EP1506163A1 - Procede de production d'alcoxybenzonitriles sans catalyseur - Google Patents

Procede de production d'alcoxybenzonitriles sans catalyseur

Info

Publication number
EP1506163A1
EP1506163A1 EP03752756A EP03752756A EP1506163A1 EP 1506163 A1 EP1506163 A1 EP 1506163A1 EP 03752756 A EP03752756 A EP 03752756A EP 03752756 A EP03752756 A EP 03752756A EP 1506163 A1 EP1506163 A1 EP 1506163A1
Authority
EP
European Patent Office
Prior art keywords
alcoholate
reaction mixture
reaction
catalyst
alkyl
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Withdrawn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
EP03752756A
Other languages
German (de)
English (en)
Inventor
Mario Gomez Andreu
Jürgen SANS
Franz Thalhammer
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
Degussa GmbH
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 Degussa GmbH filed Critical Degussa GmbH
Publication of EP1506163A1 publication Critical patent/EP1506163A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the present invention relates to a process for the catalyst-free preparation of alkoxybenzonitriles by substitution of monohalogenated starting compounds of a defined formula.
  • Alkoxybenzonitriles are very important intermediates in the synthesis of numerous agricultural and pharmaceutical products.
  • the starting compounds are not aromatic nitriles.
  • halogenated benzonitriles are reacted with metal alcoholates, an expensive palladium or nickel compound being used in combination with a corresponding expensive ligand as a catalyst.
  • the catalytic dehalogenation of halogenated aryls using a Pd / imidazole salt system according to Organometalips, 2001, 20, 6, 3607-361 2 is also known.
  • Boiling temperature to 2-chloro-6-methoxybenzonitrile whereby a yield between 75 and 80% is achieved.
  • this variant is limited to very activated nitriles.
  • the object of the present invention is therefore to provide a process for the catalyst-free preparation of alkoxybenzonitriles.
  • the target compounds should be obtained as directly as possible in good yields and purities and the use of expensive and environmentally harmful substances should be completely eliminated.
  • the process according to the invention preferably further comprises one or more steps selected from cooling the reaction mixture to 10 ° C. to 40 ° C., in particular to room temperature, for example 18 to 27 ° C., adding water to the reaction mixture and / or separating off the end product. After the reaction mixture has been kept at the final temperature, the reaction mixture is particularly preferably cooled to 10 ° C. to 40 ° C., in particular to room temperature, stirred after the addition of water and finally the end product is separated off.
  • the radical Y can be arranged ortho, metha or para to the CN grouping.
  • Y represents an alkyl group
  • the alkyl group can be straight-chain or branched.
  • Y is aryl, it is preferably a C 4 -C 30 , more preferably a C 5 -C 20 and most preferably a C 6 -C 15 aryl radical.
  • the monohalogenated benzonitriles used are preferably chlorinated or brominated benzonitriles in the 2- or 4-position, the preparation of which is well known from the literature.
  • Sodium methylate or sodium ethylate are to be regarded as preferred alcoholates.
  • the reaction is carried out at temperatures between 90 and 250.degree. C., but preferably temperatures which have been found to be particularly suitable are between 100 and 150.degree. C. and particularly preferably between 115 and 140.degree.
  • the reaction mixture should be kept for a period of 2 to 10 hours and in particular for 3 to 5 hours at the respective end temperature within the scope of the invention.
  • the pressure naturally increases in a closed system, as autoclaves represent, pressure ranges of usually 2 to 20 bar being acceptable and a pressure of about 3 to 5 bar being recommended.
  • reaction mixture can also be kept under reflux for a long time, for example three hours, and only then can the reaction mixture be reacted at the final temperature for a further 2 to 3 hours.
  • the present invention preferably provides for the reaction to be carried out under an inert gas and in particular under a nitrogen atmosphere.
  • the amount of alcoholate used in the claimed process is not critical and can be between 70 mol% and 400 mol%, based on the monohalogenated benzonitrile used. However, it is recommended that the amount of alcoholate be between 1 00 and 200 mol%, based on the halogenated benzonitrile used, and especially between 105 and 1 1 5 mol%.
  • the metal alcoholate is used in the form of a corresponding alcoholic solution.
  • concentration of this solution is also not critical and can be between 1 5 and 50 wt .-%. However, it is recommended that the concentration of the alcoholate solution to be used be between 20 and 40% by weight and in particular between 25 and 35% by weight.
  • the subsequent separation of the product is carried out according to the usual methods, with filtering off for solid products and phase separation for liquid products, of course, being recommended. Finally, if necessary, the product can be freed of the residual moisture by mild temperatures of approx. 30 to 50 ° C.
  • the reaction mixture at the end of the reaction is a suspension of sodium and / or potassium salt and alkoxybenzonitrile fractions in the corresponding alcohol.
  • the product can easily be separated from this system by adding water and stirring.
  • the salt completely dissolves and, in the case of solid benzonitrile derivatives, the product precipitates. It is particularly advantageous to cool the suspension thus obtained with thorough mixing, the product being obtained practically quantitatively.
  • the crystals obtained in this way can be separated from the liquid phase in any conventional manner.
  • the product is usually dried at pressures between 0.1 and 1000 mbar and at temperatures between 20 and 40 ° C, with pressures between 10 and 20 mbar and temperatures between 25 and 35 ° C being particularly recommended.
  • the method according to the invention is characterized by a very simple technical feasibility and also by a high degree of compatibility with the world.
  • the only by-product of the reaction is sodium or potassium halides, which further underlines the environmental compatibility and economy of the proposed process.

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

L'invention concerne un procédé de production d'alcoxybenzonitriles sans catalyseur par substitution de composés de départ monohalogénés de formule générale (I), dans laquelle X représente Cl ou Br et Y représente H, alkyle ou aryle. Selon ce procédé, le composé de départ et un alcoolate de formule générale Z-OAlk, dans laquelle Z = Na<+> ou K<+> et Alk = alkyle C1-C4, sont maintenus à la température finale pendant 2 à 10 heures après avoir été chauffés à une température comprise entre 90 et 250 DEG C, le mélange réactionnel est refroidi à température ambiante et il est remué à nouveau après addition d'eau, puis le produit final est séparé. Ce procédé, pour lequel on utilise de préférence comme composé de départ des benzonitriles chlorés et/ou bromés en position 2 ou 4 et comme alcoolate du méthylate de sodium ou de l'éthylate de sodium, permet de produire les produits finaux respectifs de manière économique et écologique avec d'excellents rendements et un grand degré de pureté.
EP03752756A 2002-05-17 2003-05-16 Procede de production d'alcoxybenzonitriles sans catalyseur Withdrawn EP1506163A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10222330A DE10222330A1 (de) 2002-05-17 2002-05-17 Verfahren zur katalysatorfreien Herstellung von Alkoxybenzonitrilen
DE10222330 2002-05-17
PCT/EP2003/005176 WO2003097584A1 (fr) 2002-05-17 2003-05-16 Procede de production d'alcoxybenzonitriles sans catalyseur

Publications (1)

Publication Number Publication Date
EP1506163A1 true EP1506163A1 (fr) 2005-02-16

Family

ID=29285603

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03752756A Withdrawn EP1506163A1 (fr) 2002-05-17 2003-05-16 Procede de production d'alcoxybenzonitriles sans catalyseur

Country Status (5)

Country Link
US (1) US20060025624A1 (fr)
EP (1) EP1506163A1 (fr)
JP (1) JP2005530793A (fr)
DE (1) DE10222330A1 (fr)
WO (1) WO2003097584A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100351226C (zh) * 2006-06-09 2007-11-28 武汉大学 一种制备2,6－二烷氧基苯腈的方法
CN100386309C (zh) * 2006-06-09 2008-05-07 武汉大学 一种制备2-氯-6-烷氧基苯腈的方法
CN100386308C (zh) * 2006-06-09 2008-05-07 武汉大学 一种制备3-氯-4-烷氧基苯腈的方法
CN102311364B (zh) * 2011-09-30 2014-07-09 江苏联化科技有限公司 一种邻(对)羟基苯甲腈的制备方法
WO2014186981A1 (fr) * 2013-05-24 2014-11-27 江苏联化科技有限公司 Procédé pour la préparation d'o(p)-hydroxybenzonitrile
DE102014007527A1 (de) 2014-05-23 2015-12-17 Alzchem Ag Verfahren zur Herstellung von Alkoxybenzonitrilen

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5917079A (en) * 1996-09-24 1999-06-29 Rohm And Haas Company Process for synthesizing benzoic acids
US5965766A (en) * 1996-09-24 1999-10-12 Rohm And Haas Company Process for synthesizing benzoic acids
US5847166A (en) * 1996-10-10 1998-12-08 Massachusetts Institute Of Technology Synthesis of aryl ethers
JPH10237016A (ja) * 1997-02-21 1998-09-08 Nippon Oil Co Ltd 光学活性化合物の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03097584A1 *

Also Published As

Publication number Publication date
US20060025624A1 (en) 2006-02-02
DE10222330A1 (de) 2003-11-27
JP2005530793A (ja) 2005-10-13
WO2003097584A1 (fr) 2003-11-27

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