Synthesizing amides and esters for the production of agrochemical actives, pharmaceutical actives, and other complicated organic molecules is challenging, as high temperatures need to be applied in current state-of-the-art processes. This often results in limited selectivity and consequently in lower yields and margin of the desired product, in some cases the side products of reactions with limited selectivity will have a negative environmental impact and can even prevent registration of agrochemicals.
Novel synthetic approaches are therefore desirable that would yield amides and esters at lower temperatures and with better selectivity. For industrial purposes atom-economic and step-economic processes are desirable, as they can save money and improve sustainability by saving energy for separation, and the disposal of side products through better atom economy and step economy. Moreover, they can make green and bio-derived raw-materials amenable.
One particularly attractive way of synthesizing amides and esters is by photochemical carbonylation of aryl-halogenides in the presence of amines or alcohols. This reaction will yield the amide or ester via an intermediate carboxylic acid chloride stage at low temperature and possibly therefore with better selectivity. Moreover, this process is extremely attractive in terms of atom economy and step economy. Photochemistry serves at activating the reatents without the need of putting in heat. The reaction follows a different pathway than the transition metal and opens up a new set of paradigms.
Photocatalytic utilization of CO will also be attractive for bulk chemicals produced via classical hydroformylation. Rather than using extremely expensive Rh-based catalysts, in the photochemical pathway H2 and CO to form an aldehyde, a novel, photochemical method will be applied that is based on a different mechanism and therefore has the potential of offering opportunities with regard to selectivity over the state-of-the art. The selection of the metal will affect catalysis and offer an opportunity for tuning the chemical product as well as yield and selectivity.
This project will require a vivid interest in organic synthetic chemistry and organocatalysis. It will consider the specifics of photo-redox-chemistry in the framework of an interdisciplinary and holistic cluster of six BASF-funded students on photochemistry.
Applications are invited for the above project, and the successful applicant will undertake the EPSRC CDT (rEaCt) programme, as part of Cohort 4 (Intake 2022).
Please note that the BASF studentship projects follow the same programme as the normal CDT studentships. The difference is that project funding comes from BASF and not EPSRC.
The project is one of a number of BASF funded projects in the area of photochemistry within the CDT, which, in turn, forms part of a wider suite of activities that BASF is supporting within the CDT, all of which follow the principles detailed below.
Objective: BASF, the world’s leading chemical company, wishes to explore the application of flow chemistry in its R&D workflow for the synthesis of novel agrochemicals, and commodities. In this project, it will assemble a multidisciplinary team of scientists and engineers to explore the value of synergies between a variety of cutting-edge technologies, to develop more effective and efficient chemical production processes.
Setup: This project will bring together a group of highly motivated graduate students to work on two representative challenges from industrial process development, where photochemistry in combination with flow chemistry methodologies will be integrated holistically with in-line screening and analytics, and chemical process engineering complemented by machine learning and modelling. The members of this interdisciplinary project team will be exposed to a broad range of competencies and interact closely with each other in working on a disruptive change of the R&D workflow in a large chemical enterprise.
Training: Industrial R&D scientists based at BASF’s site in Ludwigshafen, the largest chemical “Verbund”site in Europe, will be closely involved in the programme, combining a real-world industrial experience with cutting-edge academic research. Each of the students will be advised by an internationally renowned professor and a BASF scientist and will be part of a centre for doctoral training, bringing together fellow graduate students in closely related fields of research and building a deep understanding of the area of specialization.
This project forms part of a wider suite of activities that BASF is supporting within the CDT. The successful candidate will be able to interact with, and leverage the benefits of, this wider activity. There will be opportunities for placement(s) (total of up to one year duration) within the BASF organisation during the studentship period.
Applicant Requirements
Applicants should hold or expect to obtain a first or upper-second class honours degree or equivalent in Chemistry, Chemical Engineering, or a related field. A Master’s degree in one of the above fields is an essential requirement. Imperial College PhD entry requirements must be met.
Click here for more information on the application process for prospective students.
To apply, please email the EPSRC CDT with the following documents in PDF format.
- An up to date CV
- A copy of all transcripts
- A cover letter (please indicate here if you have any additional information you'd like the panel to take into consideration)
- Full contact details of two referees
- List of up to three projects of interest from the projects currently available
For further information please contact the CDT Programme Manager, Jinata Subba ([Email Address Removed]).
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