Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/0084—Dispersions of dyes
  • C09B67/0085—Non common dispersing agents
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
  • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
  • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
  • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/58—Metal complex; Coordination compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
  • B01J2531/62—Chromium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/821—Ruthenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/842—Iron
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/84—Metals of the iron group
  • B01J2531/845—Cobalt
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
  • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases

Definitions

• the present invention relates to cyclic compounds, processes for their preparation, their use as photoactive effect substances, such as light absorbers, light-emitting compounds, dispersants or as complex ligands, and complexes containing them.
• Light-absorbing compounds in the sense of the present invention are usually classified according to the frequency range in which they absorb light. A distinction is made between UV absorbers that absorb UV light, Vis absorbers (colorants) that absorb visible light, and IR absorbers that absorb infrared radiation. Furthermore, light absorbers are classified and distinguished on the basis of their solubility or insolubility in the application medium and on the way in which the absorbed energy is released, for example as heat or radiation.
• Soluble and insoluble compounds which absorb in the UV region and give off the absorbed energy in the form of heat are often used as UN absorbers for the purpose of UN protection.
• Derivatives of triazine, benzophenones, benzotriazoles, cyanoacrylates, as well as ZnO and TiO are usually used as chromophores for these applications. If the UN radiation is emitted in the form of fluorescent radiation, which is usually only the case with compounds which are soluble in the application medium, optical brighteners are obtained which make white materials appear less yellow.
• benzoxazoles, coumarins and ylaphthylimides are used as chromophores for these applications, see G. Pritchard, Plastic Additives, Chapmann & Hall, Weinheim 1998.
• BEST ⁇ TIGU ⁇ GSKOPIE Compounds which absorb in the visible range of light and are soluble in the application medium and which release their absorbed energy in the form of heat are referred to as dyes. If these compounds, which are soluble in the application medium, emit energy in the form of radiation, one speaks of fluorescent dyes. Compounds that absorb in the visible range and are insoluble in the application medium are referred to as pigments and release their energy in the form of heat. Pigments and fluorescent dyes are used to color plastics, paper fibers, fibers, etc.
• Perylene compounds, phthalocyanine compounds, indanthrone compounds, azo compounds, quinophthalone compounds, quinacridone compounds, isoindoline compounds, diketopyrrolopyrrole compounds are usually used for this purpose, cf. W. Herbst, K. Hunger, Industrial Organic Pigments, VCH Weinheim, 1993.
• crown ethers are often used as multidental complexing agents. It is a class of planar macrocyclic polyethers.
• the oxygen atoms are often linked by ethylene bridges, with one or more benzene or cyclohexane rings being often fused on.
• the oxygen atoms of the crown ethers can also be partially or completely replaced by other heteroatoms such as nitrogen, phosphorus or sulfur. This gives, for example, aza, phosphate or thia crown ethers.
• Organic light-emitting compounds are widely used in organic light-emitting diodes (OLED).
• OLEDs organic light-emitting diodes
• OLEDs organic light-emitting diodes
• the structure of organic light-emitting diodes was, for example, by C. W. Tang and S. A. Van Slyke, Appl. Phys. Lett. 51, 913-915, 1987 and by M.A. Baldo, M.E. Thompson and S.R. Forrest, Pure Appl. Chem. 71, 2095-2106, 1999. They can be used in many areas, for example in monochrome, multicolor and full-color screens, which in turn are used, for example, in automobiles, mobile telephones or notebooks.
• the known light-emitting materials for OLEDs in particular blue and red emitters, still have insufficient long-term stability.
• the light emission of the emitter materials can be based on fluorescence or phosphorescence.
• Phosphorescent emitters are described, for example, in WO 01/08230. They are based on heavy metal complexes that have short-lived phosphorescence.
• EP-A 0554971 describes the use of sulfonated phthalocyanines to prevent the flocculation of finely divided phthalocyanine pigments.
• DE-A 43 25 247 describes carboxylated and sulfonated perylene derivatives in combination with basic ones Polymers to prevent flocculation and to improve theological properties in highly pigmented coating systems. Sulfonated pigment derivatives are thus used for surface modification of the pigments, which depending on the formulation then have better rheological properties and improved transparency. Further explanations can be found in DE-A 10303916 and the literature cited therein, in particular in the publication Science and Technology of Pigment Dispersions A four day post graduatate intensive course presented by the Institute of Materials Science.
• red sulfonated pigment derivatives are used for the surface modification of perylene pigments (red), or for the surface modification of blue pigments, e.g. Phthalocyanines (blue) or indanthrone pigments (blue) blue sulfonated pigment derivatives. Therefore you need different sulfonated pigment derivatives for the different colored pigments.
• the object was to find a colorless sulfonated pigment derivative which can be used regardless of the color of the pigment to be modified.
• sulfonated macrocycles such as, for example, the cycloquaterbenzoaxazoles, cycloquatemaphthoxazoles, cycloquaterbenzimidazoles and cycloquaternaphthimidazoles, which practically do not absorb in the visible region of the spectrum.
• the object of the present invention is to provide cyclic compounds which can be used in particular as photoactive effect substances such as light absorbers, light emitters or as complex ligands.
• R, R, R each independently represent H or a substituent of the group C 1 -alkyl, C 12 -alkanoyl, C 3 . 7 -cycloalkyl, C 6-12 -aryl, C 7 - ⁇ 3 aralkyl, C 7-13 alkaryl, C ⁇ ⁇ -alkoxy, C 6 - ⁇ 2 aryloxy, C ⁇ - 12 hydroxyalkyl, heterocycle, C 6 , ⁇ 2 -Aroyl, which can each be substituted, hydroxy, thiol, halogen, cyano, isocyan, nitro, ammonium, amino, phosphine, phosphine oxide, sulfonic acid or derivative thereof, carbonated drinks or derivative thereof, derivatives of silicon, C 2 .
• residues in oxygen atoms can also be replaced by sulfur atoms
• R 1 , R 2 , R 3 can be different from hydrogen, or corresponding heterocyclic Neritatien in which
• R 5 each independently represents H, optionally substituted C 1 -alkyl, where COOH, COO alkali, COO (alkaline earth) 0> 5 , COONH 4 , SO 3 H, SO 3 alkali, SO 3 (alkaline earth) 0.5 , SO 3 NH 4 , NR 7 2) N + R 7 3 , 1-pyridinio, 4-
• Pyridyl, 4- (l-methyl) pyridinium are suitable as substituents, C 6 - ⁇ 2 aryl, C 7 - ⁇ 3 alkylaryl, optionally substituted C ⁇ ⁇ 2 alkanoyl, for example formyl, acetyl, chloroacetyl, optionally substituted C 7 - ⁇ 3 aryloyl, for example benzoyl, oligoethylene glycol with 1 to 6 oxygen atoms, oligoethylene glycol ether with 1 to 6
• R 7 each independently H, d - ⁇ - alkyl, C 6 . ⁇ 2 aryl
• light absorbers materials for hole injection layers in OLEDs, as light-emitting compounds in OLEDs, phase transfer catalysts, synergists for the dispersion of pigments or for optical data storage.
• N CS, R 1 , R 2 , R 3 each independently represent H or a substituent of the group C 1 -C 2 -alkyl, C M2 -
• R 1 and R 2 and / or R 2 and R 3 are each independently substituted fused ring systems
• R 2 , R 3 can be different from hydrogen
• n can represent an average if there is a mixture of compounds with different numbers of ring members. Otherwise n is an integer.
• the object is further achieved according to the invention by using metal complexes of the compounds of the general formula (I) as defined above or as oxidation catalysts.
• the compounds of the general formula (I) are notable for high stability and long-term stability in the applications mentioned. By choosing a suitable substitution pattern, the compounds of the general formula (I) can be adapted to the different applications mentioned.
• the invention therefore also relates to cyclic compounds as defined above, with the exception of compounds with the meaning
• R, ⁇ 1 , R z , R J each H, Ci- ⁇ -alkyl.
• exempted compounds are described in the synthesis publication mentioned at the outset and, according to one embodiment of the invention, are also not used in the uses according to the invention. This can also apply specifically to the cyclic quaterbenzimidazole.
• the invention also relates to a process for the preparation of these cyclic compounds of the general formula (I) by cyclization of compounds of the general formula (II)
• the cyclization is e.g. carried out in the presence of condensing agents or under dehydrating conditions, it being possible for the cyclization to be carried out in the presence of metal salts or metal powders as templates or of Lewis acids.
• R 4 stands for carboxylic acid or its derivatives such as carboxylic acid salt, carboxylic acid chloride, carboxylic acid amide, carboxylic acid ester, carboxylic acid nitrile,
• the preparation is carried out, for example, with heating in an optionally acidic (H 2 SO 4 , H 3 PO 4 , polyphosphoric acid) solvent, if appropriate in the presence of metal salt templates, and if appropriate oxidizing and reducing agents, and if appropriate with the removal of amine, if appropriate in the presence of an organic solvent ,
• an optionally acidic (H 2 SO 4 , H 3 PO 4 , polyphosphoric acid) solvent if appropriate in the presence of metal salt templates, and if appropriate oxidizing and reducing agents, and if appropriate with the removal of amine, if appropriate in the presence of an organic solvent ,
• the process can be carried out in one or two stages, with cyclic amides / esters first being produced and then being reacted further to give cyclic heteroaromatics such as oxazoles.
• the cyclization is preferably carried out in the presence of condensing agents selected from polyphosphoric acid, (poly) phosphate esters, thionyl chloride, triphenylphosphonium nhydride-bis (trifluoromethanesulfonate) or under dehydrating conditions.
• condensing agents selected from polyphosphoric acid, (poly) phosphate esters, thionyl chloride, triphenylphosphonium nhydride-bis (trifluoromethanesulfonate) or under dehydrating conditions.
• the cyclic compounds described above can be used as complex ligands.
• the invention also relates to corresponding Complexes which contain a complexed metal ion and at least one cyclic compound as defined above as complex ligands.
• the invention also relates to processes for the preparation of these complexes of cyclic compounds by preparing the cyclic compounds as described in the presence of metal salts or metal powders as templates or by reacting the cyclic compounds with metal salts or metal powders.
• At least two of the aromatic nuclei are substituted differently.
• X-Y-Z and R, R, R have the same meanings for all positions.
• radicals R 1 , R 2 and R 3 can be chosen so that they do not hinder the cyclization reaction for the preparation of the compounds of the general formula (I) or (Ia).
• the middle group is tautomeric.
• radicals R 1 , R 2 , R 3 preferably each independently have the meaning hydrogen or substituent of the group
• C 12 alkyl preferably C 6 alkyl, in particular C 3 alkyl, which may be straight-chain or branched or cyclic,
• C 7 - ⁇ 3 aralkyl preferably C 7 - ⁇ aralkyl, preference being given to phenylalkyl radicals in which the alkyl radical can be straight-chain or branched,
• C 1 -C 2 alkoxy preferably C 6 alkoxy, in particular C 1 -C alkoxy, where the alkyl radical can be straight-chain or branched or cyclic,
• radicals can each be further substituted, for example by the radicals below, hydroxy,
• Halogen preferably fluorine, chlorine, bromine, particularly preferably fluorine or chlorine
• Amino which can be derived from primary, secondary or tertiary amino groups which have alkyl or aryl radicals which correspond to the above definition of alkyl radicals and aryl radicals,
• Phosphine or phosphine oxide these radicals may contain alkyl substituents or aryl substituents as described above,
• Sulfonic acid or derivative thereof where the derivatives can be acid halides, acid amides, acid esters,
• Carboxylic acid or derivative thereof, where the derivatives can be acid halides, acid amides or acid esters.
• Silyl e.g. Silyl
• silyl groups which can have hydrogen atoms, alkyl radicals and / or alkoxy radicals.
• R 1 and R 2 and / or R 2 and R 3 can also each independently form optionally substituted fused ring systems of 1 to 3 rings which may contain heteroatom groups.
• Each such fused ring system preferably contains 1 to 2 further ring systems in addition to the aromatic nucleus shown in the general formula (I). there different fused systems can be present on the four aromatic nuclei of the general formula (I).
• the fused ring systems can be substituted as described above, it being possible for all suitable substituents to be present, from alkyl substituents to silyl groups.
• the fused ring systems can also contain heteroatom groups, so that hetaryl groups are formed. Examples of suitable basic bodies and fused ring systems are shown below.
• the fused ring systems can be linked in a suitable manner for each of the four aromatic nuclei of the general formula (I). For example, linearly or non-linearly annellated structures can be formed.
• R 1 and R 2 and / or R 2 and R 3 can also each form independently, optionally substituted, alkylene groups which can be interrupted by heteroatom groups. This creates aliphatic or heteroaliphatic rings or ring systems. The distance between the attachment points of the alkylene groups is therefore preferably chosen so that there is a 5-, 6- or 7-ring structure.
• the alkylene groups preferably have 2 to 10 carbon atoms, particularly preferably 3 to 10 carbon atoms, a 5, 6 or 7 ring preferably being formed.
• the alkylene groups can be straight-chain or branched. Suitable heteroatoms are oxygen, sulfur and nitrogen atoms (NH).
• radicals R 1 , R 2 and R 3 can also form different cyclic structures for different molecular groups.
• fused structures can exist alongside aliphatic ring structures.
• all of the radicals R, R and R can be hydrogen atoms.
• the ring systems are unsubstituted. If there are substituents, on average 0.01 to 12 of the radicals R 1 , R 2 , R 3 present in the molecule can differ from hydrogen. There are preferably 1 to 8 substituents on average. At the low degrees of substitution, the compounds are "substituted". This means that substoichiometric amounts of substituents are present, so that only some of the molecules are substituted. In this case, mixtures of unsubstituted and substituted compounds of the general formula (I) are present.
• each of the radicals indicated above can be substituted by the other of the radicals indicated above.
• Annulated ring systems can also be substituted again.
• a fused ring system can be substituted, for example, by alkyl radicals, aryl radicals, halogen atoms, amino groups, etc.
• Carbocyclic aromatic, carbocyclic non-aromatic groups, aromatic heterocycles or non-aromatic heterocycles or mixtures thereof can thus be present in the compounds of the general formula (I).
• Fused rings can be linear or branched.
• the invention also relates to compounds with n greater than 1, since these compounds are formed as by-products during the cyclization in PPA.
• Angewandte Chemie (issue 114/8 1480-1483, 2002) reports on octacyclic pyrroles with IR-absorbing properties, which are produced by cyclization in H 2 SO 4 .
• the mineral acid acts as a template and promotes the formation of the cyclo [8] pyrroles.
• a complexed metal ion and at least one cyclic compound of the general formula (I) are present as complex ligands in the complexes according to the invention.
• the complexed metal ions can be derived from metals of the main groups, the transition metals and the rare earths of the periodic table of the elements. The following elements can be mentioned in particular:
• Preferred metals for OLED applications are Eu, Tb, Re, Ru, Os, lr, Pt, Cu, Au, TI, Pb, Bi.
• Preferred metals for oxidation catalysts are Co, Fe, Mn, Cr, Ru.
• the complexes according to the invention particularly preferably contain one of the cyclic compounds of the general formula (I).
• cyclic compounds of the general formula (I) according to the invention or the corresponding cyclic compounds used according to the invention are prepared by cyclization of compounds of the general formula (II)
• Oalkali metal groups may also be present instead of OH groups.
• the cyclization can preferably be carried out in the presence of condensing agents selected from polyphosphoric acid, (poly) phosphate esters, thionyl chloride, triphenylphosphonium c-hydride bis (rifluoromethanesulfonate), or under dehydrating conditions.
• the said tetracyclic bases are produced from four identical or different aromatic precursors which can carry the substituents R 1 , R 2 and R 3 .
• a carboxylic acid ester or a carboxylic acid amide are preferably derivatives of phenolic alcohols (for example O-silyl) and aromatic amines (for example N-carbamate), both the derivative of the phenolic alcohol which is under acidic conditions is cleavable, as can the derivative of aromatic A in ortho to the carboxylic acid derivative.
• phenolic alcohols for example O-silyl
• aromatic amines for example N-carbamate
• the synthesis is generally carried out under dehydrating conditions, for example in the presence of polyphosphoric acid, concentrated sulfuric acid, by distilling off water or alcohol or using thionyl chloride.
• the R 4 group is a carboxylic acid group or a derivative thereof.
• the derivative is preferably an acid chloride, an ester, an id, a salt or another corresponding carboxylic acid derivative.
• Esters are preferably esters of lower alkanols such as C -alkanols.
• Amides are preferably derived from ammonia or primary alkylamines.
• the process is generally carried out under a protective gas atmosphere (nitrogen).
• the cyclization can be carried out without solvent or in a solvent.
• Suitable solvents are, for example, sulfolane, methylene chloride and ethylene chloride. These can also be mixed with polyphosphoric acid.
• Reaction can take place at room temperature or elevated or reduced temperatures be performed.
• the reaction temperature is selected depending on the reactivity of the components used in each case.
• the addition of Lewis acids is also possible, for example: BF 3 Et 2 O etc.
• the reaction can also be carried out in the presence of metals or metal salts which can act as a template or catalyst or as a reducing agent.
• the cyclization can be carried out in the presence of zinc chloride or copper sulfate. In this way, metal-containing cycles can also be formed.
• the cyclic compounds of the general formula (I) and their metal complexes are used according to the invention as light absorbers or as light-emitting compounds in organic light-emitting diodes (OLED) (light-emitting diodes) or as oxidation catalysts (only metal complexes).
• OLED organic light-emitting diodes
• oxidation catalysts only metal complexes.
• light absorbers they are preferably UV absorbers, Vis absorbers and / or IR absorbers. They can be used in an application medium in soluble, partially soluble or non-soluble form. Use as an absorber depends on the position of the absorption band of the respective compound.
• the compounds of the general formula (I) form a photoactive system which absorbs light of the corresponding wavelength and emits it again in the form of heat or fluorescent radiation.
• the compounds are used pigmentarily, they preferably have an average particle size in the range from 5 to 1,000 nm. Mixtures of the compounds can be used as mixed crystals, as can mixtures of the compounds with other colorants / pigments / chromophores such as phthalocyanines.
• UV absorbers they are preferably used as UV protection agents, which convert the UV light into heat, or as an optical brightener, which convert the UV light into visible light.
• UV absorbers are used, for example, in cosmetics (sun protection, for example also in clothing), in automotive top coats, in wood preservatives, in foils, in plastics (for example polystyrene, polycarbonate, polyolefins as well as in ABS and ASA plastics or PET). In plastic applications, either plastic or the contents of plastic containers can be protected. This is especially true for clear or translucent plastic bottles. The same also applies to fibers made from plastics, which are used, for example, to manufacture clothing (for example polyamides).
• Optical brighteners are used, for example, in detergents, Textiles or plastics used. The plastics can also be processed into foils, for example.
• the cyclic compounds are Vis absorbers, they can be present as soluble dyes or as insoluble pigments.
• the soluble dyes can either convert the visible radiation into heat or, as fluorescent dyes, into light.
• pigments they convert light into heat in particular.
• colored pigments they are used for coloring polymeric materials such as paints and varnishes, plastics, printing inks in a large number of application areas, for example in the automotive sector.
• the compounds are soluble in organic solvents, polymers or water, they can be used as soluble UV absorbers, vis absorbers (dyes) in the above applications.
• the compounds which are soluble in water, organic solvents or in polymeric materials, in particular sulfonic acids, sulfonic acid esters, sulfonic acid amides, the alkyl and aryl-substituted representatives and the metal complexes of the compounds mentioned can, depending on the position of the absorption maximum, be used either as UV-absorbing substances which either Release absorbed energy in the form of heat (soluble UN absorbers) or in the form of light (optical brighteners). They can be used as dyes for dyeing textiles, plastics, paper fibers and as pigment dispersing additives.
• Soluble UN absorbers can be used, for example, in cosmetic formulations, in automotive topcoats, in wood preservatives or in films.
• Optical brighteners can be used to lighten paper, natural textile fibers, plastic fibers in detergents, to lighten plastics, etc.
• cyclic Neritatien according to the invention or their metal complexes, in particular sulfonic acids, sulfonic acid esters, sulfonic acid amides, etc. can be as
• Dispersing additives of all known (organic) pigments can be used.
• colorless synergists they can work with a variety of different pigments can be combined without influencing the color with their own color. For example, they can be used in solvent-based high solid coatings.
• Nanoparticulate ZnO (Del 9907704, EP0449 888) is available as a pigmentary inorganic UV absorber for cosmetics, paint and plastic.
• these have the disadvantage that they scatter white light with insufficient fineness, so that a milky appearance is produced. Insufficient fineness occurs when the particle size is too large, either the primary particles are too large or the state of dispersion is insufficient.
• the claimed compounds have a similar absorption spectrum as ZnO, but scatter less than organic pigments in the formulations described.
• the invention also relates to the use of the light absorbers for coloring high-molecular organic materials, e.g. Polymers and similar materials.
• the invention also relates to thermoplastic molding compositions, lacquers and coating compositions which contain the light absorbers in customary amounts.
• the compounds according to the invention can be used in OLEDs. They can be used in particular as emitters in the emitter layer or for the hole injection layer between anode and hole conductor layer and can replace copper phthalocyanine, for example, in the latter application.
• An advantage over copper phthalocyanine is a lower absorption in the visible spectral range.
• complexes containing heavy metals can be used as triplet emitters in OLEDs.
• Metal-free and metal complexes of the compounds according to the invention are used for OLED applications, Cu, Zn and / or Pt preferably being used as the metal.
• the compounds of the invention can also be used in the form of metal complexes as oxidation catalysts.
• Particularly preferred oxidation catalysts are complexes of the compounds according to the invention with metals selected from Co, Fe, Mn, Cr, Ru and mixtures thereof.
• linear peptides or esters are produced from the individual building blocks of the formula (II) after standard reactions with standard protective groups. Examples of this can also be found in "Amino Acid and Peptide Synthesis", John Jones, Oxford University Press 1992.
• the cyclizations are carried out according to U. Schmidt's method at phase interfaces in order to avoid high dilutions.
• the first two schemes relate to ring structures that have no internal oxygen atoms in the five-membered rings. Schemes for 1, 2, 3 and 4 internal oxygen atoms follow. Residues 1, residues 2, residues 3, residues 4 describe possible substituents of the ring systems.
• NHPg NHCBz, OTBS, -OPg H +, Cycl H2 / Pd
• NHPg NHCBz, OCH3; -OPg HBr, Cycl H2 / Pd
• NHPg2 NHBoc cyclization H +, K2C03 H20 / CHCI3; -OPg, -NHPg2 H2
• NHPg NHBoc, NHCbz
• the suspension was made alkaline with ammonia solution and then filtered.
• the solid was washed with water and dried in vacuo at 70 ° C. 14.2 g of black-brown crude product were obtained.
• 14.0 g of crude product were introduced into 280 g of 96% sulfuric acid at 10-20 ° C. within 2 hours.
• a yellowish solid was precipitated by dropwise adding 250 ml of water over 2 hours.
• the suspension was filtered through a glass frit.
• the solid was washed with 200 g of 50% sulfuric acid.
• the filter cake was suspended in 400 ml of ice water, suction filtered, washed with water and dried at 60 ° C. in a vacuum (4.6 g).
• 0.465 g (1.00 mmol) of cycloquaterbenzimidazole are dissolved in 50 ml of dimethylformamide at room temperature with the addition of 0.448 g (4.00 mmol) of potassium tert-butoxide. After adding 0.848 g (6.00 mmol) of methyl iodide, the solution is stirred for 24 hours at room temperature. The solid is filtered off, washed with dimethylformamide and water and dried at 60 ° C in a vacuum.
• cycloquine quebenzimidazole 0.580 g (1.00 mmol) of cycloquine quebenzimidazole was dissolved in a solution of 50 ml of acetic acid and 10 ml of water. After the addition of 0.164 g (2.00 mmol) sodium acetate, the solution was stirred for 10 min and then 0.457 g (1.10 mmol) potassium tetrachloroplatinate was added. The reaction solution was heated to 85 ° C and held at this temperature for 44 hours. After cooling to room temperature, the solid was filtered off with suction, washed with dilute acetic acid and water and dried at 75 ° C. in vacuo.
• the molecular ion peak of the cyclotetramer is detected at 469.09 g / mol, and the molecular ion peak of the cyclopentamer is detected at 586.40 g / mol.
• Azo coupling 8.74 g (50.0 mmol) of 99% sulfanilic acid were dissolved in 100 ml of water by stirring with the addition of 3.4 g of 50% sodium hydroxide solution. After adding a solution of 3.46 g (50.0 mmol) of sodium nitrite in water, the reaction solution was filtered and then slowly to a solution of 50 g of ice, 50 ml of water and 14.7 g concentrated hydrochloric acid dosed. After stirring for 2 hours at 0 to 5 ° C, the excess nitrite was destroyed with 2 g of amido sulfonic acid.
• the diazonium salt solution thus obtained was metered into a solution of 11.0 g (50.0 mmol) of 85% 3-amino-2-naphthoic acid and 17.85 g (220 mmol) of sodium carbonate in 500 ml of water, the pH being added by adding 3 g of 50% NaOH -Value was kept above 8. The azo dye solution was stirred for an hour.
• NMP N-methylpyrrolidone
• the NMP-containing filtrate was concentrated to a paste at 140 ° C. in a water jet vacuum, taken up in 160 ml of methanol and heated to boiling under reflux for 4 hours. The suspension was cooled to 40 ° C, filtered, four times with 16 ml each
• the solid was introduced into 58.7 g of 95.4% sulfuric acid within 30 minutes and, after stirring for 3 hours, was dissolved at 25 ° C. To this solution
• the solution was filtered through a glass frit and 111 g of 50% strength sulfuric acid were added over the course of four hours, a crystal being formed.
• the solid was suctioned off through a G4 glass frit and washed four times with 85% and 50% sulfuric acid.
• the residue was in hot water stirred up.
• the suspension was filtered through a blue band filter.
• the residue was washed pH-neutral with hot water and dried at 80 ° C. in a circulating air dryer.
• the solution was stirred at 60 ° C for 165 minutes, then heated to 100 ° C and held at this temperature for three hours. After cooling to room temperature, the solution was precipitated on an ice-water mixture and adjusted to pH 9 with ammonia solution, the temperature being kept below 20 ° C. by adding ice. The solid was filtered off with suction, washed with water in a pH-neutral and salt-free manner and dried at 60 ° C. in vacuo.
• the solution was stirred at 60 ° C for 165 minutes, then heated to 100 ° C and held at this temperature for three hours. After cooling to room temperature, the solution was precipitated on an ice-water mixture and adjusted to pH 9 with ammonia solution, the temperature being kept below 20 ° C. by adding ice. The solid was filtered off with suction, washed with water in a pH-neutral and salt-free manner and dried at 60 ° C. in a vacuum.
• Azo coupling 4.37 g (25.0 mmol) of 99% sulfanilic acid were dissolved in 70 ml of water by stirring with the addition of 2.09 g of 50% sodium hydroxide solution. After the addition of a solution of 1.73 g (25.0 mmol) of sodium nitrite in water, the reaction solution was checked for nitrite (negative), a further 0.33 g (4.8 mmol) of sodium nitrite was added and then slowly to a mixture of 100 g of ice / water and 9.70 g (98.4 mmol) conc. HCI dosed. After stirring for 2 hours at 0-5 ° C, the excess nitrite was destroyed by adding amidosulfonic acid.
• the diazonium salt solution thus obtained was metered into a solution (pH 9-9.5) of 6.68 g (25.0 mmol) of 7-bromo-3-hydroxy-2-naphthoic acid and 1.48 g of 50% NaOH in 200 ml of water / acetonitrile (1: 1) , the pH being kept at 8-9 by adding 7.45 g of 50% NaOH.
• the azo dye solution was stirred for an hour.
• the brown crude product was dissolved in 127 g of 96-98% sulfuric acid.
• the solution was filtered through a glass frit and slowly mixed with 16.5 g of 50% sulfuric acid, a crystal being formed.
• the solid was suction filtered through a glass frit, washed with 90% sulfuric acid and with water and dried at 75 ° C. in vacuo (1.25 g).
• the solid was dissolved in 29.3 g of 100% sulfuric acid and 0.59 g of 95-97% sulfuric acid and then 1.73 g of 50% sulfuric acid were slowly added.
• Perylene-3,4-dicarboximide-9-carboxylic acid is prepared according to CAS 75: 140549j (1971).
• Solsperse 12000 (Avecia) is used as a suitable copper phthalocyanine sulfonic acid.
• Solsperse 24000 is used as the hyperdispersant.
• a) 7.50 g of a transparent, commercially available perylene pigment such as, for example, PR179 (L3885 BASF) are in each case with 225 mg of the synergists perylene-3,4-dicarboximide-9-carboxylic acid (sample 1), with 225 mg of Solsperse 12000 (sample 2) and with 225 mg of sulfonated cyclo-2,9 ': 2', 9 ": 2", 9 '": 2'", 9-quatemaphtho [l, 2-d] oxazole from Example 21 (sample 3) were mixed intensively dry with one another. For comparison, 7,725 g of a pigment without synergists are used (sample 4).
• a transparent, commercially available perylene pigment such as, for example, PR179 (L3885 BASF)
• the dispersion takes place in a 100 ml glass bottle using 27 ml glass balls with a ball diameter of 3 mm.
• 1.2 g Hyperdispersant Solsperse 24000 and 23.3 g of a high solid lacquer (acrylic resin with xylene and butyl acetate 1: 1 as a solvent, solids content 45%>) to all samples, shake for 2 hours with a Skandex dispersing unit.
• the pastes are left to stand for 24 hours.
• Pastes la-3a have a low viscosity consistency, while comparison paste 4a has a high viscosity consistency.
• the synergists have a similar effectiveness.
• ITO indium tin oxide
• a hole conductor layer made of N, N'-diphenyl-N, N. Is successively placed on the ITO layer (anode) '-bis (3-methylphenyl) - (l, - biphenyl) -4,4'-diamine (TPD), an emitter layer of cyclo-2,4 ' : 2 ' , 7 " : 2 " , 4 '" : 2 '” , 7- quaterbenzimidazole (CQBI), an electron conductor layer made of aluminum tri (8-quinolinolate) (Alq 3 ) and a cathode layer made of aluminum.
• ITO indium tin oxide
• Organic layers are evaporated in a high vacuum (10 "6 mbar) on a clean glass coated with indium tin oxide (ITO).
• ITO indium tin oxide
• a hole conductor layer made of N, N'-Di- (l- naphthyl) -N, N'-diphenyl-4,4'-benzidine ( ⁇ -NPB), an emitter layer consisting of the matrix material 4,4'- (biphenyl) -N, N'-dicarbazole (CBP) and the emitter Platinum-cyclo-2,4 ': 2', 7 ": 2", 4 '": 2'", 7-quaterbenzimidazole (Pt-CQBI) by cover evaporation, a hole blocker layer made of 2,9-dimethyl-4,7- Diphenyl-phenanthroline (BCP), an electron conductor layer made of aluminum tri- (8-quinolinolate) (Alq 3 ), an electron injection layer made of lithium fluoride and a ca
• Organic layers are evaporated in a high vacuum (10 "6 mbar) onto a clean glass coated with indium tin oxide (ITO).
• ITO indium tin oxide
• N'-di- (l-naphthyl) -N, N'-diphenyl-4,4 '-benzidine ( ⁇ -NPB)
• an emitter layer consisting of the matrix material 4,4' - (biphenyl) -N, N ' -dicarbazole (CBP) and the emitter platinum-cyclo-2,4 ': 2', 7 ": 2", 4 '": 2'", 7-quaterbenzimidazole (Pt-CQBI) by cover vaporization, a hole blocker layer of 2, 9-Dimethyl-4,7-diphenyl-phenanthroline (BCP), an electron conductor layer made of aluminum tri- (8-quinolinolate) (Alq), an electron injection layer made of lithium fluoride and a cathode layer made of aluminum.
• ITO indium tin oxide
• Electron injection layer made of lithium fluoride and a cathode layer made of aluminum evaporated.
• Nanoparticulate ZnO (DE-A 19907704, EP-A 0449888) is available as a pigmentary inorganic UV absorber for cosmetics, lacquer and plastic.
• these have the disadvantage that they scatter white light with insufficient fineness, so that a milky appearance is produced. Insufficient fineness occurs when the particle size is too large, either the primary particles are too large or the state of dispersion is insufficient.
• the claimed compounds have an absorption spectrum similar to ZnO, but scatter less than organic pigments in the formulations described. In LDPE
• the compacts which contain the Neritatien from Examples 1 and 2, were visually more transparent than the sample containing ZnO with an otherwise similar absorption strength.
• the compounds according to the invention from Examples 1 and 2 and Z-Cote were then added at this temperature and dispersed for 3 minutes using an Ultrathurax stir bar.
• a dispersion at 80 ° C. was added to this dispersion by homogenizing 3.00 g glycerol, 0.05 g EDTANa 2 (EDETA BD, BASF), 0.20 g allantoin, 0.30 g xanthan gum (Keltrol, Kleco), 1.50 g magnesium aluminum silicate (Veegum Ultra, Vanderbilt) and 50.45 g of distilled water was obtained at 80 ° C.
• the combined dispersions were cooled to 40 ° C.
• the formulation obtained can be used as a sunscreen.
• the formulations which contained the claimed compounds had a similar absorption spectrum at the same layer thickness, but are less white scattering than the formulation containing ZnO (Z-Cote, BASF), which has aesthetic advantages, in particular in the case of dark pigmented skin.

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