione of the formula (XXIII).

Melting point: 69-76 ° C; XH NMR (CDC13, 300 MHz), d [ppm]: 0.8-1.8 m / 32H, 3.03 m / lH, 7. 39 d / lH, 9.03 d / lH, J = 1.9 Hz. Example 10: 7.9 g of 3-hydroxy-5, 7-bis (1-methyl-1-phenylethyl) -3H-benzofuran-2-one (U.S. Patent No. 5,614,572, Column 35, Compound No. 111) they are introduced into 25 ml of toluene as initial charge together with 2 ml of thionyl chloride, and 3 drops of DMF and then gradually heated to 100 ° C so that the HCl and S02 evolution remains active but still controllable. Later, the reaction mixture is stirred at 100 ° C for one more hour. Approximately 25 ml of liquid are then removed by distillation to remove excess thionyl chloride. The residue is diluted with 30 ml of toluene and then mixed at room temperature with 2.8 ml of triethylamine which is added dropwise. The thick red reaction mixture is then refluxed for 30 minutes. The precipitated triethylamine hydrochloride is filtered off after cooling to room temperature and the filtrate is concentrated to an oily consistency in a rotary evaporator. Isoxindigo is isolated from the residue by chromatography on silica gel (toluene / hexane 1: 1 to 3: 1) and trituration with petroleum distillate, as 3.78 g (51% theory) of fine red crystals of 5, 7, 5 ', 7' -tetrakis- (1-tnethyl-p-ethylethyl) [3, 3 '] bibenzofuranylidene-2,2' -dione of the formula (XXIV).

Melting point: 195-198 ° C; MS (DE-EI): m / e = 536 (M +, C52H4804). Example 11: 4.9 g of 9-hydroxyphenanthrene, 4.1 g of 50% aqueous glyoxylic acid and 0.05 g of p-toluenesulfonic acid are heated for 2 hours in 70 ml of 1,2-dichloroethane under a water separator. The precipitated solid is then cooled, separated by filtration, washed with cold and dry 1,2-dichloroethane to leave 3.0 g of hydroxybenzofuranone which is introduced into 20 ml of toluene as initial charge together with 1.5 ml of thionyl chloride and 3 drops of toluene. DMF and then gradually heated to 100 ° C so that the release of HCl and S02 remains active but still controllable. The reaction mixture is subsequently stirred at 100 ° C for one hour. Approximately 20 ml of liquid are then distilled off to remove excess thionyl chloride. The residue is diluted with 10 ml of toluene and then mixed at room temperature with 1.7 ml of triethylamine which is added dropwise. The thick blue reaction mixture is then refluxed for 2 hours. The precipitated isoxindigo is filtered off after cooling to room temperature, free of triethylamine hydrochloride when washed with water, dried and recrystallized from dichloromethane / ethanol to leave 1.3 g (47% theory) of [3, 3 '] bi [1-oxacyclopenta [i] phenanthrenylidene] -2,2'-dione of the formula (XXV).

(XXV).

Melting point: above 300 ° C; MS (DE-EI): m / e = 464 (M +, C 32 H 1604) Example 12: Preparation of bisisoxyindoxae a) Preparation of 5,7-di-tert-butyl-3-oxobenzofuranone of the formula 3. 8 g (0.0146 mol) of 5, 7-di-tert-butyl-3-hydroxybenzofuranone, 6.1 g (0.032 mol) of p-toluenesulfonic acid and 6.9 g (0.032 mol) of 4-acetaminotetramethylpiperidine oxide, are stirred in 100 g. ml of dichloromethane at room temperature for 24 hours. The yellow solution is then washed three times with 200 ml of 5% hydrochloric acid, dried over magnesium sulphate and evaporated to dryness. Crystallization of the residue from hexane yields 1 g of (XXVI). Melting point: 165 - 168 ° C. b) Preparation of bis (5-cyclohexylidene) -7-tert-butyl-3-oxobenzofuranone of the formula (XXVII) . 1 g (0.01 mol) of bis (5-cyclohexylidene) -7-tert-butyl-3-hydroxybenzofuranone, 8.75 g (0.046 mole) of p-toluenesulfonic acid and 9.8 g (0.046 mole) of 4-acetaminotetramethylpiperidine oxide are stirred in 60 ml of dichloromethane at room temperature for 48 hours. The yellow solution is then washed with 50 ml of 5% hydrochloric acid and subsequently 4 times with 50 ml of water each time, then dried over magnesium sulphate and evaporated. The residue is dissolved in 100 ml of toluene, refluxed for one hour and again evaporated to leave 5 g of (XXVII) as an amorphous crystal. c) Preparation of 5-methoxy-7-tert-butylbenzofuranone of the formula (XXVIII) This compound is prepared in a manner similar to H.-D. Becker, K. Gustaffsson, J. Org. Chem. 42, 299 (1977). Colorless crystals are obtained. Melting point: 116-118 ° C. d) Preparation of bisisoxyindigo of the formula (XXIX) 4.9 g (0.02 mol) of 5,7-di-tert-butylbenzofuranone (described: H.-D. Becker, K. Gustaffsson, J. Org. Chem. 42, 2966 (1977I, 4.9 g (0.01 mol) of bis (5-cyclohexylidene) -7-tert-butyl-3-oxo-benzofuranone (XXVII) and 0.3 g of p-toluenesulfonic acid are refluxed in 25 ml of acetic acid for 10 hours Subsequently, 125 ml of water are added and the resulting precipitate is filtered off with suction.The filter residue is chromatographed on silica gel (mobile phase: hexane / toluene 2: 1) .The pure fractions are subsequently recrystallized from methanol. and they produce 1.25 g of the bisisoxyndigo of the formula (XXIX) Melting point: 304 - 308 ° C. e) Preparation of bisisoxyindigo of the formula (XXX) 22.0 g (Ol mol) of 5-methoxy-7-tert-butylbenzofuranone (XXVIII), 27.5 g (0.05 mol) of bis (5-cyclohexylidene) -7-tert-butyl -3-oxobenzofuranone (XXVII) and 1 g of p-toluenesulfonic acid are refluxed in 130 ml of acetic acid for 22 hours. Recrystallization from dichloromethane / methanol yields 9.2 g of the compound of the formula.

Melting point: 259-264 ° C. Example 13: Preparation of asymmetric isoxylenders of the formula (XXXI) 0.5 g (0.0023 mol) of 5-methoxy-7-tert-butylbenzofuranone (XXVIII), 0.6 g (0.0023 mol) of 5,7-di-tert-butyl- 3 -oxobenzofuranone (XXVI) and 0.2 g of p-toluenesulfonic acid are refluxed in 10 ml of acetic acid 16 hours. Subsequently, 20 ml of water are added, and the mixture is extracted three times with 30 ml of toluene each time.

The extracts are washed with water and evaporated to dryness.

Addition of 10 ml of methanol and filtration produces 0.5 g of the asymmetric isoxyndigo of the formula Melting point: 145-153 ° C. Thermal stabilities, light firmness and migration in EPL%% Stability Migration thermal firmness to light Pigment Ti02 (XXXI) GS4 DE3 24 hr scale 200 500 1000/80 ° C Blue hr hr hr PET 0.02% 300 300 5 7-8 5 5 4-5 Example 14a: Transesterification 1 g of the compound of the formula (XXI) according to Example 7 is refluxed for 17 hours with 1 ml of methanesulfonic acid in 60 ml of ethanol. Cooling achieves a red precipitate, which is filtered off, washed with ethanol and water and dried to leave 0.82 g (80% theory) of ethyl 3- [7,7 '-di-tert-butyl-5' - ( 2-ethoxycarbonylethyl) -2,2 '-dioxo [3, 3'] bibenzofuranylidene-5-yl] propionate of the formula (XLVIII).

Melting point: 125-130 ° C ! H NMR (CDC13, 300 MHz), d [ppm]: 1.26 t / 3H, 1.43 s / 9H, 2.68 t / 2H, 3.00 t / 2H, 4.16 q / 2H, 7.31 d / 1 H, 8.77 d / 1 H. Example 14b: Transesterification 1 g of the compound of the formula (XXI) according to example 7, is refluxed for 17 hours with 1 ml of methanesulfonic acid in 60 ml of isopropanol. The cooling achieves a red precipitate which is filtered off, washed with ethanol and water and dried to leave 0.66 g (61% theory) of isopropyl 3- [7,7 '-di-tert-butyl-5' - (2 -isopropoxycarbonylethyl) -2,2 'dioxo [3,3'] bibenzofuranyliden-5-yl] propionate of the formula Melting point: 111-116 ° C NMR (CDC13, 300 MHz), d [ppm]: 1.22 d / 3H, 1.43 s / 9H, 2.65 t / 2H, 3.00 t / 2H, 5.02 m / lH, 7.31 d / lH, 8.77 d / lH. Example 14c: Transesterification 1 g of the compound of the formula (XXI) according to Example 7, is refluxed for 17 hours with 1 ml of methanesulfonic acid in 60 ml of ethoxyethanol. The cooling achieves a red precipitate, which is filtered off, washed with ethoxyethanol and water and dried to leave 0.89 g (75% theory) of ethoxyethyl 3 - [7,7 '-di-tert-butyl-5' - (2-ethoxyethoxycarbonylethyl) -2, 2'-dioxo [3, 3 'I bibenzofuranyliden-5-yl] propionate of the formula Melting point: 142-145 ° CH NMR (CDCl3, 300 MHz), d [ppml: 1.21 t / 3H, 1.43 s / 9H, 2.73 t / 2H, 3.01 t / 2H, 3.52 q / 2H, 3.64 t / 2H , 4.26 t / 2H, 7.31 d / 1 H, 8.77 d / lH Preparation of 5, 7-di-tert-butyl-3-bromobenzofuranone of the formula 12. 9 g (0.052 mol) of 5, 7-di-tert-butyl-3-hydroxybenzofuranone are dissolved in 50 ml of toluene and treated with 2.9 ml (0.052 mol) of bromine at 30 ° C. The mixture is subsequently stirred at 60 ° C for 30 minutes. The solvent is distilled off by means of a rotary evaporator. 1 g of crude product is purified by flash chromatography on silica gel (Merck Silicagel 60, 70-230 mesh ASTM, mobile phase: 1: 1 hexane / dichloromethane) to leave 0.26 g (36% theory) of 5, 7- di-tert-butyl-3-bromobenzofuranone (XLVII). 'H NMR (CDC13, 300 MHz), d [ppm]: 1.33 s / 9H, 1.40 s / 9H, 5.47 s / 1 H, 7.30 d / 1 H, 7.36 d / 1 H Elemental analysis:% C% H% Br cale. 59.09 6.51 24.57 obs. 58.96 6.53 24.36 Example 15: Preparation of plates nolded by injection in polyethylene terephthalate (PET). 0.3 g of the compound of the formula (VIII), prepared as described in Example 1A, are mixed (briefly by hand, then in a drum stirring mixer at 50 rpm for 5 minutes) with 1500 g of polyethylene terephthalate (PET) ) (MRMELINAR PURA, ICI), dried prior to 120 ° C. This mixture is then pre-extruded at 270 ° C in a 25 mm 1-screw extruder (Collin). The compound is subsequently processed in a microprocessor controlled injection molding machine (MRFerromatik FM 40, Klóckner). The residence time of the polymer (dependent on cycle time, screw volume and plasticizing volume) is 5 minutes, during which the counter pressure and the screw speed remain low. This is beneficial for the homogeneity of the plastic and avoids the generation of friction heat. The first molded parts (plates 65 x 25 x 1.5 mm in size) are discarded. The molded parts obtained at 270 ° C, 280 ° C, 290 ° C and 300 ° C are remarkable for very high heat stability, high light fastness, good migration resistance and high color intensity.

Claims (12)

1. CLAIMS 1.- A method for coloring a high molecular weight material, characterized in that it comprises mixing the high molecular weight organic or inorganic material with at least one compound of the formula wherein Ax and A2 are independently o-arylene with 6 to 18 carbon atoms, unsubstituted, monosubstituted, disubstituted, trisubstituted or tetrasubstituted. 2. - A method according to claim 1, characterized in that the high molecular weight organic material is mixed with an isoxyndigo of the formula with a bisisoxyindigo of the formula wherein A3 is a single bond or is alkylene with 1 to 24 carbon atoms or cycloalkylene with 5 to 12 carbon atoms monosubstituted or polysubstituted with halogen-, hydroxyl-, oxo-, cyano-, R6OOC- , X + 0"0C-, R603S-, X + 03" S- or a polycycle that can be interrupted by heteroatoms such as O, N, S or P, or aryl with 6 to 24 carbon atoms and heteroaryl with 5 to 18 carbon atoms that may be uninterrupted or interrupted one or several times by O, S or NR6; Rioo / ioi 102 R-ioo1 / Rioi 'Rio?' And also R103, R10 105 and 106 each independently have the same meanings as for Rx; R1 # R3, R3, R4 and also R28, R29, R30 or R31 are independently H, halogen, cyano, N02, R5, NR5R6, NR7COR5, NR7COOR5, N = CR5R5, CONR7R8, OR5, COOR5, (alkyl with 1 to 12 carbon atoms) -COOR, C00"X +, SR5, S0R5, S02R5, S02NR7R8, S03R5 or S03" X +; And optionally Rx and R3, R2 and R3, R3 and R4 or R5 and R6 and also R28 and R29, R29 and R30 or R30 and R31 each can be additionally linked by a direct bond (with extraction of a hydrogen in each of the two atoms connected by the bond) to form a 5 or 6 member ring; R5 is hydrogen, alkyl having 1 to 25 carbon atoms, cycloalkyl with 5 to 12 carbon atoms or alkenyl having 2 to 24 carbon atoms unsubstituted or monosubstituted or polysubstituted by halogen or hydroxyl, oxo-, cyano-, R6OOC- or X ^ O'OC, which may be uninterrupted or interrupted in single or multiple form by O, S or NR6, or is aryl with 6 to 18 carbon atoms, aralkyl with 7 to 18 carbon atoms or heteroaryl with 5 a 18 carbon atoms, unsubstituted or mono-substituted or polysubstituted with halogen-, nitro-, cyano-, R60-, R6S-, R8R7N-, R8R7N02S-, R8R7N02S-, R6OOC-, X + 0 ~ OC-, R602S-, R60R -, X + 03"S-, R6OCR7N- or R6OOCR7N-; R6 is hydrogen or alkyl with 1 to 25 carbon atoms or alkenyl with 2 to 24 carbon atoms unsubstituted or mono-substituted or polysubstituted by halogen or hydroxyl-, oxo - or cyano-, which may be uninterrupted or interrupted only once or multiple times by O, S or NR7, or is aryl with 6 to 18 carbon atoms, C 7 -C 18 -alkyl or unsubstituted or mono-substituted heteroaryl with 5 to 18 carbon atoms, polysubstituted by halogen-, nitro-, cyano-, hydroxyl-, R70-, R7S-, R8R7N-, R8R7NOC-, R7OOC- , H00C- or X + 0"0C-; R7 and R8 are individually H, aryl with 6 to 18 carbon atoms, aralkyl with 7 to 18 carbon atoms, alkyl with 1 to 25 carbon atoms or alkenyl with 2 to 24 carbon atoms, unsubstituted or monosubstituted or polysubstituted by halogen-, hydroxyl- or alkoxy with 1 to 12 carbon atoms, or R7 and R8 combine with the common N to form pyrrolidine, piperidine, piperazine or unsubstituted or monosubstituted morpholine, disubstituted, trisubstituted, or tetrasubstituted with alkyl with 1 to 4 carbon atoms or to form carbazole, phenoxazine or phenothiazine; X + is a cation Li +, Na +, K +, Mg ++ 1/2, Ca ++ 1/2, Sr ++ 1/2, Ba ++ 1/2, Cu +, Cu ++ 1/2, Zn ++ 1/2, Al +++ 1/3 or [NR7R8R10Rn] +, and Rio and n are individually H, alkyl with 1 to 25 carbon atoms, aryl with 6 to 18 carbon atoms or aralkyl with 7 to 18 carbon atoms. carbon. 3. - A method according to claim 2, characterized in that the high molecular weight organic material is mixed with an isoxyndigo of the formula
2. (III), or with a bisisoxindigo of the formula wherein R12, R13, R32 and R33 independently are H, halogen, N02, R14, (alkyl having 1 to 12 carbon atoms) -COOR5, OR14, SR14, O-alkyl having 9 to 18 carbon atoms or S-alkyl with 9 to 18 carbon atoms and R34 is a single bond, alkylene with 1 to 24 carbon atoms or cycloalkylene with 5 to 12 carbon atoms, wherein R14 is alkyl with 1 to 25 carbon atoms unsubstituted or monosubstituted or polysubstituted with oxo-, cyano- or Xl + 0"OC, which may be uninterrupted or interrupted in single or multiple times by O, or is aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms unsubstituted or mono substituted or polysubstituted with halogen-, nitro-, cyano-, R160-, R17R16N-, R17R16NOC-, R16OCR18N- or R16OOCR18N-monosubstituted or polysubstituted, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms; X1 + is a cation Na +, K +, Mg1"" 1/2, Ca ++ 1/2,
3. Zn + 1/2 / Al 1/3 / o [NR16R17R18R19] +, and R16 and R17 independently are H, aryl with 6 to 10 carbon atoms, aralkyl with 7 to 10 carbon atoms, unsubstituted or mono-substituted or polysubstituted alkyl with halogen-, hydroxyl- or alkoxy with 1 to 4 carbon atoms, or R16 and R17 combine with the common N to form pyrrolidine, piperidine, piperazine or morpholine unsubstituted or monosubstituted, disubstituted, trisubstituted or tetrasubstituted with alkyl of 1 to 4 carbon atoms, and R18 and R19 independently are H, alkyl with 1 to 8 carbon atoms, aryl with 6 to 10 carbon atoms, or aralkyl with 7 to 10 carbon atoms.
4. 4. - A method according to claim 3, characterized in that the high molecular weight organic material is mixed with an isoxyndigo of the formula with a bisisoxindigo of the formula wherein R20, R2 ?, R34 and R35 are independently H, chloro, R22 C2H5-COOH, C2H5-COO (alkyl having 1 to 12 carbon atoms), OR32 / SR22, O-alkyl having 9 to 18 carbon atoms or S-alkyl having 9 to 18 carbon atoms and R37 is a single bond, alkylene with 1 to 8 carbon atoms or cycloalkylene with 5 to 6 carbon atoms, or R22 is alkyl with 1 to 8 carbon atoms unsubstituted or monosubstituted or polysubstituted with oxo-, cyano- or X2 + 0"OC-, which may be uninterrupted or interrupted in single or multiple times by 0, or is aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms carbon, X2 + is a cation Na +, K +, Mg ++ 1 2, Ca ++ 12, Zn ++ 1/2, Al +++ 1/3, or [NR24R25R26R27] +, R24 / R25 and R26 are independently H, alkyl with 1 to 4 carbon or phenyl atoms, and R27 is H, alkyl with 1 to 8 carbon atoms, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 10 carbon atoms 5. - A method according to claim 1, characterized in that the high molecular weight organic material is a polyester, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene / acrylonitrile (SAN) or acrylonitrile / butadiene / styrene (ABS) or any other polymer that has a dielectric constant > . 2.
5. 5.
6. 6. - A compound of the formula (VII), or a compound of the bisisoxyindigo structure (Iib), wherein Ax and A2 are independently arylene with 6 to 18 carbon atoms unsubstituted or monosubstituted, disubstituted, trisubstituted or tetrasubstituted, with the conditions that Ax and A2 are not both phen-1, 2-ylene, 6-methyl-phenyl-1,2-ylene, 6-isopropyl-phenyl-1,2-ylene, 6-tert-butyl-phenyl-1,2-ylene, 4-methyl-6-tert-butyl-phenyl -l, 2-ylene, 4-tert-butyl-6-methylphen-1,2-ylene, 4,6-di-tert-butylphen-1,2-ylene, 4-methoxy-6-tert-butylphen-1 , 2-ylene, 5-methoxyphen-l, 2-ylene, 3-carboxy-5-methylphen-1,2-ylene, 3-methoxycarbonyl-5-methylphen-l, 2-ylene, anthraquinone-l, 2-ylene7 phenanthren-9, 10-ylene or l-oxa-2, 2-dimethyl-3-acetoxy-5-methylaceneften-6, 7-ylene, and that when Ax is phen-1,2-ylene, A2 is not 5- methoxyphen-1, 2-ylene, 4,6-dihydroxyphen-1,2-ylene, naphth-1,2, -ylene or naphth-2, 1-ylene and when A: is 3-methoxycarbonyl-5-methylphenyl, 2- ileno A2 is not 3,5-dimethylphen-1,2-ylene, and o-arylene with 6 to 18 carbon atoms is connected to oxygen lactone co n the first site indicated by the diradical.
7. 7. A composition consisting of 2 to 10, preferably 2 or 3, compounds of the formula (I) wherein Ax and A2 are independently o-arylene with 6 to 18 carbon atoms, unsubstituted, monosubstituted, disubstituted, trisubstituted or tetrasubstituted, or (VII) and / or (IIb) according to claim 6.
8. 8. - A procedure for preparing a compound of the formula or a mixture consisting of compounds of the formulas (VIII), (IX), and (X) wherein Ax and A2 are independently are o-arylene with 6 to 18 carbon atoms, unsubstituted, monosubstituted, disubstituted, trisubstituted or tetrasubstituted, which comprises dehydrating a compound of the formula or a mixture of compounds of the formulas or its tautomers.
9. 9. A process for condensing 3-oxofuranonyl compounds with 3-methylene-furanonyl compounds characterized in that it comprises reacting differently substituted 3-methylene-furanonyl compounds of the formula (XIII), with 3-oxofuranonyl compounds of the formula (XIV) using hydrochloric acid, sulfuric acids or organic bases to form asymmetric isoxyndrics (lia) or bisisoxyndigos (Ilb), wherein Ai and A2 are different and independently adapt to the meanings given in one of claims 1 to 4.
10. 10.- A process for preparing a compound of the formula (VIII), or a mixture consisting of the compounds of the formulas (HIV), (IX), and wherein R and A2 independently are o-arylene with 6 to 18 carbon atoms, unsubstituted, monosubstituted, disubstituted, trisubstituted or tetrasubstituted, by a) reacting a compound of the formula (XIII), or b) a mixture of the compounds of The formulas with c) a halogenating agent to form a compound of the formula (XLI), (XLII), wherein X3 is halogen such as iodine, bromine or chlorine, preferably bromine or chlorine, and d) simultaneously or subsequently dimerizing at a temperature in the range of -20 to 250 ° C, preferably 50 to 200 ° C , to form a compound of the formula (VIII), (IX) and / or (X).
11. 11. A composition of matter characterized in that it comprises a high molecular weight organic material and at least one compound of the formula (I) prepared by the process of claim 1 or high molecular weight organic material and a composition in accordance with claim 7 or high molecular weight organic material and a compound of the formula (VII) or (Hb) according to claim 6.
12. 12. The use of the composition of matter according to claim 11, for preparing inks and dyes for coatings, printing inks, mineral oils, greases or waxes, or pigmented or colored plastics, impression material without impact, color filters such as cosmetics and pigments (toners).