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WO1998052885A1 - Reduction d'halogenures aromatiques - Google Patents

Reduction d'halogenures aromatiques Download PDF

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Publication number
WO1998052885A1
WO1998052885A1 PCT/AT1998/000112 AT9800112W WO9852885A1 WO 1998052885 A1 WO1998052885 A1 WO 1998052885A1 AT 9800112 W AT9800112 W AT 9800112W WO 9852885 A1 WO9852885 A1 WO 9852885A1
Authority
WO
WIPO (PCT)
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.)
Ceased
Application number
PCT/AT1998/000112
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
Sanochemia Ltd
Original Assignee
Sanochemia Pharmazeutika AG
Sanochemia Ltd
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 to HU0004681A priority Critical patent/HUP0004681A2/hu
Priority to EP98916623A priority patent/EP0983215A1/fr
Priority to CA002289992A priority patent/CA2289992A1/fr
Priority to AU70127/98A priority patent/AU7012798A/en
Priority to BR9809661-3A priority patent/BR9809661A/pt
Priority to JP54968898A priority patent/JP2001525828A/ja
Priority to KR1019997010758A priority patent/KR20010012795A/ko
Priority to NZ500733A priority patent/NZ500733A/xx
Application filed by Sanochemia Pharmazeutika AG, Sanochemia Ltd filed Critical Sanochemia Pharmazeutika AG
Priority to SK1583-99A priority patent/SK158399A3/sk
Publication of WO1998052885A1 publication Critical patent/WO1998052885A1/fr
Priority to NO995494A priority patent/NO995494D0/no
Priority to BG103880A priority patent/BG103880A/xx
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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

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 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.
  • 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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Nitrogen Condensed Heterocyclic Rings (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.
PCT/AT1998/000112 1997-05-21 1998-04-30 Reduction d'halogenures aromatiques Ceased WO1998052885A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
KR1019997010758A KR20010012795A (ko) 1997-05-21 1998-04-30 방향족 할로겐 화합물의 환원방법
CA002289992A CA2289992A1 (fr) 1997-05-21 1998-04-30 Reduction d'halogenures aromatiques
AU70127/98A AU7012798A (en) 1997-05-21 1998-04-30 Reduction of aromatic halogenides
BR9809661-3A BR9809661A (pt) 1997-05-21 1998-04-30 Redução de halogenetos aromáticos
JP54968898A JP2001525828A (ja) 1997-05-21 1998-04-30 芳香族ハロゲン化物の還元
HU0004681A HUP0004681A2 (hu) 1997-05-21 1998-04-30 Eljárás aromás halogenidek redukálására
EP98916623A EP0983215A1 (fr) 1997-05-21 1998-04-30 Reduction d'halogenures aromatiques
NZ500733A NZ500733A (en) 1997-05-21 1998-04-30 Reduction of aromatic halogenides by LiBH4 in the presence of oxygen
SK1583-99A SK158399A3 (en) 1997-05-21 1998-04-30 Reduction of aromatic halogenides
NO995494A NO995494D0 (no) 1997-05-21 1999-11-10 Reduksjon av aromatiske halogenider
BG103880A BG103880A (en) 1997-05-21 1999-11-15 Aromatic halogenide reduction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA865/97 1997-05-21
AT0086597A AT405051B (de) 1997-05-21 1997-05-21 Reduktion aromatischer halogenide

Publications (1)

Publication Number Publication Date
WO1998052885A1 true WO1998052885A1 (fr) 1998-11-26

Family

ID=3501602

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AT1998/000112 Ceased WO1998052885A1 (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) NO995494D0 (fr)
NZ (1) NZ500733A (fr)
PL (1) PL336906A1 (fr)
SK (1) SK158399A3 (fr)
WO (1) WO1998052885A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006018703A3 (fr) * 2004-08-16 2006-07-20 Ranbaxy Lab Ltd Procedes de preparation de la narwedine et son utilisation dans la synthese de galantamine
CN107602318A (zh) * 2017-09-08 2018-01-19 郑州大学 一种温和条件下卤代芳烃液相还原脱卤的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE112011104017T5 (de) * 2010-12-02 2013-09-05 The Yokohama Rubber Co., Ltd. Reifen ausgestattet mit einem Informationsbeschaffungsgerät

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0370325A1 (fr) * 1988-11-22 1990-05-30 BASF Aktiengesellschaft Procédé pour la déshalogénation réductive de composés aromatiques

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0370325A1 (fr) * 1988-11-22 1990-05-30 BASF Aktiengesellschaft Procédé pour la déshalogénation réductive de composés aromatiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
B. MEUNIER: "Reduction of aromatic halides with sodium borohydride catalysed by titanium complexes. Unexpectd role of air", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 204, no. 3, 20 January 1981 (1981-01-20), LAUSANNE CH, pages 345 - 346, XP002070291 *
J. SZEWCZYK: "An improved synthesis of galanthamine", JOURNAL OF HETEROCYCLIC CHEMISTRY, vol. 25, no. 6, 1988, pages 1809 - 1811, XP000562834 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006018703A3 (fr) * 2004-08-16 2006-07-20 Ranbaxy Lab Ltd Procedes de preparation de la narwedine et son utilisation dans la synthese de galantamine
CN107602318A (zh) * 2017-09-08 2018-01-19 郑州大学 一种温和条件下卤代芳烃液相还原脱卤的方法
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

Also Published As

Publication number Publication date
NO995494L (no) 1999-11-10
JP2001525828A (ja) 2001-12-11
CA2289992A1 (fr) 1998-11-26
PL336906A1 (en) 2000-07-17
SK158399A3 (en) 2000-07-11
BR9809661A (pt) 2000-07-11
BG103880A (en) 2000-06-30
AT405051B (de) 1999-05-25
NZ500733A (en) 2001-03-30
AU7012798A (en) 1998-12-11
CN1257467A (zh) 2000-06-21
EP0983215A1 (fr) 2000-03-08
NO995494D0 (no) 1999-11-10
HUP0004681A2 (hu) 2001-04-28
KR20010012795A (ko) 2001-02-26
ATA86597A (de) 1998-09-15

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