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EP0983215A1 - Reduction d'halogenures aromatiques - Google Patents

Reduction d'halogenures aromatiques

Info

Publication number
EP0983215A1
EP0983215A1 EP98916623A EP98916623A EP0983215A1 EP 0983215 A1 EP0983215 A1 EP 0983215A1 EP 98916623 A EP98916623 A EP 98916623A EP 98916623 A EP98916623 A EP 98916623A EP 0983215 A1 EP0983215 A1 EP 0983215A1
Authority
EP
European Patent Office
Prior art keywords
oxygen
reduction
mixture
reduced
lialh
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Withdrawn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
EP98916623A
Other languages
German (de)
English (en)
Inventor
Laszlo Czollner
Johannes Fröhlich
Ulrich Jordis
Bernhard Küenburg
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.)
Sanochemia Pharmazeutika AG
Original Assignee
Sanochemia Pharmazeutika 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
Application filed by Sanochemia Pharmazeutika AG filed Critical Sanochemia Pharmazeutika AG
Publication of EP0983215A1 publication Critical patent/EP0983215A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
    • C07D333/10—Thiophene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B31/00—Reduction in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms

Definitions

  • the invention relates to a process for the reduction of aromatic halides.
  • reducing agents such as Cr (C10 4 ) 2 / ethylenediamine [880SColl6 / 821], tin / HBr [550SColl3 / l32], the catalytic reduction with Raney nickel 91CEX109] or Pd / hydrazine hydrate [ 59JOC421], further reducing agents such as K-Selectride / Cul [NaBH 4 / (Me 3 Si) 3 SiH [89TL2733], iAlH 4 [83JA631, 82TL1643, 59JOC917, 59JOC917, 89TH3329], or similar complex hydrides such as LiAlH (OMe) 3 / CuI [73JA6452] known.
  • the reducing agent LiAlH 4 was often used together with catalytic or stoichiometric amounts of inorganic halides such as CeCl 3 [85CL1491], TiCl 4 [73CL291], FeCl 2 / CoCl 2 , TiCl 3 , NiCl 2 [78JOC1263] or at most through these additions other reducing agents produced.
  • inorganic halides such as CeCl 3 [85CL1491], TiCl 4 [73CL291], FeCl 2 / CoCl 2 , TiCl 3 , NiCl 2 [78JOC1263] or at most through these additions other reducing agents produced.
  • the simultaneous exposure [83CC907] or the use of ultrasound [82TL1643] in the reduction of aromatic halides are known as further variants of the use of iAlH 4 .
  • the invention has for its object to provide a process for the reduction of aromatic and heteroaromatic halides with which the reduction can be carried out more quickly and in high yields even when working in larger batches.
  • reducing agents can be used within the scope of the invention.
  • reducing agents that can be used are: hydride reagents such as DiBAL-H (diisobutylaluminum hydride), DiBAL-H / ZnCl 2 , Al-isopropylate, Red-Al R (sodium bis (2-methoxyethoxy) aluminum hydride (Aldrich)), K- Selectride R (potassium tri-sec.-butyl borohydride (Aldrich)), L-Selectride R (lithium tri-sec.-butyl borohydride (Aldrich)), KS-Selectride R (potassium trisiamyl borohydride (Aldrich)), LS -Selectride R (lithium-trisiamylborohydride (Aldrich)), Li-tri-t-butoxy-AlH, Li-tri-ethoxy-AlH, 9BBN
  • (hetero-) aromatic halides are reduced with a reducing agent, in particular LiAlH 4f in the presence of oxygen, for example air, or an oxygen / inert gas mixture.
  • a reducing agent in particular LiAlH 4f
  • oxygen for example air
  • inert gas for example nitrogen, argon, helium
  • oxygen which may be diluted with an inert gas, is blown into the reaction solution or sucked through.
  • the invention provides an efficient and industrially applicable process for the reduction of (hetero) aromatic halides with a reducing agent, such as LiAlH 4 , in the presence of oxygen.
  • a reducing agent such as LiAlH 4
  • the reduction of aromatic halogen compounds is significantly accelerated by introducing oxygen, in particular (synthetic) air, into a solution of the halogenated aromatic and the reducing agent in a solvent.
  • oxygen in particular (synthetic) air
  • the reduction of (hetero) aromatic halogen compounds is made possible, which cannot be reduced with LiAlH 4 alone.
  • Further advantages of the presence of oxygen or air in the reduction are the higher achievable yields and less undesirable by-products which arise from long reaction times (without oxygen).
  • the method of the invention is particularly suitable for the reduction of compounds of the bromine-narwedin type (see scheme 2) on a kilogram scale and for the economical reduction of large quantities.
  • Example 1 -X-naphthalene
  • the method according to the invention has i.a. the advantage that the reaction time is reduced when reducing (hetero) aromatic halides.
  • reducing (hetero) aromatic halides i.a. the advantage that the reaction time is reduced when reducing (hetero) aromatic halides.
  • mixtures of oxygen with one or more inert gases can be used in the invention.
  • inert gases such as nitrogen, argon, helium

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

L'invention concerne la réduction d'halogénures (hétéro)aromatiques de la formule générale (I) Ar-Xn en composés de la formule générale (II) Ar-Hn, réduction dans laquelle on utilise un agent de réduction, en particulier un réactif hydrure comme l'hydrure d'aluminium et de lithium (LiAlH4), en présence d'oxygène, en particulier sous forme d'un mélange d'oxygène et de gaz inerte. La réduction en présence d'oxygène donne de bons rendements pour des temps de réaction courts même dans des installations semi-industrielles ou industrielles. La réduction avec LiAlH4 en présence d'oxygène convient également à la réduction d'halogénures hétéroaromatiques complexes, par exemple à la réduction de cétal de bromonarwedine en cétal de narwedine à échelle industrielle.
EP98916623A 1997-05-21 1998-04-30 Reduction d'halogenures aromatiques Withdrawn EP0983215A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT86597 1997-05-21
AT0086597A AT405051B (de) 1997-05-21 1997-05-21 Reduktion aromatischer halogenide
PCT/AT1998/000112 WO1998052885A1 (fr) 1997-05-21 1998-04-30 Reduction d'halogenures aromatiques

Publications (1)

Publication Number Publication Date
EP0983215A1 true EP0983215A1 (fr) 2000-03-08

Family

ID=3501602

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98916623A Withdrawn EP0983215A1 (fr) 1997-05-21 1998-04-30 Reduction d'halogenures aromatiques

Country Status (15)

Country Link
EP (1) EP0983215A1 (fr)
JP (1) JP2001525828A (fr)
KR (1) KR20010012795A (fr)
CN (1) CN1257467A (fr)
AT (1) AT405051B (fr)
AU (1) AU7012798A (fr)
BG (1) BG103880A (fr)
BR (1) BR9809661A (fr)
CA (1) CA2289992A1 (fr)
HU (1) HUP0004681A2 (fr)
NO (1) NO995494L (fr)
NZ (1) NZ500733A (fr)
PL (1) PL336906A1 (fr)
SK (1) SK158399A3 (fr)
WO (1) WO1998052885A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006046096A2 (fr) * 2004-08-16 2006-05-04 Ranbaxy Laboratories Limited Forme polymorphe de la narwedine et son utilisation dans la synthese de la galantamine
WO2012073973A1 (fr) * 2010-12-02 2012-06-07 横浜ゴム株式会社 Pneu équipé de dispositif d'acquisition d'informations
CN107602318B (zh) * 2017-09-08 2020-06-05 郑州大学 一种温和条件下卤代芳烃液相还原脱卤的方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3839329A1 (de) * 1988-11-22 1990-05-31 Basf Ag Verfahren zur reduktiven enthalogenierung von aromaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9852885A1 *

Also Published As

Publication number Publication date
AT405051B (de) 1999-05-25
AU7012798A (en) 1998-12-11
CN1257467A (zh) 2000-06-21
KR20010012795A (ko) 2001-02-26
NZ500733A (en) 2001-03-30
JP2001525828A (ja) 2001-12-11
NO995494D0 (no) 1999-11-10
WO1998052885A1 (fr) 1998-11-26
NO995494L (no) 1999-11-10
SK158399A3 (en) 2000-07-11
CA2289992A1 (fr) 1998-11-26
BR9809661A (pt) 2000-07-11
PL336906A1 (en) 2000-07-17
HUP0004681A2 (hu) 2001-04-28
BG103880A (en) 2000-06-30
ATA86597A (de) 1998-09-15

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