Green Chemistry Blog

Jennifer Lee and George Kraus of Iowa State University have published a new method of producing dimethyl terephthalate, a precursor to polyethylene terephthalate (PET), from renewable sources. In this new work the reaction between methyl coumalate (the esterified dimer of malic acid) and methyl pyruvate (the ester of pyruvic acid) is optimised to provide dimethyl terephthalate in 95% yield.

This is the latest of several approaches currently being developed to supplant the current manufacturing process that produces PET from finite fossil resources. These include the valorisation of citrus waste and the reaction of ethylene with 2,5-dimethylfuran. As is true for the zeolite catalysed fast pyrolysis of certain bio-based resources, these other green methods produce an intermediate aromatic compound, p-xylene or sometimes p-cymene, which must later be oxidised to terephthalic acid. This oxidation reaction is present in the conventional petroleum derived synthesis of PET. The new uncatalysed, solvent-free method of Lee and Kraus circumvents the oxidation stage, and by doing so shortens the synthetic procedure and avoids the use of cobalt or manganese oxidation catalysts, which from an elemental sustainability perspective are vulnerable to depletion.

Free to access until 4th March:

One-pot formal synthesis of biorenewable terephthalic acid from methyl coumalate and methyl pyruvate, J. J. Lee and G. A. Kraus, Green Chemistry, DOI: 10.1039/C3GC42487A

Here are the latest HOT papers published in Green Chemistry, as recommended by the referees:

One-pot two-step mechanochemical synthesis: ligand and complex preparation without isolating intermediates
Michael Ferguson, Nicola Giri, Xu Huang, David Apperley and Stuart L. James  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42141D

Studies on the oxidative N-demethylation of atropine, thebaine and oxycodone using a FeIII-TAML catalyst
Duy D. Do Pham, Geoffrey F. Kelso, Yuanzhong Yang and Milton T. W. Hearn  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC41972J

Lignin extraction from biomass with protic ionic liquids
Ezinne C. Achinivu, Reagan M. Howard, Guoqing Li, Hanna Gracz and Wesley A. Henderson  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42306A

In an attempt to provide green solvent selection guide for olefin metathesis
Tomasz Krzysztof Olszewski, Krzysztof Skowerski, Andrzej Tracz and Jacek Bialecki  
Green Chem., 2013, Accepted Manuscript, DOI: 10.1039/C3GC41943F

All the papers listed above are free to access for the next 4 weeks!

Here are the latest HOT papers published in Green Chemistry, as recommended by the referees:

The potential of methylsiloxanes as solvents for synthetic chemistry applications
Mohd Azri Ab Rani, Nadine Borduas, Victoria Colquhoun, Robert Hanley, Henry Johnson, Solène Larger, Paul D. Lickiss, Veronica Llopis-Mestre, Selina Luu, Martin Mogstad, Philipp Oczipka, James R. Sherwood, Tom Welton and Jun-Yi Xing  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42036A

A mechanochemical strategy for oxidative addition: remarkable yields and stereoselectivity in the halogenation of organometallic Re(I) complexes
José G. Hernández, Neil A. J. Macdonald, Cristina Mottillo, Ian S. Butler and Tomislav Friščić 
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC42104J

A PDMS membrane with high pervaporation performance for the separation of furfural and its potential in industrial application
Fan Qin, Shufeng Li, Peiyong Qin, M. Nazmul Karim and Tianwei Tan  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC41867G

All the papers listed above are free to access for the next 4 weeks!

Issue 1 of Green Chemistry is now available to read online.

This year we celebrate our milestone of 15 years of publication, and in issue 1 you can read an Editorial from all of Green Chemistry’s Chairs of the Editorial board and Scientific Editors marking the occasion.

We have also put together a special web collection, with contributions from authors who have had highly cited articles from each of the past 15 years : 15 Years of Green Chemistry

The front cover this month (pictured left) features work by Brian Davison and co-workers. In their work they investigate the mechanism of biomass breakdown. Understanding this process should lead to more efficient use of biomass.

Read the full article:
Common processes drive the thermochemical pretreatment of lignocellulosic biomass
Paul Langan, Loukas Petridis, Hugh M. O’Neill, Sai Venkatesh Pingali, Marcus Foston, Yoshiharu Nishiyama, Roland Schulz, Benjamin Lindner, B. Leif Hanson, Shane Harton, William T. Heller, Volker Urban, Barbara R. Evans, S. Gnanakaran, Arthur J. Ragauskas, Jeremy C. Smith and Brian H. Davison  
Green Chem., 2014, 16, 63-68, DOI: 10.1039/C3GC41962B

The inside front cover this month (pictured right) features work by Kevin Moeller and co-workers from Missouri, USA. In their work they set up a simple solar-electrochemical reaction to recycle Os(VIII)-, TEMPO-, Ce(IV)-, Pd(II)-, Ru(VIII)-, and Mn(V)-oxidants.

Read the full article:
Sunlight, electrochemistry, and sustainable oxidation reactions
Bichlien H. Nguyen, Alison Redden and Kevin D. Moeller  
Green Chem., 2014, 16, 69-72, DOI: 10.1039/C3GC41650J

Both of these articles are free to access for 6 weeks!

Keep up-to-date with the latest content in Green Chemistry by registering for our free table of contents alerts.

Projectile hydrogen molecules are central to a new green method for precisely breaking one of the most abundant and industrially important bonds you can find.

The hydrogen differentiates its colliding partners by their atomic mass

C–H bonds are very stable and as such their cleavage normally requires either a temperature above 300°C or treatment with something like irradiation – both of which can cause organic molecules to lose their functionality. Now a method developed by Leo Lau of Western University in Canada and colleagues can break C–H bonds without damaging the rest of the molecule.

Lau explains that although H₂ is unreactive at room temperature, by raising its kinetic energy to more than 10eV it is possible to drive C–H cleavage when the H₂ hits the H atom of a C–H bond. The H₂ works as a light-mass projectile and differentiates its colliding partners by their atomic mass and ‘like the scalpel of a skilful surgeon’ only excises a hydrogen atom. The dissociation occurs nearly 100% of the time and all of the other bonds remain intact.

Read the full article in Chemistry World»

Read the original journal article in Green Chemistry:
Cleaving C–H bonds with hyperthermal H2: facile chemistry to cross-link organic molecules under low chemical- and energy-loads
Tomas Trebicky, Patrick Crewdson, Maxim Paliy, Igor Bello, Heng-Yong Nie, Zhi Zheng, Xiaoli Fan, Jun Yang, Elizabeth R. Gillies, Changyu Tang, Hao Liu, K. W. Wong and W. M. Lau  
Green Chem., 2014, Advance Article, DOI: 10.1039/C3GC41460D

A collaboration between scientists at Frankfurt’s DECHEMA Research Institute and the Delft University of Technology has established a biocatalytic route to make bio-based antiseptics from carvacrol and thymol. Halogenation of monoterpenes yields interesting antimicrobial compounds, some with anti-tumour activity and other desirable medicinal properties. As more is discovered about enzymatic halogenation (and significant progress on this front is only recent) it becomes increasingly viable as a benign technology for the synthesis of these important molecules.

A chloroperoxidase enzyme was used to form hypochloride from sodium chloride and hydrogen peroxide, with later experiments exploring combined electrochemical enzymatic halogenation, producing the hydrogen peroxide in situ from oxygen. The hypochloride then reacts with carvacrol or thymol to produce their respective monochloro-derivatives. For example, an ortho-chlorothymol to para-chlorothymol molar ratio of 70:30 was achieved, with yields exceeding 80% under optimised conditions.

The greenness of this methodology is apparent upon comparison to the typical reaction conditions, as highlighted by Getrey et al. and found here. In contrast to the application of copper(II) chloride as a catalyst in the chlorination of phenol derivatives with oxygen and lithium chloride, this new enzymatic process operates at a lower temperature with less catalyst, and does not require an organic solvent.

By James Sherwood

Click below to read the full article. Free to access until 8th January.

Enzymatic halogenation of the phenolic monoterpenes thymol and carvacrol with chloroperoxidase, Laura Getrey, Thomas Krieg, Frank Hollmann, Jens Schrader and Dirk Holtmann, Green Chemistry, 2014, DOI: 10.1039/C3GC42269K

The 10 most-accessed Green Chemistry articles between July and September 2013 were as follows:

Synthesis of thioesters through copper-catalyzed coupling of aldehydes with thiols in water
Chih-Lun Yi, Yu-Ting Huang and Chin-Fa Lee  
Green Chem., 2013,15, 2476-2484, DOI: 10.1039/C3GC40946E, Paper

Highly efficient iron(0) nanoparticle-catalyzed hydrogenation in water in flow
Reuben Hudson, Go Hamasaka, Takao Osako, Yoichi M. A. Yamada, Chao-Jun Li, Yasuhiro Uozumi and Audrey Moores  
Green Chem., 2013,15, 2141-2148, DOI: 10.1039/C3GC40789F, Paper 

Iodine-mediated arylation of benzoxazoles with aldehydes
Yew Chin Teo, Siti Nurhanna Riduan and Yugen Zhang  
Green Chem., 2013,15, 2365-2368, DOI: 10.1039/C3GC41027G, Communication

Polymer anchored Cu(II) complex: an efficient and recyclable catalytic system for the one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles starting from anilines in water
Susmita Roy, Tanmay Chatterjee and Sk. Manirul Islam  
Green Chem., 2013,15, 2532-2539, DOI: 10.1039/C3GC41114A, Paper

 Multicomponent reactions in unconventional solvents: state of the art
Yanlong Gu  
Green Chem., 2012,14, 2091-2128, DOI: 10.1039/C2GC35635J, Critical Review

Photocatalysis on supported gold and silver nanoparticles under ultraviolet and visible light irradiation
Sarina Sarina, Eric R. Waclawik and Huaiyong Zhu  
Green Chem., 2013,15, 1814-1833, DOI: 10.1039/C3GC40450A, Tutorial Review

Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation
Jonathan G. Huddleston, Ann E. Visser, W. Matthew Reichert, Heather D. Willauer, Grant A. Broker and Robin D. Rogers  
Green Chem., 2001,3, 156-164, DOI: 10.1039/B103275P, Paper

Deconstruction of lignocellulosic biomass with ionic liquids
Agnieszka Brandt, John Gräsvik, Jason P. Hallett and Tom Welton  
Green Chem., 2013,15, 550-583, DOI: 10.1039/C2GC36364J, Critical Review

Hydrolysis of cellulose to glucose by solid acid catalysts
Yao-Bing Huang and Yao Fu  
Green Chem., 2013,15, 1095-1111, DOI: 10.1039/C3GC40136G, Tutorial Review

Catalytic conversion of biomass to biofuels
David Martin Alonso, Jesse Q. Bond and James A. Dumesic  
Green Chem., 2010,12, 1493-1513, DOI: 10.1039/C004654J, Critical Review

Take a look at the articles and then let us know your thoughts and comments below.

Fancy submitting your own work to Green Chemistry? You can submit online today, or email us with your ideas and suggestions.

Issue 12 of Green Chemistry is now available to read online.

The front cover this month (pictured left) features work by Peter C. K. Lau and co-workers from Quebec, Canada. In their work they engineer sinapic acid decarboxylaseas an alternative to chemistry-based or thermal decarboxylation to produce canolol from canola meal.

Read the full article:
Antioxidant canolol production from a renewable feedstock via an engineered decarboxylase
Krista L. Morley, Stephan Grosse, Hannes Leisch and Peter C. K. Lau  
Green Chem., 2013, 15, 3312-3317, DOI: 10.1039/C3GC40748A

The inside front cover this month (pictured right) features work by Joerg Schrittwieser, Frank Hollmann and co-workers from Deltf, The Netherlands. In their work they show how the one-pot combination of alcohol dehydrogenase (ADH) and palladium nanoparticle (Pd-NP) catalysis provides access to aromatic 1,2-amino alcohols in high yields and excellent optical purities.

Read the full article:
One-pot combination of enzyme and Pd nanoparticle catalysis for the synthesis of enantiomerically pure 1,2-amino alcohols
Joerg H. Schrittwieser, Francesca Coccia, Selin Kara, Barbara Grischek, Wolfgang Kroutil, Nicola d’Alessandro and Frank Hollmann  
Green Chem., 2013, 15, 3318-3331, DOI: 10.1039/C3GC41666F

Both of these articles are free to access for 6 weeks!

Keep up-to-date-with the latest content in Green Chemistry by registering for our free table of contents alerts.