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
  • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
  • C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/60—Organic compounds having low molecular weight
  • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
  • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/549—Organic PV cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates Pentarylen- and Hexarylentetracarbonklarediimide and their preparation and use.
• Rylenetetracarboxylic diimides are known to be of particular application interest due to their strong absorption in the near-infrared (NIR) region of the electromagnetic spectrum.
• NIR near-infrared
• WO-A 02/77081 describes the use of quaterrylenetetracarboxylic diimides as infrared absorbers for thermal protection in glass laminates.
• Pentarylene and hexarylene derivatives which are unsubstituted or have a low degree of substitution, are described by N.G. Pschirer et al., Angew. Chem. Int. Ed. 45 (2006), 1401-1404.
• Y, Y 1 are both halogen or one of Y, Y 1 is halogen and the other is B (OFT) 2 ;
• R, R A is independently the same or different of the following radicals:
• Alkyl radicals may be substituted
• each R ' is independently hydrogen
• Radicals R mentioned radicals (i), (ii), (iii), (iv), (v), aryl and / or hetarylazo, each by Ci-Ci O alkyl, Ci-C 6 -Akoxy and / or Cyano may be substituted;
• each R is independently of one another hydrogen, C 1 -C 30 -alkyl, C 5 -C 8 -
• Cycloalkyl, aryl or hetaryl is or joined together to form a 5- to 7-membered ring containing the two oxygen atoms and the boron atom, to which unsaturated or saturated rings can be fused and which can be attached to the carbon atoms by up to 4Ci-C 30 - Alkyl, C 5 -C 8 cycloalkyl, aryl or hetaryl groups may be substituted;
• R 1 is hydrogen or C 1 -C 8 -alkyl, where the radicals R 1 may be identical or different if they occur more than once;
• R 2 , R 3 are independently hydrogen
• C 1 -C 6 -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -CO-, -SO- and / or -SO 2 - and which is mono- or polysubstituted by C 1 -C 12 -alkoxy , C 1 -C 6 -alkylthio, hydroxy, mercapto, halogen, cyano, nitro and / or -COOR 1 may be substituted;
• Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -CO- and / or -SO 2 - may be interrupted, be annelated can, wherein the entire ring system may be mono- or polysubstituted by Ci-Ci 2 alkyl and / or the above, as substituents for alkyl radicals may be substituted;
• n 2 and n, n1 are integers whose sum gives a number from 0 to 8, where the reaction is with (purple);
• step (b) Cyclodehydration of the reaction product obtained in step (a) to give a rylene compound of general formula (I) or (Ia)
• n1, n1 satisfy at least one of the following conditions.
• n + n1 are integers whose sum is a number from 5 to 8, ie 5, 6, 7 or 8, preferably 5 or 6 results.
• n + n1 are 6 + 2, 5 + 3, 4 + 4, 6 + 1.5 + 2, 4 + 3, 3 + 4, 6 + 0, 5 + 1, 4 + 2, 2 + 4, 3 + 3, 5 + 0, 4 + 1, 1 + 4, 3 + 2, 2 + 3.
• Preferred for n + n1 are 4 + 4,4 + 2,2 + 4,3 + 2.
• n + n1 are 8 + 0, 7 + 0, 6 + 0, 5 + 0, 4 + 0, 3 + 0, 2 + 0, 1 + 0, 0 + 0, 7 + 1, 6 + 1, 5 + 1.4 + 1.3 + 1.2 + 1, 1 + 1.0+ 1.
• n + n1 are 6 + 0.5 + 0.4 + 0.3 + 0, 2 + 0.6 + 1.5 + 1.4 + 1.3 + 1.2 + 1; more preferred are 6 + 0.5 + 0.4 + 0.3 + 0.
• n, n1 are integers whose sum is a number from 5 to 12, ie 5, 6, 7, 8, 9, 10, 11 or 12, preferably 5, 6 , 7 or 8 results.
• n + n1 are 6 + 6, 6 + 4, 4 + 6, 5 + 5, 6 + 3, 3 + 6, 5 + 4, 4 + 5, 6 +
• n + n1 8 + 0, 7 + 0, 6 + 0, 5 + 0, 4 + 0, 3 + 0, 2 + 0, 1 + 0, 0 + 0, 8 + 1, 7 + 1, 6 + 1, 5 + 1, 4 + 1, 3 + 1, 2 + 1, 1 + 1, 0 + 1, 8 + 2, 7 + 2, 6 + 2, 5 + 2, 4 + 2, 3 + 2, 2 + 2, 1 + 2, 0 + 2, 8 + 3, 7 + 3, 6 + 3, 5 + 3, 4 +
• n + n1 are 6 + 4, 5 + 4, 4 + 4, 3 + 4, 6 + 2, 6 + 0, 5 + 2, 5 + 0, 4 + 2, 4 + 0, 2 + 2, 2 + 0; particularly preferred are 6 + 4, 4 + 4, 6 + 2, 4 + 2, 6 + 0, 4 + 0.
• n and n1 are integers whose sum is a number from 5 to 8, ie 5, 6, 7 or 8, preferably 5 or 6, and R, R A , R ', m, m1 have the abovementioned meaning.
• n + n1 are 6 + 2, 5 + 3, 4 + 4, 6 + 1, 5 + 2, 4 + 3, 3 + 4, 6 + 0, 5 + 1, 4 + 2, 2 + 4, 3 + 3, 5 + 0, 4 + 1, 1 + 4, 3 + 2, 2 + 3.
• Preferred for n + n1 are 4 + 4, 4 + 2, 2 + 4, 3 + 2.
• the pentarylene compounds according to the invention can therefore be obtained by means of the process according to the invention by coupling a corresponding terrylene compound with the corresponding perylene compound.
• the pentarylene compounds according to the invention have a high degree of substitution, in which the radicals R and R A together are present at least five times. However, the sum of the substituents R and R A is not more than 8.
• the object is further achieved by Pentarylentetracarbonkladiimide of the general formula (Ia) or mixtures thereof, wherein n and n1 are integers whose sum is a number from 5 to 8, ie 5, 6, 7 or 8, preferably 5 or 6, and R, R A , R ', m have the abovementioned meaning. Examples of n + n1 are 8 + 0, 7 + 1, 7 + 0, 6 + 1, 6 + 0, 5 + 1, 5 + 0, 4 + 1. Preferred for n + n1 are 6 + 0, 5 + 0, 4 + 0.
• the pentarylene compounds according to the invention can thus be obtained by means of the process according to the invention by coupling a corresponding quaterrylene compound with the corresponding naphthalene compound.
• the pentarylene compounds according to the invention have a high degree of substitution, in which the radicals R and R A together are present at least five times. However, the sum of the substituents R and R A is not more than 8.
• Hexarylentetracarbon Acidiimide the general formula (I) or mixtures thereof, wherein n and n1 are integers whose
• n + n1 8 + 0, 7 + 0, 6 + 0, 5 + 0, 8 + 1, 7 + 1, 6 + 1, 5 + 1, 4 + 1, 8 + 2, 7 + 2, 6 + 2, 5 + 2,
• n + n1 are 6 + 0, 5 + 0, 6 + 2, 5 + 2, 4 + 2, 6 + 4, 5
• the hexarylene compounds according to the invention can thus be obtained by means of the process according to the invention by coupling a corresponding quaterrylene compound with the corresponding perylene compound.
• the hexarylene compounds according to the invention have a high degree of substitution, in which the radicals R and R A together are present at least five times. However, the sum of the substituents R and R A is at most 12.
• the starting compounds according to the formulas (II), (III), (IIIa) are known from the prior art or can be prepared by means of syntheses of analogous compounds known from the literature.
• terrylene and Quaterrylenderivate that can serve as starting materials for the process of the invention for the preparation of pentarylene and Hexarylentetracarbon Acidiimiden are described in the German patent application with the application number 10 2005 021362.
• the preparation of hexarylene and Pentarylentetracarbonklaiimiden in DE-A 10 2005 018241 is described.
• a preparation of the imide compounds according to the invention can be carried out analogously.
• the process according to the invention for the preparation of pentarylene- and hexarylene-tetracarboxylic diimides comprises, as a first step (a), the coupling of at least one rylen- or quaterrylene compound of the formula (II) with at least one compound of the formula (III) or (IIIa), where the linking of the two building blocks takes place in each case with the aid of the groups Y and Y 1 .
• Y and Y 1 may be halides, by means of which the desired binding of the two aromatic building blocks is made possible with the aid of a catalytic coupling. It is also possible that one of the radicals Y, Y 1 may be a halide and the other a boronic acid or a similar compound of the formula B (OFT) 2 . A coupling then takes place via the so-called Suzuki reaction.
• the halides are bromide or chloride.
• the preparation of the diimides according to the invention by means of the process according to the invention is preferably carried out in the presence of an organic solvent, if desired in admixture with water, and a transition metal catalyst and a base, wherein as stated above, one of the two building blocks, a Boronäurede- derivative and the other may represent a halide.
• a boronic acid derivative is obtainable, for example, by reacting the corresponding halogenated aromatic with the aid of diboranes of the general formula (IV) (RO) 2 BB (OR " ) 2 in the presence of an aprotic organic solvent, a transition metal catalyst and a base.
• Suitable diboranes of the general formula (IV) are, in particular, bis (1, 2 and 1, 3-diolato) diboranes, tetraalkoxydiboranes, tetracycloalkoxydiboranes and tetra (het) aryloxydiboranes and also their mixed forms.
• Examples of these compounds are: bis (pinacolato) diborane, bis (1, 2-benzodiolato) -diborane, bis (2,2-dimethyl-1,3-propanediolato) diborane, bis (1,1,3,3 -tetramethyl-1,3-pandiolato) diborane, bis (4,5-pinanediolato) diborane, bis (tetramethoxy) diborane, bis (tetra-cyclopentoxy) diborane, bis (tetraphenoxy) diborane and bis (4-pyridiyloxy) diborane ,
• diboranes of the general formula (IV) in which the two radicals R located on a boron atom are bonded together to form a five-membered or six-membered ring containing the two oxygen atoms and the boron atom.
• Aromatic or saturated, and also bicyclic, rings having 5 to 7 C atoms can be fused to the five- or six-membered rings formed as ring members.
• All rings or ring systems may be substituted by up to 4 C 1 -C 30 -alkyl, C 5 -C 8 -cycloalkyl, aryl and / or hetaryl radicals, preferably they are substituted by up to 4 C r C 4 -alkyl radicals ,
• these preferred diboranes are the above-mentioned bis (1, 2 and 1, 3-diolato) -diborane, with bis (pinacolato) diborane being particularly preferred.
• the molar ratio of diborane of the general formula (IV) to the halogenated aromatic is generally from 0.8: 1 to 3: 1, in particular from 1, 5: 1 to 2: 1.
• Suitable solvents are in principle all aprotic solvents which are stable under the reaction conditions to bases having a boiling point above the selected reaction temperature in which the starting materials are completely dissolved at reaction temperature and the catalysts and bases used at least partially, so that largely homogeneous reaction conditions are present. Both nonpolar aprotic and polar aprotic solvents can be used.
• non-polar aprotic solvents are solvents boiling at> 100 0 C from the following groups: aliphatic (especially C 8 -C 8 alkanes) unsubstituted, alkyl-substituted cycloaliphatic and fused (especially unsubstituted C 7 -C 10 cycloalkanes , C 6 -C 8 cycloalkanes substituted by one to three -C 6 - alkyl groups are substituted, polycyclic saturated hydrocarbons having 10 to 18 carbon atoms), alkyl and cycloalkyl-substituted aromatics (especially benzene substituted by one to three alkyl groups CrC ⁇ or a C 5 -C 8 -cycloalkyl radical is substituted) and fused aromatics which may be alkyl-substituted and / or partially hydrogenated (in particular naphthalene which is substituted by one to four C 1 -C 6 -alkyl groups) and mixture
• particularly preferred solvents include: octane, isooctane, nonane, isononane, decane, isodecane, undecane, dodecane, hexadecane and octadecane; Cycloheptane, cyclooctane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, propylcyclohexane, isopropylcyclohexane, dipropylcyclohexane, butylcyclohexane, tert-butylcyclohexane, methylcycloheptane and methylcyclooctane; Toluene, o-, m- and p-xylene, 1, 3,5-trimethylbenzene (mesitylene), 1, 2,4- and 1,2,3-
• Very particularly preferred solvents are xylene (all isomers), mesitylene and especially toluene.
• Suitable polar aprotic solvents are N, N-disubstituted aliphatic see carboxamides (especially N, N-di-C r C 4 alkyl-Ci-C4-carboxamides), nitrogen-containing heterocycles and aprotic ethers (especially cyclic ethers, di- aryl ethers and di-C r C 6 alkyl ethers of monomeric and oligomeric C 2 -C 3 alkylene glycols which may contain up to 6 alkylene oxide units, especially diethylene glycol di-C 4 alkyl ethers).
• solvents are: N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and N, N-dimethylbutyramide; N-methyl-2-pyrrolidone, quinoline, isoquinoline, quinaldine, pyrimidine, N-methylpiperidine and pyridine; Tetrahydrofuran, dioxane, diphenyl ether, diethylene glycol dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, di-sec-butyl and di-tert.-butyl ethers, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl and diethyl ether and triethylene glycol methyl ethyl ether.
• the amount of solvent is generally 10 to 1000 ml, preferably 20 to 300 ml, per g of halogenated aromatics.
• transition metal catalysts are palladium complexes which, in turn, are generally used in amounts of from 1 to 20 mol%, in particular from 2 to 10 mol%, based on the halogenated aromatic compounds.
• Such catalysts are tetrakis (triphenylphosphine) palladium (0), tetrakis (tris-o-tolylphosphine) palladium (0), [1,2-bis (diphenylphosphino) ethane] palladium (II) chloride, [1, 1'-bis (diphenylphosphino) ferrocene] palladium (II) chloride, bis (triethylphosphine) palladium (II) chloride, bis (tricyclohexylphosphine) palladium (II) acetate, (2,2'-bipyridyl) palladium ( II) chloride, bis (triphenylphosphine) palladium (II) chloride, tris (dibenzylideneacetone) dipalladium (O), 1,5-cyclooctadiene palladium (II) chloride, bis (acetonitrile) palla
• the simultaneous presence of free ligand molecules e.g. tri (tert-butyl) phosphine, tri (i-butyl) phosphine, triphenylphosphine and tris (o-tolyl) phosphine and 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl.
• free ligand molecules e.g. tri (tert-butyl) phosphine, tri (i-butyl) phosphine, triphenylphosphine and tris (o-tolyl) phosphine and 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl.
• Usual amounts are 80 to 500 mol%, preferably 100 to 300 mol%, based on the transition metal catalyst.
• the bases used are preferably the alkali metal salts, in particular the sodium and especially the potassium salts, weak organic and inorganic acids, such as sodium acetate, potassium acetate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, phosphates, fluorides such as potassium fluoride.
• Preferred bases are the acetates, especially potassium acetate. In general, 1 to 5 mol, preferably 2 to 4 mol, of base are used per mole of halogenated aromatic.
• the reaction temperature is usually from 20 to 180 0 C, especially at 60 to 120 0 C.
• the reaction time is usually 0.5 to 30 hours, in particular 1 to 20 hours.
• the halogenated aromatic and solvent are added, the diborane of the general formula (IV), the transition metal catalyst and the base are added in succession and the mixture is heated for 0.5 to 30 h under protective gas to the desired reaction temperature. After cooling to room temperature, the solid components are filtered from the reaction mixture and the solvent is distilled off under reduced pressure.
• reaction of the boronic acid derivative with the halogenated aromatic is preferably carried out in the presence of an organic solvent, if desired in admixture with water, and of a transition metal catalyst and a base, the molar ratio of boronic acid derivative to halogenated aromatic being generally 0.8: 1 to 3 : 1, preferably 0.9: 1 to 2: 1.
• Suitable solvents are all solvents in which the reactants are completely dissolved at reaction temperature and the catalysts and bases used at least partially, so that substantially homogeneous reaction conditions are present.
• octane, isooctane, nonane, isononane, decane, isodecane, undecane, dodecane, hexadecane and octadecane are suitable; Cycloheptane, cyclooctane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, propylcyclohexane, isopropylcyclohexane, dipropylcyclohexane, butylcyclohexane, tert-butylcyclohexane, methylcycloheptane and methylcyclooctane; Toluene, o-, m- and p-xylene, 1, 3,5-trimethylbenzene (mesitylene), 1, 2,4- and 1, 2,3-trimethylbenzen
• Butylbenzene and cyclobutene lohexylbenzol Naphthalene, decahydronaphthalene (decalin), 1- and 2-methylnaphthalene, and 1- and 2-ethylnaphthalene; Combinations of the aforementioned solvents, as they can be obtained from the high-boiling, partially or fully hydrogenated fractions of thermal and catalytic cracking processes in crude oil or naphtha, for example mixtures of Exsol ® type and alkylbenzene Vesso ® from sol type.
• Very particularly preferred solvents are xylene (all isomers), mesitylene and especially toluene.
• the amount of solvent is usually from 10 to 1000 ml, preferably from 20 to 100 ml per g of boronic acid derivative.
• water is used as an additional solvent.
• 10 to 1000 ml, in particular 250 to 500 ml, of water per I of organic solvent are generally used.
• Palladium complexes are likewise preferably used as transition metal catalysts.
• the amount of catalyst used is usually 1 to 20 mol%, in particular 1, 5 to 5 mol%, based on the boronic acid derivative.
• the simultaneous presence of free ligand molecules e.g. tri (tert-butyl) phosphine, tri (i-butyl) phosphine, triphenylphosphine and tris (o-tolyl) phosphine and 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl.
• free ligand molecules e.g. tri (tert-butyl) phosphine, tri (i-butyl) phosphine, triphenylphosphine and tris (o-tolyl) phosphine and 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl.
• Usual amounts are 80 to 500 mol%, preferably 100 to 300 mol%, based on the transition metal catalyst.
• the carbonates such as sodium carbonate and especially potassium carbonate are particularly preferred.
• Phosphates such as sodium or potassium phosphate, are also preferred here.
• the amount of base is from 0.1 to 10 mol, in particular from 0.2 to 5 mol, per mole of boronic acid derivative.
• the reaction temperature is generally from 20 to 180 0 C, preferably 60 to 120 0 C. It is used in step b) water, so it is recommended not to carry out the reaction at temperatures above 100 ° C, since it is otherwise possible to operate under pressure.
• the reaction is usually completed in 0.5 to 48 hours, especially in 5 to 20 hours.
• boronic acid derivative and the halogenated aromatic as well as solvent are introduced, transition metal catalyst and the base, preferably dissolved in water or a water / alcohol mixture, are added and the mixture is heated for 0.5 to 48 h under protective gas to the desired reaction temperature. After cooling to room temperature, the organic phase is separated from the reaction mixture and the solvent is distilled off under reduced pressure.
• step (b) of the process according to the invention for the preparation of the pentarylene- and hexarylenetetracarboximides is generally sufficient for the further reaction in step (b).
• the crude product can be further purified by washing with water and, if desired, a suitable organic solvent, in particular a chlorinated aliphatic or aromatic hydrocarbon, or by column chromatography on silica gel with a mixture of methylene chloride and hexane or pentane or with toluene as eluent.
• the yield in step a) of the process according to the invention is usually from 20 to 95%.
• a direct coupling in particular in homo couplings, can also be carried out by halides.
• reaction of the correspondingly halogenated aromatic compounds of the formula (II) and (III) or (IIIa) can be carried out in the presence of a diborane of the general formula (IV).
• a Suzuki reaction also takes place, but the corresponding boronic acid derivative is only generated in situ.
• the coupling can be carried out, for example, in the presence of 30 to 70 mol%, based on the halogenated aromatic, of a diborane of the general formula (IV), a transition metal catalyst, a base and an aprotic solvent according to a Suzuki coupling reaction, wherein the in In situ formed Boronklarederivat not intermediately isolated, but is reacted directly with the remaining halogenated aromatic.
• the procedure is analogous to the above, but for example, only 30 to 70 mol% of diborane of the general formula (IV), based on the halogenated aromatic used.
• 1 to 20 mol%, preferably 5 to 10 mol%, of transition metal catalyst and 1 to 5 mol, preferably 2 to 3 mol, of base are used per mole of halogenated aromatic th.
• the aprotic organic solvent is usually used in amounts of from 10 to 100 ml, in particular from 20 to 50 ml, per g of halogenated aromatic compounds.
• the reaction temperature is generally from 20 to 100 0 C, preferably at 60 to 80 0 C, and the reaction time at 12 to 72 h, preferably 24 to 48 h.
• the halogenated aromatic and solvent are added, the diborane of the general formula (IV), the transition metal catalyst and the base are added in succession and the mixture is heated to the desired reaction temperature for 12 to 72 hours. After cooling to room temperature, the organic phase is separated from the reaction mixture and the solvent is distilled off under reduced pressure.
• step (b) of the process according to the invention the purity of the product obtained is usually sufficient for the subsequent cyclodehydration in step (b) of the process according to the invention. Further purification is possible, for example, by column chromatography.
• the yield is usually 80 to 95%.
• This coupling can take place, for example, in the presence of an organic transition metal complex as a catalyst, free ligand molecules and an aprotic solvent in the sense of a homo-coupling.
• Suitable inert diluents are, for example, aliphatic carboxylic acid amides, such as N, N-dimethylformamide and N, N-dimethylacetamide, aliphatic and cycloaliphatic ethers, such as 1,2-dimethoxyethane, and aromatics, such as benzene, toluene and xylene, wherein N, N-dimethylformamide and N, N-dimethylacetamide are preferred.
• the amount of diluent is usually 20 to 100 g, preferably 25 to 45 g per gram of halogen compound.
• nickel complexes are suitable, for example bis (triphenyl-) phosphine) nickel (II) chloride, tetrakis (triphenylphosphine) nickel (0), [1, 2-bis (diphenylphosphino) etane] nickel (II) chloride and preferably bis (1, 5-cyclooctadiene) nickel (0).
• the catalysts can also be obtained by the addition of transition metal salts or compounds, free ligands such as cyclooctadiene, bipyridyl, triphenylphosphine, trifluorophosphine, - ⁇ , ⁇ - and ⁇ -bonded olefins, cycloolefins, aromatics and antiaromata, carbonyls, hydrogen and Halogen as well as their mixtures and, if necessary, produce oxidizing and reducing agents.
• free ligands such as cyclooctadiene, bipyridyl, triphenylphosphine, trifluorophosphine, - ⁇ , ⁇ - and ⁇ -bonded olefins, cycloolefins, aromatics and antiaromata, carbonyls, hydrogen and Halogen as well as their mixtures and, if necessary, produce oxidizing and reducing agents.
• the simultaneous presence of free ligand molecules in particular mixtures of cyclooctadiene and bipyridyl in the molar ratio of 1: 1 to 8: 1, is always recommended.
• the coupling temperature is generally 40 to 80 ° C., preferably 60 to 70 ° C.
• the reaction time is usually 24 to 48 h, in particular 36 to 48 h.
• this direct coupling is advantageously carried out by initially introducing the halogen compound, the organometallic catalyst and free ligand molecules in the inert diluent and, if appropriate under a protective gas, heating to the desired reaction temperature for 24 to 48 h. After cooling, the reaction mixture in water, which may optionally contain methanol, is a dilute inorganic acid, eg. As dilute hydrochloric acid, and filtered from the precipitate formed, washed with water and dried in vacuo.
• the purity of the product according to the invention thus produced is generally sufficient for the subsequent cyclodehydration in step (b) of the process according to the invention.
• the product can additionally be further purified by column chromatography on silica gel with a mixture of methylene chloride and hexane or pentane as the eluent.
• the yield is generally 70 to 90%.
• step (b) of the process according to the invention the cyclodehydration of the reaction product obtained in step (a) takes place.
• the Cyclodehydrierung can in a
• Base-containing organic reaction medium or in the presence of a base-stable, high-boiling, organic solvent and an alkali or alkaline earth metal-containing base and a nitrogen-containing auxiliary base are made.
• the first-mentioned process variant is preferred.
• amino alcohols having from 2 to 20, preferably from 2 to 10, carbon atoms are suitable as the organic reaction medium.
• the carbon chain of these alcohols may be interrupted by oxygen atoms in ether function.
• particularly suitable solvents are ethanolamine, triethanolamine and diethanolamine, with ethanolamine being preferred. It is also possible to use mixtures of alcohols and amines, each having a boiling point of at least 70 0 C and are liquid at the reaction temperature.
• substantially insoluble base are the alkali metal salts, in particular the sodium salts and v.a. the potassium salts, weak organic and preferably weak inorganic acids, such as formates, acetates, propionates, bicarbonates, and more preferably carbonates, especially sodium carbonate, and more preferably. Potassium carbonate.
• the amount of base is 1 to 10 mol, preferably 2 to 5 mol, per mole of starting compound.
• the reaction temperature is generally from 40 to 200 0 C, in particular from 80 to 160 ° C.
• the reaction time is usually 0.5 to 64 hours, preferably 1 to 12 hours.
• the purification of the rylene compound according to the invention can be carried out by
• Catalyst residues are removed by rapid filtration over silica gel, washed with a halogenated aliphatic hydrocarbon such as methylene chloride. Residues of unreacted starting materials can be purified by column chromatography be removed on silica gel with methylene chloride as eluent or by repeated washing with hexane or pentane.
• the yield is generally 90 to 100%.
• R, R A independently are the same or different of the following radicals:
• each R ' is independently hydrogen
• radicals R mentioned radicals (i), (ii), (iii), (iv) and / or (v) may be substituted ;
• Each R is independently hydrogen, C r C 3 o-alkyl, C 5 -C 8 cycloalkyl, aryl or hetaryl or joined together to form a 5- to 7-membered ring containing the two oxygen atoms and the boron atom to which unsaturated or saturated rings may be annelated and which may be substituted on the carbon atoms by up to 4 Ci-C 30 alkyl, Cs-C ⁇ -cycloalkyl, aryl or hetaryl groups;
• R 1 is hydrogen or C 1 -C 18 -alkyl, where the radicals R 1 may be identical or different if they occur more than once;
• R 2 , R 3 are independently hydrogen; C 1 -C 6 -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -CO-, -SO- and / or -SO 2 - and which is mono- or polysubstituted by CrCl 2 Alkoxy, C 1 -C 6 -alkylthio, hydroxy, mercapto, halogen, cyano, nitro and / or - COOR 1 ; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -CO- and / or -SO 2 - may be interrupted, be annelated can, wherein the entire ring system may be mono- or polysubstituted by d-Ci 2 alkyl and / or the above, as substituents for alkyl radicals may be substituted.
• alkyls are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl,
• oxygen-interrupted alkyls are 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3, 7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxo-octyl, 4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9 Tri
• alkyls interrupted by sulfur are 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-butylthio-ethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and 3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3, 7-dithiaoctyl, 3,7-di- thianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl, 3,6,9-trithia-und
• alkyls interrupted by amino groups are 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl, 6-methyl-3 , 6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-di-azaoctyl, 3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl, 3 , 6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12 tetraazatridecyl and 3,6,9,12-tetra
• alkyl groups which are interrupted and / or have substituents are
• Carboxymethyl 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 8-carboxyctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxytetradecyl;
• Sulfomethyl 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;
• alkyloxy examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert. Butoxy, pentoxy, isopentoxy, neopentoxy, tert. Pentoxy and hexoxy;
• alkylthio examples include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert. Butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio and hexylthio;
• triply bonded radicals are ethynyl, 1- and 2-propynyl, 1-, 2- and 3-butynyl, 1-, 2-, 3- and 4-pentynyl, 1-, 2-, 3-, 4- and 4-pentynyl 5-hexynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 1-1-dodecynyl and 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1- 1- , 12-, 13-, 14-, 15-, 16- and 17-octadecinyl;
• radicals having double bond are ethenyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and 4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 1-1-dodecenyl and 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16- and 17-octadecenyl;
• Carbamoyl methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl, decylaminocarbonyl and phenylaminocarbonyl; Aminosulfonyl, N, N-dimethylaminosulphonyl, N, N-diethylaminosulphonyl, N-methyl-N-ethylaminosulfonyl, N-methyl-N-dodecylaminosulfonyl, N-Dodecylaminosulfonyl, (N 1 N-dimethylamino) ethylaminosulfonyl, N, N- (propoxyethyl) dodecylaminosulf
• Halogens are chlorine, bromine and iodine
• Aryl or hetarylazo are, for example, phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;
• Optionally substituted cycloalkyls are, for example, cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3 and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methyl cycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-isopropylpropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-
• Optionally condensed and / or substituted and / or interrupted aryl and hetaryl groups should have at least 3 to 14 ring atoms, preferably 5 to 10 ring atoms, and are for example
• diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are preferably those in which R and R A have the same meaning.
• the diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are likewise preferably those in which R, R A are, independently of one another, aryloxy or arylthio, the entire ring system being mono- or polysubstituted by Radicals (i), (ii), (iii), (iv) and / or (v) may be substituted as indicated above. It is particularly preferred if R, R A can be mono- or poly-substituted by a radical (i) independently of one another.
• the diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are those in which R, R A are independently of one another
• X is O or S is and
• R 4 , R 5 , R 6 independently of one another may be hydrogen or the radicals (i), (ii), (iii), (iv) and / or (v) as specified above, with the proviso that at least one of the radicals R 4 , R 6 is not hydrogen. Particularly preferred is that when R 4 is C 15 C 30 alkyl or C 3 C 8 cycloalkyl, no ternary carbon atom occurs at the 1 position.
• both R 4 are not hydrogen and R 5 , R 6 is hydrogen or that R 6 is not hydrogen and R 4 , R 5 are hydrogen.
• the diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are those in which each R 'independently of one another is C 1 -C 30 -alkyl or aryl, where the entire ring system is mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v) as indicated above, may be substituted.
• R ' is monosubstituted or polysubstituted by a radical (i).
• all R ' are the same.
• the diimides of the general formula (I) and (Ia) according to the invention exhibit strong absorption in the infrared range at wavelengths from 700 to 1100 nm. Their functionalization can be selected in a targeted manner so that they can be adapted directly to the desired intended use.
• reaction product was precipitated onto water, filtered off, washed with hot water and finally with hexane until the effluent became colorless. The residue was subjected overnight to Soxleth extraction with hexane. The product was dried in vacuo at 70 0 C.
• the mixture was heated to 85 ° C under N 2 and stirred at this temperature for 24 h. After cooling to room temperature, the organic phase was separated and the solvent removed in vacuo. The crude product was subjected to a column chromatography on silica gel with a 1: 1 mixture of methylene chloride and hexane as eluent.
• Example 3 A mixture of 0.05 g (0.038 mmol) of Example 3, 0.12 g (0.86 mmol) of potassium carbonate and 2.0 ml of ethanolamine, and 1, 0 ml Deiethylglycoldientylether was heated to 120 0 C under a nitrogen atmosphere. After 24 h, much of the starting material was observed by means of TLC. After 64 h, starting material was completely converted.
• reaction product was precipitated onto water, filtered off, washed with hot water and finally with hexane until the effluent became colorless. The residue was subjected overnight to Soxleth extraction with hexane. The product was dried in vacuo at 70 0 C domestic product.
• reaction product was precipitated onto water, filtered off, washed with hot water and finally with hexane until the effluent became colorless. the Overnight residue was subjected to Soxleth extraction with hexane. The product was dried in vacuo at 70 0 C.
• v (cm-1) 2958, 2360, 2342, 1703, 1668, 1589, 1567, 1537, 1503, 1472, 1409, 1364, 1320, 1279, 1211, 1 179, 1105, 1056, 875 , 837;
• reaction product was precipitated onto water, filtered off, washed with hot water and finally with hexane until the effluent became colorless. The residue was subjected overnight to Soxleth extraction with hexane. The product was dried in vacuo at 70 0 C domestic product.

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• 2007
  • 2007-10-30 CN CN200780049057.9A patent/CN101573414B/zh not_active Expired - Fee Related
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