EP0984909A1 - Utilisation d'un catalyseur au rhodium pour l'hydroamination et/ou l'amination par oxydation d'olefines a substitution aryle, et procede de preparation d'une 2-arylvinylamine - Google Patents

Utilisation d'un catalyseur au rhodium pour l'hydroamination et/ou l'amination par oxydation d'olefines a substitution aryle, et procede de preparation d'une 2-arylvinylamine

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Publication number
EP0984909A1
EP0984909A1 EP98930677A EP98930677A EP0984909A1 EP 0984909 A1 EP0984909 A1 EP 0984909A1 EP 98930677 A EP98930677 A EP 98930677A EP 98930677 A EP98930677 A EP 98930677A EP 0984909 A1 EP0984909 A1 EP 0984909A1
Authority
EP
European Patent Office
Prior art keywords
formula
tris
phosphane
rhodium
amine
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Withdrawn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
EP98930677A
Other languages
German (de)
English (en)
Inventor
Martin Eichberger
Matthias Beller
Harald Trautwein
Jürgen HERWIG
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.)
Evonik Operations GmbH
Original Assignee
Aventis Research and Technologies GmbH and Co KG
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
Application filed by Aventis Research and Technologies GmbH and Co KG filed Critical Aventis Research and Technologies GmbH and Co KG
Publication of EP0984909A1 publication Critical patent/EP0984909A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B43/00—Formation or introduction of functional groups containing nitrogen
    • C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/06—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals
    • C07D295/073—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by halogen atoms or nitro radicals with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings

Definitions

  • the present invention relates to the use of a rhodium catalyst and a new process for the preparation of 2-aryl-substituted ethylene and ethyl amines.
  • Amines and their derivatives are of industrial importance as intermediates for dyes, fine chemicals, pharmaceuticals and agricultural products. Of particular importance are 2-aryl-substituted ethylamines, which find numerous applications as pharmaceuticals, agrochemicals and fine chemicals. As simple and multifunctional derivatives of amines, they are of particular technical interest.
  • the object of the present invention is to provide a simple process for the direct amination or hydroamination of aryl-substituted olefins, in particular a process for the preparation of 2-aryl-substituted ethylene and ethyl amines and their derivatives, with which the disadvantages of the prior art mentioned are avoided.
  • a rhodium catalyst for inter- or intramolecular hydroamination and / or inter- or intramolecular oxidative amination of aryl-substituted olefins using primary or secondary amines, characterized in that the rhodium catalyst contains a cationic rhodium compound of oxidation level I or III.
  • This special catalyst makes it possible for the first time to directly amine aryl-substituted olefins.
  • the anti-Markovnikov products are always formed in the case of asymmetrical olefins. This means that the nitrogen atom of the amine used only attacks the more highly substituted carbon atom of the olefin bond.
  • the rhodium catalyst contains a non-coordinating or only weakly coordinating anion, in particular a perchlorate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate, tetraarylborate, trifluoroacetate, alkyl or arylsulfonate anion.
  • a non-coordinating or only weakly coordinating anion in particular a perchlorate, hexafluorophosphate, hexafluoroantimonate or tetrafluoroborate, tetraarylborate, trifluoroacetate, alkyl or arylsulfonate anion.
  • the rhodium catalyst preferably contains a cationic rhodium compound of oxidation state I or III complexed by at least one ligand.
  • a phosphane in particular selected from the group of triphenylphosphine, trifurylphosphine, bis (4-methoxyphenyl) phenylphosphine, bis (3-methoxyphenyl) phenylphosphine, bis (4-fluorophenyl) phenylphosphine, diphenylmethylphosphine, tricyclohexylphosphine, n-butylphosphine, thisopropylphosphine, tris- (4-methoxyphenyl) phosphane, tris- (3-methoxyphenyl) phosphane, Ths- (4-fluorophenyl) phosphine, tris- (3-fluorophenyl) phosphane, Ths- (4-chlorophen
  • the ratio of the phosphorus atoms from the phosphine ligands to the rhodium atoms, based on the catalyst is between 0.5: 1 and 10: 1.
  • a diolefin can also be used as the ligand, which is selected in particular from cyclooctadiene, dicyclopentadiene or norbomadiene.
  • the rhodium catalyst based on the primary and / or secondary amine, is used in amounts from 0.0001 mol% to 20 mol%, in particular from 0.1 mol% to 10 mol%.
  • the rhodium catalyst described above can be used particularly well according to the invention for the preparation of a 2-arylvinylamine of the formula (I)
  • Ar represents an aryl radical, in particular from the group of the condensed or uncondensed C 6 -C 22 aromatics, such as, for example, phenyl, naphthyl, anthryl, phenanthryl and biphenylyl radicals, or the condensed or uncondensed C 5 -C 2 2-heteroaromatics which have at least one nitrogen, oxygen or sulfur atom in the ring, such as, for example, indenyl, pyridyl
  • R 1 and R 2 independently represent a hydrogen atom or a C1-C 4 alkyl radical
  • R 3 and R 4 independently of one another represent a hydrogen atom, a C1-C20-alkyl radical or one of the previously defined aryl radicals Ar, or R 3 and
  • this catalyst can also be used to prepare a 2-arylethylamine of the formula (I)
  • radicals R 1 to R and Ar have the same meaning as previously indicated.
  • the aryl radical Ar originating either from the vinylaryl compound of the formula (II) or from the amine of the formula (III), can have up to 8 substituents which independently of one another represent a fluorine, chlorine, bromine or iodine atom or are selected from the group of HO-, HC (O) -, HCO 2 -, H 2 N-, NC-, HC (O) NH-, H 2 NC (O) -, NO 2 -, HSO 3 -, CF 3 -, R 5 -, R 5 O-, R 5 C (O) -, R 5 CO 2 -, R 5 NH-, R 5 2 N-, R 5 C (O) NH-, R 5 CO 2 CHCH-, R 5 SO 2 -, R 5 S (O) -, R 5 P (O) -, and R 5 3 Si residues, as well as from five and six-membered heteroaromatics which have at least one nitrogen, oxygen or sulfur atom in the ring
  • the vinylaryl compound of the formula (II) is styrene, in particular styrene substituted in the ortho, meta or para position, preferably styrene substituted with a heteroaryl radical.
  • a primary or secondary, aromatic or aliphatic amine can be used as the amine of the formula (III).
  • Morpholine, piperidine, piperazine, dimethylamine, diethylamine, dipropylamine or dibutylamine are particularly preferred.
  • the compounds obtained according to the present process can be isolated or used directly for subsequent reactions such as hydrogenation or reaction with electrophiles (aldehydes, epoxides, alkyl halides).
  • Inert organic solvents are generally used as solvents in the process according to the invention.
  • Aromatic hydrocarbons such as toluene, xylenes, anisole, tetralin and aliphatic ethers such as tetrahydrofuran, dimethoxyethane, dioxane, tetrahydropyran, formaldehyde acetals are preferred.
  • the reaction of the amines with substituted styrenes takes place at temperatures of 20-250 ° C, preferably at 40-200 ° C and particularly preferably at 60-160 ° C.
  • the 2-arylvinylamine or the 2-arylethylamine is preferably formed.
  • the mixture of 2-arylvinylamine or 2-arylethylamine obtained in other cases can be isolated by suitable methods, in particular by column chromatography.
  • the 2-arylvinylamine obtained can then be hydrogenated in the presence of hydrogen and a hydrogenation catalyst according to standard conditions (K Weissermel, HJ Arpe, Industrielle Organische Chemie, VCH, 1988) to the corresponding 2-arylethylamine .
  • the products are generally formed in good yields of up to 99% by the process according to the invention.
  • the hydrogenation products of the vinylaryl compound used are observed as by-products and are easily separable.
  • ethylbenzene is formed as a by-product.
  • Example 2-19 are carried out analogously to Example 1.
  • the starting materials and their amounts and the reaction results are summarized in Table 1 (NBD) 2 RhBF was prepared according to TG Schenk et al., Inorg. Chem. 24 (1985), p. 2334. The subsequent hydrogenation to the amine was not carried out in experiments 14-17.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne l'utilisation d'un catalyseur au rhodium pour l'hydroamination intermoléculaire ou intramoléculaire et/ou l'amination par oxydation intermoléculaire ou intramoléculaire d'oléfines à substitution aryle au moyen d'amines primaires et secondaires, ledit catalyseur au rhodium présentant un composé rhodium cationique à degré d'oxydation I ou III. L'invention concerne également un nouveau procédé de préparation d'éthylène-amines et d'éthylamines à substitution 2-aryle.
EP98930677A 1997-05-28 1998-05-08 Utilisation d'un catalyseur au rhodium pour l'hydroamination et/ou l'amination par oxydation d'olefines a substitution aryle, et procede de preparation d'une 2-arylvinylamine Withdrawn EP0984909A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19722373 1997-05-28
DE19722373A DE19722373A1 (de) 1997-05-28 1997-05-28 Verwendung eines Rhodiumkatalysators sowie ein neues Verfahren zur Herstellung von 2-arylsubstituierten Ethylen- und Ethylaminen
PCT/EP1998/002715 WO1998054115A1 (fr) 1997-05-28 1998-05-08 Utilisation d'un catalyseur au rhodium pour l'hydroamination et/ou l'amination par oxydation d'olefines a substitution aryle, et procede de preparation d'une 2-arylvinylamine

Publications (1)

Publication Number Publication Date
EP0984909A1 true EP0984909A1 (fr) 2000-03-15

Family

ID=7830772

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98930677A Withdrawn EP0984909A1 (fr) 1997-05-28 1998-05-08 Utilisation d'un catalyseur au rhodium pour l'hydroamination et/ou l'amination par oxydation d'olefines a substitution aryle, et procede de preparation d'une 2-arylvinylamine

Country Status (6)

Country Link
EP (1) EP0984909A1 (fr)
JP (1) JP2002500653A (fr)
AU (1) AU8103798A (fr)
DE (1) DE19722373A1 (fr)
IL (1) IL133117A0 (fr)
WO (1) WO1998054115A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6281387B1 (en) * 1999-10-29 2001-08-28 Union Carbide Chemicals & Plastics Technology Corporation Process and catalyst for synthesizing aliphatic, cyclic and aromatic alkanolamines and alkyleneamines
US6384282B2 (en) * 2000-03-01 2002-05-07 Yale University Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds
DE10025114A1 (de) * 2000-05-20 2001-11-22 Aventis Res & Tech Gmbh & Co Verfahren zur Herstellung von Arylethylaminen durch Aminierung von Arylolefinen
ES2268987B1 (es) * 2005-08-05 2008-02-01 Ragactives, S.L. Procedimiento para la obtencion de 3,3-difenilpropilaminas.
CN103370302B (zh) 2011-02-21 2015-06-17 赢创德固赛有限公司 借助Xantphos催化剂体系用氨将醇直接胺化成伯胺的方法
WO2016056581A1 (fr) * 2014-10-08 2016-04-14 国立研究開発法人理化学研究所 Agent favorisant la croissance de plante et procédé pour favoriser la croissance de plante

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9854115A1 *

Also Published As

Publication number Publication date
AU8103798A (en) 1998-12-30
DE19722373A1 (de) 1998-12-03
IL133117A0 (en) 2001-03-19
WO1998054115A1 (fr) 1998-12-03
JP2002500653A (ja) 2002-01-08

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