Green Chemistry article in C&EN – Catalytic conversion of biomass using solvents derived from lignin

A recently published Green Chemistry article by Editorial Board member James Dumesic (University of Wisconsin-Madison, USA) and colleagues has just been featured in the latest issue of Chemical & Engineering News.

The paper reports the  use of depolymerised lignin as a solvent in the conversion of hemicellulose and cellulose biomass fractions into high value platform chemicals and transportation fuels via a catalytic process.  The use of lignin-derived alkylphenols as solvents in this process (carried out in a biphasic reactor) minimized side-reactions in the aqueous phase and enabled recycling of the mineral acid catalysts. 

This article is free to access for 2 weeks!  Click on the link below to find out more…

Catalytic conversion of biomass using solvents derived from lignin, Pooya Azadi, Ronald Carrasquillo-Flores, Yomaira J. Pagán-Torres, Elif I. Gürbüz, Ramin Farnood and James A. Dumesic, Green Chem., 2012, 14, 1573-1576

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“On water” direct Pd-catalysed C–H arylation of thiazolo[5,4-d]pyrimidine derivatives

Chinese scientists have developed a new method for synthesising 2-arylsubstituted thiazolo[5,4-d]pyrimidine derivatives under mild conditions.

2-Arylsubstituted thiazolo[5,4-d]pyrimidine derivatives are the main motif in many pharmacologically relevant compounds including Tie-2 inhibitors and immunosuppressive agents.  Given the interest in these compounds, finding a mild and effective route to synthesis them is important.  Existing methods involve the use of toxic reagents and harsh conditions which limit their applications.  In this work, Tu-Yan Li, Li-Ping Sun and colleagues from China Pharmaceutical University, Nanjing, China, have developed a procedure for the direct arylation of thiazolo[5,4-d]pyrimidine derivatives with aryl iodides.  They employ a combination of Pd(Ph3)4 and Ag2CO3 used exclusively in water at 60 °C, giving the products in good to excellent yields.

This article is free to access until the 6th July 2012!  Click on the link below to find out more…

“On water” direct Pd-catalysed C–H arylation of thiazolo[5,4-d]pyrimidine derivatives, Ye-Xiang Su, Ya-Hui Deng, Ting-Ting Ma, Yu-Yan Li and Li-Ping Sun, Green Chem., 2012, DOI: 10.1039/C2GC35399G

You may also be interested in these articles – free to access for 2 weeks:

Efficient and convenient C-3 functionalization of indoles through Ce(OAc)3/TBHP-mediated oxidative C–H bond activation in the presence of β-cyclodextrin, Yu Lin Hu, Hui Jiang and Ming Lu, Green Chem., 2011, 13, 3079-3087

Greener solvents for ruthenium and palladium-catalysed aromatic C–H bond functionalisation, Cedric Fischmeister and Henri Doucet, Green Chem., 2011, 13, 741-753

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Meet our Authors: Michael Meier

Michael Meier is a Professor at the Karlsruhe Institute of Technology (KIT), Germany.  His research interests are utilizing plant oil derived fatty acids and terpenes etc., to prepare (novel) monomers study their subsequent polymerisation to obtain a variety of renewable polymers.  Michael took a few moments away from his work to talk to Green Chemistry

Who or what initially inspired you to become a chemist?

I was certainly inspired to become a chemist by my high-school chemistry teacher. Apart from being a great teacher in the class room, he offered voluntary lab-courses (which are still uncommon in Germany at this stage of education) and I will never forget making my first batch of Aspirin there. Without his excellent introduction to chemistry, I would probably have chosen another subject to study. Thank you Mr. Stegmüller!

What was the motivation behind the research described in your recent Green Chemistry article?

As for all research we do, our motivation is to find sustainable alternatives to existing chemistry. More importantly, we focus on a feedstock-shift from fossil resources to renewable ones. In our latest contribution, we used organocatalysis to develop new efficient procedures for the synthesis of organic carbonates and renewable polycarbonates. Catalysis is one aspect of the sustainability of this approach, but probably more important is the use of dimethyl carbonate as a non-toxic and potentially renewable alternative to phosgene for these reactions.

What do you see as the main challenges facing research in this area?

In my opinion, a major challenge will be the implementation of all the new and exciting findings that are described in the context of Green Chemistry into the chemical industry. Only then will chemistry have a chance to actually contribute to a sustainable development of our future. This is certainly one of my goals. In order to reach this, in my opinion chemistry does not only have to be sustainable, but also simple, broadly applicable and robust.

Where do you see the field of Green Chemistry being in 5 or 10 years time?

The field will definitely keep on growing. More and more research groups are joining the field, the younger generation is more aware of ecological problems and sustainability in general, and also industry has learned that sustainability often goes along with cost-savings. I thus look forward to a bright future of the field that will hopefully see many paradigm-changing and stimulating new results.

If you could not be a scientist, but could be anything else, what would you be?

If I would not be a scientist, I would probably run a coffee shop with the best cappuccino in town and homemade (organic of course) bagels and cakes. I actually thought about this option during my studies in Regensburg, because back then coffee-shops basically did not exist in Germany. But as you can guess from reading this, chemistry has won.

A couple of Michael’s recent Green Chemistry articles are currently free to access until the 2nd July 2012:

TBD catalysis with dimethyl carbonate: a fruitful and sustainable alliance, Hatice Mutlu, Johal Ruiz, Susanne C. Solleder and Michael A. R. Meier, Green Chem., 2012, 14, 1728-1735

Thiol-ene vs. ADMET: a complementary approach to fatty acid-based biodegradable polymers, Oĝuz Türünç and Michael A. R. Meier, Green Chem., 2011, 13, 314-320

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Encaged palladium catalyst for Suzuki-Miyaura cross-coupling reaction in aqueous media

Encaging the complex PdCl2(py)2 gave a highly efficient and reusable catalyst for the Suzuki-Miyaura cross-coupling reaction.

Tao Li and colleagues from Huazhong University of Science and Technology, China, successfully encaged the PdCl2(py)2 complex in the interior space of hollow silicate-1 spheres.  This new material was then applied to the Suzuki-Miyaura cross-coupling reaction of various aryl halides and arylboronic acids in aqueous media.  Even at Pd loadings of 0.0188 mol%, the catalyst gave fast conversions to the desired products under mild conditions.  Notably, due to the ‘anti-leaching’ effect of the zeolitic shell surrounding the Pd species, the catalyst showed excellent stability and reusability and could be reused 10 times without any appreciable loss of activity. 

This article is free to access until the 29th June 2012!  Click on the link below to find out more…

PdCl2(py)2encaged in monodispersed zeolitic hollow spheres: a highly efficient and reusable catalyst for Suzuki–Miyaura cross-coupling reaction in aqueous media, Zhenhong Guan, Jianglin Hu, Yanlong Gu, Haojun Zhang, Guangxing Li and Tao Li, Green Chem., 2012, DOI: 10.1039/C2GC35302D

You may also be interested in these articles – free to access for 2 weeks:

Heterogeneous catalytic synthesis using microreactor technology, Christopher G. Frost and Lynsey Mutton, Green Chem., 2010, 12, 1687-1703

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Green Chemistry issue 6 – now online!

The latest issue of Green Chemistry is now available online.

The front cover of this issue features work by João Coutinho and colleagues from the University of Aveiro, Portugal, who report investigations into the activity of the commercial enzyme Candida antarctica lipase B (CaLB) in aqueous solutions of ionic liquid.  The group observed that it was possible to induce superactivity in CaLB by using a long chain ionic liquid, 1-decyl-3-methylimidazolium chloride.  This increase in activity did not result from changes in the reaction mechanism or in the structure of the enzyme induced by the ionic liquid.  Instead, this phenomenon may be explained by the formation of microemulsions due to self-aggregation of the ionic liquid chain. 

Ionic liquids microemulsions: the key to Candida antarcticalipase B superactivity, Sónia P. M. Ventura, Luísa D. F. Santos, Jorge A. Saraiva and João A. P. Coutinho, Green Chem., 2012, 14, 1620-1625

The inside front cover of this issue highlights work by Alexis Bell and colleagues from the University of California, Berkeley, USA, who have developed a low energy intensive process for the production of diesel fuels from 5-(hydroxymethyl)furfural (HMF) and D-(–)-fructose.  Alcoholic solutions of these chemicals in the presence of solid acid catalysts produced a variety of potential bio-diesel candidates, with Amberlyst-15 and Dowex DR2030 catalysts showing exceptional reactivity and selectivity.  The distribution of products could be altered by varying the reaction conditions, i.e.by raising or lowering the reaction temperature.  Metal catalysed hydrogenation of HMF using platinum gave exclusive selectivity for reduction of the carbonyl functionality of HMF. 

Etherification and reductive etherification of 5-(hydroxymethyl)furfural: 5-(alkoxymethyl)furfurals and 2,5-bis(alkoxymethyl)furans as potential bio-diesel candidates, Madhesan Balakrishnan, Eric R. Sacia and Alexis T. Bell, Green Chem., 2012, 14, 1626-1634

These articles are free to access for 6 weeks!

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Membrane technologies in sustainable chemistry

Membranes and membrane technologies are quickly finding applications in sustainable chemical processes.  These range from easy separation of products from reaction mixtures and purification of solvents, to the recovery of reagents or catalysts from reaction mixtures for reuse. 

Green Chemistry is an excellent forum for work in this field and a selection of recent high quality articles has been collated below.  These articles are all free to access until the 25th June 2012, so why not take a look…

Keep up-to-date with the latest reviews and primary research in this field by registering for our e-alerts today!

High performance membranes based on ionic liquid polymers for CO2 separation from the flue gas, Pei Li, D. R. Paul and Tai-Shung Chung, Green Chem., 2012, 14, 1052-1063

Direct transformation of ethanol into ethyl acetate through catalytic membranes containing Pd or Pd-Zn: comparison with conventional supported catalysts, Adriana Bonilla Sánchez, Narcís Homs, Sylvain Miachon, Jean-Alain Dalmon, José Luis G. Fierro and Pilar Ramírez de la Piscina, Green Chem., 2011, 13, 2569-2575

Enzyme immobilization on/in polymeric membranes: status, challenges and perspectives in biocatalytic membrane reactors (BMRs), Peter Jochems, Yamini Satyawali, Ludo Diels and Winnie Dejonghe, Green Chem., 2011, 13, 1609-1623

Environmentally friendly route for the preparation of solvent resistant polyimide nanofiltration membranes, Iwona Soroko, Yogesh Bhole and Andrew Guy Livingston, Green Chem., 2011, 13, 162-168

Continuous biocatalytic synthesis of (R)-2-octanol with integrated product separation, Christina Kohlmann, Susanne Leuchs, Lasse Greiner and Walter Leitner, Green Chem., 2011, 13, 1430-1436

Sustainable recovery of pure natural vanillin from fermentation media in a single pervaporation step, Carla Brazinha, Dalje S. Barbosa and João G. Crespo, Green Chem., 2011, 13, 2197-2203

Recent advances in the recycling of homogeneous catalysts using membrane separation, Michèle Janssen, Christian Müller and Dieter Vogt, Green Chem., 2011, 13, 2247-2257

Performance of solvent resistant nanofiltration membranes for purification of residual solvent in the pharmaceutical industry: experiments and simulation, Siavash Darvishmanesh, Loghman Firoozpour, Johan Vanneste, Patricia Luis, Jan Degrève and Bart Van der Bruggen, Green Chem., 2011, 13, 3476-3483

Challenges for recycling ionic liquids by using pressure driven membrane processes, Kurt Haerens, Stephanie Van Deuren, Edward Matthijs and Bart Van der Bruggen, Green Chem., 2010, 12, 2182-2188

Product recovery from ionic liquids by solvent-resistant nanofiltration: application to ozonation of acetals and methyl oleate, Charlie Van Doorslaer, Daan Glas, Annelies Peeters, Angels Cano Odena, Ivo Vankelecom, Koen Binnemans, Pascal Mertens and Dirk De Vos, Green Chem., 2010, 12, 1726-1733

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Meet our Authors: James Mack

James Mack is an Associate Professor of Chemistry at the University of Cincinnati, USA.  His current research is in the development of environmentally benign organic reactions and in particular mechano- or ball milling chemistry.  James took a few moments to speak to Green Chemistry

 Who or what initially inspired you to become a chemist?

 My parents bought me a chemistry set in grade school and I played with the set which included small experiments. I became more interested in high school chemistry. However, I knew when I took an organic chemistry sophomore year in college, that I would pursue a career in the field.

What has been the motivation behind your recent research?

When I was in graduate school I went to a seminar on Green Chemistry and thought there must be a better way to make more environmentally benign reactions. Also, chemistry should make life better for the next generation and I can be part of that change.

What do you see as the main challenges facing research in this area?

One of the challenges is explaining to world leaders that the chemical methodologies we use today will drastically impact the future. We can’t consistently borrow against the future. For example, we use resources today and hope to find alternatives tomorrow; we need to find better ways to conserve the resources we have.

Where do you see the field of Green Chemistry being in 5 or 10 years time?

In 5 to 10 years, the field will grow tremendously because students are more environmentally conscious than I was in my twenties. Green chemistry and protecting the environment is embedded in the social consciousness of today’s youth.

And finally…

If you could not be a scientist, but could be anything else, what would you be?

If I couldn’t be a chemist, my dream job would be to become the General Manager of the Boston Celtics (NBA basketball team). After all, it’s a green team! That would be magical and certainly a dream comes true! I also love to debate; therefore, pursuing a law degree would have been another great career choice.

Take a look a couple of James’ recent articles in Green Chemistryfree to access until the 19th June 2012:

Investigating the formation of dialkyl carbonates using high speed ball milling, Daniel C. Waddell, Indre Thiel, Ashley Bunger, Dominique Nkata, Ashley Maloney, Tammara Clark, Brandon Smith and James Mack, Green Chem., 2011, 13, 3156-3161

A two-step ball milling method synthesizes and purifies α,β-unsaturated esters, William C. Shearouse, Chelsea M. Korte and James Mack, Green Chem., 2011, 13, 598-601

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Top ten most accessed articles in April

This month sees the following articles in Green Chemistry that are in the top ten most accessed:-

Cellulose nanowhisker aerogels
Lindy Heath and Wim Thielemans
Green Chem., 2010,12, 1448-1453, DOI: 10.1039/C0GC00035C

One-pot conversion of CO2 and glycerol to value-added products using propylene oxide as the coupling agent
Jun Ma, Jinliang Song, Huizhen Liu, Jinli Liu, Zhaofu Zhang, Tao Jiang, Honglei Fan and Buxing Han
Green Chem., 2012, Advance Article, DOI: 10.1039/C2GC35150A

Catalytic conversion of biomass using solvents derived from lignin
Pooya Azadi, Ronald Carrasquillo-Flores, Yomaira J. Pagán-Torres, Elif I. Gürbüz, Ramin Farnood and James A. Dumesic
Green Chem., 2012, Advance Article, DOI: 10.1039/C2GC35203F

A direct synthesis of 5-alkoxymethylfurfural ethers from fructose via sulfonic acid-functionalized ionic liquids
George A. Kraus and Tezcan Guney
Green Chem., 2012, Advance Article, DOI: 10.1039/C2GC35175G

A one-pot hydrothermal synthesis of sulfur and nitrogen doped carbon aerogels with enhanced electrocatalytic activity in the oxygen reduction reaction
Stephanie-Angelika Wohlgemuth, Robin Jeremy White, Marc-Georg Willinger, Maria-Magdalena Titirici and Markus Antonietti
Green Chem., 2012,14, 1515-1523, DOI: 10.1039/C2GC35309A

Highly-efficient conversion of glycerol to solketal over heterogeneous Lewis acid catalysts
Li Li, Tamás I. Korányi, Bert F. Sels and Paolo P. Pescarmona
Green Chem., 2012, Advance Article, DOI: 10.1039/C2GC16619D

Transition metal based catalysts in the aerobic oxidation of alcohols
Camilla Parmeggiani and Francesca Cardona
Green Chem., 2012, 14, 547-564, DOI: 10.1039/C2GC16344F

TBD catalysis with dimethyl carbonate: a fruitful and sustainable alliance
Hatice Mutlu, Johal Ruiz, Susanne C. Solleder and Michael A. R. Meier
Green Chem., 2012, Advance Article, DOI: 10.1039/C2GC35191A

Solvent- and catalyst-free synthesis of new hydroxylated trisubstituted pyridines under microwave irradiation
Guodong Yin, Qiong Liu, Junrui Ma and Nengfang She
Green Chem., 2012, Advance Article, DOI: 10.1039/C2GC35243E

Hydrolysis of chitosan to yield levulinic acid and 5-hydroxymethylfurfural in water under microwave irradiation
Khaled W. Omari, Jessica E. Besaw and Francesca M. Kerton
Green Chem., 2012,14, 1480-1487, DOI: 10.1039/C2GC35048C

Why not take a look at the articles today and blog your thoughts and comments below.

Fancy submitting an article to Green Chemistry? Then why not submit to us today or alternatively email us your suggestions.

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Highly-efficient conversion of glycerol to solketal over heterogeneous Lewis acid catalysts

Several mesoporous substituted silicates were applied to the acetalization of acetone with glycerol to yield solketal.

The team of scientists led by Pablo Pescarmona from KU Leuven, Belgium, illustrate for the first time that mesoporous Lewis acid catalysts can be active for this reaction to produce solketal.  Solketal is a very valuable compound with direct applications as a fuel additive, surfactant and flavouring agent.  Of the catalysts tested, the catalyst which showed the highest conversion and turnover numbers was the novel Hf-TUD-1 material.  Along with two other materials, these catalysts gave superior results compared to a reference solid acid catalyst such as Ultrastable zeolite Y.  The active materials do not suffer from leaching and could be efficiently reused in consecutive catalytic cycles.

This article is free to access until the 12th June 2012!  Click on this link below to find out more…

Highly-efficient conversion of glycerol to solketal over heterogeneous Lewis acid catalysts, Li Li, Tamás I. Korányi, Bert F. Sels and Paolo P. Pescarmona, Green Chem., 2012, DOI: 10.1039/C2GC16619D

You may also be interested in these articles – free to access for 2 weeks:

Selective conversion of trioses to lactates over Lewis acid heterogeneous catalysts, Li Li,  Christophe Stroobants, Kaifeng LinPierre A. Jacobs, Bert F. Sels and Paolo P. Pescarmona, Green Chem., 2011, 13, 1175-1181

Zeolite-catalysed conversion of C3 sugars to alkyl lactates, Paolo P. Pescarmona, Kris P. F. Janssen, Chloë Delaet, Christophe Stroobants, Kristof Houthoofd, An Philippaerts, Chantal De Jonghe, Johan S. Paul, Pierre A. Jacobs and Bert F. Sels, Green Chem., 2010, 12, 1083-1089

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GRC Green Chemistry 2012

The 2012 ‘Olympic’ Gordon Research Conference on Green Chemistrywill be held between the 22nd-27th July 2012 at the Renaissance Tuscany II Ciocco Resort in Lucca (Braga), Italy.

The conference will will present cutting-edge research and the most important advances relevant to environmentally benign and sustainable chemistry and chemical processing.  The key scientific sessions will be of interest to both industry and academia and will focus on designing greener chemicals, greener approaches to organic synthesis, catalysis and biocatalysis, polymers and materials, bio-inspired materials, energy and fuels, and assessing our progress toward a sustainable future.

The conference Chairs are Karen I. Goldberg and Steve Howdle with Vice Chairs Kenneth Seddon and Mark A. Harmer.

Applications for this meeting must be submitted by the 24th June 2012.  Please apply early and some meetings become over subscribed before this deadline.

For full details about the conference, click here.

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