EP0804409A1 - Verfahren zur herstellung von aromatischen stickstoff derivate, die in der metaposition substituiert sind - Google Patents

Verfahren zur herstellung von aromatischen stickstoff derivate, die in der metaposition substituiert sind

Info

Publication number
EP0804409A1
EP0804409A1 EP95925881A EP95925881A EP0804409A1 EP 0804409 A1 EP0804409 A1 EP 0804409A1 EP 95925881 A EP95925881 A EP 95925881A EP 95925881 A EP95925881 A EP 95925881A EP 0804409 A1 EP0804409 A1 EP 0804409A1
Authority
EP
European Patent Office
Prior art keywords
aniline
acid
mixture
anilide
nitration
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Withdrawn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
EP95925881A
Other languages
English (en)
French (fr)
Inventor
Michel Crochemore
Gilbert Guidot
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.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
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 Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0804409A1 publication Critical patent/EP0804409A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro 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
    • C07C209/30—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
    • C07C209/365—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 by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups

Definitions

  • the present invention relates to a process for carrying out the synthesis of nitrogen derivatives substituted in the meta position. It relates more particularly to a sequence of particularly well adapted and cooperating stages allowing the above derivatives to be obtained inexpensively.
  • nitrogen derivatives are understood to mean a derivative carrying a nitrogen directly linked to the aromatic nucleus in general with a single ring, namely the aromatic benzene nucleus.
  • one of the aims of the present invention is to provide a process which allows recycling of one or more unwanted isomers to the initial stage.
  • nitroanilines according to the present invention are advantageously obtained by nitration of an aniline or better still of an anilide having the suitable substitutions, that is to say having one substitution or alternatively two substitutions in the ortho and / or para position.
  • the acid which also gives these satisfactory anilides mention should be made of the acids deriving from carbonic acid by monoesterification or monoamidation.
  • the corresponding anilides must remain stable under the conditions of high acidity necessary for the nitration operation.
  • the nitration of aromatic derivatives is an operation in itself known, however according to the present invention it has been found that one of the best media for carrying out the nitration reaction is a medium which comprises nitric acid sulfuric acid and a carboxylic acid.
  • the reaction mixture can also comprise a significant proportion of water which can be introduced as such or else introduced in the form of one of the abovementioned mineral acids.
  • the water content in the reaction medium is between 1 / 10th and once the amount of pure nitric acid used.
  • nitro function during nitration is introduced in high proportion in the ortho or para position of the amine or anilide function
  • the reaction of the cleavage of the anilides to restore the anilines is carried out in the same reaction system as that of the nitration. To do this, it suffices to heat to a temperature at least equal to 50oC. preferably at least equal to 80 ° C., the reaction mixture resulting from the nitration after addition. optional, a certain amount of water.
  • This cleavage operation can be carried out without separation or after separation.
  • the aniline thus obtained can be used directly in the reaction mixture. It is also possible to separate the aniline sei thus obtained in order to use it during the desammation operation.
  • This deamination operation is carried out by reducing diazotization. All the reducing diazotizations known in the literature give good results, in particular those using hypophosbhorous acid or its salts. This reduction diazotization can be done either by preparing the diazonium salt separately by the action of a solution of sodium nitrite generally dissolved in water.
  • nitro products thus selected can be particularly interesting synthesis intermediates. But one of the advantages of this method is to provide a pathway for metasuostituted anilines.
  • steps can optionally be supplemented by a step a) of protection of the aniline in the form of an anilide by means of an anhydride or of an acid halide and by step e) of reduction of the nitro derivative. obtained in d).
  • One of the advantages of the process according to the present invention is the fact that it requires no separation between each step and that the reaction mixture of the previous step does not harm. even favese the next step.
  • the reaction mixture can comprise an acid, generally a carboxylic acid which can play the role of a solvent or of a third solvent allowing the reactions to take place in homogeneous onase.
  • the temperature goes from 30 ° to 67o.
  • the salt and washing waters are neutralized with sodium hydroxide and then extracted with 3 x 500 ml of CH 2 CI 2 . After concentration, a second jet of 53 g is obtained, grading 98%.
  • the overall yield is 99%.
  • thermometer In a 2 I glass reactor fitted with a half-moon type mechanical stirring, a condenser and a liquid inlet. of a thermometer, we load:
  • reaction mixture is then poured onto 1,800 g of ice contained in a 4-liter cylindrical reactor.
  • the casting lasts 1 hour and the final temperature of 7o.
  • reaction mixture containing the diazonium salt.
  • the mixture is left to stir for another hour at 20 ° and then 200 ml of water and 200 ml of isooropyl ether are added.
  • the aqueous layer is exhausted with 3 x 100 mt of isopropyl ether.
  • the two amino isomers are then separated by distillation.
  • Example 4 reduction of difiuoro 3,5 nitrobenzene according to the so-called "Béchamp" reaction 155 g of difluoronitrobenzene containing 0.94 moles of isomers 3.5 and 0.3 moles of isomers 2.4 are poured onto a bottom with 217 g of sieve cast iron mixture, washed beforehand with acetone and then dried and made up of 310 ml of 0.78 N ammonium chloride in water. The duration of the addition of the mixture of difluorobenzenes is 1 h and is maintained at reflux for 4 h.
  • reaction mixture is subjected to a steam drive for 8 h. 124.3 g of a colorless oil crystallizing at around 40 ° C. are obtained in white needles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP95925881A 1994-07-20 1995-07-12 Verfahren zur herstellung von aromatischen stickstoff derivate, die in der metaposition substituiert sind Withdrawn EP0804409A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9408969A FR2722785B1 (fr) 1994-07-20 1994-07-20 1procede pour l'obtention de derives2substitue(s) en position meta.
FR9408969 1994-07-20
PCT/FR1995/000941 WO1996002493A1 (fr) 1994-07-20 1995-07-12 Procede pour l'obtention de derives aromatiques azotes substitues en position meta

Publications (1)

Publication Number Publication Date
EP0804409A1 true EP0804409A1 (de) 1997-11-05

Family

ID=9465568

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95925881A Withdrawn EP0804409A1 (de) 1994-07-20 1995-07-12 Verfahren zur herstellung von aromatischen stickstoff derivate, die in der metaposition substituiert sind

Country Status (4)

Country Link
EP (1) EP0804409A1 (de)
AU (1) AU2984195A (de)
FR (1) FR2722785B1 (de)
WO (1) WO1996002493A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19720341C1 (de) * 1997-05-15 1998-08-27 Clariant Gmbh Verfahren zur Herstellung von 3,5-Difluoranilin
US5977412A (en) * 1998-08-14 1999-11-02 Basf Corporation Process for preparing 3,5-difluoroaniline
AU2002339579A1 (en) * 2002-10-24 2004-05-13 Dr. Reddy's Laboratories Ltd. A process for the preparation of 3,4,5-trifluoronitrobenzene

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2555736C2 (de) * 1975-12-11 1978-01-26 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Halogennitrobenzolen
EP0038465A1 (de) * 1980-04-17 1981-10-28 Hoechst Aktiengesellschaft Verfahren zur Herstellung von 2-Trifluormethylanilin
US5294742A (en) * 1992-03-21 1994-03-15 Hoechst Atkiengesellschaft Process for preparing 3,5-difluoroaniline

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9602493A1 *

Also Published As

Publication number Publication date
FR2722785A1 (fr) 1996-01-26
AU2984195A (en) 1996-02-16
WO1996002493A1 (fr) 1996-02-01
FR2722785B1 (fr) 1996-10-25

Similar Documents

Publication Publication Date Title
BE1006426A6 (fr) Procede de preparation de la n-methyl-3-phenyl-3-[4-(trifluoromethyl)-phenoxy]-propylamine et de ses sels d'addition d'acide.
EP0054464B1 (de) Verfahren zur Herstellung von ortho-Trifluormethylanilin
EP0876331B1 (de) Verfahren zur herstellung von arylhydrazin durch reduktion von azo-derivate
EP0804409A1 (de) Verfahren zur herstellung von aromatischen stickstoff derivate, die in der metaposition substituiert sind
CA1026379A (en) Process for the preparation of nitro-2 halogenphenols
EP0211775B1 (de) Verfahren zur Nitrierung von Phenolverbindungen
FR2558464A1 (fr) Procede de preparation de trifluoromethylanilines
FR2547815A1 (fr) Procede d'halogenation-nitration-fluoration de derives aromatiques
EP0131526B1 (de) Verfahren zur Herstellung von Aminophenolen durch Hydroxylierung von Anilinen mit Wasserstoffperoxid in Supersäuremedium
FR2522652A1 (fr) Procede pour la fabrication d'ortho- ou de para-nitrophenetole pratiquement pur
EP0599704B1 (de) Syntheseweg zu desaktivierten Anilinen
CA1338353C (fr) Procede de preparation d'imides halogenes
FR2700538A1 (fr) Procédé de préparation de 2-méthyl-3-aminobenzotrifluorure.
WO2000061523A1 (fr) Halogenation en position meta de phenols proteges
EP0912492B1 (de) Verfahren zur herstellung von halogenierten derivaten des 2-amino oder 2-acetamido trifluormethylbenzols
CA2149195C (fr) Procede de synthese d'halogenoalkylferrocenes
FR3158731A1 (fr) Procédé de préparation de para-aminophénol et de ses dérivés
FR2584394A1 (fr) Procede de valorisation sous-forme de produits perbromes de produits sous-bromes obtenus en solutions
EP0105008B1 (de) Verfahren zur Eliminierung der nitrosierenden Verbindungen von aromatischen Nitroverbindungen
CA2377743A1 (fr) Perfectionnement a l'echange et a la liberation d'une amine, de son fluorure de carbamoyle
BE819380A (fr) Procede de racemisation d'amines optiquement actives
FR2601003A1 (fr) Procede de preparation de dinitroalkylbenzenes
FR2708931A1 (fr) Procédé de fonctionnalisation d'un noyau aromatique à partir d'un dérivé nitré ou nitroso.
FR2796068A1 (fr) Procede de deshydrogenofluoration d'un fluorure de carbamoyle aromatique
EP0347283A1 (de) Verfahren zur Herstellung von 2,6-Dichloro-4-aminophenol

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

AK Designated contracting states

Kind code of ref document: A1

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

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

Owner name: RHODIA CHIMIE

17P Request for examination filed

Effective date: 19970428

17Q First examination report despatched

Effective date: 20020610

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: 20021022