Ateneo - UPO

Definition of Green Chemistry
Description of the main indicators (green metrics: atom economy, e-factor, mass index, reaction mass efficiency, stoichiometric factor, mass recovery parameter) of effectiveness and environmental performance of organic synthesis.
Role of catalysis. Catalysis of the reductions, oxidation, and formation of carbon-carbon bond reactions. Enzymatic catalysis. Enzymes in organic solvent. Reactions of hydrolysis
Carboxyalkylation and alkylation processes with reduced environmental impact.
Phosgene and green reagents as substitutes.
Alternative reaction media and biphasic systems
Products from renewable natural sources. Circular bioeconomy.
Process integration and cascade catalyzed reactions.
Laboratory
Introduction to experiments. Use of green chemistry indicators for the evaluation of a synthetic process and their application to laboratory experiences.

Green Chemistry and Catalysis. I. Arends, R. Sheldon, U. Hanefeld, 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-30715-9

The course falls within the training activities that characterize the three-year degree course in Green Chemistry, which are dedicated to the in-depth study of the issues related to the concept of eco-sustainable chemistry.
The specific educational objective of the course is to provide knowledge, at least basic, which allows the student to face a complex chemical problem such as the study and analysis of organic synthesis procedures with a low impact on the environment, through modern methodological tools. that with the use of indicators such as atom economy, e-factor, mass index, etc., allow to quantify the efficiency or environmental performance of a chemical process in relation to the principles of Green Chemistry.
By examining the development of fundamental transformations of organic chemistry, also with attention to industrial applications, the course aims to offer students both the general concepts for the implementation of eco-compatible syntheses, and to develop a certain critical capacity in the application of these notions to the use of reagents, solvents and green catalysts, and to the choice of the related reaction conditions. These aspects are integrated in the laboratory section of the course which is articulated through the implementation of some organic transformations with low environmental impact and the relative analysis with the indicators already mentioned.

The student should have a solid knowledge of the structure, properties, and reactivity of the organic compounds. It is therefore highly recommended that the student has achieved the training objectives of the course of Fundamentals of Organic Chemistry and Laboratory.

The theoretical part is organized in lectures on the topics indicated extended program. The laboratory part includes both a brief introduction by the teacher to each laboratory experience and a teacher / student comparison during the material execution of the experiments, to well understand the content of the experimental procedures, the laboratory techniques adopted, and the results/methods of product analysis. The slides projected in the classroom during lectures and introduction to the laboratory will be available and downloadable from the University's DIR platform.

Oral exam consisting of a series of open questions aimed at ascertaining the knowledge acquired by the student on the entire program, including the laboratory part, starting with the critical analysis of a literature article related to the program topics, that possibly includes the application of process indicators (green metrics) and a written report for the laboratory session.

Definition of Green Chemistry.
Description of the main indicators (green metrics: atom economy, e-factor, mass index, reaction mass efficiency, stoichiometric factor, mass recovery parameter) of effectiveness and environmental performance of an organic synthesis.
Role of catalysis. Acid and basic catalysis: acid clays, zeolites, SO3H groups supported on solids, heteropolyacids; aromatic electrophilic substitution reactions, addition and elimination, rearrangements, cyclizations. Basic clays and zeolites, organic bases supported on silica.
Reduction reaction catalysis: heterogeneous and homogeneous catalysis, hydrogen transfer catalysis, heterogeneous and homogeneous chiral catalysts and their applications. Biocatalytic reductions: enzymes and whole cells.
Catalytic oxidations: metal-catalyzed oxidations, enzymatic and biocatalytic oxidations. Catalyst design; dihydroxylation, epoxidation, oxidation and oxidative cleavage of alkenes, allyl oxidation, oxidation of alkanes, alcohols, phenol ethers, amines and sulphides. Oxidative cleavage of diols. Baeyer-Villiger oxidation. Asymmetric oxidations: epoxidation, dihydroxylation, Baeyer-Villiger, asymmetric oxidation of sulphides.
Formation of carbon-carbon bonds: use of enzymes, oxynitrilases, cyanohydrins, aldolases; carbonylation and hydroformylation. Cross coupling reactions: Suzuki, Sonogashira, Heck. Reactions of metathesis. Organocatalysis.
Reactions of hydrolysis: hydrolases and their properties, enzymatic resolutions, application to esters, amides and nitriles.
Carboxyalkylation and alkylation processes with reduced environmental impact.
Phosgene and green reagents as substitutes: dimethyl carbonate. Use of dimethyl carbonate in alkylation and esterification reactions. Polycarbonates.
Alternative reaction media and biphasic systems.
Choice of solvents, unconventional reaction media, biphasic reaction systems, fluorosis biphasic systems, oxidation, reduction, carbonylation reactions in unconventional media.
Products from renewable natural sources. Circular bioeconomy.
Carbohydrates and their fermentation products, lactic acid, indigo, riboflavin, chemical and chemoenzymatic transformations of carbohydrates into fine chemicals and building blocks, oils and fats, biodiesel, biodegradable polymers from natural sources.
Process integration and cascade catalyzed reactions.
Dynamic enzyme kinetic resolution coupled to metal catalysis, asymmetric hydrogenation coupled to enzymatic hydrolysis, enzyme immobilization.
Laboratory: introduction on safety, efficacy and environmental performance indicators.
Essentials on the use of NMR spectroscopy for the determination of the structure of organic compounds.
Introduction to laboratory experiences.
1. Grignard-like reaction in water
2. Synthesis of biodiesel
3. Aldol condensation without solvent
4. Synthesis of glycerol carbonate
5. Friedel-Crafts reaction with graphite
6. Epoxidation with dimethyldioxirane generated in situ
The reactions will be analyzed with the parameters introduced in the theoretical lessons.

1. Knowledge and understanding
Know the principles of Green Chemistry and some of the most modern synthetic solutions for the implementation of various types of organic reactions with reagents, solvents and catalysts with reduced environmental impact.
Know the tools and indicators that allow to quantify the efficiency or environmental performance of a chemical process in relation to the principles of Green Chemistry.
2. Ability to apply knowledge and understanding.
Knowing how to use the concepts learned to logically examine the environmental impact characteristics of an organic synthesis.
Knowing how to formulate original ideas and conclusions on the effects of a synthetic process in terms of benefits, possible drawbacks and aspects that can be improved from an economic / environmental point of view. The laboratory session and the homework described in the training objectives contribute to the development of this knowledge.
3. Evaluation skills
being able to compare the effectiveness and environmental performance in terms of the choice of reaction conditions, and the chemical-physical and toxicological properties of the chemical compounds involved.
4. Communication skills
Discuss and critically evaluate eco-compatible solutions on the merits of a synthesis process both in the context of sector specialists and by sensitizing non-expert interlocutors and public opinion. Knowing how to constructively interact with the teacher and fellow students during both frontal lessons and laboratory sessions.
5. Learning skills
Knowing how to autonomously enrich one's training by acquiring new specialist knowledge from the scientific and technical literature in the topics explored during the course