General part. Uniqueness of carbon. The chemical bond. Ionic, covalent and polar bonds. Atomic, molecular and hybrid orbitals. Single, double and triple bond. Methane, ethane, ethylene, acetylene, ammonia and water. The concept of resonance. The arrows in organic chemistry. How to represent molecules. Extended and abbreviated structural formulas. Structural isomers. Classification of organic compounds: based on their structure and functional groups. Intermolecular forces. Dipole-dipole interactions, Van der Waals forces, hydrogen bond. Solubility. Organic solvents. Hydrophilicity and lipophilicity. Types of reactions. How organic reactions occur. Thermodynamic and kinetic aspects. Energy diagrams.
Alkane. Alkanes, branched alkanes and cycloalkanes. Nomenclature. Conformational analysis in alkanes: ethane and butane. Newman projections. Conformational analysis in cycloalkanes: cyclopropane, cyclobutane, cyclopentane, cyclohexane. Mono and disubstituted cyclohexanes. Cis-trans isomerism in cycloalkanes. Condensed cycloalkanes. Physical properties of alkanes. Radical reactions. What is a radical. Reactivity of alkanes: halogenation and oxidation. Alkanes preparation. Reduction of alkenes and alkynes and carbonyl compounds.
Stereochemistry. Introduction to chirality. Asymmetric objects and atoms. Chiral and achiral molecules. Enantiomers. Polarimetry. Specific rotation. Enantiomeric excess and optical purity. Assignment of the absolute configuration. C.I.P. convention (Cahn-Ingold-Prelog), system R, S. Rules for substituents priorities. Fischer projections. Molecules with more stereocenters: diastereomers. Meso-compounds. Chirality in substituted cycloalkanes. Racemes and resolution. Solvents reagents. Prochirality of sp2 and sp3 carbons. Chirality in atoms other than carbon. Non-symmetrical but not asymmetric molecules: C2 symmetry in allenes, spiranes and hindered biphenyls. Atropisomerism. Importance of the chirality in the biological world and in pharmacological active molecules.
Alkenes. Structure and physical properties nomenclature. Cis-trans isomerism in alkenes. The E / Z system. Reactivity. Carbocations. Electrophilic addition to alkenes: generalities. Markovnikov rule. Addition of hydrogen halides. Carbocation rearrangement. Stereochemical aspects. Addition of halogens: the ion ion. Addition of halogens and hypohalides acids. Acid catalysed addition of water, oxymercuration/reduction and hydroboration/oxidation reactions. Regio- and stereo-chemical consequences. Catalytic reduction reactions of the double bond. Heats of hydrogenation and stability of alkenes. Oxidation reactions: oxidation and oxidative demolition. Stereochemical aspects. Preparation of alkenes by elimination reaction from alcohols, from alkyl halides and from quaternary ammonium salts. Zaitsev and Hofmann rules. Preparation for partial reduction of alkynes.
Acids and bases. Acids and bases according to Arrhenius. Acids and bases according to Brønsted-Lowry. Acid dissociation constants, pKa and strength of acids and bases. Positions of equilibrium in acid-base reactions. Molecular structure and acidity. Acids and bases according to Lewis. Factors that influence the acidity in organic molecules. Nucleophilicity and electrophilicity.
Alkynes. Nomenclature and physical properties. Acidity. Reactivity. Alkylation of acetylides. Electrophilic additions: addition of halogens, hydrogen halides, water and comparison of reactivity with alkenes. Reductions. Acetylene.
Conjugated dienes. Nomenclature and physical properties. Reactivity. Hydrogenation heat. Addition reactions 1,2 and 1,4. Addition of halogen halide and halogen acids. Factors influencing the distribution of products. The Diels-Alder cycloaddition. Stereo-and region-chemical aspects. Mechanism.
Aliphatic halogen compounds. Structure and physical properties nomenclature. Reactivity. Nucleophilic substitution reactions. Mechanisms SN1 and SN2, factors that influence the course and stereochemical aspects. E1 and E2 mechanisms, factors that influence the course and stereochemical aspects. Pseudohalides as alternative leaving groups. Competition between nucleophilic substitution and elimination reactions E. Preparation of halogen compounds from alcohols.
Alcohols. Structure and physical properties nomenclature. Classification. Acidity and basicity. Reactivity. Oxidation. Dehydration. Synthesis. Preparation by hydration of alkenes and by reduction of carbonyl compounds.
Organometallic compounds. Carbon-metal bond. Reactivity depending on the nature of the metals. Grignard and organo-lithium reagents. Basicity and nucleophilicity. Preparation of organometallic compounds. Reactions with aldehydes, ketones, esters, epoxides, carbon dioxide.
Ethers. Structure and physical properties nomenclature. Synthesis. From dehydration of alcohols. Williamson reaction. Addition of alcohols to alkenes. Split with HX.
Epoxides. Structure and physical properties nomenclature. Nucleophilic reactions in acid and basic environment. Stereochemical implications. Synthesis. Dehydrohalogenation of halohydrins and alkenes oxidation.
Sulfur compounds. Tiol and sulfides. Structure and physical properties. Nomenclature. Acidity. Oxidation reactions. Preparation. Notes on the chemistry of thioethers, disulfides, sulfoxides, sulfones and sulphonic acids.
Aldehydes and ketones. Structure and physical properties nomenclature. Reactivity. Nucleophilic additions to the carbonyl: water, alcohols, ammonia and derivatives, thiols, cyanides. Reduction with hydrides. Wittig reaction. Oxidation. Deoxygenation to alkanes (Clemmensen, Wolff-Kishner, thioacetal hydrogenolysis). Synthesis. From Grignard and nitrile compounds, by partial reduction of carboxylic acids (and derivatives) with hydrides and by oxidation of alcohols. Important aldehydes and ketones: formaldehyde, acetaldehyde, acetone.
Carboxylic acids. Structure and physical properties nomenclature. Acidity. Effect of substituents on acidity. Salts formation. Reactivity. Alcohol reduction. Preparation methods of carboxylic acids: oxidative, carbonation of organometallic reagents, hydrolysis of derivatives. Reactions to hydroxyl H: carboxylate as nucleophile, formation of methyl esters with diazomethane. Reactions to hydroxyl OH: nucleophilic acyl substitution. Formation of halides, anhydrides, esters and amides. Fischer esterification. Decarboxylation of beta-ketoacids. Esters of nitric and phosphoric acid.
Derivatives of carboxylic acids (acyl halides, anhydrides, esters, amides and nitriles). Structure and physical properties nomenclature. Reactivity. Nucleophilic acyl substitution: mechanism and applications. Hydrolysis. Transformations between the derivatives of carboxylic acids, allowed and not. Reduction. Lactones, lactams, imides and cyclic anhydrides: preparation and reactivity. Acidity of amides, sulfonamides and imides.
Amines. Structure and physical properties nomenclature. Basicity and acidity. Reactivity. Alkylation and acylation. Quaternary ammonium salts. Elimination of Hofmann. Diazotization and reactions of diazonium ions of aliphatic amines. Synthesis. Gabriel synthesis. Reducing amination reactions. Hofmann rearrangement. Reduction of nitro compounds, nitriles, amides, azides.
Benzene and derivatives. Structure and physical properties nomenclature. Reactivity. Hydrogenation heat. Electronic structure of benzene. Resonance of benzene and other important systems. Representations of benzene. Hückel's rule. Electrophilic aromatic substitution on benzene and monosubstituted derivatives. Nitration. Sulfonation. Halogenation. Friedel-Crafts alkylation and acylation. Activating and deactivating substituents. Inductive and mesomeric effect. Orienting effects. SEAr on substituted benzenes: agonist and antagonist effects. Reduction of the aromatic ring. Oxidation in the benzyl position.
Aniline and Phenols. Structure and physical properties nomenclature. Partial deactivation. Acidity and basicity of anilines and phenols. Arendiazonium salts: synthesis and use. Synthesis of phenolic ethers. Aromatic electrophilic substitution. Synthesis. Alkaline fusion. Preparation from diazonium salts.
Chemistry of enols and enolate ions. Formation of enols and enolates. Reactions via enol and via enolate. The role of the base. Halogenation of aldehydes and ketones via enol and enolate. Acid alogenation: the Hell-Volhard-Zelinsky reaction. Direct alkylation of enolates. Stork reaction. Malonic synthesis. Acetacetic synthesis. Condensation reactions: Aldol condensation and dehydration. Intramolecular and mixed aldolic reactions. Knovenagel reaction. Claisen and Dieckmann condensation reactions. Mixed Claisen reaction. Mannich reaction.
Carbonyl compounds and α, β-unsaturated nitriles. Structure and physical properties nomenclature. Addition conjugated reactions with nucleophiles. Michael's addition and its applications. Reactions with organometallic compounds. Robinson ringing. Reduction. Preparation with aldol type reactions.
Carbohydrates. Structure and physical properties nomenclature. Classification and properties. Fischer projections. Monosaccharide structures: stereochemistry and configuration, cyclic structures. Mutarotation. Monosaccharide reactions: glycoside formation. Monosaccharide reactions: formation of ethers, esters and acetals. Selective hydrolysis. Oxidation reactions: formation of aldonic acids. Tollens, Fehling and Benedict tests. Reducing and non-reducing sugars. Oxidation reactions: formation of aldaric acids and oxidation with periodic acid. Reduction reactions: formation of alditols. Kiliani-Fischer synthesis. Ruff degradation. Test for glucose stereochemistry. Disaccharides: sucrose, maltose, lactose, cellobiose. Polysaccharides: starch, glycogen and cellulose. Functionalized polysaccharides: ethers, acetates and nitric esters: celluloid and flash cotton.
Amino acids, peptides, proteins. Natural amino acids. Biological role, stereochemistry and classification. Acid-base properties, titration, isoelectric point. Electrophoresis. Reactivity of the amino and carboxylic group. Esterification and acylation reactions. Cysteine oxidation. Synthesis of amino acids: from -haloacids, malonic synthesis and Strecker synthesis. Resolution. Peptide synthesis. Protecting groups for amine and carboxy terminus. Protection and selective deprotection. Formation of the peptide bond with dicyclohexylcarbodiimide (DCC). Peptide synthesis in liquid and solid phase (Merrifield). Secondary structure of proteins: alpha-helix, beta-sheet, beta-turn. Tertiary structure: fibrous and globular proteins. Quaternary structure: protein subunits.
Lipids. Fatty acids, triglycerides, oils and fats. Rancidity and hydrogenation. Cere. Soaps and saponification. Detergents. Phospholipids, eicosanoids, steroids, fat-soluble vitamins (outline).
Aromatic heterocyclic compounds. Structure and physical properties nomenclature. Acidity and basicity. Reactivity of furan, pyrrole, thiophene, indole and benzofuran. Electrophilic substitutions. Paal-Knorr synthesis of furan, pyrrole and thiophene. Fischer synthesis of indole. Pyridine and quinoline reactivity. Electrophilic and nucleophilic substitutions. Chichibabin reaction. Hantzsch synthesis of pyridine and Friedländer synthesis of quinoline.
Nucleic acids. Structure and physical properties nomenclature. Pyrimidine and purine bases: tautomerism, protonability.
Prerequisites for admission
- Basic concepts of general chemistry and stoichiometry: atom, atomic number and mass number, atomic and molecular weight, mole and molar weight, structure of the atom, shells and atomic orbitals, rules for filling orbitals (Aufbau, Pauli, Hund), valence, electronic configuration, Lewis structures, octet rule, VSEPR theory, atomic and molecular orbitals, acids and bases (Arrhenius Broensted-Lowry and Lewis).
- Basic concepts of physical chemistry: chemical equilibrium, Keq, thermodynamics and kinetics of chemical reactions, free energy, enthalpy, entropy.
- Brown - Foote - Iverson, Organic Chemistry, EDISES
- Bruice, Organic Chemistry, EDISES
- McMurry, Organic Chemistry, PICCIN
- Botta, Organic Chemistry, EDI-ERMES
- Vollhardt, Organic Chemistry, ZANICHELLI
- Streitwieser - Heathcock, Introduction to Organic Chemistry, PICCIN
- Iverson - Iverson, Guide to solving problems from organic chemistry by Brown, Iverson, Anslyn, Foote, EDISES
- D'Auria - Taglialatela Scafati - Zampella, Reasoned guide to carrying out organic chemistry exercises, LOGHIA
- Nicotra - Cipolla, Exercise Book of Organic Chemistry, EDISES
- Ariel website (http://gabbiatico.ariel.ctu.unimi.it
) with: slides of the lectures, exercises, examination texts, videos, websites of interest, forum, self-evaluation test.
- App Exam Manager from EDISES publisher.