Project 275 / 2011

Heterogeneous catalytic synthesis of aminic derivatives through hydroamination and NC coupling reactions

 

Financing: State budget

Subprogram: Exploratory Research 

Duration: 60 months

Project Summary

The basic idea of the project is the replacement of homogeneous palladium catalysts with heterogeneous catalysts containing as active centers elements from copper transitional group. Preparation of catalysts follows several routes, following that by comparison with characterization data and quantum chemistry calculations to determine optimal configurations which give the optimal electron density for abstraction of the proton linked to the amine nitrogen atom of the amine participating in the reaction.

General objectives and expected results

Objectives

Results

1. Design of active catalysts in the hydroamination reaction

 

Mesoporous zeolite catalysts, results regarding the structural and textural characterization

Reactions of coupling alkenes with amines for the production of interest molecules

2.  A new concept of a microreactor for Buchwald-Hartwig and hydroamination reactions

Catalytic results of the coupling of aniline with bromobenzene

Catalytic results of the coupling of alkenes with amines

3. Optimisation of the heterogeneous catalytic process in the Buchwald-Hartwig reactions

Catalytic results using molecular solvents having different polarities

Catalytic results using different materials as support

Catalytic results using  different metallic alkoxides

4. Optimisation of the heterogeneous catalytic process in hydroamination reactions

Catalytic results using molecular solvents having different polarities

Catalytic results using catalysts with different Lewis/Bronsted ratios and physiscal mixes of catalysts with Lewis/Bronsted acidity

5. Establishment of the reaction mechanism on the classes of invesitigated heterogeneous catalysts

Experimental evidences for the established reaction mechanism

Experimental evidences for the established reaction mechanism

Coordinating institution

University of Bucharest

Faculty of Chemistry

Department of Organic Chemistry, Biochemistry and Catalysis

Bucuresti, bd. Mihail Kogalniceanu, nr.36-46, tel. 0213077300, fax. 0213131760, cod fiscal (CUI) 4505502

 

Contracting authority

Executive Agency for Higher Education, Research, Development and Innovation Funding(UEFISCDI),

Bucureşti, Str. D. I. Mendeleev nr. 21-25, sector 1, tel 021 3023850, fax. 021 3115992, cod fiscal 12354176, cont IBAN RO83 TREZ 7015 003X XX01 1609, Trez. Sect.1, e-mail office@uefiscsdi.ro, reprezentată prin Ordonator de credite Director General Adrian CURAJ şi Contabil Şef Elena TIŢA

 

Research Team: Vasile I. Parvulescu,  Cojocaru Bogdan, Jurca Alina, Opris Cristina Madalina, Verziu Marian, Cernat Georgiana.

 

Duration of the project: 36 months

 

Implementation Plan

Activities:

- Synthesis of mesoporous zeolite acid catalysts

- Hydroamination reaction on mesoporous zeolite acid catalysts

- Flow microreactor for Buchwald-Hartwig reactions

- Flow microreactor for hydroamination reactions

- Investigation of the role of solvent in Buchwald-Hartwig reaction

- Investigation of the role of the ration of Lewis / Bronsted acid centers in the hydroamination reaction

- Investigation of the nature of the base in the Buchwald-Hartwig reaction

- Investigation of the role of solvent in the hydroamination reaction

- Investigation of the role of support in the Buchwald-Hartwig reaction

- Establish the mechanism for the hydroamination reaction

- Establish the mechanism for the Buchwald-Hartwig reaction

 

Budget of the project

1.500.000 lei

 

Specific results of the project:

-         Catalysts for Buchwald-Hartwig reaction

-         Au/TiO2 catalysts prepared by deposition-precipitation method

-          Full characterisation of the catalysts

-          Catalysts for hydroamination reaction: Preparation and characterisation of ScTf-UVM-7 catalysts

-          Catalytic tests: reaction conditions 

 

Results presented in international conferences

  1. M. Besnea, C. Dobrinescu, V.I. Parvulescu, Heterogeneous Buchwald-Hartwig amination over Au/TiO2 catalysts, 15th International Congress on Catalysis 2012, 1 – 6 July 2012, Munich, Germany
  2. S. Buchholz, A. Prokofyeva, R. Fehrmann, V.I. Parvulescu, Synthesis of nitriles in continuous-flow for sustainable chemical production, Green solvents conference,Boppard/Rhine valley, Germany, October 8-10, 2012.
  3. M. Ciobanu, F. Neatu, A. Tirsoaga, V.I. Parvulescu, Green attempts to improve Buchwald-Hartwig amination, Green solvents conference, Boppard/Rhine valley, Germany, October 8-10, 2012.
  4. A. Moragues, J. El Haskouri, D. Beltrán, P. Amorós, C. Opris, V.I. Parvulescu, New multicomponent catalysts for the selective aerobic oxidative condensation of benzylamines to N‐benzylidenbenzilimine, A.F. Volpe Jr., A.M. Gaffney, R. Fushimi (Eds), 7th World Congress on Oxidation Catalysis (7WCOC), Saint Louis, Missouri, USA, June 8th - 12th 2013, 1145 (ORAL PRESENTATION).
  5. M. Ciobanu, S.M. Coman, W. Leitner, V.I. Parvulescu, T6-169, New Supported Gold Catalysts for the Heterogeneous Amina-tion of Bromobenzene, XIth European Congress on Catalysis "20 years of European Catalysis... and beyond", Lyon, France - September 1-6, 2013
  6. V.I. Parvulescu, Nanomaterials: CONCEPT, SYNTHESIS, CHARACTERIZATION AND APLICATIONS, Summer School of the Spanish Catalytic Society, Seville, June 24-25, 2013, Spain. ORALA
  7. V.I. Parvulescu, Green synthesis of fine chemicals using Lewis acid/base heterogeneous catalysts, SECAT-2013, Structurated catalysts and reactors, Seville, June 26-28, 2013, Spain. ORALA

Plenary Conference:

 

  1. V.I. Parvulescu, Chemo- and stereoselectivity induced by heterogeneous catalysts in synthesis of natural compounds intermediates, Quo vadis synthesis? Can the chemist replace mother Nature in the creation of molecules of life? symposium, Rome, May 19-20, 2014, Italy.
  2. V.I. Parvulescu, Graphenes-Excellent substitutes for Noble Metals in Catalysis, 15th International Balkan Workshop on Applied Physics and Materials Science, Constanta, Romania, 2-4, July, 2015.
  3. V.I. Parvulescu, Lewis Acid-base Catalysts for the Synthesis of Fine Chemicals, EUROPACAT XII, Kazan, Russia,30 August - 4 September, 2015

 

 

Contact data of the project leader

Professor Vasile PARVULESCU tel./fax: +40(21) 410 02 41, e-mail: vasile.parvulescu@chimie.unibuc.ro

 

 

Published results of the project

Fisier de tip .pdf ! Publications 

Anual Reports:

Fisier de tip .pdf ! 2011 

Fisier de tip .pdf ! 2012 

Fisier de tip .pdf ! 2013 

Fisier de tip .pdf ! 2014 

Fisier de tip .pdf ! 2015 

Fisier de tip .pdf ! 2016 

 

 

 

Pagină actualizată la 29 Noiembrie 2016.