Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
  • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
  • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
  • C07D279/18—[b, e]-condensed with two six-membered rings
  • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
  • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
• • 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
• • 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
  • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2603/00—Systems containing at least three condensed rings
  • C07C2603/93—Spiro compounds
  • C07C2603/94—Spiro compounds containing "free" spiro atoms
• • 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

Definitions

• aryl oligoamines which have several amine units
• they can be used as hole conductors in xerography (see, for example, PM Borsenberger, DS Weiss, Organic Photoreceptors for Imaging Systems, Marcel Dekker, Inc.), in organic electroluminescent devices (see, for example, JJ Kido, Bull. Electrochem. 1994, 10, 1-13; DE-A-197 11 714) and dye-sensitized photovoltaic cells (see, for example, DE-A 197 1 1 714).
• Aryloligoamines are generally built up via variants of the Ullmann reaction (J. March. Adv. Org. Chem. 4th Ed., P. 665, John Wiley & Sons, New York 1992). For example, the representation of 4,4 ', 4 "tris (N, N-diphenylamino) triphenylamine (Shirota et al., Chem. Lat. 1989, 1 145-1 148) and tris
• aryl oligoamines In general, the production of aryl oligoamines is more difficult than that of aryl monoamines.
• Ullmann reactions can be carried out under optimal conditions with a yield of about 80%. Applying this to a tri or
• aryloligoamines can be prepared simply and in good yields by directly coupling a primary or secondary amine with an activated aromatic in the presence of a base, a palladium component and a phosphine ligand.
• the invention therefore relates to a process for the preparation of aryloligoamines, characterized in that an amine with an activated
• aryloligoamine means a compound which contains at least two amine units bonded to aromatic groups.
• Preferred starting compounds are activated aromatics of the general formula (I),
• A is an aromatic and / or heteroaromatic radical with 2 to 200 carbon atoms, which may contain several aromatic and / or heteroaromatic groups, such groups then condensing (for example Anthracene, triphenylene) or uncondensed (for example biphenyl, terphenyl, 1, 3,5-triphenylbenzene);
• R ⁇ R 2 are identical or different H, CN, C r C 12 alkyl, C 4 -C 10 aryl;
• R 3 , R 4 are identical or different C r C 12 alkyl, C 4 -C 10 aryl;
• R 5 is CC 12 alkyl, C 4 -C 10 aryl
• X is Cl, Br, I, mesylate, tosylate or C 1 -C 12 perfluoroalkyl sulfonate;
• m is a natural number, where 2 ⁇ m ⁇ y;
• n is a natural number, where 0 ⁇ n ⁇ y-m;
• y is the number of free valences on the base body A
• R is the same or different NO 2 , CN, F, an unbranched or branched alkyl group with 1 to 22 C atoms.
• A is benzene, naphthalene, anthracene, pyrene, triphenylene, biphenyl, fluorene, terphenyl, 1, 3,5-triphenylbenzene, spiro-9,9'-bifluorene, 2,2 ', 7,7'-tetraphenylspiro-9,9 '-bifluoren, 2,2', 7,7'-tetra (4'-biphenylyl) spiro-9,9'-biphenyl, 2,4,7,2'4, 7'-Hexaphenylspiro-9,9, -bifluoren and 2,4,7,2, 4 ', 7'-hexa (4'-biphenylyl) spiro-9,9'-bifluorene or other oligophenylene- substituted derivative of the spiro-9,9'-bifluorens;
• R is the same or different NO 2 , CN, F, an unbranched or branched alkyl group with 1 to 22 C atoms.
• X is Br, I
• n 4, 5 or 6
• n 0, 1, 2, 3, 4, 5, 6.
• Particularly preferred activated aromatics of the formula (I) are those of the formula (Ia)
• X is the same or different, Br, I or H and k, l, p, q, r, s 0, 1, 2, 3, 4, with the proviso that at least two, preferably at least four, of the radicals X Br or I are.
• Preferred amine components are those of the formula (II)
• the ratio of the starting materials is not critical and can therefore be varied within a wide range, a ratio of activated group to amine of 1: 0.8 to 2, particularly preferably 1: 1 to 1.5, is preferred.
• the starting compounds, amine and activated aromatic are converted into an aryloligoamine in a coupling reaction.
• the amine, the activated aromatic, a base and catalytic amounts of a phosphine ligand are contained
• Palladium catalyst or a palladium salt and a phosphane are taken up in a solvent and at a temperature of 0 ° C to 150 ° C, preferably at 30 ° C to 140 ° C, particularly preferably at 50 ° C to 120 ° C, particularly preferably at 80 ° C to 120 ° C for a period of 1 h to 200 h, preferably 5 h to 100 h, particularly preferably 10 h to 80 h, implemented.
• the process according to the invention is generally carried out in a solvent, an excess of the base or of a starting material, preferably the amine component, also being able to serve as such a solvent.
• organic solvents or a mixture of water and one or more organic solvents is preferred, in which case at least one of the organic solvents should preferably be water-insoluble.
• Preferred organic solvents are ethers, e.g. B. diethyl ether, dimethoxymethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dioxolane, diisopropyl ether, tert-butyl methyl ether, hydrocarbons, e.g. B. hexane, iso ⁇
• alcohols e.g. B. methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, 1-butanol, 2-butanol, tert-butanol, ketones, e.g. B. acetone,
• organic solvents are ethers, such as dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, diisopropyl ether, hydrocarbons, such as hexane, heptane, cyclohexane, toluene, xylene, alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol,
• Ethylene glycol ketone, iso-butyl methyl ketone, amides such as Dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and mixtures thereof.
• organic solvents are ethers, e.g. B. dimethoxyethane, tetrahydrofuran, dioxane, hydrocarbons, e.g. B. cyclohexane,
• water and organic solvents examples are mixtures of water and toluene and water, toluene and tetrahydrofuran.
• Bases which are preferably used in the process according to the invention are alkali and alkaline earth metal hydroxides, alkali and
• Provided excess can also act as a base.
• Alkali and alkaline earth metal hydroxides, alkali and alkaline earth metal carbonates and alkali and alkaline earth metal alcoholates are particularly preferred.
• Alkali metal hydroxides such as sodium hydroxide and, are particularly preferred.
• Potassium hydroxide and alkali and alkaline earth metal alcoholates, such as sodium ethanolate and sodium or potassium tert-butoxide.
• the base is preferably present in a proportion of 50 to 500 mol%, particularly preferably 50 to 250 mol%, very particularly preferably 75 to 200 mol%, in particular 90 to 120 mol%, based on the moles present NH, used.
• the palladium component contains palladium metal or a palladium (0) or (II)
• Palladium component and phosphine ligand can be used as a complex, for example as the preferred Pd (PPh 3 ) 4 , or separately.
• Suitable palladium components are, for example, palladium compounds, such as palladium ketonates, palladium acetylacetonates, nitrile palladium halides,
• Palladium can also serve as a palladium component in metallic form, hereinafter only called palladium, preferably palladium in powdered form or on a support material, for example palladium on activated carbon, palladium on aluminum oxide, palladium on barium carbonate, palladium on barium sulfate, palladium on aluminum silicates, such as montmorillonite, Palladium on SiO 2 and
• Palladium on calcium carbonate each with a palladium content of 0.5 to 10 wt .-%.
• Palladium on activated carbon with a palladium content of is particularly preferred
• the palladium component is used in a proportion of 0.01 to 10 mol%, preferably 0.05 to 5 mol%, particularly preferably 0.1 to 3 mol%, particularly preferably 0.1 to 1.5 Mol%, based on the N-
• Suitable phosphine ligands for the process according to the invention are, for example, trialkylphosphines, tricycloalkylphosphanes, triarylphosphines, where the three substituents on the phosphorus can be the same or different, chiral or achiral and one or more of the ligands can link the phosphorus groups of several phosphines and part of this linkage also includes or can be several metal atoms.
• phosphanes which can be used in the process according to the invention are trimethylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, tritolylphosphine, tris (4-dimethylaminophenyl) phosphine, bis (diphenylphosphano) methane, 1,2-bis (diphenylphosphano) ethane, 1,3
• Triphenylphosphine tris (o-tolyl) phosphane, 1,2-bis (diphenylphosphano) ethane, 1,3-bis (diphenylphosphano) propane and 1,1'-bis (diphenylphosphano) ferrocene, especially triphenylphosphane and tris, are very particularly preferred (o-tolyl) phosphine.
• water-soluble phosphine ligands which contain, for example, sulfonic acid salt and / or sulfonic acid residues and / or carboxylic acid salt and / or carboxylic acid residues and / or phosphonic acid salt and / or phosphonic acid residues and / or phosphonium groups and / or peralkylammonium groups and / or hydroxyl groups and / or Contain polyether groups with a suitable chain length.
• Preferred classes of water-soluble phosphine ligands are trialkylphosphines substituted with the above groups, tricycloalkylphosphanes, triarylphosphines,
• the phosphine ligand is used in a proportion of 0.1 to 20 mol%, preferably 0.2 to 15 mol%, particularly preferably 0.5 to 10 mol%, particularly preferably 1 to 6 mol%, based on the NH present - Groups.
• Mixtures of two or more different phosphine ligands can optionally also be used.
• the products of the method according to the invention are e.g. for use in electroluminescent devices, dye-sensitized photovoltaic cells or in xerography, for example as hole conductor materials.
• Example 1 implemented. DPPF was used as the ligand.
• the workup was also carried out analogously, but the product proved to be significantly more difficult to clean.
• the mixture was first filtered twice over a silica gel column and then initially recrystallized from ethyl acetate / methanol (2: 1), then repeatedly from dioxane. After drying, 26% product was obtained (purity:> 99.9% according to HPLC).
• Example 2 implemented. The processing was also carried out analogously. After drying, 31% of product was obtained (purity:> 99.7% according to HPLC).

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• 1997
  • 1997-09-05 DE DE19738860A patent/DE19738860A1/de not_active Withdrawn
• 1998
  • 1998-08-26 JP JP2000510701A patent/JP2001515879A/ja active Pending
  • 1998-08-26 EP EP98946429A patent/EP1009731B1/de not_active Expired - Lifetime
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  • 1998-08-26 WO PCT/EP1998/005398 patent/WO1999012888A1/de not_active Ceased
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