EP0983215A1 - Reduktion aromatischer halogenide - Google Patents

Reduktion aromatischer halogenide

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Withdrawn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)
French (fr)
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/de
Withdrawn legal-status Critical Current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)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
EP98916623A 1997-05-21 1998-04-30 Reduktion aromatischer halogenide Withdrawn EP0983215A1 (de)

Applications Claiming Priority (3)

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

Publications (1)

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

Family

ID=3501602

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98916623A Withdrawn EP0983215A1 (de) 1997-05-21 1998-04-30 Reduktion aromatischer halogenide

Country Status (15)

Country Link
EP (1) EP0983215A1 (hu)
JP (1) JP2001525828A (hu)
KR (1) KR20010012795A (hu)
CN (1) CN1257467A (hu)
AT (1) AT405051B (hu)
AU (1) AU7012798A (hu)
BG (1) BG103880A (hu)
BR (1) BR9809661A (hu)
CA (1) CA2289992A1 (hu)
HU (1) HUP0004681A2 (hu)
NO (1) NO995494D0 (hu)
NZ (1) NZ500733A (hu)
PL (1) PL336906A1 (hu)
SK (1) SK158399A3 (hu)
WO (1) WO1998052885A1 (hu)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006018703A2 (en) * 2004-08-16 2006-02-23 Ranbaxy Laboratories Limited Processes for preparation of narwedine and its use in the synthesis of galantamine
DE112011104017T5 (de) * 2010-12-02 2013-09-05 The Yokohama Rubber Co., Ltd. Reifen ausgestattet mit einem Informationsbeschaffungsgerät
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
ATA86597A (de) 1998-09-15
KR20010012795A (ko) 2001-02-26
BR9809661A (pt) 2000-07-11
AU7012798A (en) 1998-12-11
PL336906A1 (en) 2000-07-17
NZ500733A (en) 2001-03-30
JP2001525828A (ja) 2001-12-11
HUP0004681A2 (hu) 2001-04-28
NO995494L (no) 1999-11-10
WO1998052885A1 (de) 1998-11-26
CN1257467A (zh) 2000-06-21
CA2289992A1 (en) 1998-11-26
SK158399A3 (en) 2000-07-11
NO995494D0 (no) 1999-11-10
BG103880A (en) 2000-06-30

Similar Documents

Publication Publication Date Title
CH649980A5 (de) Phenoxybenzylalkohole und verfahren zu ihrer herstellung.
Burckhalter et al. Ethylene and Phenylacetyl Chloride in the Friedel-Crafts Reaction. Novel Syntheses of 2-Tetralones and Benzofuranones1
CN108689866B (zh) 一种(r)-3-氨基丁醇的合成方法
CN108675948A (zh) 一种β-羟基硒醚化合物及制备方法
WO1998052885A1 (de) Reduktion aromatischer halogenide
CN108863878A (zh) 一种β-羟基硒醚化合物及制备方法
CN109232447A (zh) 1h-1,2,3-三氮唑的制备方法
Hampton et al. Cuprous chloride catalyzed dimerizations of. beta.-dicarbonyl compounds via their dicarbanions
Lumma Jr et al. Synthesis of two benzothiacyclanones via a novel two-carbon ring expansion of thiolactones with vinyllithium
Bell et al. Synthesis of alkenyl sulphoxides by intramolecular and intermolecular addition of sulphenic acids to alkynes
Moon et al. Solvent effects in heteroaromatic SRN1 reactions
CA1171098A (en) Process for producing cyclopropyl carboxylic amides
CN108484518A (zh) 一种2-（2,4,6-三甲基苯硒基）-5-甲基苯并恶唑化合物及制备方法
Sakamoto et al. Synthesis of methyl 2-(heteroaryl) propanoates via palladium-catalyzed reaction
DE2305214C3 (de) Ungesättigte Sulfone
Takeda et al. Copper (I) iodide-catalyzed regioselective allylation of α-(2-pyridylthio) allylstannanes. A new route to δ, ε-unsaturated ketones
CN110804012A (zh) 一种还原缩硫醛或缩硫酮脱硫的方法
JPS5899473A (ja) α−アセチルラクトン類の製造方法
KUNIEDA et al. Mild Dehalogenative Reduction of Tri-and Di-halogenomethyl Compounds to Lower Halides by Nickel Tetracarbonyl
CN108912045A (zh) 一种2-苯硒基喹啉化合物及制备方法
US3849442A (en) Manufacture of 1-alkenyl-2-aminomethyl pyrrolidines
DE3405332A1 (de) Neue allylamine, verfahren zu ihrer herstellung und ihre verwendung
Rieke et al. Preparation of Functionalized α-Chloromethyl Ketones Using Rieke Zinc
DE962789C (de) Verfahren zur Herstellung von Dimethylsulfid
JPS5890571A (ja) 新規な中員環アミドスルフイド化合物及びその合成法

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: 19991008

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Free format text: AL PAYMENT 19991008;LT PAYMENT 19991008;LV PAYMENT 19991008;RO PAYMENT 19991008;SI PAYMENT 19991008

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20011201