Course program
A- Revision of basic chemistry concepts.
Electronic configuration of elements and octet rule. Electronic spin, exclusion principle of Pauli and principle of maximum multiplicity. Chemical bonds: Ionic and covalent (homopolar, polar and dative). Polarity of bonds and molecules. Formal charge and oxidation number of atoms in organic compounds. REDOX reactions in organic chemistry. Atomic and molecular orbitals. Hybrid Orbitals sp, sp2, sp3. Definition of acid and base species according to Arrhenius, Bronsted-Lowry and Lewis theories. Intra- and inter-molecular forces: hydrogen bond and van der Waals bond. Homolytic and heterolytic bond cleavage. Heterolysis of carbon bonds: formation of carbocations and carbanions. Homolysis of carbon bonds: formation of free radicals.
B- Molecular structure.
B1-Definition (constitution and stereochemistry). Representation of organic molecules by means of Lewis and Kekulè structures, both in compact and corner-line version. Definition of resonance and rules for writing correct resonance structures of organic molecules. Functional groups and their possible electrophilic / nucleophilic properties.
B2-Stereochemistry. Molecular symmetry: essential concepts (centers, planes and proper and improper axes of symmetry). Essential concepts concerning the stereochemistry of organic molecules. Classification: constitutional and steric isomerism. Diastereomers and enantiomers. Differences of conformational and configurational nature. Optical and geometric stereoisomerism. Stereogenic centers, axes and planes. Molecular chirality and elements responsible for it (centers, axes and planes). Racemic mixtures. Configurational descriptors cis/trans, E/Z, R/S. Cahn-Ingold-Prelog rules. Fischer projections of organic molecules (rules for their correct writing and manipulation). Mesoforms. Epimers. Optical activity of chiral molecules. Relative configuration of asymmetric centers in monosaccarides and alpha-amino acids: D/L descriptors. Outlines on the resolution of enantiomers.
C- Reactions and main classes of Organic Compounds.
Equations of organic reactions. Basic types of organic reactions (substitution, elimination, addition). Making and breaking of chemical bonds (radicals, carbocations, carbanions). Bond-dissociation energy. Thermodynamics (equilibrium constant and change in free anergy). [concepts introduced during the course]
C1- Linear and cyclic Alkanes. Structure. IUPAC nomenclature. Common names. Chemical-physical properties. Conformational isomerism (ethane, butane). Cis/trans isomerism in cycloalkanes. Insights on the structure of the Cyclohexane and of its derivatives: chair and boat conformations, hydrogens, and substituents in axial and equatorial positions. Halogenation of alkanes. Radical mechanism. Regioselectivity of substitution in alkanes halogenation. Stability of alkyl radicals.
C2- Alkenes. Structure. IUPAC nomenclature. Geometric isomerism: cis/trans and E/Z nomenclature. Addition of HBr via radical mechanism. Electrophilic addition reactions: HX (X = halogens) [ionic (carbocations: structure, stability)], water, halogens.
C3- Alkynes. Structure. IUPAC nomenclature. Chemical properties. The acidity of terminal alkynes. Electrophilic addition reactions. Reactions of acetylide anions.
C4- Alkyl halides. Structure. IUPAC nomenclature. Electrophilic character of the halogen-substituted carbon within alkyl halides. Aliphatic nucleophilic substitution reactions. SN2 and SN1 reaction mechanisms and their competition. Stereochemical aspects involved in the two mechanisms. Substrate structure, nucleophile type, living group, and solvent effects. Elimination reactions. E2 and E1 reaction mechanisms. Competition between the E1 and E2 mechanisms. Zaitsev's and Hofmann's rules. Competition between elimination and aliphatic nucleophilic substitution reactions.
C5- Benzene and its derivatives. Structure. IUPAC nomenclature. General properties of benzene and its derivatives. Concept of aromaticity: rules for its identification (Huckel's rule). Aromatic heterocyclic compounds. Electrophilic aromatic substitutions (SEAr): halogenation; nitration; sulfonation; alkylation and acylation of Friedel-Crafts. Inductive and mesomeric effects of groups linked to the benzene ring: their ability to modulate the reactivity of the aromatic ring and to orient the position of substitution.
C6- Alcohols and thiols, ethers. Structure. IUPAC nomenclature. Physical and chemical-physical properties. Acid-base properties. Reactions of Alcohols and phenols. Epoxides as a special case of strongly reactive ethers (electrophilic character of the carbon atoms bonded to the epoxydic oxygen).
C7- Aliphatic and aromatic amines. Structure and bonding. IUPAC nomenclature. Basicity. Preparation by direct nucleophilic substitution and by reduction of chemical groups containing nitrogen (stereochemistry). Gabriel’s synthesis. Halogenation.
C8- Aldehydes and Ketones. Structure. IUPAC nomenclature. Nucleophilic addition reactions: Grignard reagents, hydride ions, 1° and 2° amines, water, alcohols. Nucleophilic addition to α,β-unsaturated aldehydes and ketones.
C9- Carboxylic acids and their derivatives. Structure. IUPAC nomenclature. Acidity constants. Esters. Acid-catalysed hydrolysis, saponification. Acyl halides. Anhydrides. Amides. Nitriles.
C10- Enols and enolates. Acidity possessed by alpha hydrogens (aptitude to enolate ion formation). Keto-enol tautomerism. Reactivity of enols and enolates (halogenation reactions, aldol condensation, and others). Acidity and reactivity of beta-dicarbonyl compounds.
Prerequisites
It is strongly suggested a good knowledge of general and inorganic chemistry.
Books
Bruno Botta, a cura di: Chimica Organica Essenziale, Edi-Ermes, 2012. ISBN 978-880870513547.
W. H. Brown “Chimica Organica” Ed. Edises 2010.
J. Mc Murry “Chimica Organica” 9 Ed. Ed. Piccin 2017.
Frequency
Attendance at course is not mandatory, however it is highly encouraged the frequency of lessons for a better understanding of the topics. For an easy understanding of the topics covered in the course it is recommended to have passed the General and Inorganic Chemistry exam.
Exam mode
The exam consists of a written test that serves for the admission to the oral exam, followed by the oral test.
The written test consists in 10 exercises (lasting 1 hour) which may contain practical or theoretical questions on the whole program. To access the written exam, students must register on the E-learning platform.
The oral exam consists of 3 questions on the whole program (average exam duration: 30 minutes). To achieve a score of 30/30 cum laude, the student must demonstrate that he has acquired excellent knowledge of all the topics covered during the course, showing a natural ability to quickly link between them. To access the oral exam, students must register on INFOSTUD.
Lesson mode
The course consists of taught classes and numerical exercises on the interactive whiteboard that are intended to prepare students for the written test.
During the lessons, the teacher stimulates the students with questions related to what it has just been presented, with the aim of making them participate and stimulate the study at home, lesson by lesson. Students are invited to read the various textbooks recommended at the beginning of the course and to find on them, the discussion of the various topics proposed in class.