Biodegradable Catalytic Asymmetric Methods - A study of solvents, organocatalysts and magnetic-nanoparticlesupported catalysts

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Resource or Project Abstract

We successfully improved the activity of the acid catalysts, allowing a decrease in the quantity of catalyst from 10 mol% to 0.05 mol% (i.e. 200x less), while maintaining excellent yields. During the development phase of the project, antimicrobial toxicity data for several acid catalysts was unacceptably high. The tandem approach of toxicity screening and acid catalyst performance evaluation meant we could direct the research towards lower toxicity targets. The recommended final acid catalysts have low antimicrobial toxicity. In addition, green chemistry metrics to analyse the efficiency of the synthesis of the acid catalyst and waste generation were applied. By identifying the most environmentally damaging processes, and developing greener alternatives, we now have a cleaner synthesis of our recommended acid catalysts. A major challenge of the project was to prepare biodegradable acid catalysts. Predicting accurately biodegradation (i.e. computer modelling) of this class of compound (imidazolium salts) is not currently possible. This is in part due to the lack of experimental data to train modelling programmes. We successfully obtained biodegradation data for our imidazolium acid catalysts: however, none of these chemicals passed the CO2 Headspace Test. No significant breakdown of the imidazolium structure was observed, despite the wide range of modifications explored. While disappointing, this data directs future biodegradable chemical investigations towards alternative structures. In addition, this experimental data will assist in the refinement of biodegradation prediction calculations. The impact of the work over the duration of the project has been stepwise. Our first publication reported catalyst performance only. The second combined performance and antimicrobial toxicity and was published in the leading Royal Society of Chemistry journal in the field, Green Chemistry (IF 6.8) in 2010. Our latest dissemination is a series of three back-to-back papers in Green Chemistry, reporting catalyst performance, antimicrobial toxicity, biodegradation, green chemistry metrics and catalyst recycling. These papers are the triple front cover articles for the Green Chemistry 2013 October issue, with the first of the series also highlighted as a ?Hot Article? by reviewers. This justifies and validates the current research decision to our approach to jointly assess the toxicity, biodegradation, synthesis and performance of the catalysts at the development stage, which to the best of our knowledge, is unique to our Dublin City University (DCU)/Trinity College Dublin (TCD) team. When presenting our findings at conferences in Europe and the US, the overwhelming feedback is that this type of joint assessment should be the rule rather than the exception, and this is our key recommendation.

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Contact Information for This Resource

Dr. Nick Gathergood
Dublin City University
Environmental Scientist
Room X126, Dublin City University , School of Chemical Sciences and National Institute for Cellular Biotechnology, Dublin City University Glasnevin, Dublin 9, Ireland
Telephone: +353 1 7007860

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Att: 1    STRIVE_119_-_Summary_of_Findings.pdf  (0.29 Mb)
Project Report Optimised For Online Viewing    STRIVE_119_Gathergood_AcidCatalysts_web.pdf  (2.45 Mb)

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Author(s)Gathergood, N.
Title Of WebsiteSecure Archive For Environmental Research Data
Publication InformationBiodegradable Catalytic Asymmetric Methods - A study of solvents, organocatalysts and magnetic-nanoparticlesupported catalysts
Name of OrganisationEnvironmental Protection Agency Ireland
Electronic Address or URL
Unique Identifier8046d7ab-55bc-11e3-b233-005056ae0019
Date of AccessLast Updated on SAFER: 2017-03-26

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Gathergood, N.   "Biodegradable Catalytic Asymmetric Methods - A study of solvents, organocatalysts and magnetic-nanoparticlesupported catalysts". Associated datasets and digitial information objects connected to this resource are available at: Secure Archive For Environmental Research Data (SAFER) managed by Environmental Protection Agency Ireland (Last Accessed: 2017-03-26)


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SAFER-Data Display URL
Resource KeywordsGreen Chemistry, toxicity, biodegradation, green chemistry metrics, cleaner synthesis, catalysis, asymmetric catalysis, organocatalysis, ionic liquids, imidazolium salts
EPA/ERTDI/STRIVE Project Code2008-ET-MS-6-S2
EPA/ERTDI/STRIVE Project ThemeEnvironmental Technologies
Resource Availability: Any User Can Download Files From This Resource
Limitations on the use of this ResourceThe reliability, quality and completeness of data gained through SAFER-Data is intended to be used in an education or research context. These data are not guaranteed for use in operational or decision-making settings. The EPA and SAFER-Data requests an acknowledgement (in publications, conference papers, etc) from those who use data/information received with SAFER-Data. This acknowledgement should state the original creators of the data/information. An automated citation is provided below. It is not ethical to publish data/information without proper attribution or co-authorship. The data/information are the intellectual property of the collecting investigator(s). The data/information may be freely downloaded and used by all who respect the restrictions and requirements in the previous paragraphs.
Number of Attached Files (Publicly and Openly Available for Download): 2
Project Start Date Monday 1st September 2008 (01-09-2008)
Earliest Recorded Date within any attached datasets or digital objects Monday 1st September 2008 (01-09-2008)
Most Recent Recorded Date within any attached datasets or digital objects Monday 1st April 2013 (01-04-2013)
Published on SAFERMonday 25th November 2013 (25-11-2013)
Date of Last EditFriday 3rd January 2014 at 17:02:55 (03-01-2014)
Datasets or Files Updated On Friday 3rd January 2014 at 17:02:55 (03-01-2014)

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Description of Geographical Characteristics of This Project or Dataset
This was a laboratory based study. Work completed in the School of Chemical Sciences, Dublin City University and School of Chemistry, Trinity College Dublin. Both labs are fully equiped organic synthesis labs, with access to standard organic synthesis apparatus (stirrers, rot evaps), HPLC, GC and NMR.

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Supplementary Information About This Resource

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Lineage information about this project or dataset
European Union REACH (Registration, Evaluation, Authorisation, and Restriction of Chemical Substances) chemical control laws were implemented in 2007 to protect humans and the environment by ensuring information was available on the hazards of chemicals so they can be assessed and managed. This is now a global trend: for instance, amendments to TSCA (Toxic Substances Control Act) in the US in 2010 shifted the burden of demonstrating the safety of chemicals from the US Environmental Protection Agency to manufacturers. China?s Ministry of Environmental Protection (formed in 2008) strengthened safety initiatives and recently greatly expanded the toxicity data requirement before import or production of chemicals not listed on their current chemical inventory. Current national policy includes the government?s promotion and strategy of a SMART Green Economy, national priority areas (including processing technologies and materials), the EPA?s 2020 Vision - Sustainable Use of Resources and EU policy Horizon 2020 and 2013 - COST Action CM1206 (Exchange of Ionic liquids), which demonstrate the relevance of green chemistry projects. Part of the research strategy was to replace ?traditional synthetic methods? with ?a greener alternative?. The inherent advantage of green chemical transformations are improved resource efficiency. This is realised by: (i) reducing the quantity of chemicals required to produce the target material; (ii) reducing the number of steps to manufacture the product; and (iii) reducing the waste generated. In the first two points, one must consider the benefit of utilising less chemicals (including solvent), together with the positive effect on the environment (e.g. lower energy consumption, reduced CO2 emissions, improved air quality, and less waste treatment) when producing these raw materials. Also, by reducing the toxicity and increasing the biodegradability of chemicals utilised, the waste stream can be more easily treated, avoiding the need for landfill or incineration. Green chemistry can thus lead to significant reductions on the impact on the environment. Cost savings due to reduced chemical consumption and cheaper chemical manufacture are a stimulus for industry uptake of green chemistry methodologies. The design of safer chemicals is a worthwhile goal. Anastas and Warner (1998) provided a roadmap for this when they published the 12 Principles of Green Chemistry. Fundamental to their approach was a combined interdisciplinary strategy where the toxicity and biodegradation assessment of chemicals (e.g. acid catalysts) is combined with a ?greener? or less environmentally damaging synthetic route for preparing them. To realise this, where possible environmentally benign chemicals should be utilised. This should be coupled with short syntheses (few steps) of the target acid catalysts. Acid catalysts (e.g. hydrochloric and sulfuric acid) are corrosive chemicals which require careful handling and storage. Accidental spillage and clean-up requires special personal protection equipment. Of interest to industry are safer acid catalysts, in particular catalysts that are only acidic when activated as required. The advantage is that this type of acid catalyst is convenient to handle and store due to its counter-intuitive classification as "non-acidic". The main objective of this work was to design and synthesise a range of low-antimicrobial toxicity and biodegradable acid catalysts, and to explore their use in several classes of reactions. The project had five main aims: 1 Developing short green synthetic routes to our target acid catalysts; 2 Identifying acid catalysts with undesirable high antimicrobial toxicity; 3 Completing biodegradation studies (CO2 Headspace Test) to evaluate target acid catalysts breakdown; 4 Determining the reactions where our catalyst is effective, including reaction scope and role as solvent; 5 Applying green chemistry metrics to reduce the environmental impact of synthetic methods. Previous work by the team lead to the discovery of a class of non-acidic chemicals which could be activated (switched-on), when added to solvent. Limitations of this work, however, included low catalytic activity, requiring the use of large quantities of catalyst to ensure high yields. We proposed that a new class of acid catalysts (imidazolium salts) would have higher activity. Over the last decade, there has been great interest in industry regarding this class of compounds as replacement chemicals. The team has studied the biodegradation of these salts, and previously reported poor breakdown under the CO2 Headspace Test conditions. Thus, the development of biodegradable imidazolium salts is a major and worthwhile goal. Our hypothesis was that the modifications performed to change the catalyst?s molecular structure to improve performance would also improve biodegradation and reduce toxicity. This in turn results in reducing the negative impact on the environment.
Supplementary Information
Details of co-authors and researchers who worked on this project:

Stephen J. Connon (Professor) Trinity Biomedical Sciences Institute School of Chemistry University of Dublin Trinity College Dublin 2 Ireland. Email: connons [at] tcd [dot] ie

Rohitkumar G. Gore (PhD student) School of Chemical Sciences and National Institute for Cellular Biotechnology Dublin City University Glasnevin Dublin 9 Ireland Email: rohitggore [at] gmail [dot] com

Lauren Myles (PhD student) Trinity Biomedical Sciences Institute School of Chemistry University of Dublin Trinity College Dublin 2 Ireland Email: lauren [dot] myles21 [at] gmail [dot] com

Important Outputs Summary

Tandem catalyst performance and toxicity assessment has led to the development of a low antimicrobial toxicity and very active fourth- generation catalyst. This approach was successful and is advised for future studies;

Modifications which were expected to improve biodegradation and catalyst performance only promoted the latter;

Introduction of an ester or amide group into the imidazolium ring does not give a readily biodegradable compound;

Boethling?s ?rules of thumb? for designing biodegradable molecules should be modified to account for poor biodegradation of first fourth-generation ILs;

Two fourth-generation catalysts are recommended for further study. These are an iodide and BF4 IL. Based on consideration allmetrics assessed the iodide is preferred. Although the BF4 gives a slightly superior performance in the catalysis study, the synthesis and use of the iodide creates less waste;

A low antimicrobial toxicity fourth-generation IL/ catalyst can be used to replace mercury reagents in the deprotection reaction of dithianes, a commonly used transformation in synthetic organic chemistry;

N-decyl amide imidazolium ILs should not be used as solvents and/or catalysts due to their high antimicrobial toxicity. These examples were subsequently dropped from our catalyst performance assessment; ? Several ILs were effective replacements for dichloromethane in palladium catalysed asymmetric carbonyl-ene reactions, with efficient recycling demonstrated;

The use of green chemistry metric assessment successfully highlighted parameters which can be targeted for further improvements in the reduction of waste for fourth-generation IL preparation.

2 PhD students graduated. 3 Book Chapters. 5 papers.
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