EP1345888A1 - Method for the production of 1,5-naphthalenediamine - Google Patents

Method for the production of 1,5-naphthalenediamine

Info

Publication number
EP1345888A1
EP1345888A1 EP01990532A EP01990532A EP1345888A1 EP 1345888 A1 EP1345888 A1 EP 1345888A1 EP 01990532 A EP01990532 A EP 01990532A EP 01990532 A EP01990532 A EP 01990532A EP 1345888 A1 EP1345888 A1 EP 1345888A1
Authority
EP
European Patent Office
Prior art keywords
nitro
amino
dihydro
naphthylamine
nitrophenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01990532A
Other languages
German (de)
French (fr)
Inventor
Michael Schelhaas
Katrin Joschek
Manfred Jautelat
Joachim Zechlin
Dietmar Wastian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE10149041A external-priority patent/DE10149041A1/en
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1345888A1 publication Critical patent/EP1345888A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/45—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by at least one doubly—bound oxygen atom, not being part of a —CHO group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/24—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds
    • C07C209/28—Preparation of compounds containing amino groups bound to a carbon skeleton by reductive alkylation of ammonia, amines or compounds having groups reducible to amino groups, with carbonyl compounds by reduction with other reducing agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
    • C07C211/60—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton containing a ring other than a six-membered aromatic ring forming part of at least one of the condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/11—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/42—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being further bound to other hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

  • the invention relates to a process for the preparation of 1,5-naphthalenediamine by reacting ortbo-nitrotoluene with an acrylic acid derivative and the im
  • 1,5-naphthalenediamine Various processes for the preparation of 1,5-naphthalenediamine are already known in the literature. In general, the preparation of 1,5-naphthalenediamine starts from naphthalene, which is appropriately substituted.
  • JP-A-2-07 278 066 describes the synthesis of 1,5-naphthalenediamine via an amine-bromine
  • JP-A2-04 154 745, JP-A2-56 059 738 and DE-Al-2 523 351 describe the synthesis of 1,5-naphthalenediamine in combination with 1,8-naphthalenediamine by reducing a mixture of 1,5- and 1,8-dinitronaphthalene.
  • DE-Cl-3 840 618 describes the synthesis of 1,5-naphthalenediamine by alkaline hydrolysis of disodium naphthalene-1,5-disulfonate and subsequent reaction with ammonia.
  • the object of the present invention is therefore to provide a simple process for the preparation of 1,5-naphthalenediamine, according to which 1,5-naphthalenediamine can be prepared in basic steps from basic chemicals, without other isomers occurring and being separated off in appreciable amounts have to.
  • the object is achieved according to the invention by a process for the preparation of 1,5-naphthalenediamine which comprises a step in which ortbo-nitrotoluene is reacted with an acrylic acid derivative.
  • acrylic acid derivatives are acrylic acid esters, such as, for example, methyl acrylate and ethyl acrylate, acrylic acid amide and acrylonitrile.
  • the process for the preparation of 1,5-naphthalenediamine contains the steps
  • step b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give the nitro-imine and / or nitro-enamine, c) aromatizing the nitro-imine and / or nitro-enamine formed in step b) to 5-nitro-1-naphthylamine and / or 5-nitroso-1-naphthylamine,
  • step c) hydrogenating the 5-nitro-1-naphthylamine and / or 5-nitroso-1-naphthylamine formed in step c) to 1,5-naphthalenediamine.
  • 4- (2-nitrophenyl) -butyromtril is preferably produced from ortbo-nitrotoluene and acrylonitrile at temperatures from -10 ° C to 100 ° C. It is particularly preferred to work at 20 ° C. to 75 ° C., very particularly preferably at temperatures from 30 ° C. to 60 ° C.
  • the reaction is carried out under base catalysis.
  • Oxides, hydroxides and carbonates of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium or aluminum and mixtures thereof can be used as bases.
  • Sodium and potassium hydroxide are particularly suitable.
  • Phase transfer catalyst used are e.g. quaternary ammonium salts.
  • Suitable ammonium compounds are tetraalkylammonium halides and hydrogen sulfates such as tributylmethylammonium chloride, trioctylammonium chloride, tetrabutylammonium chloride or tetrabutylammonium hydrogen sulfate.
  • suitable is the use of corresponding tertaalkyl or tetraaryl phosphonium salts such as tetramethylphosphonium bromide and tetraphenylphosphonium bromide, and the use of solubilizers such as polyethylene glycol dimethyl ether.
  • Aromatic solvents such as benzene, toluene, xylene, chlorobenzene, nitrobenzene or nitrotoluene and dimethyl sulfoxide are preferred; Dimethylformamide and aliphatic hydrocarbons such as ligroin, cyclohexane, pentane, hexane, heptane, octane are used.
  • Ortbo-nitrotoluene is particularly preferably used as starting material and at the same time as solvent, and an excess of ortbo-nitrotoluene of 1 to 40 equivalents, very particularly 5 to 20 equivalents, based on acrylonitrile, is used.
  • cyclization of 4- (2-nitrophenyl) butyronitrile to 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine is carried out in bulk or carried out in an inert solvent in the presence of strong acids.
  • Suitable solvents are linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, pentane, hexane, heptane, octane and aromatic solvents such as nitrotoluene. It is preferred to work in bulk or in ortbo-nitrotoluene.
  • Suitable acids are strong Lewis or Bronsted acids such as e.g. Aluminum chloride, boron trifluoride, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or
  • Mixtures of antimony pentafluoride and fluorosulfuric acid can also be used.
  • the acid is generally used in 0.1 to 100 molar equivalents, based on 4- (2-nitrophenyl) butyronitrile. 0.5 to 20 equivalents are preferably used, particularly preferably 1 to 10 equivalents.
  • the reaction is generally carried out at temperatures from 0 ° C. to 200 ° C., preferably between 40 ° C. to 150 ° C., particularly preferably between 60 ° C. and 110 ° C.
  • the hydrolysis-sensitive nitro-imine and / or nitro-enamine formed in step b) is preferably first reacted, for example by hydrolysis, to give the nitroketone 5-nitro-3,4-dihydro-l (2H) -naphthalinone and the nitroketone is isolated. The isolation takes place, for example, by phase separation.
  • step c) the nitroketone is then converted back to the nitroimine and / or nitroenamine by reaction with ammonia, preferably in the presence of ammonium salts such as ammonium chloride, and then aromatized. The aromatization then preferably takes place in ammonia as the solvent.
  • the aromatization or dehydrogenation of the nitro-enamine 5-nitro-3,4-dihydro-1-naphthylamine or the nitro-imine 5-nitro-3,4-dihydro-1 (2H) -naphthylimine to 5-nitro-1 -naphthylamine or 5-nitroso-l-naphthylamine or a mixture of the compounds is carried out, for example in an inert solvent, in the presence of a catalyst.
  • the 5-nitroso-1-naphthylamine formally formed by synproportionation can also be formed. 1,5-naphthalenediamine is also produced in traces.
  • the products can be processed in any mixing ratio.
  • Suitable solvents are ammonia and linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, and acetonitrile and aromatic solvents such as benzene, toluene, xylene, nitrobenzene, nitrotoluene or chlorobenzene.
  • the flavoring can also be carried out in the absence of a solvent.
  • Suitable catalysts are dehydrogenation catalysts which are described in the literature (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 891, chapter “Dehydration", section 1; Ullmann's Encyclopedia of Industrial Chemistry, NCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989, Vol A13, chapter “Hydrogenation and Dehydrogenation", subsection 2. "Dehydrogenation”, pp. 494-497). These include the metals of the 8th-10th group of the
  • Periodic table (GJ Leigh [Editor], omenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.),
  • platinum Palladium, ruthenium and iridium, iron, cobalt, nickel and combinations thereof.
  • the metals can also be used together with other metals such as lanthanum, scandium, vanadium, chromium, molybdenum, tungsten, manganese, tin, Zinc, copper, silver or indium can be used.
  • the metals mentioned can be present as pure elements, as oxides, sulfides, halides, carbides or nitrides or can be used in combination with organic ligands.
  • Suitable ligands are hydrocarbon compounds with donor groups such as, for example, amines, nitriles, phosphines, thiols, thioethers, alcohols, ethers or
  • Carboxylic acids are optionally applied to a support material.
  • Suitable carrier materials are activated carbon, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, zeolites.
  • reaction is generally carried out at temperatures from 50 ° C. to 250 ° C., preferably at 100 ° C. to 200 ° C.
  • the nitro group is reduced to the product 1,5-naphthalenediamine by hydrogenation in the presence of suitable hydrogenation catalysts.
  • Rhodium, platinum and palladium are particularly preferred. More preferred Raney nickel and supported nickel catalysts are catalysts. It is also possible to use the above-mentioned metals or their compounds in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
  • the catalysts can be used in amounts of 0.01 to 50% by weight, based on the 5-nitro- or 5-nitroso-1-naphthylamine used, preferably in amounts of 0.01 to 20% by weight. %, particularly preferably in amounts of 0.01 to 10% by weight.
  • reaction temperatures are generally from -20 ° C to 150 ° C, especially
  • the hydrogen pressure is generally 0.1 to 150 bar, in particular 0.5 to 70 bar, very particularly preferably 1 to 50 bar.
  • the same catalyst is preferably used for the aromatization and the subsequent hydrogenation, it being possible for the two steps to be carried out in one reaction vessel.
  • All reaction steps in this preferred embodiment of the process can be carried out continuously or batchwise, for example in stirred tank reactors or tubular reactors.
  • the process for the preparation of 1,5-naphthalenediamine contains the steps
  • step b) cyclizing the 4- (2-aminophenyl) butyronitrile formed in step b) to the amino-imine and / or amino-enamine,
  • step c) Flavoring the amino imine and / or amino enamine formed in step c) to give 1,5-naphthalenediamine.
  • 4- (2-nitrophenyl) butyronitrile is prepared from ort ⁇ o-nitrotoluene and acrylonitrile analogously to step a) of the first preferred embodiment.
  • This compound is then reduced to 4- (2-aminophenyl) butyronitrile.
  • the transformation can be carried out by hydrogenation in the presence of a hydrogenation catalyst.
  • a hydrogenation catalyst Practically all heterogeneous catalysts known as hydrogenation catalysts are suitable as hydrogenation catalysts for the process according to the invention (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 1831, chapter "Hydrogenation”; Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
  • Catalysts are the metals from 8th to 10th Group of the Periodic Table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Copper or chromium on a suitable carrier with a metal content of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total weight of the catalyst. Catalysts containing one or more of the metals mentioned above can also be used. Preferred metals are in particular platinum, palladium and rhodium, platinum and palladium are particularly preferred. More preferred
  • Raney nickel and supported nickel catalysts are catalysts. It can the abovementioned metals or their compounds can also be used in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
  • the nitro group can be reduced by conversion with metal hydrides, if appropriate with the addition of additives, or by conversion with base metals such as iron.
  • Preferred metal hydrides are sodium borohydride, potassium borohydride, lithium borohydride, sodium cyanoborohydride, lithium cyanoborohydride, lithium aluminum hydride and diisobutyl aluminum hydride.
  • Suitable additives are nickel salts, tellurium compounds and antimony compounds.
  • Preferred base metals for the reaction under acidic conditions are iron, zinc, magnesium, aluminum and tin, iron and are particularly preferred
  • Suitable solvents for this are water or alcohols or alcohol mixtures which are acidified with acids such as acetic acid, hydrochloric acid, sulfuric acid, ammonium chloride.
  • Suitable alcohols are methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol or cyclohexanol. Methanol and ethanol are particularly preferred.
  • Aminophenyl) butyronitrile at least one molar equivalent of acid (based on 4- (2-aminophenyl) butyronitrile) are additionally added. 1.5 to 21 equivalents of acid are preferably used, particularly preferably 1.5 to 11 equivalents.
  • the reaction is carried out in bulk or in an inert solvent in the presence of strong acids.
  • Suitable solvents are linear, branched or Cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, pentane, hexane, heptane, octane and aromatic solvents such as nitrotoluene. Is preferably carried out in bulk or in place / io-nitrotoluene.
  • Suitable acids are strong Lewis or Bronsted acids such as e.g. Aluminum chloride, boron trifluoride, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or mixtures of antimony pentafluoride and fluorosulfuric acid. Mixtures of the acids can also be used.
  • the reaction is generally carried out at temperatures from 0 ° C. to 150 ° C., preferably between 60 ° C. and 110 ° C.
  • reaction mixture is usually neutralized. This is done, for example, by adding sodium hydroxide solution.
  • the amino-imine and / or amino-enamine formed in step c) is preferably first reacted, for example by hydrolysis, to give the amino ketone 5-amino-3,4-dihydro-l (2H) -naphthalinone and the amino ketone is isolated. The isolation takes place, for example, by phase separation. Then the amino ketone is in
  • Step d) is converted to the amino-imine and / or amino-enamine by reaction with ammonia, preferably in the presence of ammonium chloride, and then flavored.
  • the aromatization then preferably takes place in ammonia.
  • the aromatization of 5-amino-3,4-dihydro-l-naphthylamine or the imine tautomer 5-amino-3,4-dihydro-l (2H) -naphthylimine to 1,5-naphthalenediamine is carried out analogously to the aromatization of the nitro compounds 5- Nitro-3,4-dihydro-1-naphthylamine or 5-nitro-3,4-dihydro-1 (2H) -naphthylimine (step c) of the first preferred embodiment).
  • the reaction is carried out in an inert solvent in the presence of a catalyst.
  • Suitable solvents are ammonia and linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, and acetonitrile and aromatic solvents such as benzene, toluene, xylene, nitrobenzene, nitrotoluene or chlorobenzene.
  • Suitable catalysts are dehydrogenation catalysts which are described in the literature (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 891, chapter “Dehydration", section 1; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
  • the metals can also be used together with other metals such as lanthanum, scandium, vanadium, chromium, molybdenum, tungsten, manganese, tin, zinc, copper, silver or indium.
  • the metals mentioned can be present as pure elements, as oxides, sulfides, halides, carbides or nitrides or can be used in combination with organic ligands.
  • Suitable ligands are hydrocarbon compounds with donor groups such as amines, nitriles, phosphines, thiols, thioethers, alcohols, ethers or carboxylic acids.
  • the catalysts are optionally applied to a support material. Suitable carrier materials are activated carbon, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide,
  • reaction is generally carried out at temperatures from 50 ° C. to 250 ° C., preferably at 100 ° C. to 200 ° C.
  • Tube reactors are carried out.
  • the process for the preparation of 1,5-naphthalenediamine contains the steps
  • step b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give the nitro-imine and / or nitro-enamine,
  • step b) reducing the nitro-imine and / or nitro-enamine formed in step b) to the amino-imine and / or amino-enamine
  • 4- (2-nitrophenyl) butyronitrile is prepared from ortbo-nitrotoluene and acrylonitrile analogously to step a) of the first preferred embodiment.
  • This compound is then cyclized to 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine analogously to step b) of the first preferred embodiment.
  • the compound 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine is now converted into 5-amino-3,4-dihydro-l - naphthylamine or the tautomeric 5-amino-3,4-dihydro-l (2H) -naphthylimine reduced.
  • the transformation can be carried out by hydrogenation in the presence of a hydrogenation catalyst.
  • Suitable hydrogenation catalysts for the process according to the invention are virtually all heterogeneous catalysts known as hydrogenation catalysts (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 1831, chapter "Hydrogenation”; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
  • Catalysts are the metals from 8th to 10th Group of the Periodic Table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Copper or chromium on a suitable carrier with a metal content of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total weight of the catalyst. Catalysts containing one or more of the metals mentioned above can also be used. Preferred metals are in particular platinum, palladium and rhodium, platinum and palladium are particularly preferred. More preferred
  • Raney nickel and supported nickel catalysts are catalysts. It is also possible to use the metals mentioned above or their compounds in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
  • step d) second preferred embodiment The final aromatization of 5-amino-3,4-dihydro-l-naphthylamine or the tautomeric 5-amino-3,4-dihydro-l (2H) -naphthylimine to 1,5-naphthalenediamine is analogous to step d) second preferred embodiment performed. All reaction steps in this preferred embodiment of the process can be carried out continuously or batchwise, for example in stirred tank reactors or tubular reactors.
  • step b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give nitro-imine and / or nitro-enamine, conversion to nitro-ketone 5-nitro-3,4-dihydro-1 (2H) -naphthalenone, and Isolation of nitroketone,
  • step b) reducing the nitroketone formed in step b) to the aminoketone 5-
  • step d) converting the amino ketone formed in step c) to the amino-imine and / or amino-enamine and aromatizing to the 1,5-naphthalenediamine.
  • 4- (2-nitrophenyl) butyronitrile is prepared from ortbo-nitrotoluene and acrylonitrile analogously to step a) of the first preferred embodiment.
  • 4- (2-nitrophenyl) butyronitrile is then converted to 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine analogously to step b) the first preferred embodiment cyclized.
  • the 5-nitro-3,4-dihydro-l-naphthylamine and or 5-nitro-3,4-dihydro-l (2H) -naphthylimine is then, for example by hydrolysis, to the nitroketone 5-nitro-3,4-dihydro -l (2H) -naphthalenone implemented and the nitroketone isolated.
  • the nitroketone is isolated, for example, by phase separation.
  • the compound 5-nitro-3,4-dihydro-l (2H) -naphthalinone is now reduced to 5-amino-3,4-dihydro-1 (2H) -naphthalinone.
  • the transformation can be carried out by hydrogenation in the presence of a hydrogenation catalyst.
  • Suitable hydrogenation catalysts for the process according to the invention are virtually all heterogeneous catalysts known as hydrogenation catalysts (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 1831, chapter “Hydrogenation”; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989, Vol AI 3, chapter “Hydrogenation and Dehydrogenation", subsection 1.2
  • Catalysts p. 488.
  • Preferred catalysts are the metals of the 8th-10th group of the periodic table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapters 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Or copper and / or chrome on a suitable carrier with a metal content of 0.01 to
  • Catalysts containing one or more of the metals mentioned above can also be used.
  • Preferred metals are in particular platinum, palladium and rhodium, platinum and palladium are particularly preferred.
  • Other preferred catalysts are Raney nickel and supported nickel catalysts. It is also possible to use the above-mentioned metals or their compounds in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
  • the 5-amino-3,4-dihydro-l (2H) -naphthalinone produced in the reduction is then converted to 5-amino-3,4-dihydro-l -naphthylamine and / by reaction with ammonia, preferably in the presence of ammonium chloride. or 5-amino-3, 4-dihy dro-1 (2H) -naphthylimine.
  • the conversion of 5-amino-3,4-dihydro-1 (2H) -naphthalenone to 5-amino-3,4-dihydro-1-naphthylamine and / or 5-amino-3,4-dihydro-1 (2H) -naphthylimine and the subsequent aromatization are preferably carried out in a reaction vessel.
  • All reaction steps in this preferred embodiment of the process can be carried out continuously or batchwise, for example in stirred tank reactors or tubular reactors.
  • the process for making 1,5-naphthalenediamine includes the steps
  • step b) cyclization of the butyric acid ester or butyric acid amide formed in step a) to give 5-nitro-3,4-dihydro-l (2H) -naphthalinone,
  • step d) hydrogenating the 5-nitro-1-naphthylamine and / or 5-nitroso-1-naphthylamine formed in step d) to 1,5-naphthalenediamine.
  • 4- (2-nitrophenyl) butyric acid esters or 4- (2-nitrophenyl) butyric acid amides are preferably prepared from ortbo-nitrotoluene and acrylic acid esters or acrylic acid amides at temperatures from -10 ° C. to 100 ° C. It is particularly preferred to work at 20 ° C. to 75 ° C., very particularly preferably at temperatures from 30 ° C. to 60 ° C.
  • Hydroxides and carbonates of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium or aluminum and mixtures thereof can be used.
  • Sodium and potassium hydroxide are particularly suitable.
  • the aqueous solutions are used in combination with a phase transfer catalyst.
  • phase transfer catalysts are, for example, quaternary ammonium salts.
  • Suitable ammonium compounds are tetraalkyl - 18 -
  • Chloride trioctylammonium chloride, tetrabutylammonium chloride or tetrabutylammonium hydrogen sulfate.
  • tertaalkyl or tetraaryl phosphonium salts such as tetramethylphosphonium bromide and tetraphenylphosphonium bromide and solubilizers such as polyethylene glycol dimethyl ethers.
  • Aromatic solvents such as benzene, toluene, xylene, chlorobenzene, nitrobenzene or nitrotoluene and dimethyl sulfoxide, dimethylformamide and aliphatic hydrocarbons such as ligroin, cyclohexane are preferred.
  • Pentane, hexane, heptane, octane are used.
  • Ortbo-nitrotoluene is particularly preferably used as starting material and at the same time as solvent, and an excess of ort ⁇ o-nitrotoluene of 1 to 40 equivalents, very particularly 5 to 20 equivalents, based on the acrylic acid derivative, is used.
  • Solvents are linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, pentane, hexane, heptane, octane and aromatic solvents such as nitrotoluene. It is preferred to work in bulk or in ⁇ rtbo nitrotoluene.
  • Suitable acids are strong Lewis or Bronsted acids such as e.g. Aluminum chloride, boron trifluoride, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or mixtures of antimony pentafluoride and fluorosulfuric acid. Mixtures of these acids can also be used. Sulfuric acid or is preferred
  • the acid is generally used in 0.1 to 100 molar equivalents, based on 4- (2-nitrophenyl) butyric acid derivative. 0.5 to 20 equivalents are preferably used, particularly preferably 1 to 10 equivalents.
  • the reaction is generally carried out at temperatures from 0 ° C. to 150 ° C., preferably between 60 ° C. and 110 ° C.
  • Compounds is carried out, for example in an inert solvent, in the presence of a catalyst.
  • a catalyst In addition to the dehydrated product 5-nitro-1-naphthylamine, the 5-nitroso-1-naphthylamine that is formally formed by synproportionation can also be formed. 1,5-naphthalenediamine is also produced in traces.
  • the products can be processed in any mixing ratio.
  • Suitable solvents are ammonia and linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, and acetonitrile and aromatic solvents such as benzene, toluene, xylene, nitrobenzene, nitrotoluene or chlorobenzene.
  • the flavoring can also be carried out in the absence of a solvent.
  • Suitable catalysts are dehydrogenation catalysts which are described in the literature (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 891, chapter “Dehydration", section 1; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
  • the metals can also be used together with other metals such as lanthanum, scandium, vanadium, chromium, molybdenum, tungsten, manganese, tin, zinc, copper, silver or indium.
  • the metals mentioned can be present as pure elements, as oxides, sulfides, halides, carbides or nitrides or can be used in combination with organic ligands.
  • Suitable ligands are hydrocarbon compounds with donor groups such as amines, nitriles, phosphines, thiols, thioethers, alcohols, ethers or carboxylic acids.
  • the catalysts are optionally applied to a support material. Suitable carrier materials are activated carbon, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, zeolites.
  • reaction is generally carried out at temperatures from 50 ° C. to 250 ° C., preferably at 100 ° C. to 200 ° C.
  • X OAlkyl, OAryl, NH 2 , NHAlkyl, N (alkyl) 2 , NHAryl, N (aryl) 2 , NAIkylAryl
  • the 1,5-naphthalene diamine can be phosgenated to 1,5-naphthalene diisocyanate in a manner known per se (DE-Al-19 651 041).
  • 5-nitro-3,4-dihydro-l (2H) -na ⁇ hthylimine is 77% according to GC.
  • 5-Amino-3,4-dihydro-l (2H) -naphthylimine can also be named 5-imino-5,6,7,8-tetrahydro-l-naphthylamine.

Abstract

The invention relates to a method for the production of 1,5-naphthalenediamine and the intermediates obtained in the course of said synthesis, 4-(2-nitrophenyl)-butyronitrile, 5-nitro-3,4-dihydro-1(2H)-naphthylimine, 5-nitroso-1-naphthylamine, 5-nitro-1-naphthylamine, 4-(2-aminophenyl)-butyronitrile, 5-amino-3,4-dihydro-1(2H)-naphthalenimine, ethyl 4-(2-nitrophenyl)-butyrate and 4-(2-nitrophenyl)-butyramide.

Description

Verfahren zur Herstellung von 1,5-NaphthalindiaminProcess for the preparation of 1,5-naphthalenediamine
Die Erfindung betrifft ein Verfahren zur Herstellung von 1,5-Naphthalindiamin durch Umsetzung von ortbo-Nitrotoluol mit einem Acrylsäurederivat sowie die imThe invention relates to a process for the preparation of 1,5-naphthalenediamine by reacting ortbo-nitrotoluene with an acrylic acid derivative and the im
Laufe des Verfahrens erhältlichen Zwischenprodukte 4-(2-Nitrophenyl)-butyronitril, 5-Nitro-3,4-dihydro- 1 (2H)-naphthylimin, 5-Nitroso- 1 -naphthylamin, 5-Nitro- 1 - naphthylamin, 4-(2-Aminophenyl)-butyronitril, 4-(2-Nitrophenyl)-buttersäureethyl- ester, 4-(2-Nitrophenyl)-buttersäurebutylester, 4-(2-Nitrophenyl)-buttersäureamid und 5-Amino-3,4-dihydro-l(2H)-naphthalinimin.Intermediates obtainable during the process 4- (2-nitrophenyl) butyronitrile, 5-nitro-3,4-dihydro-1 (2H) -naphthylamine, 5-nitroso-1-naphthylamine, 5-nitro-1 - naphthylamine, 4- (2-aminophenyl) butyronitrile, 4- (2-nitrophenyl) butyric acid ethyl ester, 4- (2-nitrophenyl) butyric acid butyl ester, 4- (2-nitrophenyl) butyric acid amide and 5-amino-3,4-dihydro- l (2H) -naphthalinimin.
Verschiedene Verfahren zur Herstellung von 1,5-Naphthalindiamin sind in der Literatur bereits bekannt. Im Allgemeinen geht die Darstellung von 1,5-Naphtha- lindiamin von Naphthalin aus, das geeignet substituiert wird. So wird in JP- A-2-07 278 066 die Synthese von 1,5-Naphthalindiamin über einen Amin-Brom-Various processes for the preparation of 1,5-naphthalenediamine are already known in the literature. In general, the preparation of 1,5-naphthalenediamine starts from naphthalene, which is appropriately substituted. For example, JP-A-2-07 278 066 describes the synthesis of 1,5-naphthalenediamine via an amine-bromine
Austausch an 1,5-Bromaminonaphthalin beschrieben. Das benötigte Edukt wird bei diesem Verfahren durch Bromierung von 1-Nitronaphthalin erzeugt.Exchange on 1,5-bromoaminonaphthalene described. In this process, the required starting material is generated by bromination of 1-nitronaphthalene.
In JP-A2-04 154 745, JP-A2-56 059 738 und DE-Al-2 523 351 wird die Synthese von 1,5-Naphthalindiamin in Kombination mit 1,8-Naphthalindiamin durch Reduktion eines Gemisches aus 1,5- und 1,8-Dinitronaphthalin beschrieben. In DE-Cl- 3 840 618 wird die Synthese von 1 ,5-Naphthalindiamin durch alkalische Hydrolyse von Dinatrium Naphthalin- 1, 5 -disulfonat und anschließende Umsetzung mit Ammoniak beschrieben.JP-A2-04 154 745, JP-A2-56 059 738 and DE-Al-2 523 351 describe the synthesis of 1,5-naphthalenediamine in combination with 1,8-naphthalenediamine by reducing a mixture of 1,5- and 1,8-dinitronaphthalene. DE-Cl-3 840 618 describes the synthesis of 1,5-naphthalenediamine by alkaline hydrolysis of disodium naphthalene-1,5-disulfonate and subsequent reaction with ammonia.
Alle diese Verfahren haben den Nachteil, dass das Produkt oder ein im Laufe des Verfahrens erzeugtes Zwischenprodukt als Isomerenmischung anfällt, die neben dem 1,5 -Isomeren noch weitere Isomere enthält, die abgetrennt werden müssen. Zudem verläuft insbesondere das in DE-Cl-3 840 618 beschriebene Verfahren unter sehr drastischen und korrosiven Reaktionsbedingungen ab. Aufgabe der vorliegenden Erfindung ist daher, ein einfaches Verfahren zur Herstellung von 1,5-Naphthalindiamin bereit zu stellen, nach dem 1,5-Naphthalindiamin ausgehend von Basischemikalien in wemgen Schritten hergestellt werden kann, ohne dass andere Isomere in nennenswerten Mengen anfallen und abgetrennt werden müssen.All these processes have the disadvantage that the product or an intermediate product produced in the course of the process is obtained as an isomer mixture which, in addition to the 1,5 isomer, also contains further isomers which have to be separated off. In addition, the process described in DE-Cl-3 840 618 in particular takes place under very drastic and corrosive reaction conditions. The object of the present invention is therefore to provide a simple process for the preparation of 1,5-naphthalenediamine, according to which 1,5-naphthalenediamine can be prepared in basic steps from basic chemicals, without other isomers occurring and being separated off in appreciable amounts have to.
Es wurde nun ein Verfahren gefunden, durch das ausgehend von ortbo-Nitrotoluol und Acrylsäurederivaten wie beispielsweise Acrylnitril, zweier wohlfeiler Basischemikalien, 1,5-Naphthalindiamin in wemgen Schritten einfach und weitgehend isomerenrein dargestellt werden kann.A method has now been found by which, starting from ortbo-nitrotoluene and acrylic acid derivatives such as acrylonitrile, two inexpensive basic chemicals, 1,5-naphthalenediamine can be prepared simply and largely isomerically pure in a few steps.
Die Aufgabe wird erfindungsgemäß gelöst durch ein Verfahren zur Herstellung von 1 ,5-Naphthalindiamin, das einen Schritt enthält, in dem man ortbo-Nitrotoluol mit einem Acrylsäurederivat umsetzt.The object is achieved according to the invention by a process for the preparation of 1,5-naphthalenediamine which comprises a step in which ortbo-nitrotoluene is reacted with an acrylic acid derivative.
Bevorzugte Acrylsäurederivate sind Acrylsäureester, wie beispielsweise Acrylsäure- methylester und Acrylsäureethylester, Acrylsäureamid und Acrylnitril.Preferred acrylic acid derivatives are acrylic acid esters, such as, for example, methyl acrylate and ethyl acrylate, acrylic acid amide and acrylonitrile.
Die Aufgabe wird insbesondere erfindungsgemäß gelöst durch ein Verfahren zur Herstellung von 1,5-Naphthalindiamin, das einen Schritt enthält, in dem man ortho-The object is achieved in particular according to the invention by a process for the preparation of 1,5-naphthalenediamine which comprises a step in which ortho-
Nitrotoluol mit Acrylnitril zu 4-(2-Nitrophenyl)-butyronitril umsetzt.Reacts nitrotoluene with acrylonitrile to 4- (2-nitrophenyl) butyronitrile.
In einer ersten bevorzugten Ausführung enthält das Verfahren zur Herstellung von 1,5-Naphthalindiamin die SchritteIn a first preferred embodiment, the process for the preparation of 1,5-naphthalenediamine contains the steps
a) Umsetzung von ortbo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitrophenyl)- butyronitril,a) reaction of ortbo-nitrotoluene with acrylonitrile to give 4- (2-nitrophenyl) butyronitrile,
b) Cyclisierung des in Schritt a) gebildeten 4-(2-Nitrophenyl)-butyronitril zum Nitro-Imin und / oder Nitro-Enamin, c) Aromatisieren des in Schritt b) gebildeten Nitro-Imin und/oder Nitro-Enamin zu 5-Nitro-l -naphthylamin und/oder 5-Nitroso-l -naphthylamin,b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give the nitro-imine and / or nitro-enamine, c) aromatizing the nitro-imine and / or nitro-enamine formed in step b) to 5-nitro-1-naphthylamine and / or 5-nitroso-1-naphthylamine,
d) Hydrieren des in Schritt c) gebildeten 5-Nitro-l -naphthylamin und/oder 5- Nitroso-1 -naphthylamin zu 1,5-Naphthalindiamin.d) hydrogenating the 5-nitro-1-naphthylamine and / or 5-nitroso-1-naphthylamine formed in step c) to 1,5-naphthalenediamine.
4-(2-Nitrophenyl)-butyromtril wird aus ortbo-Nitrotoluol und Acrylnitril bevorzugt bei Temperaturen von -10°C bis 100°C hergestellt. Besonders bevorzugt arbeitet man bei 20°C bis 75°C, ganz besonders bevorzugt bei Temperaturen von 30°C bis 60°C.4- (2-nitrophenyl) -butyromtril is preferably produced from ortbo-nitrotoluene and acrylonitrile at temperatures from -10 ° C to 100 ° C. It is particularly preferred to work at 20 ° C. to 75 ° C., very particularly preferably at temperatures from 30 ° C. to 60 ° C.
Die Reaktion wird basenkatalysiert durchgeführt. Als Basen können Oxide, Hydroxide und Carbonate von Lithium, Natrium, Kalium, Rubidium, Cäsium, Magnesium, Calcium, Strontium, Barium oder Aluminium sowie Mischungen daraus eingesetzt werden. Besonders geeignet sind Natrium- und Kaliumhydroxid. In einer bevorzugten Ausführung werden die wässrigen Lösungen in Kombination mit einemThe reaction is carried out under base catalysis. Oxides, hydroxides and carbonates of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium or aluminum and mixtures thereof can be used as bases. Sodium and potassium hydroxide are particularly suitable. In a preferred embodiment, the aqueous solutions in combination with a
Phasentransferkatalysator eingesetzt. Solche Phasentransferkatalysatoren sind z.B. quartäre Ammoniumsalze. Geeignete Ammoniumverbindungen sind Tetraalkyl- ammonium-Halogenide und -Hydrogensulfate wie Tributylmethylammonium- Chlorid, Trioctylammonium-Chlorid, Tetrabutylammonium-Chlorid oder Tetra- butylammonium-Hydrogensulfat. Ebenso geeignet ist die Verwendung von entsprechenden Tertaalkyl- bzw. Tetraaryl-Phosphoniumsalzen wie Tetramethylphos- phonium-Bromid und Tetraphenylphosphonium-Bromid sowie die Verwendung von Löslichkeitsvermittlern wie Polyethylenglycoldimethylethem.Phase transfer catalyst used. Such phase transfer catalysts are e.g. quaternary ammonium salts. Suitable ammonium compounds are tetraalkylammonium halides and hydrogen sulfates such as tributylmethylammonium chloride, trioctylammonium chloride, tetrabutylammonium chloride or tetrabutylammonium hydrogen sulfate. Likewise suitable is the use of corresponding tertaalkyl or tetraaryl phosphonium salts such as tetramethylphosphonium bromide and tetraphenylphosphonium bromide, and the use of solubilizers such as polyethylene glycol dimethyl ether.
Als Lösungsmittel sind grundsätzlich Wasser sowie alle basenstabilen organischenWater and all base-stable organic solvents are basically used as solvents
Lösungsmittel geeignet. Bevorzugt werden aromatische Lösungsmittel wie Benzol, Toluol, Xylol, Chlorbenzol, Nitrobenzol oder Nitrotoluol sowie Dimethylsulfoxid; Dimethylformamid und aliphatische Kohlenwasserstoffe wie Ligroin, Cyclohexan, Pentan, Hexan, Heptan, Octan eingesetzt. Besonders bevorzugt wird ortbo-Nitrotoluol als Edukt und gleichzeitig als Lösungsmittel verwendet und im Uberschuss an ortbo-Nitrotoluol von 1 bis 40 Äquivalenten, ganz besonders von 5 bis 20 Äquivalenten, bezogen auf Acrylnitril, eingesetzt.Suitable solvent. Aromatic solvents such as benzene, toluene, xylene, chlorobenzene, nitrobenzene or nitrotoluene and dimethyl sulfoxide are preferred; Dimethylformamide and aliphatic hydrocarbons such as ligroin, cyclohexane, pentane, hexane, heptane, octane are used. Ortbo-nitrotoluene is particularly preferably used as starting material and at the same time as solvent, and an excess of ortbo-nitrotoluene of 1 to 40 equivalents, very particularly 5 to 20 equivalents, based on acrylonitrile, is used.
Die Cyclisierung von 4-(2-Nitrophenyl)-butyronitril zu 5-Nitro-3,4-dihydro-l- naphthylamin bzw. dem tautomeren 5-Nitro-3,4-dihydro-l(2H)-naphthylimin wird in Substanz oder in einem inerten Lösungsmittel in Gegenwart starker Säuren durchgeführt. Geeignete Lösungsmittel sind lineare, verzweigte oder cyclische aliphatische Kohlenwasserstoffe wie Ligroin oder Cyclohexan, Pentan, Hexan, Heptan, Octan so- wie aromatische Lösungsmittel wie Nitrotoluol. Bevorzugt wird in Substanz oder in ortbo-Nitrotoluol gearbeitet.The cyclization of 4- (2-nitrophenyl) butyronitrile to 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine is carried out in bulk or carried out in an inert solvent in the presence of strong acids. Suitable solvents are linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, pentane, hexane, heptane, octane and aromatic solvents such as nitrotoluene. It is preferred to work in bulk or in ortbo-nitrotoluene.
Geeignete Säuren sind starke Lewis- oder Bronstedsäuren wie z.B. Aluminium- chlorid, Bortrifluorid, Schwefelsäure, Phosphorsäure, Polyphosphorsäure, Phosphor- pentoxid, Methansulfonsäure, Trifluormethansulfonsäure, Trifluoressig-säure oderSuitable acids are strong Lewis or Bronsted acids such as e.g. Aluminum chloride, boron trifluoride, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or
Gemische aus Antimonpentafluorid und Fluorschwefelsäure. Es können auch Mischungen der Säuren eingesetzt werden.Mixtures of antimony pentafluoride and fluorosulfuric acid. Mixtures of the acids can also be used.
Die Säure wird im Allgemeinen in 0,1 bis 100 Mol-Äquivalenten, bezogen auf 4-(2- Nitrophenyl)-butyronitril, eingesetzt. Bevorzugt werden 0,5 bis 20 Äquivalente verwendet, besonders bevorzugt 1 bis 10 Äquivalente.The acid is generally used in 0.1 to 100 molar equivalents, based on 4- (2-nitrophenyl) butyronitrile. 0.5 to 20 equivalents are preferably used, particularly preferably 1 to 10 equivalents.
Die Reaktion wird im Allgemeinen bei Temperaturen von 0°C bis 200°C durchgeführt, bevorzugt zwischen 40°C bis 150°C , besonders bevorzugt zwischen 60°C und 110°C.The reaction is generally carried out at temperatures from 0 ° C. to 200 ° C., preferably between 40 ° C. to 150 ° C., particularly preferably between 60 ° C. and 110 ° C.
Vorzugsweise wird das in Schritt b) gebildete hydrolyseempfindliche Nitro-Imin und /oder Nitro-Enamin zunächst beispielsweise durch Hydrolyse zum Nitroketon 5- Nitro-3,4-dihydro-l(2H)-naphthalinon umgesetzt und das Nitroketon isoliert. Die Isolierung erfolgt beispielsweise durch Phasentrennung. Anschließend wird das Nitroketon in Schritt c) durch Umsetzung mit Ammoniak, vorzugsweise in Gegenwart von Ammomumsalzen wie Ammoniumchlorid, zum Nitro-Imin und/oder Nitro-Enamin zurückgebildet und anschließend aromatisiert. Die Aromatisierung findet dann bevorzugt in Ammoniak als Lösungsmittel statt.The hydrolysis-sensitive nitro-imine and / or nitro-enamine formed in step b) is preferably first reacted, for example by hydrolysis, to give the nitroketone 5-nitro-3,4-dihydro-l (2H) -naphthalinone and the nitroketone is isolated. The isolation takes place, for example, by phase separation. In step c), the nitroketone is then converted back to the nitroimine and / or nitroenamine by reaction with ammonia, preferably in the presence of ammonium salts such as ammonium chloride, and then aromatized. The aromatization then preferably takes place in ammonia as the solvent.
Die Aromatisierung bzw. Dehydrierung des Nitro-Enamins 5-Nitro-3,4-dihydro-l- naphthylamin bzw. des Nitro-Imins 5-Nitro-3,4-dihydro-l(2H)-naphthylimin zu 5- Nitro-1 -naphthylamin oder 5-Nitroso-l-naphthylamin oder einem Gemisch der Verbindungen wird, beispielsweise in einem inerten Lösungsmittel, in Gegenwart eines Katalysators durchgeführt. Dabei kann neben dem dehydrierten Produkt 5-Nitro-l- naphthylamin auch das formal durch Synproportionierung entstandene 5-Nitroso-l- naphthylamin entstehen. In Spuren entsteht auch 1,5-Naphthalindiamin. Die Produkte können in beliebigen Mischungsverhältnissen weiter verarbeitet werden. Geeignete Lösungsmittel sind Ammoniak und lineare, verzweigte oder cyclische aliphatische Kohlenwasserstoffe wie Ligroin oder Cyclohexan, sowie Acetonitril und aromatische Lösungsmittel wie Benzol, Toluol, Xylol, Nitrobenzol, Nitrotoluol oder Chlorbenzol. Die Aromatisierung kann auch in Abwesenheit eines Lösungsmittels durchgeführt werden.The aromatization or dehydrogenation of the nitro-enamine 5-nitro-3,4-dihydro-1-naphthylamine or the nitro-imine 5-nitro-3,4-dihydro-1 (2H) -naphthylimine to 5-nitro-1 -naphthylamine or 5-nitroso-l-naphthylamine or a mixture of the compounds is carried out, for example in an inert solvent, in the presence of a catalyst. In addition to the dehydrated product 5-nitro-1-naphthylamine, the 5-nitroso-1-naphthylamine formally formed by synproportionation can also be formed. 1,5-naphthalenediamine is also produced in traces. The products can be processed in any mixing ratio. Suitable solvents are ammonia and linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, and acetonitrile and aromatic solvents such as benzene, toluene, xylene, nitrobenzene, nitrotoluene or chlorobenzene. The flavoring can also be carried out in the absence of a solvent.
Geeignete Katalysatoren sind Dehydrierungskatalysatoren, die in der Literatur beschrieben sind (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10. Auflage 1997, S. 891, Kapitel „Dehydrierung", 1. Abschnitt; Ullmann's Encyclopedia of Industrial Chemistry, NCH Verlagsgesellschaft mbH, Weinheim, 5. Auflage 1989, Vol A13, Kapitel „Hydrogenation and Dehydrogenation", Unterkapitel 2. „De- hydrogenation", S. 494-497). Dazu gehören die Metalle der 8.-10. Gruppe desSuitable catalysts are dehydrogenation catalysts which are described in the literature (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 891, chapter "Dehydration", section 1; Ullmann's Encyclopedia of Industrial Chemistry, NCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989, Vol A13, chapter "Hydrogenation and Dehydrogenation", subsection 2. "Dehydrogenation", pp. 494-497). These include the metals of the 8th-10th group of the
Periodensystems (G. J. Leigh [Editor], Νomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 „Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), insbesondere Platin, Palladium, Ruthenium und Iridium, Eisen, Cobalt, Nickel und Kombinationen davon. Die Metalle können auch gemeinsam mit weiteren Metallen wie Lanthan, Scandium, Vanadium, Chrom, Molybdän, Wolfram, Mangan, Zinn, Zink, Kupfer, Silber oder Indium eingesetzt werden. Die genannten Metalle können dabei als reine Elemente, als Oxide, Sulfide, Halogenide, Carbide oder Nitride vorliegen oder aber kombiniert mit organischen Liganden eingesetzt werden. Als Liganden geeignet sind Kohlenwasserstoffverbindungen mit Donorgruppen wie beispielsweise Amine, Nitrile, Phosphine, Thiole, Thioether, Alkohole, Ether oderPeriodic table (GJ Leigh [Editor], omenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), In particular platinum , Palladium, ruthenium and iridium, iron, cobalt, nickel and combinations thereof. The metals can also be used together with other metals such as lanthanum, scandium, vanadium, chromium, molybdenum, tungsten, manganese, tin, Zinc, copper, silver or indium can be used. The metals mentioned can be present as pure elements, as oxides, sulfides, halides, carbides or nitrides or can be used in combination with organic ligands. Suitable ligands are hydrocarbon compounds with donor groups such as, for example, amines, nitriles, phosphines, thiols, thioethers, alcohols, ethers or
Carbonsäuren. Gegebenenfalls sind die Katalysatoren auf einem Trägermaterial aufgebracht. Geeignete Trägermaterialien sind Aktivkohle, Aluminiumoxid, Silicium- oxid, Zirkonoxid, Zinkoxid, Zeolithe.Carboxylic acids. The catalysts are optionally applied to a support material. Suitable carrier materials are activated carbon, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, zeolites.
Gegebenenfalls wird in Gegenwart eines Oxidationsmittels wie Sauerstoff oder Luft gearbeitet. Die Reaktion wird im Allgemeinen bei Temperaturen von 50°C bis 250°C durchgeführt, bevorzugt bei 100°C bis 200°C.If appropriate, work is carried out in the presence of an oxidizing agent such as oxygen or air. The reaction is generally carried out at temperatures from 50 ° C. to 250 ° C., preferably at 100 ° C. to 200 ° C.
Die Reduktion der Nitrogruppe zum Produkt 1,5-Naphthalindiamin geschieht durch Hydrierung in Gegenwart geeigneter Hydrierkatalysatoren.The nitro group is reduced to the product 1,5-naphthalenediamine by hydrogenation in the presence of suitable hydrogenation catalysts.
Als Hydrierkatalysatoren eignen sich für das erfindungsgemäße Verfahren praktisch alle heterogenen Katalysatoren, die als Hydrierkatalysatoren bekannt sind (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10. Auflage 1997, S. 1831, Kapitel „Hydrierung"; Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5. Auflage 1989, Vol A13, Kapitel „Hydrogenation and Dehydrogenation", Unterkapitel 1.2 „Catalysts", S. 488). Bevorzugte Katalysatoren sind die Metalle der 8.-10. Gruppe des Periodensystems (G. J. Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 „Groups ofPractically all heterogeneous catalysts known as hydrogenation catalysts are suitable as hydrogenation catalysts for the process according to the invention (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 1831, chapter "Hydrogenation"; Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989, Vol A13, chapter "Hydrogenation and Dehydrogenation", subsection 1.2 "Catalysts", p. 488). Preferred catalysts are the metals of the 8th-10th group of the periodic table (GJ Leigh [Editor ], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of
Elements in the Periodic Table and their Subdivision, p. 41-43.), Kupfer oder Chrom auf geeignetem Träger mit einem Metallgehalt von 0,01 bis 50 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Katalysators. Es können auch Katalysatoren eingesetzt werden, die eines oder mehrere der oben genannten Metalle enthalten. Bevorzugte Metalle sind insbesondere Platin, Palladium undElements in the Periodic Table and their Subdivision, p. 41-43.), Copper or chromium on a suitable carrier with a metal content of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total weight of the catalyst. Catalysts containing one or more of the metals mentioned above can also be used. Preferred metals are in particular platinum, palladium and
Rhodium, besonders bevorzugt sind Platin und Palladium. Weitere bevorzugte Katalysatoren sind Raney-Nickel und geträgerte Nickelkatalysatoren. Es können auch die obengenannten Metalle oder ihre Verbindungen in reiner Form als Feststoff eingesetzt werden. Als Beispiele für ein Metall in reiner Form seien Palladium- und Platinschwarz genannt.Rhodium, platinum and palladium are particularly preferred. More preferred Raney nickel and supported nickel catalysts are catalysts. It is also possible to use the above-mentioned metals or their compounds in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
Die Katalysatoren können in diskontinuierlichen Verfahrensvarianten in Mengen von 0,01 bis 50 Gew.-%, bezogen auf eingesetztes 5-Nitro- bzw. 5 -Nitroso-1 -naphthylamin verwendet werden, bevorzugt in Mengen von 0,01 bis 20 Gew.-%, besonders bevorzugt in Mengen von 0,01 bis 10 Gew.-%. Bei kontinuierlicher Durchführung der Reaktion, beispielsweise in einem Rührkessel mit pulverförmigen Katalysator oder in der Rieselphase am Festbettkatalysator, können Belastungen von 0,01 bis 500 g, bevorzugt 0,1 - 200 g, besonders bevorzugt 1 bis 100 g 5-Nitro- bzw. 5- Nitroso-1 -naphthylamin pro g Katalysator und Stunde eingestellt werden.In batch process variants, the catalysts can be used in amounts of 0.01 to 50% by weight, based on the 5-nitro- or 5-nitroso-1-naphthylamine used, preferably in amounts of 0.01 to 20% by weight. %, particularly preferably in amounts of 0.01 to 10% by weight. When the reaction is carried out continuously, for example in a stirred tank with powdered catalyst or in the trickle phase over the fixed bed catalyst, loads of from 0.01 to 500 g, preferably 0.1-200 g, particularly preferably 1 to 100 g of 5-nitro- or 5-nitroso-1-naphthylamine per g of catalyst per hour.
Die Reaktionstemperaturen betragen im Allgemeinen - 20°C bis 150°C, insbesondereThe reaction temperatures are generally from -20 ° C to 150 ° C, especially
-10°C bis 80°C; der Wasserstoffdruck liegt im Allgemeinen bei 0,1 bis 150 bar, insbesondere bei 0,5 bis 70 bar, ganz besonders bevorzugt bei 1 bis 50 bar.-10 ° C to 80 ° C; the hydrogen pressure is generally 0.1 to 150 bar, in particular 0.5 to 70 bar, very particularly preferably 1 to 50 bar.
Bevorzugt wird für die Aromatisierung und die anschließende Hydrierung der gleiche Katalysator verwendet, wobei die beiden Schritte in einem Reaktionsgefäß durchgeführt werden können.The same catalyst is preferably used for the aromatization and the subsequent hydrogenation, it being possible for the two steps to be carried out in one reaction vessel.
Alle Reaktionsschritte in dieser bevorzugten Ausführung des Verfahrens können kontinuierlich oder diskontinuierlich, beispielsweise in Rührkesselreaktoren oder Rohrreaktoren, durchgeführt werden.All reaction steps in this preferred embodiment of the process can be carried out continuously or batchwise, for example in stirred tank reactors or tubular reactors.
In einer zweiten bevorzugten Ausführung enthält das Verfahren zur Herstellung von 1,5-Naphthalindiamin die SchritteIn a second preferred embodiment, the process for the preparation of 1,5-naphthalenediamine contains the steps
a) Umsetzung von ortAo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitrophenyl)- butyronitril, b) Reduzieren des in Schritt a) gebildeten 4-(2-Nitrophenyl)-butyronitril zum 4- (2-Aminophenyl)-butyronitril,a) reaction of ortAo-nitrotoluene with acrylonitrile to 4- (2-nitrophenyl) - butyronitrile, b) reducing the 4- (2-nitrophenyl) butyronitrile formed in step a) to 4- (2-aminophenyl) butyronitrile,
c) Cyclisieren des in Schritt b) gebildeten 4-(2-Aminophenyl)-butyronitril zum Amino-Imin und/oder Amino-Enamin,c) cyclizing the 4- (2-aminophenyl) butyronitrile formed in step b) to the amino-imine and / or amino-enamine,
d) Aromatisieren des in Schritt c) gebildeten Amino-Imin und/oder Amino- Enamin zum 1,5-Naphthalindiamin.d) Flavoring the amino imine and / or amino enamine formed in step c) to give 1,5-naphthalenediamine.
4-(2-Nitrophenyl)-butyronitril wird aus ortΛo-Nitrotoluol und Acrylnitril analog zu Schritt a) der ersten bevorzugten Ausführung dargestellt.4- (2-nitrophenyl) butyronitrile is prepared from ortΛo-nitrotoluene and acrylonitrile analogously to step a) of the first preferred embodiment.
Diese Verbindung wird dann zu 4-(2-Aminophenyl)-butyronitril reduziert. Die Transformation kann durch Hydrierung in Gegenwart eines Hydrierkatalysators durchgeführt werden. Als Hydrierkatalysatoren eignen sich für das erfindungsgemäße Verfahren praktisch alle heterogenen Katalysatoren, die als Hydrierkatalysatoren bekannt sind (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10. Auflage 1997, S. 1831, Kapitel „Hydrierung"; Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5. Auflage 1989,This compound is then reduced to 4- (2-aminophenyl) butyronitrile. The transformation can be carried out by hydrogenation in the presence of a hydrogenation catalyst. Practically all heterogeneous catalysts known as hydrogenation catalysts are suitable as hydrogenation catalysts for the process according to the invention (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 1831, chapter "Hydrogenation"; Ullmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
Vol AI 3, Kapitel „Hydrogenation and Dehydrogenation", Unterkapitel 1.2 „Catalysts", S. 488). Bevorzugte Katalysatoren sind die Metalle der 8.-10. Gruppe des Periodensystems (G. J. Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 „Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Kupfer oder Chrom auf geeignetem Träger mit einem Metallgehalt von 0,01 bis 50 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Katalysators. Es können auch Katalysatoren eingesetzt werden, die eines oder mehrere der oben genannten Metalle enthalten. Bevorzugte Metalle sind insbesondere Platin, Palladium und Rhodium, besonders bevorzugt sind Platin und Palladium. Weitere bevorzugteVol AI 3, chapter "Hydrogenation and Dehydrogenation", subsection 1.2 "Catalysts", p. 488). Preferred catalysts are the metals from 8th to 10th Group of the Periodic Table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Copper or chromium on a suitable carrier with a metal content of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total weight of the catalyst. Catalysts containing one or more of the metals mentioned above can also be used. Preferred metals are in particular platinum, palladium and rhodium, platinum and palladium are particularly preferred. More preferred
Katalysatoren sind Raney-Nickel und geträgerte Nickelkatalysatoren. Es können auch die obengenannten Metalle oder ihre Verbindungen in reiner Form als Feststoff eingesetzt werden. Als Beispiele für ein Metall in reiner Form seien Palladium- und Platinschwarz genannt.Raney nickel and supported nickel catalysts are catalysts. It can the abovementioned metals or their compounds can also be used in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
In einer weiteren Ausführung kann die Nitrogruppe durch Umsatz mit Metallhydriden, gegebenenfalls unter Zusatz von Additiven, oder durch Umsatz mit Nichtedelmetallen wie Eisen reduziert werden.In a further embodiment, the nitro group can be reduced by conversion with metal hydrides, if appropriate with the addition of additives, or by conversion with base metals such as iron.
Bevorzugte Metallhydride sind Natriumborhydrid, Kaliumborhydrid, Lithiumbor- hydrid, Natriumcyanoborhydrid, Lithiumcyanoborhydrid, Lithiumaluminiumhydrid und Diisobutylaluminiumhydrid. Geeignete Additive sind Nickelsalze, Tellurverbindungen und Antimonverbindungen.Preferred metal hydrides are sodium borohydride, potassium borohydride, lithium borohydride, sodium cyanoborohydride, lithium cyanoborohydride, lithium aluminum hydride and diisobutyl aluminum hydride. Suitable additives are nickel salts, tellurium compounds and antimony compounds.
Bevorzugte Nichtedelmetalle für die Umsetzung unter sauren Bedingungen sind Eisen, Zink, Magnesium, Aluminium und Zinn, besonders bevorzugt sind Eisen undPreferred base metals for the reaction under acidic conditions are iron, zinc, magnesium, aluminum and tin, iron and are particularly preferred
Zink. Geeignete Lösungsmittel hierfür sind Wasser oder Alkohole oder Alkohol- Mischungen, die mit Säuren wie Essigsäure, Salzsäure, Schwefelsäure, Ammoniumchlorid angesäuert werden. Geeignete Alkohole sind Methanol, Ethanol, n-Propanol, iso-Propanol, n-Butanol, sec.-Butanol, tert.-Butanol oder Cyclohexanol. Besonders bevorzugt sind Methanol und Ethanol.Zinc. Suitable solvents for this are water or alcohols or alcohol mixtures which are acidified with acids such as acetic acid, hydrochloric acid, sulfuric acid, ammonium chloride. Suitable alcohols are methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol or cyclohexanol. Methanol and ethanol are particularly preferred.
Die Cyclisierung zu 5-Amino-3,4-dihydro-l -naphthylamin bzw. dem Imintautomeren 5-Amino-3,4-dihydro-l(2H)-naphthylimin wird analog der Cyclisierung der Nitroverbindung (Schritt b der ersten bevorzugten Ausführung) durchgeführt. Jedoch muss wegen der Basizität der Aminogruppe in 4-(2-The cyclization to 5-amino-3,4-dihydro-l-naphthylamine or the imine tautomer 5-amino-3,4-dihydro-l (2H) -naphthylimine is carried out analogously to the cyclization of the nitro compound (step b of the first preferred embodiment) carried out. However, because of the basicity of the amino group in 4- (2-
Aminophenyl)-butyronitril mindestens ein Mol-Äquivalent Säure (bezogen auf 4-(2- Aminophenyl)-butyronitril) zusätzlich zugegeben werden. Bevorzugt werden 1 ,5 bis 21 Äquivalente Säure verwendet, besonders bevorzugt 1,5 bis 11 Äquivalente.Aminophenyl) butyronitrile at least one molar equivalent of acid (based on 4- (2-aminophenyl) butyronitrile) are additionally added. 1.5 to 21 equivalents of acid are preferably used, particularly preferably 1.5 to 11 equivalents.
Die Reaktion wird in Substanz oder in einem inerten Lösungsmittel in Gegenwart starker Säuren durchgeführt. Geeignete Lösungsmittel sind lineare, verzweigte oder cyclische aliphatische Kohlenwasserstoffe wie Ligroin oder Cyclohexan, Pentan, Hexan, Heptan, Octan sowie aromatische Lösungsmittel wie Nitrotoluol. Bevorzugt wird in Substanz oder in ort/io-Nitrotoluol gearbeitet.The reaction is carried out in bulk or in an inert solvent in the presence of strong acids. Suitable solvents are linear, branched or Cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, pentane, hexane, heptane, octane and aromatic solvents such as nitrotoluene. Is preferably carried out in bulk or in place / io-nitrotoluene.
Geeignete Säuren sind starke Lewis- oder Bronstedsäuren wie z.B. Aluminiumchlorid, Bortrifluorid, Schwefelsäure, Phosphorsäure, Polyphosphorsäure, Phosphor- pentoxid, Methansulfonsäure, Trifluormethansulfonsäure, Trifluoressig-säure oder Gemische aus Antimonpentafluorid und Fluorschwefelsäure. Es können auch Mischungen der Säuren eingesetzt werden.Suitable acids are strong Lewis or Bronsted acids such as e.g. Aluminum chloride, boron trifluoride, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or mixtures of antimony pentafluoride and fluorosulfuric acid. Mixtures of the acids can also be used.
Die Reaktion wird im Allgemeinen bei Temperaturen von 0°C bis 150°C durchgeführt, bevorzugt zwischen 60°C und 110°C.The reaction is generally carried out at temperatures from 0 ° C. to 150 ° C., preferably between 60 ° C. and 110 ° C.
Nach der Cyclisierung wird das Reaktionsgemisch üblicherweise neutralisiert. Dies geschieht beispielsweise durch die Zugabe von Natronlauge.After the cyclization, the reaction mixture is usually neutralized. This is done, for example, by adding sodium hydroxide solution.
Vorzugsweise wird das in Schritt c) gebildete Amino-Imin und / oder Amino-Enamin zunächst, beispielsweise durch Hydrolyse, zum Aminoketon 5-Amino-3,4-dihydro- l(2H)-naphthalinon umgesetzt und das Aminoketon isoliert. Die Isolierung erfolgt beispielsweise durch Phasentrennung. Anschließend wird das Aminoketon inThe amino-imine and / or amino-enamine formed in step c) is preferably first reacted, for example by hydrolysis, to give the amino ketone 5-amino-3,4-dihydro-l (2H) -naphthalinone and the amino ketone is isolated. The isolation takes place, for example, by phase separation. Then the amino ketone is in
Schritt d) durch Umsetzung mit Ammoniak, vorzugsweise in Gegenwart von Ammoniumchlorid, zum Amino-Imin und / oder Amino-Enamin zurückgebildet und anschließend aromatisiert. Die Aromatisierung findet dann bevorzugt in Ammoniak statt.Step d) is converted to the amino-imine and / or amino-enamine by reaction with ammonia, preferably in the presence of ammonium chloride, and then flavored. The aromatization then preferably takes place in ammonia.
Die Aromatisierung von 5-Amino-3,4-dihydro-l -naphthylamin bzw. dem Imintautomeren 5-Amino-3,4-dihydro-l(2H)-naphthylimin zu 1,5-Naphthalindiamin wird analog der Aromatisierung der Nitroverbindungen 5-Nitro-3,4-dihydro-l -naphthylamin bzw. 5-Nitro-3,4-dihydro-l(2H)-naphthylimin (Schritt c) der ersten bevor- zugten Ausführung) durchgeführt. Die Reaktion wird in einem inerten Lösungsmittel in Gegenwart eines Katalysators durchgeführt. Geeignete Lösungsmittel sind Ammoniak und lineare, verzweigte oder cyclische aliphatische Kohlenwasserstoffe wie Ligroin oder Cyclohexan, sowie Acetonitril und aromatische Lösungsmittel wie Benzol, Toluol, Xylol, Nitrobenzol, Nitrotoluol oder Chlorbenzol.The aromatization of 5-amino-3,4-dihydro-l-naphthylamine or the imine tautomer 5-amino-3,4-dihydro-l (2H) -naphthylimine to 1,5-naphthalenediamine is carried out analogously to the aromatization of the nitro compounds 5- Nitro-3,4-dihydro-1-naphthylamine or 5-nitro-3,4-dihydro-1 (2H) -naphthylimine (step c) of the first preferred embodiment). The reaction is carried out in an inert solvent in the presence of a catalyst. Suitable solvents are ammonia and linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, and acetonitrile and aromatic solvents such as benzene, toluene, xylene, nitrobenzene, nitrotoluene or chlorobenzene.
Geeignete Katalysatoren sind Dehydrierungskatalysatoren, die in der Literatur beschrieben sind (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10. Auflage 1997, S. 891, Kapitel „Dehydrierung", 1. Abschnitt; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5. Auflage 1989,Suitable catalysts are dehydrogenation catalysts which are described in the literature (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 891, chapter "Dehydration", section 1; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
Vol AI 3, Kapitel „Hydrogenation and Dehydrogenation", Unterkapitel 2. „Dehydro- genation", S. 494-497). Dazu gehören die Metalle der 8.-10. Gruppe des Periodensystems (G. J. Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommen- dations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 „Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), insbesondere Platin,Vol AI 3, chapter "Hydrogenation and Dehydrogenation", subsection 2. "Dehydrogenation", pp. 494-497). These include the metals of the 8th-10th Group of the Periodic Table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43. ), especially platinum,
Palladium, Ruthenium und Iridium, Eisen, Cobalt, Nickel und Kombinationen davon. Die Metalle können auch gemeinsam mit weiteren Metallen wie Lanthan, Scandium, Vanadium, Chrom, Molybdän, Wolfram, Mangan, Zinn, Zink, Kupfer, Silber oder Indium eingesetzt werden. Die genannten Metalle können dabei als reine Elemente, als Oxide, Sulfide, Halogenide, Carbide oder Nitride vorliegen oder aber kombiniert mit organischen Liganden eingesetzt werden. Als Liganden geeignet sind Kohlenwasserstoffverbindungen mit Donorgruppen wie beispielsweise Amine, Nitrile, Phosphine, Thiole, Thioether, Alkohole, Ether oder Carbonsäuren. Gegebenenfalls sind die Katalysatoren auf einem Trägermaterial aufgebracht. Geeignete Träger- materialien sind Aktivkohle, Aluminiumoxid, Siliciumoxid, Zirkonoxid, Zinkoxid,Palladium, ruthenium and iridium, iron, cobalt, nickel and combinations thereof. The metals can also be used together with other metals such as lanthanum, scandium, vanadium, chromium, molybdenum, tungsten, manganese, tin, zinc, copper, silver or indium. The metals mentioned can be present as pure elements, as oxides, sulfides, halides, carbides or nitrides or can be used in combination with organic ligands. Suitable ligands are hydrocarbon compounds with donor groups such as amines, nitriles, phosphines, thiols, thioethers, alcohols, ethers or carboxylic acids. The catalysts are optionally applied to a support material. Suitable carrier materials are activated carbon, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide,
Zeolithe.Zeolites.
Gegebenenfalls wird in Gegenwart eines Oxidationsmittels wie Sauerstoff oder Luft gearbeitet. Die Reaktion wird im Allgemeinen bei Temperaturen von 50°C bis 250°C durchgeführt, bevorzugt bei 100°C bis 200°C.If appropriate, work is carried out in the presence of an oxidizing agent such as oxygen or air. The reaction is generally carried out at temperatures from 50 ° C. to 250 ° C., preferably at 100 ° C. to 200 ° C.
Alle Reaktionsschritte in dieser bevorzugten Ausführung des Verfahrens können kontinuierlich oder diskontinuierlich, beispielsweise in Rührkesselreaktoren oderAll reaction steps in this preferred embodiment of the process can be carried out continuously or batchwise, for example in stirred tank reactors or
Rohrreaktoren, durchgeführt werden.Tube reactors are carried out.
In einer dritten bevorzugten Ausführung enthält das Verfahren zur Herstellung von 1,5-Naphthalindiamin die SchritteIn a third preferred embodiment, the process for the preparation of 1,5-naphthalenediamine contains the steps
a) Umsetzung von ort/zo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitrophenyl)- butyronitril,a) reaction of ort / zo-nitrotoluene with acrylonitrile to give 4- (2-nitrophenyl) butyronitrile,
b) Cyclisierung des in Schritt a) gebildeten 4-(2-Nitrophenyl)-butyronitril zum Nitro-Imin und/oder Nitro-Enamin,b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give the nitro-imine and / or nitro-enamine,
c) Reduzieren des in Schritt b) gebildeten Nitro-Imin und/oder Nitro-Enamin zum Amino-Imin und /oder Amino-Enamin,c) reducing the nitro-imine and / or nitro-enamine formed in step b) to the amino-imine and / or amino-enamine,
d) Aromatisieren des in Schritt c) gebildeten Amino-Imin und/oder Amino-d) flavoring the amino imine and / or amino
Enamin zum 1,5-Naphthalindiamin.Enamine to 1,5-naphthalenediamine.
4-(2-Nitrophenyl)-butyronitril wird aus ortbo-Nitrotoluol und Acrylnitril analog zu Schritt a) der ersten bevorzugten Ausführung dargestellt.4- (2-nitrophenyl) butyronitrile is prepared from ortbo-nitrotoluene and acrylonitrile analogously to step a) of the first preferred embodiment.
Diese Verbindung wird dann zu 5-Nitro-3,4-dihydro-l-naphthylamin bzw. dem tautomeren 5-Nitro-3,4-dihydro-l(2H)-naphthylimin analog zu Schritt b) der ersten bevorzugten Ausführung cyclisiert. Die Verbindung 5-Nitro-3,4-dihydro-l -naphthylamin bzw. das tautomere 5-Nitro- 3,4-dihydro-l(2H)-naphthylimin wird nun zu 5 -Amino-3,4-dihydro-l -naphthylamin bzw. dem tautomeren 5-Amino-3,4-dihydro-l(2H)-naphthylimin reduziert.This compound is then cyclized to 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine analogously to step b) of the first preferred embodiment. The compound 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine is now converted into 5-amino-3,4-dihydro-l - naphthylamine or the tautomeric 5-amino-3,4-dihydro-l (2H) -naphthylimine reduced.
Die Transformation kann durch Hydrierung in Gegenwart eines Hydrierkatalysators durchgeführt werden. Als Hydrierkatalysatoren eignen sich für das erfindungsgemäße Verfahren praktisch alle heterogenen Katalysatoren, die als Hydrierkatalysatoren bekannt sind (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10. Auflage 1997, S. 1831, Kapitel „Hydrierung"; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5. Auflage 1989,The transformation can be carried out by hydrogenation in the presence of a hydrogenation catalyst. Suitable hydrogenation catalysts for the process according to the invention are virtually all heterogeneous catalysts known as hydrogenation catalysts (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 1831, chapter "Hydrogenation"; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
Vol AI 3, Kapitel „Hydrogenation and Dehydrogenation", Unterkapitel 1.2 „Catalysts", S. 488). Bevorzugte Katalysatoren sind die Metalle der 8.-10. Gruppe des Periodensystems (G. J. Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 „Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Kupfer oder Chrom auf geeignetem Träger mit einem Metallgehalt von 0,01 bis 50 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Katalysators. Es können auch Katalysatoren eingesetzt werden, die eines oder mehrere der oben genannten Metalle enthalten. Bevorzugte Metalle sind insbesondere Platin, Palladium und Rhodium, besonders bevorzugt sind Platin und Palladium. Weitere bevorzugteVol AI 3, chapter "Hydrogenation and Dehydrogenation", subsection 1.2 "Catalysts", p. 488). Preferred catalysts are the metals from 8th to 10th Group of the Periodic Table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Copper or chromium on a suitable carrier with a metal content of 0.01 to 50% by weight, preferably 0.1 to 20% by weight, based on the total weight of the catalyst. Catalysts containing one or more of the metals mentioned above can also be used. Preferred metals are in particular platinum, palladium and rhodium, platinum and palladium are particularly preferred. More preferred
Katalysatoren sind Raney-Nickel und geträgerte Nickelkatalysatoren. Es können auch die oben genannten Metalle oder ihre Verbindungen in reiner Form als Feststoff eingesetzt werden. Als Beispiele für ein Metall in reiner Form seien Palladium- und Platinschwarz genannt.Raney nickel and supported nickel catalysts are catalysts. It is also possible to use the metals mentioned above or their compounds in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
Die abschließende Aromatisierung von 5-Amino-3,4-dihydro-l -naphthylamin bzw. dem tautomeren 5-Amino-3,4-dihydro-l(2H)-naphthylimin zu 1,5-Naphthalindiamin wird analog zu Schritt d) der zweiten bevorzugten Ausführung durchgeführt. Alle Reaktionsschritte in dieser bevorzugten Ausführung des Verfahrens können kontinuierlich oder diskontinuierlich, beispielsweise in Rührkesselreaktoren oder Rohrreaktoren, durchgeführt werden.The final aromatization of 5-amino-3,4-dihydro-l-naphthylamine or the tautomeric 5-amino-3,4-dihydro-l (2H) -naphthylimine to 1,5-naphthalenediamine is analogous to step d) second preferred embodiment performed. All reaction steps in this preferred embodiment of the process can be carried out continuously or batchwise, for example in stirred tank reactors or tubular reactors.
In einer vierten bevorzugten Ausführung enthält des Verfahren zur Herstellung vonIn a fourth preferred embodiment, the process for the production of
1,5-Naphthalindiamin die Schritte1,5-naphthalenediamine the steps
a) Umsetzung von ortΛo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitrophenyl)- butyronitril,a) reaction of ortΛo-nitrotoluene with acrylonitrile to 4- (2-nitrophenyl) - butyronitrile,
b) Cyclisierung des in Schritt a) gebildeten 4-(2-Nitrophenyl)-butyronitril zum Nitro-Imin und / oder Nitro-Enamin, Umsetzung zum Nitroketon 5-Nitro-3,4- dihydro-l(2H)-naphthalinon, sowie Isolierung des Nitroketons,b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give nitro-imine and / or nitro-enamine, conversion to nitro-ketone 5-nitro-3,4-dihydro-1 (2H) -naphthalenone, and Isolation of nitroketone,
c) Reduzieren des in Schritt b) gebildeten Nitroketons zum Aminoketon 5-c) reducing the nitroketone formed in step b) to the aminoketone 5-
Amino-3 ,4-dihydro- 1 (2H)-naphthalinon,Amino-3,4-dihydro-1 (2H) -naphthalenone,
d) Überführen des in Schritt c) gebildeten Aminoketons zum Amino-Imin und /oder Amino-Enamin und Aromatisieren zum 1,5-Naphthalindiamin.d) converting the amino ketone formed in step c) to the amino-imine and / or amino-enamine and aromatizing to the 1,5-naphthalenediamine.
4-(2-Nitrophenyl)-butyronitril wird aus ortbo-Nitrotoluol und Acrylnitril analog zu Schritt a) der ersten bevorzugten Ausführung dargestellt.4- (2-nitrophenyl) butyronitrile is prepared from ortbo-nitrotoluene and acrylonitrile analogously to step a) of the first preferred embodiment.
4-(2-Nitrophenyl)-butyronitril wird dann zu 5-Nitro-3,4-dihydro-l -naphthylamin bzw. dem tautomeren 5-Nitro-3,4-dihydro-l(2H)-naphthylimin analog zu Schritt b) der ersten bevorzugten Ausführung cyclisiert. Das 5-Nitro-3,4-dihydro-l -naphthylamin und oder 5-Nitro-3,4-dihydro-l(2H)-naphthylimin wird anschließend, beispielsweise durch Hydrolyse, zum Nitroketon 5-Nitro-3,4-dihydro-l(2H)-naphthali- non umgesetzt und das Nitroketon isoliert. Die Isolierung des Nitroketons erfolgt beispielsweise durch Phasentrennung. Die Verbindung 5-Nitro-3,4-dihydro-l(2H)-naphthalinon wird nun zu 5-Amino-3,4- dihydro- 1 (2H)-naphthalinon reduziert.4- (2-nitrophenyl) butyronitrile is then converted to 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-l (2H) -naphthylimine analogously to step b) the first preferred embodiment cyclized. The 5-nitro-3,4-dihydro-l-naphthylamine and or 5-nitro-3,4-dihydro-l (2H) -naphthylimine is then, for example by hydrolysis, to the nitroketone 5-nitro-3,4-dihydro -l (2H) -naphthalenone implemented and the nitroketone isolated. The nitroketone is isolated, for example, by phase separation. The compound 5-nitro-3,4-dihydro-l (2H) -naphthalinone is now reduced to 5-amino-3,4-dihydro-1 (2H) -naphthalinone.
Die Transformation kann durch Hydrierung in Gegenwart eines Hydrierkatalysators durchgeführt werden. Als Hydrierkatalysatoren eignen sich für das erfindungsgemäße Verfahren praktisch alle heterogenen Katalysatoren, die als Hydrierkatalysatoren bekannt sind (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10. Auflage 1997, S. 1831, Kapitel „Hydrierung"; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5. Auflage 1989, Vol AI 3, Kapitel „Hydrogenation and Dehydrogenation", Unterkapitel 1.2The transformation can be carried out by hydrogenation in the presence of a hydrogenation catalyst. Suitable hydrogenation catalysts for the process according to the invention are virtually all heterogeneous catalysts known as hydrogenation catalysts (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 1831, chapter "Hydrogenation"; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989, Vol AI 3, chapter "Hydrogenation and Dehydrogenation", subsection 1.2
„Catalysts", S. 488). Bevorzugte Katalysatoren sind die Metalle der 8.-10. Gruppe des Periodensystems (G. J. Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 „Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), oder Kupfer und/oder Chrom auf geeignetem Träger mit einem Metallgehalt von 0,01 bis"Catalysts", p. 488). Preferred catalysts are the metals of the 8th-10th group of the periodic table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapters 1-3.8.1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), Or copper and / or chrome on a suitable carrier with a metal content of 0.01 to
50 Gew.-%, bevorzugt 0,1 bis 20 Gew.-%, bezogen auf das Gesamtgewicht des Katalysators. Es können auch Katalysatoren eingesetzt werden, die eines oder mehrere der oben genannten Metalle enthalten. Bevorzugte Metalle sind insbesondere Platin, Palladium und Rhodium, besonders bevorzugt sind Platin und Palladium. Weitere bevorzugte Katalysatoren sind Raney-Nickel und geträgerte Nickelkatalysatoren. Es können auch die obengenannten Metalle oder ihre Verbindungen in reiner Form als Feststoff eingesetzt werden. Als Beispiele für ein Metall in reiner Form seien Palladium- und Platinschwarz genannt.50 wt .-%, preferably 0.1 to 20 wt .-%, based on the total weight of the catalyst. Catalysts containing one or more of the metals mentioned above can also be used. Preferred metals are in particular platinum, palladium and rhodium, platinum and palladium are particularly preferred. Other preferred catalysts are Raney nickel and supported nickel catalysts. It is also possible to use the above-mentioned metals or their compounds in pure form as a solid. Examples of a metal in pure form are palladium and platinum black.
Anschließend wird das in der Reduktion erzeugte 5-Amino-3,4-dihydro-l(2H)- naphthalinon durch Umsetzung mit Ammoniak, vorzugsweise in Gegenwart von Ammomumchlorid, zum 5 -Amino-3,4-dihydro-l -naphthylamin und/oder 5-Amino- 3 ,4-dihy dro- 1 (2H)-naphthylimin umgesetzt. Die abschließende Aromatisierung von 5-Amino-3,4-dihydro-l-naphthylamin bzw. dem tautomeren 5-Amino-3,4-dihydro-l(2H)-naphthylimin zu 1,5-Naphthalindiamin wird analog zu Schritt d) der zweiten bevorzugten Ausführung durchgeführt.The 5-amino-3,4-dihydro-l (2H) -naphthalinone produced in the reduction is then converted to 5-amino-3,4-dihydro-l -naphthylamine and / by reaction with ammonia, preferably in the presence of ammonium chloride. or 5-amino-3, 4-dihy dro-1 (2H) -naphthylimine. The final aromatization of 5-amino-3,4-dihydro-l-naphthylamine or the tautomeric 5-amino-3,4-dihydro-l (2H) -naphthylimine to 1,5-naphthalenediamine is analogous to step d) second preferred embodiment performed.
Die Umsetzung des 5-Amino-3,4-dihydro-l(2H)-naphthalinon zum 5-Amino-3,4- dihydro-1 -naphthylamin und/oder 5-Amino-3,4-dihydro-l(2H)-naphthylimin und die anschließende Aromatisierung werden bevorzugt in einem Reaktionsgefäß durchgeführt.The conversion of 5-amino-3,4-dihydro-1 (2H) -naphthalenone to 5-amino-3,4-dihydro-1-naphthylamine and / or 5-amino-3,4-dihydro-1 (2H) -naphthylimine and the subsequent aromatization are preferably carried out in a reaction vessel.
Alle Reaktionsschritte in dieser bevorzugten Ausführung des Verfahrens können kontinuierlich oder diskontinuierlich, beispielsweise in Rührkesselreaktoren oder Rohrreaktoren, durchgeführt werden.All reaction steps in this preferred embodiment of the process can be carried out continuously or batchwise, for example in stirred tank reactors or tubular reactors.
Die erfindungsgemäßen Verfahren auf Basis von ortbo-Nitrotoluol und Acrylnitril lassen sich in idealisierter Weise am folgenden Reaktionsschema verdeutlichen: The processes according to the invention based on ortbo-nitrotoluene and acrylonitrile can be illustrated in an idealized manner using the following reaction scheme:
4-(2-Aminophenyl)- 5-Amino-3,4-dihydro- 5-Amino-3,4-dihydro- 1 ,5-Naphthalindiamin butyronitril 1 -naphthylamin 1 (2H)-naphthalinon bzw.4- (2-aminophenyl) -5-amino-3,4-dihydro-5-amino-3,4-dihydro-1,5-naphthalenediamine butyronitrile 1 -naphthylamine 1 (2H) -naphthalinone or
5-Amino-3,4-dihydro- 1(2H)-naphthylimin5-amino-3,4-dihydro-1 (2H) -naphthylimine
Kat. Cat.
- 16b -- 16b -
In einer fünften bevorzugten Ausführung enthält das Verfahren zur Herstellung von 1,5-Naphthalindiamin die SchritteIn a fifth preferred embodiment, the process for making 1,5-naphthalenediamine includes the steps
ERSATZBLAπ (REGEL 26) - 17 -REPLACEMENT BLAπ (RULE 26) - 17 -
a) Umsetzung von ortAo-Nitrotoluol mit einem Acrylsäureester oder Acrylsäureamid zum 4-(2-Nitrophenyl)-buttersäureester bzw. 4-(2- Nitrophenyl)-buttersäureamid,a) reaction of ortAo-nitrotoluene with an acrylic acid ester or acrylic acid amide to give 4- (2-nitrophenyl) butyric acid ester or 4- (2-nitrophenyl) butyric acid amide,
b) Cyclisierung des in Schritt a) gebildeten Buttersäureesters bzw. des Buttersäureamids zum 5-Nitro-3,4-dihydro-l(2H)-naphthalinon,b) cyclization of the butyric acid ester or butyric acid amide formed in step a) to give 5-nitro-3,4-dihydro-l (2H) -naphthalinone,
c) Aminierung des in Schritt b) gebildeten 5-Nitro-3,4-dihydro-l(2H)- naphthalinon zu 5 -Nitro-3,4-dihydro-l -naphthylamin bzw. dem tautomeren 5-c) Amination of the 5-nitro-3,4-dihydro-l (2H) -naphthalinone formed in step b) to 5 -nitro-3,4-dihydro-l -naphthylamine or the tautomeric 5-
Nitro-3,4-dihydro- 1 (2H)-naphthylimin,Nitro-3,4-dihydro-1 (2H) -naphthylimine,
d) Aromatisierung des in Schritt c) gebildeten 5 -Nitro-3,4-dihydro-l -naphthylamin bzw. des tautomeren 5-Nitro-3,4-dihydro-l(2H)-naphthylimin zu 5- Nitro-1 -naphthylamin und oder 5-Nitroso-l -naphthylamin,d) aromatization of the 5-nitro-3,4-dihydro-1-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-1 (2H) -naphthylamine to 5-nitro-1-naphthylamine and or 5-nitroso-1-naphthylamine,
e) Hydrieren des in Schritt d) gebildeten 5-Nitro-l -naphthylamin und / oder 5- Nitroso-1 -naphthylamin zu 1,5-Naphthalindiamin.e) hydrogenating the 5-nitro-1-naphthylamine and / or 5-nitroso-1-naphthylamine formed in step d) to 1,5-naphthalenediamine.
4-(2-Nitrophenyl)-buttersäureester bzw. 4-(2-Nitrophenyl)-buttersäureamide werden aus ortbo-Nitrotoluol und Acrylsäureestern bzw. Acrylsäureamiden bevorzugt bei Temperaturen von -10°C bis 100°C hergestellt. Besonders bevorzugt arbeitet man bei 20°C bis 75°C, ganz besonders bevorzugt bei Temperaturen von 30°C bis 60°C.4- (2-nitrophenyl) butyric acid esters or 4- (2-nitrophenyl) butyric acid amides are preferably prepared from ortbo-nitrotoluene and acrylic acid esters or acrylic acid amides at temperatures from -10 ° C. to 100 ° C. It is particularly preferred to work at 20 ° C. to 75 ° C., very particularly preferably at temperatures from 30 ° C. to 60 ° C.
Die Reaktion wird basenkatalysiert durchgeführt. Als Basen können Oxide,The reaction is carried out under base catalysis. Oxides,
Hydroxide und Carbonate von Lithium, Natrium, Kalium, Rubidium, Cäsium, Magnesium, Calcium, Strontium, Barium oder Aluminium sowie Mischungen daraus eingesetzt werden. Besonders geeignet sind Natrium- und Kaliumhydroxid. In einer bevorzugten Ausführung werden die wässrigen Lösungen in Kombination mit einem Phasentransferkatalysator eingesetzt. Solche Phasentransferkatalysatoren sind z.B. quartäre Ammoniumsalze. Geeignete Ammoniumverbindungen sind Tetraalkyl- - 18 -Hydroxides and carbonates of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium or aluminum and mixtures thereof can be used. Sodium and potassium hydroxide are particularly suitable. In a preferred embodiment, the aqueous solutions are used in combination with a phase transfer catalyst. Such phase transfer catalysts are, for example, quaternary ammonium salts. Suitable ammonium compounds are tetraalkyl - 18 -
Chlorid, Trioctylammonium-Chlorid, Tetrabutylammonium-Chlorid oder Tetrabutyl- ammonium-Hydrogensulfat. Ebenso geeignet ist die Verwendung von entsprechenden Tertaalkyl- bzw. Tetraaryl-Phosphoniumsalzen wie Tetramethylphos- phonium-Bromid und Tetraphenylphosphonium-Bromid sowie die Verwendung von Löslichkeitsvermittlem wie Polyethylenglycoldimethylethern.Chloride, trioctylammonium chloride, tetrabutylammonium chloride or tetrabutylammonium hydrogen sulfate. Likewise suitable is the use of corresponding tertaalkyl or tetraaryl phosphonium salts such as tetramethylphosphonium bromide and tetraphenylphosphonium bromide and the use of solubilizers such as polyethylene glycol dimethyl ethers.
Als Lösungsmittel sind grundsätzlich Wasser sowie alle basenstabilen organischen Lösungsmittel geeignet. Bevorzugt werden aromatische Lösungsmittel wie Benzol, Toluol, Xylol, Chlorbenzol, Nitrobenzol oder Nitrotoluol sowie Dimethylsulfoxid, Dimethylformamid und aliphatische Kohlenwasserstoffe wie Ligroin, Cyclohexan,Water and all base-stable organic solvents are generally suitable as solvents. Aromatic solvents such as benzene, toluene, xylene, chlorobenzene, nitrobenzene or nitrotoluene and dimethyl sulfoxide, dimethylformamide and aliphatic hydrocarbons such as ligroin, cyclohexane are preferred.
Pentan, Hexan, Heptan, Octan eingesetzt.Pentane, hexane, heptane, octane are used.
Besonders bevorzugt wird ortbo-Nitrotoluol als Edukt und gleichzeitig als Lösungsmittel verwendet und im Uberschuss an ortΛo-Nitrotoluol von 1 bis 40 Äquivalenten, ganz besonders von 5 bis 20 Äquivalenten, bezogen auf das Acrylsäurederivat, eingesetzt.Ortbo-nitrotoluene is particularly preferably used as starting material and at the same time as solvent, and an excess of ortΛo-nitrotoluene of 1 to 40 equivalents, very particularly 5 to 20 equivalents, based on the acrylic acid derivative, is used.
Die Cyclisierung von 4-(2-Nitrophenyl)-buttersäureestern bzw. 4-(2-Nitrophenyl)- buttersäureamiden zu 5-Nitro-3,4-dihydro-l(2H)-naphthalinon wird in Substanz oder in einem inerten Lösungsmittel in Gegenwart starker Säuren durchgeführt. GeeigneteThe cyclization of 4- (2-nitrophenyl) butyric acid esters or 4- (2-nitrophenyl) butyric acid amides to 5-nitro-3,4-dihydro-l (2H) -naphthalinone is carried out in bulk or in an inert solvent in the presence strong acids. suitable
Lösungsmittel sind lineare, verzweigte oder cyclische aliphatische Kohlenwasserstoffe wie Ligroin oder Cyclohexan, Pentan, Hexan, Heptan, Octan sowie aromatische Lösungsmittel wie Nitrotoluol. Bevorzugt wird in Substanz oder in σrtbo-Nitrotoluol gearbeitet.Solvents are linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, pentane, hexane, heptane, octane and aromatic solvents such as nitrotoluene. It is preferred to work in bulk or in σrtbo nitrotoluene.
Geeignete Säuren sind starke Lewis- oder Bronstedsäuren wie z.B. Aluminiumchlorid, Bortrifluorid, Schwefelsäure, Phosphorsäure, Polyphosphorsäure, Phosphor- pentoxid, Methansulfonsäure, Trifluormethansulfonsäure, Trifluoressig-säure oder Gemische aus Antimonpentafluorid und Fluorschwefelsäure. Es können auch Mischungen dieser Säuren eingesetzt werden. Bevorzugt wird Schwefelsäure oderSuitable acids are strong Lewis or Bronsted acids such as e.g. Aluminum chloride, boron trifluoride, sulfuric acid, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or mixtures of antimony pentafluoride and fluorosulfuric acid. Mixtures of these acids can also be used. Sulfuric acid or is preferred
Phosphorsäure eingesetzt. - 19 -Phosphoric acid used. - 19 -
Die Säure wird im Allgemeinen in 0,1 bis 100 Mol-Äquivalenten, bezogen auf 4-(2- Nitrophenyl)-buttersäurederivat, eingesetzt. Bevorzugt werden 0,5 bis 20 Äquivalente verwendet, besonders bevorzugt 1 bis 10 Äquivalente.The acid is generally used in 0.1 to 100 molar equivalents, based on 4- (2-nitrophenyl) butyric acid derivative. 0.5 to 20 equivalents are preferably used, particularly preferably 1 to 10 equivalents.
Die Reaktion wird im Allgemeinen bei Temperaturen von 0°C bis 150°C durchgeführt, bevorzugt zwischen 60°C und 110°C.The reaction is generally carried out at temperatures from 0 ° C. to 150 ° C., preferably between 60 ° C. and 110 ° C.
Die Arnim erung von 5-Nitro-3,4-dihydro-l(2H)-naphthalinon zum Nitro-Imin bzw. Nitro-Enamin geschieht durch Umsetzung mit Ammoniak, vorzugsweise in Gegenwart von Ammoniumsalzen wie Ammoniumchlorid.The amination of 5-nitro-3,4-dihydro-1 (2H) -naphthalinone to give the nitro-imine or nitro-enamine takes place by reaction with ammonia, preferably in the presence of ammonium salts such as ammonium chloride.
Die Aromatisierung bzw. Dehydrierung des Nitro-Enamins 5-Nitro-3,4-dihydro-l- naphthylamin bzw. des Nitro-Imins 5-Nitro-3,4-dihydro-l(2H)-naphthylimin zu 5- Nitro-1 -naphthylamin oder 5-Nitroso-l-naphthylamin oder einem Gemisch derThe aromatization or dehydrogenation of the nitro-enamine 5-nitro-3,4-dihydro-1-naphthylamine or the nitro-imine 5-nitro-3,4-dihydro-1 (2H) -naphthylimine to 5-nitro-1 -naphthylamine or 5-nitroso-l-naphthylamine or a mixture of the
Verbindungen wird, beispielsweise in einem inerten Lösungsmittel, in Gegenwart eines Katalysators durchgeführt. Dabei kann neben dem dehydrierten Produkt 5- Nitro-1 -naphthylamin auch das formal durch Synproportionierung entstandene 5- Nitroso-1 -naphthylamin entstehen. In Spuren entsteht auch 1,5-Naphthalindiamin. Die Produkte können in beliebigen Mischungsverhältnissen weiter verarbeitet werden. Geeignete Lösungsmittel sind Ammoniak und lineare, verzweigte oder cyclische aliphatische Kohlenwasserstoffe wie Ligroin oder Cyclohexan, sowie Acetonitril und aromatische Lösungsmittel wie Benzol, Toluol, Xylol, Nitrobenzol, Nitrotoluol oder Chlorbenzol. Die Aromatisierung kann auch in Abwesenheit eines Lösungsmittels durchgeführt werden.Compounds is carried out, for example in an inert solvent, in the presence of a catalyst. In addition to the dehydrated product 5-nitro-1-naphthylamine, the 5-nitroso-1-naphthylamine that is formally formed by synproportionation can also be formed. 1,5-naphthalenediamine is also produced in traces. The products can be processed in any mixing ratio. Suitable solvents are ammonia and linear, branched or cyclic aliphatic hydrocarbons such as ligroin or cyclohexane, and acetonitrile and aromatic solvents such as benzene, toluene, xylene, nitrobenzene, nitrotoluene or chlorobenzene. The flavoring can also be carried out in the absence of a solvent.
Geeignete Katalysatoren sind Dehydrierungskatalysatoren, die in der Literatur beschrieben sind (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10. Auflage 1997, S. 891, Kapitel „Dehydrierung", 1. Abschnitt; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5. Auflage 1989,Suitable catalysts are dehydrogenation catalysts which are described in the literature (Römpp Lexikon Chemie; Georg Thieme Verlag, Stuttgart, 10th edition 1997, p. 891, chapter "Dehydration", section 1; UUmann's Encyclopedia of Industrial Chemistry, VCH Verlagsgesellschaft mbH, Weinheim, 5th edition 1989,
Vol AI 3, Kapitel „Hydrogenation and Dehydrogenation", Unterkapitel 2. „Dehydro- - 20 -Vol AI 3, chapter "Hydrogenation and Dehydrogenation", subchapter 2. "Dehydro- - 20 -
genation", S. 494-497). Dazu gehören die Metalle der 8.-10. Gruppe des Periodensystems (G. J. Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommen- dations 1990, Blackwell Scientific Publications, Oxford, Chapter 1-3.8.1 „Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), insbesondere Platin, Palladium, Ruthenium und Iridium, Eisen, Cobalt, Nickel und Kombinationen davon.genation ", pp. 494-497). These include the metals of the 8th-10th group of the periodic table (GJ Leigh [Editor], Nomenclature of Inorganic Chemistry, Recommendations 1990, Blackwell Scientific Publications, Oxford, Chapters 1-3.8 .1 "Groups of Elements in the Periodic Table and their Subdivision, p. 41-43.), In particular platinum, palladium, ruthenium and iridium, iron, cobalt, nickel and combinations thereof.
Die Metalle können auch gemeinsam mit weiteren Metallen wie Lanthan, Scandium, Vanadium, Chrom, Molybdän, Wolfram, Mangan, Zinn, Zink, Kupfer, Silber oder Indium eingesetzt werden. Die genannten Metalle können dabei als reine Elemente, als Oxide, Sulfide, Halogenide, Carbide oder Nitride vorliegen oder aber kombiniert mit organischen Liganden eingesetzt werden. Als Liganden geeignet sind Kohlen- wasserstoffverbindungen mit Donorgruppen wie beispielsweise Amine, Nitrile, Phosphine, Thiole, Thioether, Alkohole, Ether oder Carbonsäuren. Gegebenenfalls sind die Katalysatoren auf einem Trägermaterial aufgebracht. Geeignete Trägermaterialien sind Aktivkohle, Aluminiumoxid, Siliciumoxid, Zirkonoxid, Zinkoxid, Zeolithe.The metals can also be used together with other metals such as lanthanum, scandium, vanadium, chromium, molybdenum, tungsten, manganese, tin, zinc, copper, silver or indium. The metals mentioned can be present as pure elements, as oxides, sulfides, halides, carbides or nitrides or can be used in combination with organic ligands. Suitable ligands are hydrocarbon compounds with donor groups such as amines, nitriles, phosphines, thiols, thioethers, alcohols, ethers or carboxylic acids. The catalysts are optionally applied to a support material. Suitable carrier materials are activated carbon, aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, zeolites.
Gegebenenfalls wird in Gegenwart eines Oxidationsmittels wie Sauerstoff oder Luft gearbeitet. Die Reaktion wird im Allgemeinen bei Temperaturen von 50°C bis 250°C durchgeführt, bevorzugt bei 100°C bis 200°C.If appropriate, work is carried out in the presence of an oxidizing agent such as oxygen or air. The reaction is generally carried out at temperatures from 50 ° C. to 250 ° C., preferably at 100 ° C. to 200 ° C.
Die anschließende Hydrierung von 5-Nitro-l -naphthylamin oder 5-Nitroso-l- naphthylamin oder einem Gemisch der Verbindungen zu 1,5-Naphthalindiamin wird analog zu Schritt d) der ersten bevorzugten Ausführung durchgeführt.The subsequent hydrogenation of 5-nitro-1-naphthylamine or 5-nitroso-1-naphthylamine or a mixture of the compounds to 1,5-naphthalenediamine is carried out analogously to step d) of the first preferred embodiment.
Das erfindungsgemäße Verfahren auf Basis von ortbo-Nitrotoluol und Acryl- säureestern und Acrylsäureamiden lässt sich in idealisierter Weise am folgenden Reaktionsschema verdeutlichen: m o-Nitrotoluol Acrylsäure- 4-(2-Nitrophenyl)- 5-Nitro-3,4-dihydro- 5-Nitro-3,4-dihydro- 5-Nitro-1 -naphthylamin 1 ,5-Naphthalindiamin ester bzw. buttersäureester 1(2H)-naphthalinon 1 -naphthylamin und /oder a -amid bzw. -amid bzw. 5-Nitroso-1 -naphthylaminThe process according to the invention based on ortbo-nitrotoluene and acrylic acid esters and acrylic acid amides can be illustrated in an idealized manner using the following reaction scheme: m o-Nitrotoluene Acrylic acid 4- (2-nitrophenyl) -5-nitro-3,4-dihydro-5-nitro-3,4-dihydro-5-nitro-1-naphthylamine 1, 5-naphthalenediamine ester or butyric acid ester 1 (2H) -naphthalenone 1 -naphthylamine and / or a -amide or -amide or 5-nitroso-1 -naphthylamine
5-Nitro-3,4-dihydro- und/oder 1 (21-1 )-naphthylimin 1 ,5-Naphthalindiamin5-nitro-3,4-dihydro and / or 1 (21-1) naphthylimine 1, 5-naphthalenediamine
X = OAlkyl, OAryl, NH2, NHAlkyl, N(Alkyl)2, NHAryl, N(Aryl)2, NAIkylArylX = OAlkyl, OAryl, NH 2 , NHAlkyl, N (alkyl) 2 , NHAryl, N (aryl) 2 , NAIkylAryl
- 21a -- 21a -
Das 1,5-Naphthalindiamin kann in an sich bekannter Weise zum 1,5-Naphthalin- diisocyanat phosgeniert werden (DE-Al-19 651 041).The 1,5-naphthalene diamine can be phosgenated to 1,5-naphthalene diisocyanate in a manner known per se (DE-Al-19 651 041).
ERSATZBLAπ (REGEL 26) - 22 -REPLACEMENT BLAπ (RULE 26) - 22 -
BeispieleExamples
Ausführung 1:Version 1:
Beispiel 1 Darstellung von 4-(2-Nitrophenyl)-butyronitrilExample 1 Preparation of 4- (2-nitrophenyl) butyronitrile
In einem 100 ml Dreihalskolben mit Tropftrichter, Rückflusskühler und Innen- thermometer wird unter Rühren 0,75 ml 45 % Natronlauge und 175 mg Tributyl- methylammonium-Chlorid gegeben. Bei 40°C wird eine Mischung von 1,4 ml Acrylnitril (21,15 mmol) und 25 ml ortbo-Nitrotoluol zugetropft und 3 h bei dieser0.75 ml of 45% sodium hydroxide solution and 175 mg of tributylmethylammonium chloride are added to a 100 ml three-necked flask with a dropping funnel, reflux condenser and internal thermometer with stirring. A mixture of 1.4 ml of acrylonitrile (21.15 mmol) and 25 ml of ortbo-nitrotoluene is added dropwise at 40 ° C. and for 3 hours
Temperatur gehalten. Die Phasen werden getrennt, die organische Phase getrocknet und abfiltriert. Bei quantitativem Umsatz an Acrylnitril werden 1,61 g 4-(2-Nitro- phenyl)-butyronitril (8,5 mmol, 40 %) erhalten.Temperature maintained. The phases are separated, the organic phase is dried and filtered off. With quantitative conversion of acrylonitrile, 1.61 g of 4- (2-nitrophenyl) butyronitrile (8.5 mmol, 40%) are obtained.
Beispiel 2 Darstellung von 5 -Nitro-3 ,4-dihydro- 1 (2H)-naphthyliminExample 2 Preparation of 5-nitro-3,4-dihydro-1 (2H) -naphthylimine
In einem 50 ml Glasrundkolben werden unter Schutzgas 107 mg 4-(2-Nitrophenyl)- butyronitril (0,89 mmol) mit 4 ml konzentrierte Schwefelsäure (75 mmol) versetzt und die Mischung 12 h auf 100°C erhitzt. Die erkaltete Mischung wird auf Eis gegeben und sofort mit Toluol extrahiert. Die Ausbeute an 5-Nitro-3,4-dihydro- l(2H)-naρhthylimin beträgt laut GC 85 % (Flächenprozent).In a 50 ml round-bottomed flask, 4 ml of concentrated sulfuric acid (75 mmol) are added to 107 mg of 4- (2-nitrophenyl) butyronitrile (0.89 mmol) under a protective gas, and the mixture is heated to 100 ° C. for 12 h. The cooled mixture is poured onto ice and immediately extracted with toluene. According to GC, the yield of 5-nitro-3,4-dihydro-l (2H) -naρhthylimine is 85% (area percent).
Beispiel 2a Darstellung von 5-Nitro-3,4-dihydro-l(2H)-naphthalinonExample 2a Preparation of 5-nitro-3,4-dihydro-l (2H) -naphthalinone
In einem 50ml Glasrundkolben werden unter Schutzgas 1,00 g Fluorschwefelsäure1.00 g of fluorosulfuric acid are placed in a 50 ml glass flask under a protective gas
(10 mmol) zu 1,30 g Antimon-(V)-fluorid (6 mmol) gegeben und die Mischung auf 0°C gekühlt. Dann werden vorsichtig 380 mg 4-(2-Nitrophenyl)-butyronitril (2 mmol) zugegeben. Die Mischung erwärmt sich auf etwa 50°C und wird 12h bei Raumtemperatur weitergerührt. Die Mischung wird auf eiskalte Natronlauge ge- geben, bei Raumtemperatur 30 Min. nachgerührt und dann mit Toluol extrahiert.(10 mmol) was added to 1.30 g of antimony (V) fluoride (6 mmol) and the mixture was cooled to 0 ° C. Then 380 mg of 4- (2-nitrophenyl) butyronitrile (2 mmol) are carefully added. The mixture heats up to about 50 ° C and is further stirred for 12 hours at room temperature. The mixture is poured onto ice-cold sodium hydroxide solution, stirred at room temperature for 30 minutes and then extracted with toluene.
Durch die Nachrührzeit wird eine weitgehend vollständige Hydrolyse ermöglicht. - 23 -A largely complete hydrolysis is made possible by the subsequent stirring time. - 23 -
Die organische Phase wird über Natriumsulfat getrocknet, abfiltriert und das Lösungsmittel unter vermindertem Druck abdestilliert. Der Rückstand wird durch Chromatographie an Kieselgel gereinigt (Eluent Cyclohexan Ethylacetat 5:1 v/v). Die Ausbeute an 5-Nitro-3,4-dihydro-l(2H)-naphthalinon beträgt 297 mg mit einer GC-Reinheit von 97 % (76 % der Theorie).The organic phase is dried over sodium sulfate, filtered off and the solvent is distilled off under reduced pressure. The residue is purified by chromatography on silica gel (eluent cyclohexane ethyl acetate 5: 1 v / v). The yield of 5-nitro-3,4-dihydro-l (2H) -naphthalinone is 297 mg with a GC purity of 97% (76% of theory).
Beispiel 3 Darstellung von 5-Nitro-l -naphthylamin:Example 3 Preparation of 5-nitro-1-naphthylamine:
1,0 g 5-Nitro-3,4-dihydro-l(2H)-naphthalinon (5,2 mmol), 5,2 mg Ammonium- chlorid (0,1 mmol) und 10,9 mg Ruthem'umtrichloridhydrat (0,05 mmol) werden in einem 0,11 Autoklaven vorgelegt. 10 ml Ammoniak werden einkondensiert, der Autoklav auf 80°C erwärmt und dann wird der Druck mit Stickstoff auf 200 bar erhöht. Nach 20h Rühren unter den angegebenen Bedingungen wird abgekühlt, vorsichtig entspannt und die Reaktionsmischung mit 20 ml Dichlormethan aus dem Autoklaven gelöst. Man erhält eine Mischung, die laut GC neben 12 % Edukt zu1.0 g 5-nitro-3,4-dihydro-l (2H) -naphthalenone (5.2 mmol), 5.2 mg ammonium chloride (0.1 mmol) and 10.9 mg Ruthem ' umtrichloridhydrat (0 , 05 mmol) are placed in a 0.11 autoclave. 10 ml of ammonia are condensed in, the autoclave is heated to 80 ° C. and the pressure is then increased to 200 bar with nitrogen. After stirring for 20 hours under the specified conditions, the mixture is cooled, carefully let down and the reaction mixture is dissolved from the autoclave with 20 ml of dichloromethane. A mixture is obtained which, according to GC, also has 12% starting material
68 % 5-Nitro-3,4-dihydro-l-naρhthylamin bzw. 5-Nitro-3,4-dihydro-l(2H)-naphthyl- imin, zu 17 % 5 -Nitro-1 -naphthylamin und in Spuren 1,5-Naphthalindiamin enthält (GC-Flächenprozente).68% 5-nitro-3,4-dihydro-l-naphthylamine or 5-nitro-3,4-dihydro-l (2H) -naphthyl-imine, 17% 5 -nitro-1-naphthylamine and in traces 1 , 5-Naphthalenediamine contains (GC area percent).
Beispiel 4 Hydrierung von 5-Nitro- 1 -naphthylaminExample 4 Hydrogenation of 5-nitro-1-naphthylamine
In einem 0,1 1 Autoklaven werden 8,20 g 5 -Nitro-1 -naphthylamin (43,6 mmol) in 35 ml Toluol mit 0,5 g Palladium auf Kohle (5 %) vorgelegt und unter Rühren bei 50°C bei 40 bar Wasserstoffdruck für 5 h hydriert. Nach beendeter Reaktion wird der abgekühlte Autoklav entspannt und der Katalysator abfiltriert. Bei quantitativem8.20 g of 5-nitro-1-naphthylamine (43.6 mmol) in 35 ml of toluene with 0.5 g of palladium on carbon (5%) are placed in a 0.1 l autoclave and stirred at 50 ° C. 40 bar hydrogen pressure hydrogenated for 5 h. When the reaction has ended, the cooled autoclave is let down and the catalyst is filtered off. With quantitative
Umsatz werden 6,72 g 1,5-Naphthalindiamin (42,5 mmol, 97,5 %) gebildet. - 24 -6.72 g of 1,5-naphthalenediamine (42.5 mmol, 97.5%) are formed. - 24 -
Ausführung 2:Version 2:
Beispiel 5 Synthese von 4-(2-Aminophenyl)-butyronitrilExample 5 Synthesis of 4- (2-aminophenyl) butyronitrile
In einem 100 ml Glasrundkolben werden zu einer Mischung von 412 mg EisenpulverIn a 100 ml glass round bottom flask, a mixture of 412 mg iron powder
(7,5 mmol) und 663 mg Ammoniumchlorid (12,5 mmol) in 12,5 ml Wasser bei Raumtemperatur und unter Schutzgas 450 mg 4-(2-Nitrophenyl)-butyronitril, gelöst in 12,5 ml Methanol, zugetropft. Die Mischung wird 5 Stunden auf Rückfluss erhitzt. Die erkaltete Mischung wird mit 25 ml Wasser versetzt und mit Toluol extrahiert. Die vereinigten Toluolphasen werden getrocknet und das Lösungsmittel unter vermindertem Druck abdestilliert. Der Rückstand wird säulenchromatographisch an Kieselgel (Eluent Toluol/Ethylacetat 10:1 v/v) gereinigt. Ausbeute: 276 mg (1,73 mmol, 72 %).(7.5 mmol) and 663 mg ammonium chloride (12.5 mmol) in 12.5 ml of water at room temperature and under protective gas 450 mg of 4- (2-nitrophenyl) butyronitrile, dissolved in 12.5 ml of methanol, are added dropwise. The mixture is heated to reflux for 5 hours. The cooled mixture is mixed with 25 ml of water and extracted with toluene. The combined toluene phases are dried and the solvent is distilled off under reduced pressure. The residue is purified by column chromatography on silica gel (eluent toluene / ethyl acetate 10: 1 v / v). Yield: 276 mg (1.73 mmol, 72%).
Beispiel 6 Synthese von 5 - Amino-3 ,4-dihydro- 1 (2H)-naphthyliminExample 6 Synthesis of 5-amino-3,4-dihydro-1 (2H) -naphthylimine
Unter Argon werden in einem 50 ml Glaskolben zu 122 mg 4-(2-Aminophenyl)- butyronitril (0,74 mmol) und 495 mg Antimon-(V)-fluorid (2,29 mmol) unter Rühren 380 mg Fluorschwefelsäure (3,8 mmol) getropft und die Mischung für 4 Stunden auf 100°C erhitzt. Nach dem Abkühlen wird die Mischung auf Eis gegeben, direkt mitUnder argon in a 50 ml glass flask to 122 mg 4- (2-aminophenyl) butyronitrile (0.74 mmol) and 495 mg antimony (V) fluoride (2.29 mmol) with stirring 380 mg fluorosulfuric acid (3, 8 mmol) was added dropwise and the mixture was heated to 100 ° C. for 4 hours. After cooling, the mixture is poured onto ice, directly with
Natronlauge neutralisiert und mit Toluol extrahiert. Die Ausbeute an 5-Nitro-3,4- dihydro-l(2H)-naρhthylimin beträgt laut GC 77 %. 5-Amino-3,4-dihydro-l(2H)- naphthylimin kann auch 5-Imino-5,6,7,8-tetrahydro-l-naphthylamin benannt werden.Neutralized sodium hydroxide solution and extracted with toluene. The yield of 5-nitro-3,4-dihydro-l (2H) -naρhthylimine is 77% according to GC. 5-Amino-3,4-dihydro-l (2H) -naphthylimine can also be named 5-imino-5,6,7,8-tetrahydro-l-naphthylamine.
Beispiel 6a Synthese von 5- Amino-3 ,4-dihydro- 1 (2H)-naphthalinonExample 6a Synthesis of 5-amino-3,4-dihydro-1 (2H) -naphthalinone
Unter Argon werden in einem 50 ml Glaskolben zu 122 mg 4-(2-Aminophenyl)- butyronitril (0,74 mmol) und 495 mg Antimon-(N)-fluorid (2,29 mmol) unter Rühren 380 mg Fluorschwefelsäure (3,8 mmol) getropft und die Mischung für 4 Stunden auf 100°C erhitzt. Nach dem Abkühlen wird die Mischung auf Eis gegeben, mit Natronlauge neutralisiert, bei Raumtemperatur 30 Min. gerührt und mit Toluol extrahiert. - 25 -Under argon in a 50 ml glass flask to 122 mg 4- (2-aminophenyl) - butyronitrile (0.74 mmol) and 495 mg antimony (N) fluoride (2.29 mmol) with stirring 380 mg fluorosulfuric acid (3, 8 mmol) was added dropwise and the mixture was heated to 100 ° C. for 4 hours. After cooling, the mixture is poured onto ice, neutralized with sodium hydroxide solution, stirred at room temperature for 30 minutes and extracted with toluene. - 25 -
Durch die Nachrührzeit von 30 Min. wird eine weitgehend vollständige Hydrolyse ermöglicht. Die Ausbeute an 5-Amino-3,4-dihydro-l(2H)-naphthalinon beträgt 64 %.The subsequent stirring time of 30 minutes enables largely complete hydrolysis. The yield of 5-amino-3,4-dihydro-l (2H) -naphthalinone is 64%.
Beispiel 6b Synthese von 5-Amino-3,4-dihydro-l(2H)-naphthalinonExample 6b Synthesis of 5-amino-3,4-dihydro-l (2H) -naphthalinone
Unter Argon werden in einem 20 ml Schlenkgefäß zu 100 mg 4-(2-Aminophenyl)- butyronitril (0,62 mmol) 1 g 96 %ige Schwefelsäure (9,79 mmol) gegeben. Unter Rühren wird 66h auf 100°C erhitzt. Nach dem Abkühlen wird mit wässriger Ammoniak-Lösung (Eiskühlung) neutralisiert, das Produkt anschließend mit Chloro- form extrahiert und mittels GC nachgewiesen.Under argon, 1 g of 96% sulfuric acid (9.79 mmol) is added to 100 mg of 4- (2-aminophenyl) butyronitrile (0.62 mmol) in a 20 ml Schlenk vessel. The mixture is heated to 100 ° C. for 66 hours with stirring. After cooling, the mixture is neutralized with aqueous ammonia solution (ice cooling), the product is then extracted with chloroform and detected by means of GC.
Beispiel 7 Synthese von 1,5-Naphthalindiamin aus 5-Amino-3,4-dihydro-l(2H)- naphthalinonExample 7 Synthesis of 1,5-naphthalenediamine from 5-amino-3,4-dihydro-l (2H) -naphthalinone
In einem 0,1 1 VA-Autoklaven werden 419.1 mg (2.6 mmol) Aminotetralon, 52 mgIn a 0.1 1 VA autoclave, 419.1 mg (2.6 mmol) aminotetralone, 52 mg
(0,97 mmol) Ammoniumchlorid, 230.5 mg (1.3 mmol) Palladium(II)chlorid in 1 ml Acetonitril vorgelegt. Es werden 5 ml Ammoniak zugeben, auf 130°C erwärmt und dann der Druck mit Stickstoff auf 200 bar erhöht. Es wird 20 h unter den angegebenen Reaktionsbedingungen gerührt, dann auf Raumtemperatur abgekühlt und langsam entspannt. Der Rückstand wird in einer Mischung von Acetonitril, Toluol und Dichlormethan gelöst, über Natriumsulfat filtriert, und dann das Lösungsmittel im Vakuum entfernt.(0.97 mmol) ammonium chloride, 230.5 mg (1.3 mmol) palladium (II) chloride in 1 ml of acetonitrile. 5 ml of ammonia are added, the mixture is heated to 130 ° C. and the pressure is then increased to 200 bar with nitrogen. The mixture is stirred for 20 h under the stated reaction conditions, then cooled to room temperature and slowly let down. The residue is dissolved in a mixture of acetonitrile, toluene and dichloromethane, filtered over sodium sulfate and then the solvent is removed in vacuo.
Ausbeute: 321 mg (78 %).Yield: 321 mg (78%).
Ausführung 4:Version 4:
Beispiel 8 Synthese von 5-Amino-3,4-dihydro-l(2H)-naphthalinon aus 5-Nitro-3,4- dihydro- 1 (2H)-naphthalinon - 26 -Example 8 Synthesis of 5-amino-3,4-dihydro-l (2H) -naphthalinone from 5-nitro-3,4-dihydro-1 (2H) -naphthalinone - 26 -
In einem 11 Vierhalskolben werden 9,18 g Eisenpulver und 16,64 g Ammoniumchlorid in 274 ml Wasser vorgelegt. Unter Rühren werden 10g 5-Nitro-3,4-dihydro- l(2H)-naphthalinon (52,4mmol) in 550 ml Methanol gelöst innerhalb von 3,5 h bei 25°C zugetropft. Nach beendetem Zutropfen wird 3,5 h zum Rückfluss erhitzt. Nach dem Abkühlen erfolgt mit wässriger Ammoniak-Lösung (25 %ig) die Einstellung auf pH 11. Das Produkt wird aus der wässrigen Phase mit Chloroform extrahiert, über Natriumsulfat getrocknet und im Vakuum eingeengt. Das Produkt wird als rotbrauner Feststoff in 81 % Ausbeute (6,8 g) erhalten.9.18 g of iron powder and 16.64 g of ammonium chloride in 274 ml of water are placed in a 11 four-necked flask. With stirring, 10 g of 5-nitro-3,4-dihydrol (2H) -naphthalenone (52.4 mmol) dissolved in 550 ml of methanol are added dropwise at 25 ° C. in the course of 3.5 h. When the dropwise addition has ended, the mixture is heated under reflux for 3.5 h. After cooling, the pH is adjusted to 11 with aqueous ammonia solution (25%). The product is extracted from the aqueous phase with chloroform, dried over sodium sulfate and concentrated in vacuo. The product is obtained as a red-brown solid in 81% yield (6.8 g).
Ausführung 5:Version 5:
Beispiel 9 Synthese von 4-(2-Nitrophenyl)-buttersäuremethylesterExample 9 Synthesis of 4- (2-nitrophenyl) butyric acid methyl ester
Zu einer Mischung aus 14,4g 67 % Kalilauge und 1,7 g Tetrabutylammoniumchlorid wird bei 40°C eine Mischung aus 400 g (2,92 mol) ortbo-Nitrotoluol und 12,7 g (0,148 mol) Acrylsäuremethylester gegeben und die Mischung 1 h gerührt. Die Mischung wird mit 30 % Schwefelsäure neutralisiert und die Phasen getrennt. Laut GC- Analyse mit internem Standard beträgt die Ausbeute 50 %.A mixture of 400 g (2.92 mol) of ortbo-nitrotoluene and 12.7 g (0.148 mol) of methyl acrylate is added to a mixture of 14.4 g of 67% potassium hydroxide solution and 1.7 g of tetrabutylammonium chloride, and the mixture is 1 h stirred. The mixture is neutralized with 30% sulfuric acid and the phases are separated. According to GC analysis with an internal standard, the yield is 50%.
Die organischen Phasen von 4 identischen Versuchen werden vereinigt und über Na2SO getrocknet. Bei einem Druck von 0,1 bar wird überschüssiges Nitrotoluol bis zu einer Kopftemperatur von 110°C abdestilliert. Bei einer Kopftemperatur von 120 - 130°C erhält man 59,1 g (265 mmol) 4-(2-Nitrophenyl)-buttersäuremethylester mit einer Reinheit von ca. 98%. Die isolierte Ausbeute entspricht 45%.The organic phases from 4 identical experiments are combined and dried over Na 2 SO 4. At a pressure of 0.1 bar, excess nitrotoluene is distilled off up to a top temperature of 110 ° C. At a head temperature of 120-130 ° C, 59.1 g (265 mmol) of 4- (2-nitrophenyl) butyric acid methyl ester with a purity of about 98% is obtained. The isolated yield corresponds to 45%.
Beispiel 10 Synthese von 5-Nitro-3,4-dihydro-l(2H)-naphthalinonExample 10 Synthesis of 5-nitro-3,4-dihydro-l (2H) -naphthalinone
In 1,68 g Trifluormethansulfonsäure werden 100 mg (0,45 mmol) 4-(2-Nitrophenyl)- buttersäuremethylester gelöst und für 24 h auf 100°C erhitzt. Zu der erkalteten - 27 -100 mg (0.45 mmol) of 4- (2-nitrophenyl) butyric acid methyl ester are dissolved in 1.68 g of trifluoromethanesulfonic acid and heated to 100 ° C. for 24 h. To the cold - 27 -
Reaktionsmischung werden vorsichtig 5 ml Wasser und 5 ml Toluol gegeben. Die Phasen werden getrennt und die organische Phase gaschromatographisch mit internem Standard untersucht. Die Ausbeute an 5-Nitro-3,4-dihydro-l(2H)- naphthalinon beträgt 81%.5 ml of water and 5 ml of toluene are carefully added to the reaction mixture. The phases are separated and the organic phase is examined by gas chromatography using an internal standard. The yield of 5-nitro-3,4-dihydro-l (2H) - naphthalinone is 81%.
Beispiel 10a Synthese von 5-Nitro-3,4-dihydro-l(2H)-naphthalinonExample 10a Synthesis of 5-nitro-3,4-dihydro-l (2H) -naphthalinone
In 5,49 g 98 % Schwefelsäure werden 250 mg (1,12 mmol) 4-(2-Nitrophenyl)- buttersäuremethylester gelöst und für 24 h auf 100°C erhitzt. Zu der erkaltetenIn 5.49 g of 98% sulfuric acid, 250 mg (1.12 mmol) of 4- (2-nitrophenyl) butyric acid methyl ester are dissolved and heated to 100 ° C. for 24 h. To the cold
Reaktionsmischung werden vorsichtig 5 ml Wasser und 5 ml Toluol gegeben. Die Phasen werden getrennt und die organische Phase gaschromatographisch mit internem Standard untersucht. Die Ausbeute an 5-Nitro-3,4-dihydro-l(2H)-naphtha- linon beträgt 42%. 5 ml of water and 5 ml of toluene are carefully added to the reaction mixture. The phases are separated and the organic phase is examined by gas chromatography using an internal standard. The yield of 5-nitro-3,4-dihydro-l (2H) -naphthalenone is 42%.

Claims

- 28 -Patentansprüche - 28 patent claims
1. Verfahren zur Herstellung von 1,5-Naphthalindiamin, das einen Schritt enthält, in dem man ortbo-Nitrotoluol mit einem oder mehreren Acrylsäure- derivaten umsetzt.1. A process for the preparation of 1,5-naphthalenediamine which contains a step in which ortbo-nitrotoluene is reacted with one or more acrylic acid derivatives.
2. Verfahren nach Anspruch 1, bei dem man als Acrylsäurederivat Acrylsäure- methylester, Acrylsäureethylester, Acrylsäurebutylester oder Acrylsäureamid einsetzt.2. The method according to claim 1, in which the acrylic acid derivative is acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid butyl ester or acrylic acid amide.
3. Verfahren nach Anspruch 1, das einen Schritt enthält, in dem man ortho- Nitrotoluol mit Acrylnitril zu 4-(2-Nitrophenyl)-butyronitril umsetzt.3. The method according to claim 1, which contains a step in which ortho-nitrotoluene is reacted with acrylonitrile to 4- (2-nitrophenyl) butyronitrile.
4. Verfahren zur Herstellung von 1,5-Naphthalindiamin nach Anspruch 3, ent- haltend die Schritte4. A process for the preparation of 1,5-naphthalenediamine according to claim 3, comprising the steps
a) Umsetzung von ortbo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitro- phenyl)-butyronitril,a) reaction of ortbo-nitrotoluene with acrylonitrile to 4- (2-nitrophenyl) butyronitrile,
b) Cyclisierung des in Schritt a) gebildeten 4-(2-Nitrophenyl)-butyronitril zum Nitro-Imin und/oder Nitro-Enamin,b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give the nitro-imine and / or nitro-enamine,
c) Aromatisieren des in Schritt b) gebildeten Nitro-Imin und/oder Nitro- Enamin zu 5-Nitro-l -naphthylamin und oder 5-Nitroso-l-naphthyl- amin,c) aromatizing the nitro-imine and / or nitro-enamine formed in step b) to 5-nitro-l-naphthylamine and or 5-nitroso-l-naphthylamine,
d) Hydrieren des in Schritt c) gebildeten 5-Nitro-l -naphthylamin und/oder 5 -Nitroso-1 -naphthylamin zu 1 ,5-Naphthalindiamin.d) hydrogenating the 5-nitro-1-naphthylamine and / or 5 -nitroso-1-naphthylamine formed in step c) to 1, 5-naphthalenediamine.
5. Verfahren nach Anspruch 4, bei dem das in Schritt b) gebildete Nitro-Imin und/oder Nitro-Enamin zunächst zum Nitroketon 5 -Nitro-3,4-dihydro-l(2H)- - 29 -5. The method according to claim 4, wherein the nitro-imine and / or nitro-enamine formed in step b) first to give nitroketone 5 -nitro-3,4-dihydro-l (2H) - 29 -
naphthalinon umgesetzt wird, das Nitroketon anschließend isoliert wird, anschließend zum Nitro-Imin und/oder Nitro-Enamin zurückgebildet wird und anschließend in Schritt c) aromatisiert wird.naphthalinone is implemented, the nitroketone is then isolated, then reformed to nitro-imine and / or nitro-enamine and then aromatized in step c).
6. Verfahren zur Herstellung von 1,5-Naphthalindiamin nach Anspruch 3, enthaltend die Schritte6. A process for the preparation of 1,5-naphthalenediamine according to claim 3, comprising the steps
a) Umsetzung von ortbo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitro- phenyl)-butyronitril,a) reaction of ortbo-nitrotoluene with acrylonitrile to 4- (2-nitrophenyl) butyronitrile,
b) Reduzieren des in Schritt a) gebildeten 4-(2-Nitrophenyl)-butyronitril zum 4-(2-Aminophenyl)-butyronitril,b) reducing the 4- (2-nitrophenyl) butyronitrile formed in step a) to 4- (2-aminophenyl) butyronitrile,
c) Cyclisieren des in Schritt b) gebildeten 4-(2-Aminophenyl)-butyro- nitril zum Amino-Imin und/oder Amino-Enamin,c) cyclizing the 4- (2-aminophenyl) -butyronitrile formed in step b) to the amino-imine and / or amino-enamine,
d) Aromatisieren des in Schritt c) gebildeten Amino-Imin und/oder Amino-Enamin zum 1,5-Naphthalindiamin.d) Flavoring the amino imine and / or amino enamine formed in step c) to give 1,5-naphthalenediamine.
7. Verfahren nach Anspruch 6, bei dem das in Schritt c) gebildete Amino-Imin und/oder Amino-Enamin zunächst zum Aminoketon 5-Amino-3,4-dihydro- l(2H)-naphthalinon umgesetzt wird, das Aminoketon anschließend isoliert wird, anschließend zum Amino-Imin und/oder Amino-Enamin zurückgebildet wird und anschließend in Schritt d) aromatisiert wird.7. The method according to claim 6, wherein the amino-imine and / or amino-enamine formed in step c) is first converted to the amino ketone 5-amino-3,4-dihydro-l (2H) -naphthalinone, the amino ketone is then isolated is then reformed to the amino-imine and / or amino-enamine and then aromatized in step d).
8. Verfahren zur Herstellung von 1,5-Naphthalindiamin nach Anspruch 3, enthaltend die Schritte8. A method for producing 1,5-naphthalenediamine according to claim 3, comprising the steps
a) Umsetzung von ortbo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitro- phenyl)-butyronitril, - 30 -a) reaction of ortbo-nitrotoluene with acrylonitrile to 4- (2-nitrophenyl) butyronitrile, - 30 -
b) Cyclisierung des in Schritt a) gebildeten 4-(2-Nitrophenyl)- butyronitril zum Nitro-Imin und/oder Nitro-Enamin,b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give the nitro-imine and / or nitro-enamine,
c) Reduzieren des in Schritt b) gebildeten Nitro-Imin und /oder Nitro- Ena in zum Amino-Imin und /oder Amino-Enamin,c) reducing the nitro-imine and / or nitro-ena formed in step b) to the amino-imine and / or amino-enamine,
d) Aromatisieren des in Schritt c) gebildeten Amino-Imin und/oder Amino-Enamin zum 1,5-Naphthalindiamin.d) Flavoring the amino imine and / or amino enamine formed in step c) to give 1,5-naphthalenediamine.
9. Verfahren zur Herstellung von 1,5-Naphthalindiamin nach Anspruch 3, enthaltend die Schritte9. A process for the preparation of 1,5-naphthalenediamine according to claim 3, comprising the steps
a) Umsetzung von ortbo-Nitrotoluol mit Acrylnitril zu 4-(2-Nitro- phenyl)-butyronitril,a) reaction of ortbo-nitrotoluene with acrylonitrile to 4- (2-nitrophenyl) butyronitrile,
b) Cyclisierung des in Schritt a) gebildeten 4-(2-Nitrophenyl)- butyronitril zum Nitro-Imin und/oder Nitro-Enamin, Umsetzung zum Nitroketon 5-Nitro-3,4-dihydro-l(2H)-naphthalinon, sowie Isolierung des Nitroketons,b) cyclization of the 4- (2-nitrophenyl) butyronitrile formed in step a) to give nitro-imine and / or nitro-enamine, conversion to nitro-ketone 5-nitro-3,4-dihydro-l (2H) -naphthalenone and Isolation of nitroketone,
c) Reduzieren des in Schritt b) gebildeten Nitroketons 5-Nitro-3,4- dihydro-l(2H)-naphthalinon zum Aminoketon 5-Amino-3,4-dihydro- 1 (2H)-naphthalinon,c) reducing the nitroketone 5-nitro-3,4-dihydro-l (2H) -naphthalinone formed in step b) to the amino ketone 5-amino-3,4-dihydro-1 (2H) -naphthalinone,
d) Überführen des in Schritt c) gebildeten Aminoketons zum Amino-d) converting the amino ketone formed in step c) to the amino
Imin 5-Amino-3,4-dihydro-l(2H)-naphthylimin und/oder Amino-Enamin 5-Amino-3,4-dihydro-l -naphthylamin und Aromatisieren zum 1 ,5-Naphthalindiamin.Imine 5-amino-3,4-dihydro-l (2H) -naphthylimine and / or amino-enamine 5-amino-3,4-dihydro-l -naphthylamine and flavoring to 1,5-naphthalenediamine.
10. Verfahren zur Herstellung von 1,5-Naphthalindiamin nach Anspruch 1, enthaltend die Schritte - 31 -10. A process for the preparation of 1,5-naphthalenediamine according to claim 1, comprising the steps - 31 -
a) Umsetzung von ortbo-Nitrotoluol mit einem Acrylsäureester oder Acrylsäureamid zum 4-(2-Nitrophenyl)-buttersäureester bzw. 4-(2- Nitrophenyl)-buttersäureamid,a) reaction of ortbo-nitrotoluene with an acrylic acid ester or acrylic acid amide to give 4- (2-nitrophenyl) butyric acid ester or 4- (2-nitrophenyl) butyric acid amide,
b) Cyclisierung des in Schritt a) gebildeten Buttersäureesters bzw. des Buttersäureamids zum 5-Nitro-3,4-dihydro-l(2H)-naphthalinon,b) cyclization of the butyric acid ester or butyric acid amide formed in step a) to give 5-nitro-3,4-dihydro-l (2H) -naphthalinone,
c) Aminierung des in Schritt b) gebildeten 5-Nitro-3,4-dihydro-l(2H)- naphthalinon zu 5 -Nitro-3,4-dihydro-l -naphthylamin bzw. dem tautomeren 5-Nitro-3,4-dihydro- 1 (2H)-naphthylimin,c) Amination of the 5-nitro-3,4-dihydro-l (2H) -naphthalinone formed in step b) to 5 -nitro-3,4-dihydro-l -naphthylamine or the tautomeric 5-nitro-3,4 -dihydro- 1 (2H) -naphthylimine,
d) Aromatisierung des in Schritt c) gebildeten 5-Nitro-3,4-dihydro-l- naphthylamin bzw. des tautomeren 5-Nitro-3,4-dihydro-l(2H)- naphthylimin zu 5-Nitro-l -naphthylamin und/oder 5-Nitroso-l- naphthylamin,d) aromatization of the 5-nitro-3,4-dihydro-1-naphthylamine formed in step c) or the tautomeric 5-nitro-3,4-dihydro-1 (2H) -naphthylimine to 5-nitro-1-naphthylamine and / or 5-nitroso-l-naphthylamine,
e) Hydrieren des in Schritt d) gebildeten 5-Nitro-l -naphthylamin und / oder 5-Nitroso-l -naphthylamin zu 1,5-Naphthalindiamin.e) hydrogenating the 5-nitro-1-naphthylamine and / or 5-nitroso-1-naphthylamine formed in step d) to 1,5-naphthalenediamine.
11. Verbindungen der Bezeichnung 5 -Nitro-3,4-dihydro-l -naphthylamin bzw. das tautomere 5-Nitro-3,4-dihydro- 1 (2H)-naphthylimin, 5-Nitroso-l -naphthylamin, 4-(2-Aminophenyl)-butyronitril, 5-Amino-3,4-dihydro-l(2H)-naphthyl- imin bzw. das tautomere 5-Amino-3,4-dihydro-l -naphthylamin, 4-(2- Nitrophenyl)-buttersäureethylester, 4-(2-Nitrophenyl)-buttersäurebutylester,11. Compounds of the designation 5-nitro-3,4-dihydro-l-naphthylamine or the tautomeric 5-nitro-3,4-dihydro-1 (2H) -naphthylamine, 5-nitroso-l -naphthylamine, 4- ( 2-aminophenyl) butyronitrile, 5-amino-3,4-dihydro-l (2H) -naphthyl-imine or the tautomeric 5-amino-3,4-dihydro-l -naphthylamine, 4- (2-nitrophenyl) -butyric acid ethyl ester, 4- (2-nitrophenyl) -butyric acid butyl ester,
4-(2-Nitrophenyl)-buttersäureamid.4- (2-nitrophenyl) -buttersäureamid.
12. Verwendung von Acrylsäurederivaten und ort zo-Nitrotoluol als Edukte zur Herstellung von 1,5-Naphthalindiamin.12. Use of acrylic acid derivatives and ort zo-nitrotoluene as starting materials for the production of 1,5-naphthalenediamine.
13. Verwendung nach Anspruch 12, wobei das Acrylsäurederivat Acrylnitril ist. - 32 -13. Use according to claim 12, wherein the acrylic acid derivative is acrylonitrile. - 32 -
14. Verfahren zur Herstellung von 1,5-Naphthalindiisocyanat, bei dem man 1,5- Naphthalindiamin, hergestellt nach einem der Ansprüche 1 bis 10, phosgeniert. 14. A process for the preparation of 1,5-naphthalenediisocyanate, in which 1,5-naphthalenediamine, prepared according to one of claims 1 to 10, is phosgenated.
EP01990532A 2000-12-22 2001-12-10 Method for the production of 1,5-naphthalenediamine Withdrawn EP1345888A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10064779 2000-12-22
DE10064779 2000-12-22
DE10149041 2001-10-05
DE10149041A DE10149041A1 (en) 2000-12-22 2001-10-05 Production of 1,5-naphthalenediamine involves reaction of o-nitrotoluene with acrylic acid derivatives, e.g. with acrylonitrile to give 4-o-nitrophenyl-butyronitrile, followed by cyclization, aromatization and reduction
PCT/EP2001/014449 WO2002051792A1 (en) 2000-12-22 2001-12-10 Method for the production of 1,5-naphthalenediamine

Publications (1)

Publication Number Publication Date
EP1345888A1 true EP1345888A1 (en) 2003-09-24

Family

ID=26008078

Family Applications (1)

Application Number Title Priority Date Filing Date
EP01990532A Withdrawn EP1345888A1 (en) 2000-12-22 2001-12-10 Method for the production of 1,5-naphthalenediamine

Country Status (6)

Country Link
US (1) US6706924B2 (en)
EP (1) EP1345888A1 (en)
JP (1) JP4206270B2 (en)
CN (1) CN1275934C (en)
HK (1) HK1061675A1 (en)
WO (1) WO2002051792A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1295864B1 (en) 2001-05-08 2008-12-03 Mitsui Chemicals Polyurethanes, Inc. Process for preparation of 1,5-diaminonaphthalenes
DE10224463A1 (en) * 2002-06-03 2003-12-11 Bayer Ag Process for the preparation of 5-nitro-3,4-dihydro-1 (2H) -naphthalinone, 1,5-naphthalenediamine and 1,5-naphthalenediisocyanate
KR100521933B1 (en) * 2002-06-05 2005-10-13 엘지전자 주식회사 Method for managing a summary of information for editing in rewritable optical disc
EP1568681B1 (en) * 2002-12-04 2010-04-28 Mitsui Chemicals, Inc. Process for producing 1,5-diaminonaphthalene
US7439369B2 (en) * 2004-06-22 2008-10-21 Loa Alamos National Security, Llc Method and system for hydrogen evolution and storage
JP4598486B2 (en) * 2004-11-17 2010-12-15 三井化学株式会社 Method for producing 1,5-diaminonaphthalene
CN1687011B (en) * 2005-03-31 2010-05-05 聂天明 Method for refining amino naphthalenes
CN107835669A (en) 2015-05-22 2018-03-23 Ebm融合解决方案有限责任公司 Joint or section bone implant for malformation correction
CN106432320B (en) * 2016-09-14 2019-04-05 山西大学 A kind of organic sulfide hydrogen donor and preparation method thereof containing ethylidene ether structure

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3840618C1 (en) * 1988-12-02 1990-03-15 Bayer Ag, 5090 Leverkusen, De
DE19651041A1 (en) * 1996-12-09 1998-06-10 Bayer Ag Process for the preparation of isocyanates from poorly soluble primary amines

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2523351C2 (en) 1975-05-27 1982-12-02 Bayer Ag, 5090 Leverkusen Process for the preparation of 1,5- and 1,8-diaminonaphthalene
JPS5851946B2 (en) 1979-10-19 1983-11-19 大阪曹達株式会社 Method for producing diaminonaphthalene
JPH04154745A (en) 1990-10-16 1992-05-27 Nippon Steel Chem Co Ltd Production of diaminonaphthalene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3840618C1 (en) * 1988-12-02 1990-03-15 Bayer Ag, 5090 Leverkusen, De
DE19651041A1 (en) * 1996-12-09 1998-06-10 Bayer Ag Process for the preparation of isocyanates from poorly soluble primary amines

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO02051792A1 *

Also Published As

Publication number Publication date
US20020103401A1 (en) 2002-08-01
CN1483017A (en) 2004-03-17
JP4206270B2 (en) 2009-01-07
HK1061675A1 (en) 2004-09-30
JP2004516309A (en) 2004-06-03
CN1275934C (en) 2006-09-20
WO2002051792A1 (en) 2002-07-04
US6706924B2 (en) 2004-03-16

Similar Documents

Publication Publication Date Title
US5739403A (en) Process for the production of optionally substituted 4-aminodiphenylamines
DD153835A5 (en) PROCESS FOR PREPARING 5-CARBONYL-10-OXO-10,11-DIHYDRO-5H-DIBENZ [B, F] AZEPIN
EP1345888A1 (en) Method for the production of 1,5-naphthalenediamine
DE2148223A1 (en) PROCESS FOR THE PRODUCTION OF NITRODIPHENYLAMINE DERIVATIVES
EP0325892B1 (en) Process for the preparation of halogenated primary amines
EP1527042B1 (en) Method for producing aminoalkoxy benzylamines and aminoalkoxy benzonitriles as intermediates
EP1369412B1 (en) Process for the preparation of 5-nitro-3,4-dihydro-1(2H)-naphthalenone, 1,5-naphthalendiamine and 1,5-naphthalendiisocyanate
DE2263715A1 (en) PROCESS FOR PRODUCING ETHAMBUTOL
EP0057871B1 (en) Process for the preparation of optionally p-chloro-substituted 2,6-diamino toluene
EP1205469A1 (en) Process for the preparation of 4-amino diphenylamine
EP0104531B1 (en) Cycloaliphatic diisocyanates, possibly in the form of a mixture of isomers, method for their preparation and their use as starting products in the preparation of synthetic products of the polyurethane type
DE10149041A1 (en) Production of 1,5-naphthalenediamine involves reaction of o-nitrotoluene with acrylic acid derivatives, e.g. with acrylonitrile to give 4-o-nitrophenyl-butyronitrile, followed by cyclization, aromatization and reduction
EP0180890B1 (en) Process for the diastereoselective reduction of 3-amino-1-benzoxepin-5(2h)-ones
DE2547654A1 (en) PRODUCTION OF 2-AMINO-1-ALCOHOLS
EP1268400B1 (en) Method for producing n-butyryl-4-amino-3-methyl-methyl benzoate and the novel compound n-(4-bromine-2-methylphenyl)-butanamide
DE69911757T2 (en) METHOD FOR PRODUCING 3-BROMANISOL AND 3-BROMNITROBENZOL
DD142331A5 (en) PROCESS FOR THE PREPARATION OF P-AMINO-DIPHENYLAMINE
WO2000055138A1 (en) Method of producing oxcarbazepine (=10,11- dihydro- 10- oxo- 5h- dibenz(b,f)- azepine- 5- carboxamide) and its intermediate products
DE2452015C2 (en) Process for the production of diaminonaphthalene
DE102004038577B4 (en) Preparation of 1,5-naphthalenediamine by Selective Halogenation
EP0307777B1 (en) 2-methyl-4-fluoro-phenols and process for their preparation
EP0743299B1 (en) Process for the preparation of 2-fluorocyclopropylamine sulfonic acid salts
EP0820981A1 (en) Process for the preparation of 2-trifluoromethoxy-aniline
EP0292885A2 (en) Catalytic transfer-hydrogenation with aromatic nitro compounds as hydrogen acceptor
DE2713431A1 (en) PROCESS FOR THE PRODUCTION OF DIACYLATED 4-IMIDAZOLINONE-2 AND THEIR USE FOR CYCLOADDITIONS

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030722

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WASTIAN, DIETMAR

Inventor name: ZECHLIN, JOACHIM

Inventor name: JAUTELAT, MANFRED

Inventor name: JOSCHEK, KATRIN

Inventor name: SCHELHAAS, MICHAEL

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BAYER MATERIALSCIENCE AG

17Q First examination report despatched

Effective date: 20090508

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BAYER INTELLECTUAL PROPERTY GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150812

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: COVESTRO DEUTSCHLAND AG

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20151111