Learning outcomes of the course unit
At the end of the course the student is expected to strengthen knowledge of basic organic chemistry and acquire learning and knowledge of advanced organic chemistry as a platform for the study of subsequent courses and the study of drugs.
In particular, the student will be able of:
1. Understanding the importance of organic chemistry in the study of drugs and living organisms.
2. knowledge of the basic and advanced functional groups and applying this knowledge for the classification of simple polyfunctionalized organic molecules (low molecular weight).
3. Applying basic physical-chemistry principles (chemical equilibria, structural theory, thermodynamics and kinetics of organic reactions, acids and bases, nucleophiles and electrophiles) to simple polyfunctionalized organic molecules.
4. Knowledge, understanding and prevision of the relationship between the structure of simple polyfunctionalized organic molecules (containing the functional groups detailed in the contents section) and their physical properties, in particular their solubility in aqueous or non-aqueous solvents.
5. Knowledge, understanding and prevision of the relationship between the structure of simple organic molecules (containing the functional groups detailed in the contents section) and their reactivity, also doing suitable exercises.
6. Knowledge and understanding the methods of synthesis and interconversion of simple polyfunctionalized organic molecules (containing the functional groups detailed in the contents section) and applying these methods for the synthesis and transformation of unknown organic molecules, also doing suitable exercises.
7. Knowledge the international rules for the nomenclature of simple polyfunctionalized organic molecules (containing the functional groups detailed in the contents section) and applying them to unknown molecules, also doing suitable exercises.
8. Communication skills of the contents of the course to specialized audience.
To fully appreciate the content of the course, it is necessary to acquire knowledge of general and inorganic chemistry and organic chemistry basics in previous courses. To access the final examination, it is necessary to pass bot the “General and Inorganic Chemistry” examination and the Organic Chemistry Basics” written examination.
Course contents summary
The first part of the course is devoted to recall and advance knowledge acquired in the (Organic Chemistry Basics) course. The following subjects are then treated: nucleophilic addition to carbon-oxygen double bond, acyl nucleophilic substitution, brief description of the role of protecting groups in organic synthesis, brief survey of qualitative identification of the main functional groups. The systematic study of the following compound classes is then placed, comprising the structure, nomenclature, natural occurrence, physical properties, reactivity, and synthesis of the following compound classes: aldehydes, ketones, carboxylic acids, acyl halides, acid anhydrides, esters, thioesters, lactones, amides, lactams, imides, nitriles, 1,3-dicarbonyl compounds, alpha,beta-unsaturated compounds, amines, nitro- and nitroso-derivatives.
The second part of the course allows students to acquire knowledge on carbon-carbon bond-forming reactions, synthesis of enols and enolates, imines and enamines, alpha-alkylation and alpha-halogenation of enols and enolates, aldol additions and condensations and variants thereof, Claisen condensations and related reactions, Michael and Mannich addition reactions, examples of transposition reactions.
The third part of the course allows students to acquire knowledge on the aromatic domain including the concept of aromaticity and the systematic study of aromatic compounds including the structure, nomenclature, natural occurrence, physical properties, reactivity, and synthesis of the following compound classes: benzene, substituted benzenes and, in particular, phenols, aryl halides, and aromatic amines, simple aromatic heterocycles, azo-compounds.
Lastly, the following topics will be briefly surveyed: monosaccharides, cyclic structures, glucose , disaccharides and oligosaccharides. Brief introduction on fatty acids, lipids, triglycerides.
Recalling the contents of the previous course of Basic Organic Chemistry.
Epoxides: opening the ring with nucleophiles under basic or acidic conditions.
Carbonyl Compounds, the carbon-oxygen double bond. Aldehydes and ketones, structure, resonance, keto-enolic tautomerism, occurrence in Nature, physical properties. Nucleophilic additions: formation of germinal diols, hemiacetal, acetal, cianhydrins, reactions with Grignard reactants. Brief introduction to protecting groups of carbonyl compounds. Brief introduction to the hemiacetal structure of simple monosaccharides such as glucopyranose. Reactons of aldehydes and ketone with nitrogen nucleophiles: formation of imines, iminium ions, hydrazones, oximes. Reactions of aldehydes and ketones con reducing agents; reactions with oxidant reagents. Baeyer-Villiger reaction. Wittig reaction. Synthesis methods for aldehydes and ketones.
Carboxylic acids and derivatives. Structure, nomenclature, physical properties, occurrence in nature of carboxylic and bicarboxylic acids, acyl halides, anhydrides, esters, lactones, amides, lactams, nitriles, carboxylate ions. Brief introduction on the sulfur counterparts (sulfonic acids and esters, thioesters). Reaction of acyl nucleophilic substitution of carboxylic acids and derivatives with nucleophiles (water, alcohols, amines), reactions with hydrides, with organometallic reactants (Grignard, organocuprates).
Acidity of carboxylic acids, factors which influence the acidity.
Methods of synthesis of carboxylic acids including reaction with CO2, nitrile hydrolysis, malonic synthesis, saponification. Synthesis of acyl halides, anhydrides, esters, amides, nitriles. Brief introduction on the amide (peptide) linkage between amino acids.
Reactions involving the alpha-carbon of enolizable carbonyl compounds: formation of enols, enolates, enamines. Alpha-halogenation of ketones; alpha-alkylation of ketones (direct, acetoacetic synthesis, via enamine).
Aldol addition and aldol condensation reaction (inter- ad intramolecular).
Claisen condensation and related reactions.
Carbon-carbon bond-forming reactions.
Alpha,beta-unsaturated compounds: structure, resonance, synthesis, 1,2 versus 1,4 reactivity with nucleophiles. Michael reaction.
Carbonic acid derivatives: brief introduction to functional groups including carbonates, carbamates, urea, carbamic acid.
Phosphorus and sulfur derivatives: brief introduction to functional groups including phosphates, phosphonates, phosphites, phosphines, sulfates, sulfonates, sulfoxides, sulfones, sulfides.
Aromatic compounds. Concept of aromaticity. Huckel rule. Structure, nomenclature, natural occurrence, physical properties and reactivity of benzene. Reactions of aromatic electrophilic substitution (halogenation, nitration, sulfonation, Friedel-Crafts alkylation, Friedel-Crafts acylation, Gatterman-Koch reaction).
Reactions of aromatic electrophilic substitution on mono- and poly-substituted benzenes: activation/unactivation and orientation effects by pre-existing groups on the benzene ring.
Phenols: structure, acidic properties, nucleophilic properties. Reactions of aromatic electrophilic substitution. Protection of the phenolic group. Kolbe reaction. Synthesis methods.
Aryl halides: strucutre, aromatic nucleophilic substitution reaction (two mechanisms).
Aliphatic and aromatic amines: structure, nomenclature, natural occurrence, physical properties, baic properties. Relationship between basic properties and structure. Nucleophilic properties. Aniline, protection methods. Reactivity with nitrosonium ion. Benzendiazonium salts: substitution reactions and coulation to azo-compounds.
Aromatic heterocyclic compounds: structure, resonance, tautomeric forms and nomenclature of simple mono- and bicyclic derivatives.
Choose one of the following textbooks (mandatory):
1. W.H. Brown, B. L. Iverson, E. V. Anslyn, C.S. Foote, “Chimica Organica”, V Edizione, EdiSES, Napoli, 2014
2. Autori vari, “Chimica Organica” (a cura di B. Botta), Edi.Ermes, Milano, 2016.
3. J. McMurry, “Chimica Organica”, VIII Edizione, Piccin, Padova, 2012.
4. Bruice, P. Y. “Chimica Organica”, Terza Edizione, EdiSE, Napoli, 2017.
Choose one of the following exercise books (mandatory):
1. M. V. D’Auria, O. Taglialatela Scafati, A. Zampella, “Guida Ragionata allo Svolgimento di Esercizi di Chimica Organica”, seconda Edizione, Loghia Ed., Napoli, 2011.
2. B. Iverson, S. Iverson, “Guida alla soluzione dei problemi da Brown, Foote, Iverson – Chimica Organica”, 4° Ed., EdiSES, Napoli, 2014.
3. T.W.G. Solomons, C.B. Fryhle, R.G. Johnson, “La chimica organica attraverso gli esercizi”, Seconda Edizione, Zanichelli, Bologna, 2010.
4. S. Cacchi, F. Nicotra, “Esercizi di Chimica Organica”, Casa Editrice Ambrosiana, 1998
Further readings (as a suggestion for specific subjects, not mandatory):
1. M. Loudon, “Chimica Organica”, V Edizione, EdiSES, Napoli, 2010.
2. J. G. Smith, "Chimica Organica", McGraw-Hill, Milano, 2007.
3. G.H. Schmid, “Chimica Organica”, Casa Editrice Ambrosiana, Milano, 1997
4. J. Clayden, N. Greeves, S. Warren, P. Wothers, “Organic Chemistry”, Oxford Edition, 2001.
5. R. Norman, J.M. Coxon, “Principi di Sintesi Organica”, 2a Edizione Italiana, Piccin Editore, Padova, 1997.
Several copies of the text of written examinations of the past academic years are loaded and updated in the Elly platform, to provide further tools in preparation of the examination.
The course is carried out through frontal oral lessons at the blackboard (total 56 hours corresponding to 7 CFU) including exercises. The exercises are carried out by either the teacher or the students and are considered an essential part of the course to:
-applying the theory to solve practical problems dealing with the contents of the course;
-verifying the status of knowledge before passing to the subsequent subject;
-acquire a method for the execution of exercises in both the synthetic direction (synthesis of a target molecule) and retrosynthetic direction (disconnection of a target molecule).
The student is expected to read and study the contents of the lessons by him/herself by using notes and textbook, and applying this knowledge in the execution of exercises, including both the exercises made in classroom, and exercises in the textbook and study guides.
The teacher is available for further explanations about theory and exercises at the end of the lesson, during the break or in office on e-mail appointment.
The teacher may sometimes use additional teaching material (slides) loaded on Elly platform; this material is considered optional and does not substitute the textbook and the exercise study guide, which are mandatory.
Many copies of the text of written examinations of the past academic years are loaded and updated in the Elly platform, to provide further tools in preparation of the examination.
Assessment methods and criteria
To verify the status of knowledge and learning of the student, a written examination is mandatory (2 hour and 15 minutes maximum length) consisting of 4-5 (open-answer) questions having different weight and corresponding to a score detailed in the text. The result is marked in thirtieth, with a minimum pass of 18; it contributes for the 45% of the final quotation of the whole examination.
To access the final oral examination and subsequent recording of the integrated course Basic Organic Chemistry/Organic Chemistry, it is necessary to pass the written examination of both the first and the second modules. It is possible to do the written examination of both modules (Basic Organic Chemistry and Organic Chemistry) in the same day since they are at different (subsequent) times.
Once both written examinations are passed, the student must do the final oral examination (10-20 minutes, 10% weight) in the same session of the last written examination. The on-line registration for the oral examination is suggested but not mandatory.
To access the written examination, the student must register on-line (via Essetre) in the dates according to the official examination schedule of the Food and Drug Department.
The written exam is judged positive (> or equal to 18/30) when the student demonstrates knowledge and learning of the following contents:
-identification and knowledge of the functional groups (as detailed in the contents) within natural or drug-like polyfunctional molecules; identification of carbon stereocenters and chirality;
-knowledge and resonance structures of the main aromatic and heteroaromatic cyclic compounds;
-execution (even partial) of synthesis sequences and interconversion of functional groups;
-execution (even partial) of the total synthesis of a simple organic compound.
The laude (30/30 cum laude) is assigned as a maximum quotation when all questions are correctly answered and when specialized language is used.
While doing the examination, no books, notes nor whatever information system must be available.
The result of the written examination is given within one week and anyway before the oral examination of that session via Essetre portal. The student is expected to view his/her work (either passed or negative) which is consigned the day of the oral session. If the student cannot be present that day, he/she has to inform the teacher by e-mail; the teacher will show the work to the student on another date, to be fixed with the student.