Dimethyl carbonate: a versatile reagent for a sustainable valorization of renewables

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC02118F, Critical Review
G. Fiorani, A. Perosa, M. Selva
Green upgrading of renewables via methylations and carboxymethylations with non-toxic dimethyl carbonate (DMC).

Dimethyl carbonate: a versatile reagent for a sustainable valorization of renewables

 Author affiliations

Giulia Fiorani

Postdoctoral Research Fellow presso University of Oxford
Dr. Fiorani earned her PhD in Chemical Sciences from the University of Rome “Tor Vergata” (2010) on synthesis and applications of ionic liquids. After several post-doctoral experiences (University of Padua, Italy 2010-2012, Ca’ Foscari University of Venice 2012-2013), Giulia was awarded a Marie Curie Intra-European Fellow in 2014 at ICIQ (Institute of Chemical Research of Catalonia, Tarragona, Spain) working under the supervision of Prof. Arjan W. Kleij  on the preparation of cyclic organic carbonates from CO2 and terpene based oxiranes. Giulia joined the Williams group in 2016 and is working on renewable based polymers.

Abstract

Dimethyl carbonate (DMC) is an environmentally sustainable compound which can be used efficiently for the upgrading of several promising renewables including glycerol, triglycerides, fatty acids, polysaccharides, sugar-derived platform molecules and lignin-based phenolic compounds. This review showcases a thorough overview of the main reactions where DMC acts as a methylating and/or methoxycarbonylating agent for the transformation of small bio-based molecules as well as for the synthesis of biopolymers. All processes exemplify genuine green archetypes since they couple innocuous reactants of renewable origin with non-toxic DMC. Each section of the review provides a detailed overview on reaction conditions and scope of the investigated reactions, and discusses the rationale behind the choice of catalyst(s) and the proposed mechanisms. Criticism and comments have been put forward on the pros and cons of the described methods and their perspectives, as well as on those studies which still require follow-ups and more in-depth analyses.

STR1STR2

Image result for Giulia Fiorani oxford

Giulia Fiorani

Ph. D. in Chemical Sciences
Post Doctoral Research Assistant
Research experience
  • Sep 2016–present
    Post Doctoral Research Assistant
    University of Oxford · Department of Chemistry · Prof. Charlotte K. Williams
    United Kingdom
    Polymer chemistry and catalysis applied to polymers preparation.
  • Mar 2016–Sep 2016
    Post Doctoral Research Assistant
    Imperial College London · Department of Materials · Prof. Charlotte K. Williams
    United Kingdom · London, England
    Polymer chemistry and catalysis applied to polymers preparation.
  • Mar 2014–Feb 2016
    Marie Curie Intra-European Fellow
    ICIQ Institute of Chemical Research of Catalonia · Prof. Arjan W. Kleij
    Spain
    Novel applications of renewable based molecules for the preparation of cyclic carbonate and polycarbonates (FP7-PEOPLE-2013-IEF, project RENOVACARB, Grant Agreement no. 622587).
  • Apr 2012–Oct 2013
    Post Doctoral Research Assistant
    Università Ca’ Foscari Venezia · Department of Molecular Science and Nanosystems · Prof. Maurizio Selva, Prof. Alvise Benedetti
    Italy
    Synthesis and characterization of luminescent Ionic Liquids.
  • Jan 2011–Feb 2012
    Post Doctoral Research Assistant
    Italian National Research Council · Institute on Membrane Technology ITM · Prof. Marcella Bonchio, Dr Alberto Figoli
    Italy · Rome
    Project BioNexGen – development of a new generation of membrane reactors.
  • Jan 2010–Dec 2010
    Research Assistant
    University of Padova · Department of Chemical Sciences · Dr Mauro Carraro
    Italy · Padova
    Hybrid nanostructures organized by hybrid ligands for the preparation of new functional materials.

Teaching experience

  • Sep 2016–Oct 2016
    Visiting Scholar
    Università degli Studi di Sassari · Department of Chemistry and Pharmacy
    Italy · Sassari
    10 hour course on terpene chemistry for PhD students.

Education

  • Nov 2006–Mar 2010
    University of Rome Tor Vergata
    Chemical Sciences · PhD
    Italy
  • Oct 2004–Jul 2006
    University of Rome Tor Vergata
    Chemistry · Master of Science
    Italy
  • Sep 2001–Oct 2004
    University of Rome Tor Vergata
    Chemistry · BSc
    Italy

Other

  • Languages

    English, Italian, Spanish

  • Scientific Societies

    Member of the Italian Chemical Society since 2007.

 

PEROSA Alvise

Qualifica Professore Associato
Telefono 041 234 8958
E-mail alvise@unive.it 
Fax 041 234 8979
Web http://www.unive.it/persone/alvise (scheda personale)
http://venus.unive.it/alvise/
Struttura Dipartimento di Scienze Molecolari e Nanosistemi
Sito web struttura: http://www.unive.it/dsmn 
Sede: Campus scientifico via Torino
Research team Environmental technology and green economy
Research team Science of complex economic, human and natural systems
Incarichi Delegato per il Dipartimento all’Internazionalizzazion

logo unive

Currently: Associate professor of Organic Chemistry with tenure.

Department of Molecular Sciences and Nanosystems, University Ca’ Foscari Venice.

 

Born in Venice in 1965. Married to Paola, two children: Alberto (2000) and Marta (2002).

 

  • Career

– 2011, was offered the senior position as Associate professor of Chemistry with Tenure at UMAss Boston.

– 2005-2014 Assistant professor of Organic Chemistry with tenure (SSD CHIM/06), University Ca’ Foscari Venice.

– 2007 Visiting scientist, University of Sydney.

– 1996-2005 Post-doctoral researcher University Ca’ Foscari Venice.

 

  • Education

– 1996 Ph.D. in Chemistry, Case Western Reserve University, Cleveland OH, USA.

– 1992 Laurea in Industrial Chemistry @ University Ca’ Foscari Venice.

 

  • Fellowships

– 2007 Endeavour Research Fellow (Austrlian Government, Department of Education, Employment and Workplace Relations) at the University of Sydney.

– 1992-1996 Fulbright Fellow (U.S. Department of State, International Educational Exchange Program) at Case Western Reserve University.

– 1993 CNR Research Fellow (1993) at Case Western Reserve University, Cleveland OH, USA.

 

  • Awards

– Ca’ Foscari Research Prize (2014, category Advanced Research).

– Royal Society of Chemistry International Journal Grants Awards (2007, 2009).

– CNR prize for research (1994).

– Outstanding teaching award CWRU (1993).

– Prize for the Laurea thesis from the Consorzio Venezia Ricerche (1992).

 

  • Editorial Board memberships

– Advisory Board of the journal “Green Chemistry” (Royal Society of Chemistry, UK).

– Editorial Advisory Board of the journal “ACS Sustainable Chemistry and Engineering” (American Chemical Society, USA).

 

  • Training and editorial activities.

– Scientific coordinator and organizer of the Summer School on Green Chemistry from 1998 to 2006 (funded by the European Commission, UNESCO, and NATO).

– Editor of the volume “Methods and Reagents for Green Chemistry” Wiley Interscience 2007.

– Editor of “Green Nanoscience”, volume 8 of the 12 volume set of the “Handbook of Green Chemistry” P. Anastas Ed., Wiley-VCH 2011.

– Author of over 60 scientific papers and chapters and of one patent in the field of organic chsmistry, with emphasis on green chemistry. Hirsch index (Scopus, Feb. 2014) = 21.

 

  • Invited talks

– Green chemistry applied to the upgrading of bio-based chemicals: towards sustainable chemical production. University of Sydney, 19 March 2014.

– Sustainable (Chemical) Solutions, Rethinking Nature in Contemporary Japan, Università Ca’ Foscari, Venezia, 25-26 February 2013

– Carbonate based ionic liquids and beyond, Green Solvents Conference, Frankfurt am Main, Dechema Gesellschaft fur Chemische Technik und Biotechnologie e. V., pp. 27, Green Solvents for Synthesis, Boppard, 8-10 Ottobre 2012

– Chemicals e Fuels da Fonti Rinnovabili, Bioforum. Biotecnologie: dove scienza e impresa si incontrano, Milano, ITER, vol. VII Edizione, Bioforum, Confindustria Venezia, 24.02.2011

– Green Chemistry for Sustainability: Teaching ionic liquids new tricks & A breath of oxygen for bio-based chemicals., Slovenian-Italian conference on Materials and Technologies for Sustainable Growth, Ajdovscina, Slovenia, 4-6 Maggio 2011

– Benign molecular design, WORKSHOP ON ECOPHARMACOVIGILANCE, Verona, 26-27 Marzo 2009

– Not merely solvents: task specific ionic liquids made by green syntheses, COIL-3 Pre-symposium workshop, Cairns, Australia, 31/05/2009

– Multiphase catalysis: a tool for green organic synthesis, Royal Australian Chemical Institute NSW Organic Chemistry Group, 28th Annual One-Day Symposium, MacQuarie University, Sydney, Australia, 5 December 2007

– Catalytic Reactions in Liquid Multiphasic Systems The acronym talk, INTAS Project on POPs, Moscow, 12-14 Giugno 2005

– Catalytic reactions in liquid multiphasic systems, Convegno: Eurogreenpol – First European Summer School on Green Chemistry of Polymers, Iasi – Rumania, 21-27 Agosto 2005

– Multiphase hydrodehalogenation reactions, RWTH Aachen – Germany, 12 Febbraio 2003

– Mechanism and Synthetic Applications of the Multiphase Catalytic Systems, International Workshop on Hazardous Halo-Aromatic Pollutants: Detoxification and Analysis, Venezia, 14-16 Maggio 2002

– The multiphase catalytic hydrodehalogenation of haloaromatics, European Summer School on Green Chemistry, Venezia, 10-15 September 2001

 

  • Academic committees

– Quality assurance board of Ca’ Foscari University

– Teaching council of the International College, Ca’ Foscari merit school.

– Academic Council of Venice International University VIU.

– Delegate for international relations of the Department of Molecular Sciences and Nanosystems.

– Scientific board of Edizioni Ca’ Foscari – Digital Publishing.

– Research committee of the Department of Molecular Sciences and Nanosystems.

– Teaching board of the Doctorate in Chemical Sciences (2012-2014).

– Teaching board of the degree course Bio- and Nanomaterials science and Technology.

– Erasmus selection committee.

– Overseas selection committee

– Post-doctoral selection committees.

 

  • Referee, reviewer, and examiner for:

– Valutazione della Qualità della Ricerca (VQR), ANVUR

– Progetti di Rilevante Interesse Nazionale (PRIN), MIUR

– American Chemical Society Petroleum Research Fund (USA).

– Ph.D. Theses, University of Nottingham (UK) and University of Sydney (Aus).

– European Science Foundation

– Journals published by: Royal Society of Chemistry, American Chemical Society, Wiley, Elsevier, Springer, IUPAC

 

  • Funded projects

– Coordinator of a Cooperlink project funded by the Italian Ministry for Education, University and Research, 2011, 12 months, entitled “Joint PhD between Università Ca’ Foscari and the University of Sydney: integration of experiment and theory towards the green synthesis of self-assemblying materials and the use of renewable resources”.

– Participant in the Project of Relevant National Interest (PRIN) “Green organic syntheses mediated by new catalytic systems”, 2010, 24 months.

– Tutor of a PhD scholarship funded by the Regione Veneto through the European Social Fund, entitled “Organic syntheses of active principles and chemicals for the pharmaceutical industry using green solvents “ 2009-2011, 36 months.

– Principal Scientist of a post-doctoral fellowship funded by the Regione Veneto through the European Social Fund entitled “New reduced environmental impact chemical synthesesfor the preparation of monomers for advanced polymers, April 2012, 12 months.

– Principal Scientist of a post-doctoral fellowship funded by the Regione Veneto through the European Social Fund entitled “Environmentally compatible chemical syntheses of fluorinated monomers for advanced materials” April 2013, 12 months.

– Principal Scientist of a post-doctoral fellowship funded by the Regione Veneto through the European Social Fund entitled “Valorisation of renewable substrates from biomass, such as glycerol and its derivatives, using green chemistry” April 2014, 12 Months

– Principal Scientist of a research contract between the chemical company Aussachem (Santandrà di Povegliano, TV), entitled: “Green Chemistry for the valorisation of glycerol and of its derivatives: new ecofriendly products” December 2013.

 

  • International collaborations and networks

– Teaching and research collaboration with the University of Sydney, School of Chemistry Laboratory for Advanced Catalysis and Sustainability prof. Thomas Maschmeyer. A joint PhD program in Chemistry was established and is currently running. Up to date 5 students (3 outgoing, 2 incoming) have benefited from this agreement The first joint PhD has been awarded in December 2013 (Marina Gottardo). Four joint publications have already been produced, and others are in preparation.

– Research collaboration with the Queen’s University of Belfast, Queen’s University Ionic Liquids Laboratory, prof. Kenneth R. Seddon, for the exchange of Erasmus students who carry out research towards their MS thesis. Currently the student Riccardo Zabeo is in Belfast w research towards his thesis, tutor dr. Perosa. Previously, the PhD student Marco Noè (tutor Perosa) spent 4 months in Belfast carrying out research that was published on an international journal.

– In the framework of a scientific collaboration with prof. Janet Scott of the Centre for Sustainable Chemical Technologies of the University of Bath, an Erasmus Mundus Joint Doctorate project entitled “Bio-Based Chemicals and Materials” was submitted in 2011 and was evaluated positively albeit not funded. Nonetheless the collaboration has already produced a joint publication.

– Summer School on Green Chemistry Network. Following the 8 editions of the “Summer school on Green Chemistry” (1998-2005) coordinated and organized by the applicant, a Green Chemistry Network was initiated that involves the following institutions: RWTH-Aachen, QUB-QUILL Belfast, UNSW-Sydney, ARKEMA-France, University of Groningen-NL, Dow Europe-CH, Universite de Poitiers, ETH-Zurich, TU-Darmstadt, Universidad Politecnica de Valencia, Delft University of Technology, TU-Munchen.

– Since 1993 Alvise Perosa is a member of the American Chemical Society.

 

  • MoU’s and International agreements

– Alvise Perosa started the Joint PhD degree in Chemistry between the University of Sydney and the Università Ca’ Foscari Venezia.

– Erasmus, Alvise Perosa is the contact person for the following Erasmus agreements: Universitat Autonoma de Barcelona, Universidad Rey Juan Carlos, Universidad Rovira i Virgili,UNIVERSITE D’AVIGNON ET DES PAYS DE VAUCLUSE, ARISTOTLE UNIVERSITY THESSALONIKI, Queen’s University of Belfast.

 

  • Academic tutoring

– Marco Noè (PhD 2009-11: 24° cycle)

– Jessica N. G. Stanley (PhD cotutelle University of Sydney, 2012-2014)

– Alessio Caretto (PhD 2012-14: 27° cycle)

– Manuela Facchin (PhD 2014-16: 29° cycle)

– Tutor if BSc and MSc level students of the degree corse in Sustainable Chemistry and Technologies and, and of the MSc degree course in Science and Technolgy of Bio- and Nanomaterials.

 

  • Teaching

– 1992-94, Case Western Reserve University, Chemistry BS: Organic Chemistry 1 Laboratory (teaching assistant award in 1993).

– 1997-2000, Università Ca’ Foscari Venezia, degree course in Environmental Sciences: Organic Chemistry Exercises.

– 1997-2000, Università Ca’ Foscari Venezia, degree course in Industrial Chemistry: Organic Chemistry 1 & 2 Laboratory, Industrial Chemistry 2 Exercises, Organic Chemistry 1 (part-time students) and Advanced Organic Chemistry.

– 2006-09, Università Ca’ Foscari Venezia, degree course in Chemical Sciences and Technologies for Cultural Heritage Conservation and Restoration: Organic Chemistry Laboratory.

– 2006-07, Università Ca’ Foscari Venezia, degree course in Chemistry, Industrial Chemistry, Materials Chemistry, Environmental Sciences: Organic Chemistry 1 and Laboratory for part-time students.

– 2005-06, 2011-12, 2012-13, 2013-14: Università Ca’ Foscari Venezia, degree course in Chemistry and in sustainable Chemical Technologies: Organic Chemistry 2 and Laboratory.

– 2011-12, Università Ca’ Foscari Venezia, degree course in Chemistry and in sustainable Chemical Technologies: Green Organic synthesis Laboratory.

– 2012-13, 2013-14 Università Ca’ Foscari Venezia, MS degree course in Bio e Nanomaterials: Colloids and Interfaces.

– 2013-14 Università Ca’ Foscari Venezia, Graduate course in Organic syntheses from renewable building blocks.

SELVA Maurizio 

Qualifica Professore Ordinario
Telefono 041 234 8687
E-mail selva@unive.it 
Fax 041 234 8979
Web http://www.unive.it/persone/selva (scheda personale)
Struttura Dipartimento di Scienze Molecolari e Nanosistemi
Sito web struttura: http://www.unive.it/dsmn 
Sede: Campus scientifico via Torino

http://www.unive.it/data/persone/5591976/pubb_tipo

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http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C7GC02118F?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

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A roadmap towards green packaging: the current status and future outlook for polyesters in the packaging industry

DOI: 10.1039/C7GC02521A, Tutorial Review
M. Rabnawaz, I. Wyman, R. Auras, S. Cheng
Approximately 99% of the plastics used in the packaging industry today are petroleum-based. However, the adoption of biobased plastics could help to greatly reduce the environmental footprint of packaging materials and help to conserve our non-renewable petroleum resources. This tutorial review provides an overview of renewable polyesters and their potential packaging materials.

A roadmap towards green packaging: the current status and future outlook for polyesters in the packaging industry

 Author affiliations

Muhammad Rabnawaz

Assistant Professor

Muhammad Rabnawaz

rabnawaz@msu.edu
Telephone: 517-432-4870


Rabnawaz’s Research Group
School of Packaging

Shouyun Cheng at Michigan State University

Shouyun Cheng

Doctor of Philosophy
Research Associate
Michigan State University
East Lansing, MI, United States

Dr. Cheng earned his PhD from South Dakota State University in May 2017. He has extensive research experiences in biomass pyrolysis and liquefaction, bio-oil catalytic cracking and hydrodeoxygenation, catalyst design, preparation, characterization and evaluation, food extruding, nano cellulose and protein peptides production, polymer synthesis, characterization and application.

Project Titles worked on: Innovation for Improved Sustainability: Scalable Approach for the Preparation of Thermoplastic Starches and their Composites for Applications in Biodegradable Packaging .

Duration in the group: August 2017- Present

Areas of Interest: Polycarbonates and polyesters synthesis, characterization and application.

MSU email Id: chengsho@msu.edu

Ian Wyman

Education: Ph.D., Queen’s University, Kingston, Ontario
M.Sc., St. Francis Xavier University, Antigonish, Nova Scotia
B.Sc. Chemistry, Dalhousie University, Halifax, Nova Scotia

Email: wymani@chem.queensu.ca

Abstract

Approximately 99% of the plastics produced today are petroleum-based, and the packaging industry alone consumes over 38% of these plastics. In this review, we argue that renewable polyesters can provide a key milestone as renewable plastics in the route toward green packaging. This review describes different classes of polyesters with particular regard to their potential use as packaging materials. Some of the families of polyesters discussed include poly(ethylene terephthalate) and its renewable analogs, poly(lactic acid), poly(hydroxyalkanoates), and poly(epoxy anhydrides). The synthesis of polyesters is discussed from a green chemistry perspective. A structure–property correlation among the various polyesters is also discussed. The challenges that currently hinder the widespread adoption of polyesters as leading packaging materials are reviewed. The environmental footprint and end of life scenario of polyesters are discussed. Finally, future research directions are summarized as a possible roadmap towards the widespread adoption of renewable polyesters as sustainable packaging materials.

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Muhammad Rabnawaz

Assistant Professor

Muhammad Rabnawaz

rabnawaz@msu.edu
Telephone: 517-432-4870

Michigan State University white graphic


Rabnawaz’s Research Group
School of Packaging


Research Interests

I have published more than 20 research articles in the field of polymer and materials sciences. Our initial endeavors can be divided into three broad categories:

  1. Polymer synthesis from renewable feedstocks.
  2. Design and preparation of smart materials.
  3. Polymer composites.

Our projects are highly applied, and we expect close collaboration with world-leading industries. These partnerships will offer unique training and career opportunities for the group members.

Experience

  • Assistant Professor, School of Packaging, Michigan State University (2016-currrent)
  • Postdoctorate, University of Illinois, Urbana-Champaign, 2015-2016
  • Postdoctorate, Queen’s University, Canada, 2013-2015

Education

  • Ph.D., Chemistry, Queen’s University, Canada, 2013
  • M.Sc., Chemistry, University of Peshawar, Pakistan, 2004

Increasing global access to the high-volume HIV drug nevirapine through process intensification

New Drug Approvals

Increasing global access to the high-volume HIV drug nevirapine through process intensification

Green Chem., 2017, 19,2986-2991
DOI: 10.1039/C7GC00937B, Paper
Jenson Verghese, Caleb J. Kong, Daniel Rivalti, Eric C. Yu, Rudy Krack, Jesus Alcazar, Julie B. Manley, D. Tyler McQuade, Saeed Ahmad, Katherine Belecki, B. Frank Gupton
Fundamental elements of process intensification were applied to generate efficient batch and continuous syntheses of the high-volume HIV drug nevirapine.

Green Chemistry

View original post 953 more words

Green Synthesis of Veratraldehyde Using Potassium Promoted Lanthanum–Magnesium Mixed Oxide Catalyst

 Abstract Image

Veratraldehyde is an important chemical used in perfumery, agrochemical, and pharmaceutical industries. Current processes of manufacture of veratraldehyde use homogeneous catalysts, which make them highly polluting, creating problems of disposal of effluents and product purity. In the current work, veratraldehyde was synthesized from O-alkylation of vanillin with an environmentally benign reagent, dimethyl carbonate. A series of potassium loaded La2O3–MgO were prepared by the incipient wetness impregnation method, and their performance was evaluated vis-à-vis MgO, La2O3, La2O3–MgO, and a series of 1–4 wt % K/La2O3–MgO. All catalysts were characterized by different techniques, such as N2 adsorption/desorption, XRD, TGA-DSC, FT-IR, CO2-TPD, and SEM techniques. The effect of different loadings (1–4 wt %) of potassium on La2O3–MgO was studied, among which 2 wt % K/La2O3–MgO showed the best activity and selectivity due to high dispersion of potassium and high basicity in comparison with the rest. The activity of 2 wt % K/La2O3–MgO in O-methylation of vanillin with dimethyl carbonate (DMC) was closely associated with basicity. Various parameters were studied to achieve the maximum yield of the desired product. The maximum conversion was found with catalyst loading of 0.03 g/cm3 and mole ratio of vanillin and DMC of 1:15 at 160 °C in 2 h. The reaction follows pseudo-first-order kinetics for the O-methylation of vanillin. The energy of activation was found to be 13.5 kcal/mol. Scale-up was done using the kinetic model to observe that the process could be scaled up using the process parameters. The overall process is clean and green.

Figure

Green Synthesis of Veratraldehyde Using Potassium Promoted Lanthanum–Magnesium Mixed Oxide Catalyst

Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga Mumbai-400 019, India
Org. Process Res. Dev., Article ASAP
DOI: 10.1021/acs.oprd.7b00127
*E-mail: gd.yadav@ictmumbai.edu.in, Phone: +91-22-3361-1001, Fax: +91-22-3361-1020; +91-22-3361-1002.

Conclusion


Synthesis of veratraldehyde using a catalytic green process is desirable in today’s environmentally conscious world. Therefore, a new process was devised in this work using a novel catalyst using mixed metal oxides. Different loadings of potassium promoted on La2O3–MgO (1–4 wt %) catalysts were synthesized and characterized by various techniques. The activity of catalyst was studied in the reaction of vanillin with DMC for the synthesis of veratraldehyde in comparison with several other catalysts, such as MgO, La2O3, La2O3–MgO, 1 wt % K/La2O3–MgO, 2 wt % K/La2O3–MgO, 3 wt % K/La2O3–MgO, and 4 wt % K/La2O3–MgO. Potassium promoted mixed oxides showed much higher catalytic activity than the corresponding pure La2O3–MgO mixed oxide, due to an increase in moderate, strong, superbasic sites. Moreover, loading of potassium on La2O3–MgO changes the structural properties, such as pore volume and surface area, and it gives higher conversion toward the desired product. Two wt % K/La2O3–MgO is the best and gives 96% of conversion at mole ratio 1:15 of vanillin to DMC and 0.03 g/cm3 catalyst loading at 160 °C. By using this catalyst, we studied various parameters systematically to establish kinetics. The catalyst is reusable up to four cycles. The energy of activation for O-methylation of vanillin was found to be 13.5 kcal/mol. A scale up was also attempted. Experimental and theoretical values matched very well. The process is green and clean.
Jayaram Molleti
Institute Of Chemical Technology
Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga Mumbai-400 019, India
Image result
Prof. GD Yadav, Vice-Chancellor, ICT, Mumbai
*E-mail: gd.yadav@ictmumbai.edu.in, Phone: +91-22-3361-1001, Fax: +91-22-3361-1020; +91-22-3361-1002.
Institute Of Chemical Technology
Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga Mumbai-400 019, India

Is water a suitable solvent for the catalytic amination of alcohols?

Is water a suitable solvent for the catalytic amination of alcohols?

Green Chem., 2017, 19,2839-2845
DOI: 10.1039/C7GC00422B, Paper
Johannes Niemeier, Rebecca V. Engel, Marcus Rose
The catalytic aqueous-phase amination of biogenic alcohols with solid catalysts is reported for future development of renewable amine value-added chains.

Green Chemistry

Is water a suitable solvent for the catalytic amination of alcohols?

Abstract

The catalytic conversion of biomass and biogenic platform chemicals typically requires the use of solvents. Water is present already in the raw materials and in most cases a suitable solvent for the typically highly polar substrates. Hence, the development of novel catalytic routes for further processing would profit from the optimization of the reaction conditions in the aqueous phase mainly for energetic reasons by avoiding the initial water separation. Herein, we report the amination of biogenic alcohols in aqueous solutions using solid Ru-based catalysts and ammonia as a reactant. The influence of different support materials and bimetallic catalysts is investigated for the amination of isomannide as a biogenic diol. Most importantly, the transferability of the reaction conditions to various other primary and secondary alcohols is successfully proved. Hence, water appears to be a suitable solvent for the sustainable production of biogenic amines and offers great potential for further process development.

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Selective hydrogenation of N-heterocyclic compounds using Ru nanocatalysts in ionic liquids

Selective hydrogenation of N-heterocyclic compounds using Ru nanocatalysts in ionic liquids

Green Chem., 2017, 19,2762-2767
DOI: 10.1039/C7GC00513J, Communication
Hannelore Konnerth, Martin H. G. Prechtl
N-Heterocyclic compounds have been tested in the selective hydrogenation catalysed by small 1-3 nm sized Ru nanoparticles (NPs) embedded in various imidazolium based ionic liquids (ILs).

http://pubs.rsc.org/en/Content/ArticleLanding/2017/GC/C7GC00513J?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

From the journal:

Green Chemistry

Selective hydrogenation of N-heterocyclic compounds using Ru nanocatalysts in ionic liquids

Abstract

N-Heterocyclic compounds have been tested in the selective hydrogenation catalysed by small 1–3 nm sized Ru nanoparticles (NPs) embedded in various imidazolium based ionic liquids (ILs). Particularly a diol-functionalised IL shows the best performance in the hydrogenation of quinoline to 1,2,3,4-tetrahydroquinoline (1THQ) with up to 99% selectivity.

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Selective synthesis of dimethoxyethane via directly catalytic etherification of crude ethylene glycol

Selective synthesis of dimethoxyethane via directly catalytic etherification of crude ethylene glycol

Green Chem., 2017, Advance Article
DOI: 10.1039/C7GC00659D, Paper
Weiqiang Yu, Fang Lu, Qianqian Huang, Rui Lu, Shuai Chen, Jie Xu
A potential diesel fuel additive, dimethoxyethane, was highly selectively produced via etherification of crude ethylene glycol over SAPO-34

From the journal:

Green Chemistry

Selective synthesis of dimethoxyethane via directly catalytic etherification of crude ethylene glycol

Abstract

Etherification of ethylene glycol with methanol provides a sustainable route for the production of widely used dimethoxyethane; dimethoxyethane is a green solvent and reagent that is applied in batteries and used as a potential diesel fuel additive. SAPO-34 zeolite was found to be an efficient and highly selective catalyst for this etherification via a continuous flow experiment. It achieved up to 79.4% selectivity for dimethoxyethane with around 96.7% of conversion. The relationship of the catalyst’s structure and the dimethoxyethane selectivity was established via control experiments. The results indicated that the pore structure of SAPO-34 effectively limited the formation of 1,4-dioxane from activated ethylene glycol, enhanced the reaction of the activated methanol with ethylene glycol in priority, and thus resulted in high selectivity for the desired products. The continuous flow technology used in the study could efficiently promote the complete etherification of EG with methanol to maintain high selectivity for dimethoxyethane.

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