Teaching code

4S00091

Teacher

Roberto Fiammengo

Coordinator

Roberto Fiammengo

Credits

12

Language

Italian

Scientific Disciplinary Sector (SSD)

CHIM/06 - ORGANIC CHEMISTRY

Period

FARMACIA annuale dal Oct 1, 2024 al Sep 30, 2025.

Courses Single

Not Authorized

Lessons timetable Moodle Seminars 0

Learning objectives

At the end of the course the student:
• knows how to classify a molecule on the basis of the functional groups present;
• knows and is able to attribute the rational and current name to molecules and vice versa;
• understands and knows how to predict the chemical-physical characteristics of a compound on the basis of its molecular structure
• know and understand the fundamental principles of organic chemistry, the main synthesis methodologies and the mechanisms through which organic compounds are formed and transformed
• know and understand the structure-reactivity relationships with reference also to the stereochemical aspects;
• will be able to apply the knowledge acquired on the chemistry of organic molecules to the solution of problems both in the strictly chemical field and in the broader context of the life sciences (with particular reference to those relating to pharmaceutical chemistry, biochemistry and pharmacology)

Prerequisites and basic notions

The student must have the fundamentals of general and inorganic chemistry and stoichiometry. In particular: atom structure, atomic shells and orbitals, rules for filling orbitals (Aufbau, Pauli, Hund), electronic configuration, Lewis structures, octet rule, VSEPR theory and valence bond theory, atomic and molecular orbitals; atomic number and mass number, atomic and molecular weight, mole, Arrhenius, Broensted-Lowry and Lewis acids and bases. Furthermore, the student must have some fundamental concepts of physical chemistry such as: chemical equilibrium, Keq, thermodynamics and kinetics of chemical reactions, free energy, enthalpy, entropy.

Program

1) Covalent bond and molecular geometry--Electronic structure of atoms. The chemical bond. Ionic, pure covalent and polar covalent bonds. Atomic, molecular and hybrid orbitals. Single, double and triple bonds. Functional groups. Bond angles and molecular geometry. Polar and nonpolar molecules. Resonance. Molecular orbitals in delocalized systems. Formal charge and oxidation number.
2) Alkanes and cycloalkanes--Structure of alkanes. Constitutional (or structural) isomerism in alkanes. Nomenclature. Conformational analysis of alkanes and cycloalkanes. Chair conformation of cyclohexane, axial and equatorial bonds. Cis, trans isomerism in cycloalkanes and bicycloalkanes. Physical properties and notes on reactivity.
3) Stereoisomerism and chirality--Chirality of molecules. Stereoisomerism. Nomenclature of chiral centers: assignment of the absolute configuration. Cahn-Ingold-Prelog convention and priority assignment rules. The R, S system. Molecules with two or more stereocenters: enantiomers and diastereoisomers. Chirality in atoms other than carbon. Dissymmetric but not asymmetric molecules: C2 symmetry in allenes, spiranes and bulky biphenyls. Atropisomerism. Separation of enantiomers: resolution of racemic mixtures. Prochiral centers. Importance of chirality in the biological world and in molecules with pharmacological activity.
4) Acids and bases--Brønsted-Lowry acids and bases. Acid dissociation constants, pKa and relative strength of acids and bases. Molecular structure and acidity. Lewis acids and bases.
5) Alkenes--Structure, nomenclature and physical properties of alkenes. Reactions of alkenes: an overview. Definition of nucleophilicity and electrophilicity. Electrophilic addition to alkenes: general information. Carbocations. Markovnikov's rule. Addition of halogen acids. Carbocation rearrangement. Stereochemical aspects. Addition of halogens. Addition of water catalyzed by acids. Reduction. Hydroboration-oxidation. Regio- and stereochemical consequences. Heats of hydrogenation and stability of alkenes. Oxidation reactions. Polymerization reactions.
6) Alkynes--Structure, nomenclature and physical properties of alkynes. Acidity of alkynes. Electrophilic addition to alkynes. Hydration of alkynes to aldehydes and ketones. Reduction of alkynes.
7) Dienes and conjugated systems--Stability of conjugated dienes. Electrophilic addition to conjugated dienes. Notes on pericyclic reactions. The Diels-Alder reaction.
8) Benzene and derivatives--Structure of benzene. The concept of aromaticity. Nomenclature. Phenols. Electrophilic aromatic substitution. Dissubstitution and polysubstitution. Nucleophilic aromatic substitution Reactions at the benzylic position.
9) Haloalkanes, halogenation and radical reactions--Structure, nomenclature and physical properties of haloalkanes. Preparation of haloalkanes by halogenation of alkanes. Mechanism of halogenation of alkanes. Allylic halogenation. Radical autoxidation. Addition of HBr to alkenes by radical pathway.
10)Nucleophilic substitution and β-elimination--Nucleophilic substitution in alkyl halides. Mechanisms of aliphatic nucleophilic substitution. Experimental evidence for the SN1 and SN2 mechanisms. Basicity and nucleophilicity. Analysis of various nucleophilic substitution reactions and their stereochemistry. Beta-elimination. Mechanisms of beta-elimination. Zaitsev's rule. Hofmann's rule. Experimental evidence for the E1 and E2 mechanisms. Competition between substitution and elimination. Participation of the vicinal group.
11) Alcohols and thiols--Structure, nomenclature and physical properties of alcohols. Acidity and basicity of alcohols. Reactions of alcohols with metals. Conversion of alcohols into alkyl halides and sulfonates. Dehydration. Pinacolic rearrangement. Oxidation of alcohols. Thiols: structure and acidity, nomenclature, physical properties. Synthesis and reactivity in SN2 reactions. Oxidation reactions.
12) Ethers, epoxides and sulfides--Structure, nomenclature and physical properties of ethers. Preparation of ethers. Reactions of ethers. Silyl ethers as protecting groups. Epoxides: structure and nomenclature. Preparation of epoxides. Reactions of epoxides. Crown ethers. Sulfides and their reactivity.
13) Aldehydes and ketones--Structure, nomenclature and physical properties of aldehydes and ketones. Addition of nucleophiles to carbon: water, alcohols, ammonia and derivatives, thiols, cyanides. Reduction with hydrides. Wittig reaction. Oxidation. Deoxygenation to alkanes (Clemmensen, Wolff-Kishner). Methods of preparation. Introduction to organometallic compounds. Keto-enol tautomerism. Alpha-carbon reactions. Alkylation of enolates. Aldol condensation.
14) Carboxylic acids--Structure, nomenclature and physical properties of carboxylic acids. Acidity. Preparation of carboxylic acids. Reduction. Nucleophilic acyl substitution: formation of esters, anhydrides and acyl chlorides.
15) Functional derivatives of carboxylic acids--Structure and nomenclature of all carboxylic acid derivatives. Resonance structures and stability. Acidity of amides, imides and sulfonamides. Characteristic reactions. Nucleophilic acyl substitution. Interconversion of functional derivatives. Reactions with organometallic compounds. Reduction.
16) Enolate anions and enamines--Formation and reactions of enolate anions: an overview. Aldol reaction. Claisen and Dieckmann condensations. Knovenagel reaction. Mannich reaction. Malonic synthesis. Acetoacetic synthesis. Conjugate addition to alpha,beta-unsaturated carbonyl compounds. Michael addition.
17) Amines--Structure, classification, nomenclature and physical properties of amines. Aniline. Basicity. Preparation. Quaternary ammonium salts. Hofmann elimination. Cope elimination. Reduction of nitro compounds, nitriles, amides and azides. Reductive amination. Reaction with nitrous acid. Diazotization and reaction of arendiazonium salts.
18) Heterocyclic compounds--Nomenclature. Electron-rich heterocyclic compounds. Electron-poor heterocyclic compounds. Basicity of nitrogenous heterocyclic compounds.
19) Carbohydrates--Monosaccharides. Cyclic structure of monosaccharides. Epimers. Reactions of monosaccharides. Reducing and non-reducing sugars. Disaccharides and polysaccharides.
20) Lipids--Triglycerides. Soaps and detergents. Steroids. Phospholipids.
21) Amino acids and proteins--Amino acids. Acid-base properties of amino acids. Isoelectric point. Polypeptides and proteins. Synthesis of amino acids: malonic synthesis and Strecker synthesis. Asymmetric resolution and synthesis. Synthesis of peptides in liquid and solid phase. Protecting groups of the alpha amino group and of the carboxyl group. Selective protection and deprotection. Racemization.
22) Nucleic acids--Nucleosides and nucleotides. Structure of DNA and RNA. Basicity of nucleobases. Formation of the phosphodiester bond. The chemical synthesis of oligonucleotides. Synthesis on solid phase.
23) Synthesis of polymers--Step-wise and chain-wise polymerizations.
24) Catalytic formation of carbon-carbon bonds--Organometallic compounds and catalysis. The Heck reaction. Catalytic allylic alkylation. Palladium-catalyzed coupling reactions. Alkene metathesis. Click chemistry.
The program may undergo small changes during the semester.

Bibliography

Didactic methods

Lectures, exercises and classwork. Attendance at classes is strongly recommended.

Learning assessment procedures

The students are required to take a written exam of 120 minutes and an oral test of up to 30 minutes to verify their understanding of organic chemistry.
The written exam consists of multiple-choice questions and exercises and open-ended questions. The students are requested to have the ability to recognize the functional groups of an organic molecule and to know their reactivity, the ability to choose reagents and predict the products of a reaction in organic synthesis. The minimum score required to pass the written test and access the oral test corresponds to the correct resolution of 60% of the proposed questions (grade 18/30).
Oral exam score from -3/30 to +6/30.
It will be possible to take a partial written test at the end of the first semester.

Evaluation criteria

The exam will evaluate the scientific correctness of the proposed solutions, the ability of critical reasoning, the quality of the presentation and the competence in the use of specialized vocabulary.

Criteria for the composition of the final grade

The final mark is the sum of the scores (in thirtieths) of the written and oral exams.

Exam language

italiano

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