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Pyridinecarboxylic Acids Dinitriles

#K-1480


Catalytic Synthesis of Pyridinecarboxylic Acids Dinitriles by Ammoxidation of Dimethylpyridines

Tech Area / Field

  • CHE-IND/Industrial Chemistry and Chemical Process Engineering/Chemistry

Status
3 Approved without Funding

Registration date
13.12.2006

Leading Institute
Institute of Chemical Sciences, Kazakstan, Almaty

Supporting institutes

  • Institute of Physics and Technology, Kazakstan, Almaty

Collaborators

  • Institut für Angewandte Chemie Berlin-Adlershof e.V., Germany, Berlin\nSymyx Technologies, Inc., USA, CA, Santa Clara

Project summary

Various oxygen- and nitrogen-containing products of transformation of pyridinecarboxylic acids dinitriles possess biological activity and find application in medicine. The most rational method of obtaining of dinitriles is ammoxidation of 2,3-, 2,4-, 2,5-, 2,6- and 3,5-dimethylpyridines. Today the yield of dinitriles is at the level of 50-70 %. The development of a new approach to the synthesis of an efficient catalyst for ammoxidation, carried out in our laboratory, can increase significantly selectivity of the transformation of dimethylpyridines into corresponding dinitriles.

The project aims at the creation of an efficient catalyst for ammoxidation of 2,3-, 2,4-, 2,5-, 2,6-, and 3,5-dimethylpyridines into pyridinecarboxylic acids dinitriles and determination of optimal conditions of a catalytic reaction with the maximum selectivity.

At present in the Laboratory an efficient multicomponent vanadium-containing oxide catalysts for monomethylpyridines ammoxidation have already been created. On these catalysts picolinic, nicotinic and isonicotinic acids nitriles are obtained with the yield of 92-95 %.

In 1993-2003 the Laboratory effectively cooperated with the company "LONZA" (Switzerland) - Lonza Ltd. Münchensteinerstrasse 38. CH-4002 Basel, Switzerland (www.lonzagroup.com). The Institute of Chemical Sciences has sold to the company " LONZA " the license on a catalyst for the production of nicotinic acid nitrile by ammoxidation of 3-methylpyridine. Now the catalyst created in our Laboratory is used by the company "LONZA" for the industrial production of nicotinic acid nitrile, which then is converted by hydrolysis into nicotinic acid amide - vitamin PP. The method of the catalyst production has been patented in Kazakhstan, Switzerland, USA, Russia, Germany and other 44 countries. The patentees are the Institute of Chemical Sciences (Kazakhstan) and the company "LONZA" (Switzerland). The developers of the catalyst and co-authors of the patent are 2 participants of this project. (Sembaev D.Kh., Ivanovskaya F.A., Guseinov E.M., Chuck R.D. Catalytic composition for the ammoxidation of alkylpyridines. Pat. Kazakhstan N 3460, B 01 J 23/28, C07D 213/84, 10.06.1996; Pat. Schweiz N 9400561, EP N 0760709, 1999; Pat. USA N 5,698,701, 16.12.1997; Pat. Russian N 2123880, 27.12.1998; Pat. Deutschland (BRD) N 69509519, EP N 0760709, 25.11.1999; EP N 0760709, 06.05.1999, Bulletin 1999/18. etc. more than 40).

On the basis of a new approach to the synthesis of vanadium oxide catalysts, based on the regulation of chemical and phase composition of a multi-component catalyst by way of the directed obtaining of definite vanadium oxide compounds and stabilization of necessary crystalline modifications of polymorphic oxides, as well as an effect upon reactivity of vanadium (V) oxide, there will be found compositions and routes of synthesis of efficient vanadium oxide catalysts for ammoxidation of 2,3-, 2,4-, 2,5-, 2,6- and 3,5-dimethylpyridines into corresponding pyridinecarboxylic acids dinitriles.

Optimal conditions of ammoxidation of dimethylpyridines, ensuring the formation of pyridinecarboxylic acids dinitriles with the yield of about 75-80 % mol., will be found.

The results of the work will permit one to produce pyridinecarboxylic acids nitriles in one stage, using the continuous flow operation plants with a fixed catalyst bed, which are similar to those used in industry, for example, in the production of phthalic anhydride from o-xylene.

The results of the project can significantly increase a number of biologically active nitrogenous compounds due to efficient method of obtaining of pyridinecarboxylic acids dinitriles, which can be transformed by hydrolysis into carboxylic acids and their amides. Functional groups of these compounds possess high reactivity and hence they can be easily transformed into other derivatives of nitrogenous bases. Besides, one can increase persity of biologically active multi-functional nitric bases by synthesis of the compounds, containing simultaneously CN- and CH3-groups.

One of the results of the project will be new information of ammoxidation of all isomer series dimethylpyridines, which will amplify a notion of the reaction mechanism of ammoxidation of nitric bases.

The suggested project is important for the realization of the ISTC purposes as it will give an opportunity to the weapon-scientists and engineers from Kazakhstan to redirect their abilities to the researches in the peaceful field, and will promote their integration into the international scientific community.

As a result of the realization of the project phase and chemical composition of multi-component catalysts will be established and an interconnection with selectivity of their activity in the dimethylpyridines ammoxidation into dinitriles will be revealed.

There will be established an influence of different modifiers of vanadium oxide catalyst upon reactivity of vanadium (V) oxide and catalyst activity, connected therewith. The result of the work will be an establishing of the role of the conditions of catalysts preparation in the formation of their composition and the development of a technology, providing necessary activity and selectivity of the catalysts in ammoxidation of dimethylpyridines.

The form of our cooperation with Collaborators may be an exchange of information during the project implementation, joint discussion of the results, representation of the comments for technical reports (annual, final, etc.), meetings and/or consultations. The joint publications and patenting of the resulting data are not excluded.

Ammoxidation will be carried out on laboratory units with flow reactors with a stationary catalyst layer. Testing of some catalysts will be carried out on a pilot unit, the reactor of which is an element of an industrial apparatus. The methods of chromatography and polarography will be used for the quantitative analysis of the products of a catalytic reaction. Identification of some reaction products will be carried out with the help of NMR-, IR- and chromatomas-spectroscopy. For the investigation of the catalysts there will be used X-ray, IR-spectroscopic, thermal and chemical methods of analysis. There will be determined surface acidity, specific surface, porosity and mechanical strength of the catalysts. The preparation of the catalyst samples will be carried out on the available equipment by a wasteless technology.


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The International Science and Technology Center (ISTC) is an intergovernmental organization connecting scientists from Kazakhstan, Armenia, Tajikistan, Kyrgyzstan, and Georgia with their peers and research organizations in the EU, Japan, Republic of Korea, Norway and the United States.

 

ISTC facilitates international science projects and assists the global scientific and business community to source and engage with CIS and Georgian institutes that develop or possess an excellence of scientific know-how.

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