Ateneo - UPO

Structural and semantic bases of organic chemistry
Alkanes, alkenes and alkynes.
Haloalcanes.
Alcohols and ethers
Aldehydes e ketones
Aromatic hydrocarbons
Carboxylic acids
Aliphatic and aromatic amines
Aromatic aldehyides
Phenols
Outline on main sulfur containing compounds

Structure, nomenclature and properties of the main penta- and hexacyclic etherocyclic systems
Functionalization of electron-rich and electron-poor heterocyclic systems
Synthetic entries into the main heterocyclic systems and their products of benzo-condensation

N. E. Shore, P. Vollhardt, Chimica organica, Zanichelli
W.H. Brown, C.S. Foote, Chimica organica, Edises
J. McMurry, Chimica organica, Piccin
Broggini-Zecchi. La Chimica degli Eterocicli. La Scientifica, 2009 (paperback/e-Book)

D’Auria et al.. Guida Ragionata allo Svolgimento degli Esercizi di Chimica Organica. Loghia

G. Broggini, C. Loro, G. Palmisano. Chimica Organica: 800 esercizi con soluzione. Zanichelli

Additional textbook
R. Norman, J.M. Coxon, Principi di sintesi organica, Ed. Piccin

Knowledge of the reactivity of the main functional groups of organic molecules, with emphasis on reaction mechanisms, also with links to biological examples to exemplify the prerequisites to other disciplines. Introduction of the basic concepts of organic synthesis, to prepare the student to the construction of even polyfunctional molecules. Applications of these concepts to the chemistry of heterocycles. Development of an adequate self-learning ability. Ability to apply their knowledge, understanding, and ability to solve problems to new or unfamiliar issues, inserted in a more general (or interdisciplinary) context.

Basic knowledge of fundamental chemistry concepts: chemical bonding and valence orbital theory; chemical kinetics and thermodynamics. Balancing of reactions. Chemical equilibrium.

Lectures with multimedia support and exercises. In particular, the use of concepts in facing specific problems will be shown in order to provide a problem-solving ability.

Supporting material for the course will be added to the DIR platform.
Students with physical disabilities, Learning Disabilities or Special Education Needs can request specific services and tools via the Staff Sviluppo e Coordinamento Carriere e Servizi alle Studentesse e agli Studenti, consulting the University webpage: https://www.uniupo.it/en/services/services-students-physical-or-learning-disabilities.
Students with disabilities, learning disabilities or special education needs, once they have contacted the University Staff, can refer to the tutor in charge of the course to define the examination modalities, concerning academic aspects.

The exam will be conducted in two parts. The organic chemistry part will be conducted orally with a requirement for the synthesis of a polyfunctional molecule, resulting in a discussion of synthetic and mechanistic aspects, with emphasis on the ability to make logical connections between different topics. The examination on the chemistry of heterocyclic compounds module will be written and will focus on nomenclature, synthesis and reactivity of the heterocyclic compounds discussed in class. Access to the exam on the chemistry of heterocyclic compounds module requires passing the organic chemistry module.

Structure and properties of organic compounds. Nature of the chemical bond. Ionic anc covalent bond; bond geometries and properties. Modern theories on the nature of chemical bond. Lewis formulas and formal charges. Aromaticity. Problem solving activities.
Functional groups, physical properties and nomenclature. Representation of molecules. Functional groups. Effect of functional groups on physical properties. Acidity and basicity. Molecular interactions Nomenclature of organic compounds. Problem solving activities.
Isomerism and conformational analysis. Isomerism: definition and classification. Conformational analysis of acyclic and cyclic compounds. Biological relevance of conformational analysis. Configurational analysis of alkenes. Chirality. Kinetics and thermodynamic of chemical processes. Problem solving activites.
Stereochemistry: Chirality and stereogenicity. Configurational descriptors. Configurational analysis of diastereomers and enantiomers. Biological relevance of chirality and stereogenicity. Resolution of mixtures of diastereomers and enantiomers. Problem solving activities.
Alkanes: Reactivity. Combustion and heats of formation. Halogenation. Reactivity and selectivity. Dissociation energies. Homolytic and heterolytic cleavages. Hammond postulate.
Alkenes: Synthesis, stability and reactivity. Formation and stability of carbocations. Elimination reations (dehydration, dehalogenation). E2, E1 and e1cb mechanisms: kinetics, stereochemistry, stereoselectivity and stereospecificity. Regioselectivity. Hydrogenation, Electrophilic addition to double bonds: halogenation, formation of halohydrines and haloethers, Hydration, Addition of HX. Epoxidation. Ozonolysis. Hydroboration-oxidation. Osmilation and reation with permanganate. Dienes and polyenes. Isoprene rule. Conjugated dienes. Thermodynamic and kinetic control of reactions. Diels-Alder reaction. Polymerization.
Alkynes: Synthesis and reactivity. Acidity and organometallic derivatives. Addition reactions (comparison with alkenes)
Alkyl halides: Synthesis and reactivity. Aliphatic nucleophilic substitution (SN). Mechanisms (SN1, SN2: kinetics and thermodynamics. Solvents and solvent effects.
Alcohols: nomenclature and properties. Preparation and reactivity. Cromium oxidations (Jones, CrO3-pyridine, PDC, PCC) Swern oxidation. Diols. Degradation with periodate and permanganate. Pinacolinic trasposition, mechanism and stereochemistry.Substitutions of the hydroxyl group with halogens. Sulfonates. Lithium, magnesium and copper (mention) organometallic reagents: comparison of reactivity.
Ethers: nomenclature and properties. Preparation and reactivity.
Aldehydes and ketons: nomenclature and properties. Preparation and carbonyl reactivity. Keto-enol tautomerism. Acyl nucleophilic addition reactions: addition of organometallic compounds, hydrides, HCN, alcohols ammonia derivatives. Bayer-Villiger reaction. Mention to the concept of protecting groups. Acetals as protecting groups. Wittig reaction. Enolate ions. Mechanism of base and acid catalyzed ketones halogenation. Aldol condensation with mention to stereochemical aspects.
Aromatic hydrocarbons. Aromaticity. Huckel rule. Omoaromatic and structures of main heterocyclic compounds. Aromatic ions.
Electrophilic aromatic substitution: nitration, sulfonation, Halogenation, Friedel-Crafts alkylation and acylation, chloromethylation reaction. Mechanism and substituent effect on reactivity and orientation. Electrophilic substitution on polycyclic aromatic compounds.
Nucleophilic aromatic substitution. Mechanisms of addition-elimination and elimination-addition.
Carboxylic acids: acyl halides, esters and amides. Nucleophilic acyl substitution reactions. Mechanisms of basic and acid hydrolysis of esters. Hofmann transposition of amides. Hell-Vohlard-Zelinsky.
Dicarboxylic acids; alkylation of malonates and acetacetates. Ketoacids and ketoesters; Claisen and Dieckmann condensation acid and basic cleavage and keto-enol tautomerism.. Claisen reaction. Perkin condensation. Oxyacids. Reformatsky reaction. Mannich condensation. -Unsaturated carbonyl compounds: Preparation and reactivity. Michael reaction and Robinson annulation. Mention to aliphatic nitroderivatives.
Aliphatic and aromatic amines: basicity and preparations. Reactivity: quaternari ammonium salts and Hofmann degradation, amides and sulfonamides, Hinsberg test, reaction with nitrous acid. Diazonium salts: formation and reactivity. Azo-, azoxi e idrazoderivatives.
Aromatic aldehyides: formylation reactions (Gattermann, Gattermann-Koch, Vielsmeier).
Phenols: acidity and preparations. Reactivity. Fries transposition. Kolbe and Reimer-Tiemann reaction. Quinones.
Mention on main sulfur containing compounds: Thiols, thiophenols, sulfides, sulfoxides, sulfones, sulfenic, sulfynic and sulfonic acids, sulfonyl chlorides and sulfonamides.

Structure and properties of the main heterocycles systems (nomenclature, aromaticity, tautomerism, acid-base properties)
General synthetic methods for heterocyclic compounds.
Survey of the major electron-rich (pyrrole, furan, thiophene, 1,2-azoles, 1,3-azoles and their products of benzo-condensation) and electron-poor systems (pyridine, pyrilium ion and their benzo-condensed products. Coumarins.

The student has to demonstrate an adequate knowledge and understanding of the topics developed during the course, with particular focus on the proper comprehension of the logic of organic chemistry. It is expected the student to be able to apply knowledge and understanding in dealing even with complex problems with sufficient personal independence of judgment.