Catalogo dei Corsi di studio

Expected learning outcomes
Organic chemistry is a chemistry discipline involving the scientific study of the structure, reactivity, properties and applications of compounds which are formed mainly by carbon atoms, forming covalent bonds, both from natural and artificial sources The general objective, is to provide students with the knowledge and competences necessary to understand the structure, reactivity and synthetic methods of different functional groups, and the mechanisms of organic reactions. For a Natural Science student, this learning is essential, to understand physical or macroscopic properties of matter on molecular basis and to know the role and impact of organic chemistry in natural sciences, modern technology and society.
This knowledge will allow the student to be able to understand biochemistry, genetics and physiology, crucial topics in different next courses.

Dublin Descriptors
The Organic Chemistry course is devoted to provide students with the adequate knowledge to be independent in solving the examination problems or exercises.
This ability will be acquired by the means of frontal lesson and guided exercitations that will be organized in ascending order of the difficulties they pose.
Teaching materials, available on line will support students during the lessons even though studying the recommended text book is essential to acquire the skills and the competence that are necessary to perform the final exam.
In order to improve the exposure ability, students will be constantly encouraged to communicate their ideas to both specialists and non specialists audiences. The Erasmus programme will enable students to improve their communications skills, by exchanging informations, problems and solutions.
The specific objectives consist in acquiring the following knowledge and expertise:
1) to understand the importance of stereochemistry on the reactivity of organic compounds;
2) to understand the relationship between structure and reactivity for the different functional groups;
3) to acquire the basic knowledge of organic chemistry in order to understand the basic mechanism of organic reactions.
4) to acquire the basic knowledge of the organic synthesis
5) to apply the main concepts of stereochemistry to the reactivity of organic compounds.
6) to predict the reactivity and the physical properties of organic compounds.
7) to speculate about mechanistic aspect of the organic reactions.
8) to design the synthesis of organic molecules through their retrosynthetic analysis.






CFU CONTACT HOURS
5 Lectures: 40
1 Laboratory exercises: 12
The course (6 CFU) is provided through traditional lessons integrated with exercises. The lessons are held in classrooms where there are devices suitable for projecting the slides of the course, available to students on the Sapienza E-learning platform. The exercises, provided throughout the course, cover all the topics covered during the theoretical lessons and prepare students for the written test. There are several summarizing sessions in which different quiz that are representative of those given to the exam are shown. Students have at their disposal self-assessment tests related to all the chapters dealt with during the theoretical course.
Attendance to lectures and exercises, although very useful for achieving the course's educational objectives, is not mandatory.

Programme

Description of contents:
Historical background. Formulas of organic compounds, Lewis structure, stick and ball structures.
Atomic structure and bonding (review): chemical bond (bond length, angle, energy, polarity, dipole moment), molecular structure, hybridization, resonance. Arrhenius acidity, Brønsted acids and bases: Ka and pKa, O-H bond acidity (carboxylic acids, phenols, alcohol), C-H bond acidity. Lewis acids. Intermolecular forces: van der Waals, dipolar interaction, hydrogen bonding.
Saturated hydrocarbons. Linear and branched alkanes, cycloalkanes. Constitutional isomerism. Common names and systematic (IUPAC) nomenclature. Alkyl radicals. Molecular models. Perspective and projective formulas. Conformations of ethane: Newman projections and sawhorse diagrams. Cyclohexane conformations, axial and equatorial bonds, 1,3-diaxial interactions. Disubstituted cycloalkanes: cis trans isomerism. Physical properties: boiling point, solubility, density. Natural sources of alkanes and cycloalkanes. Reactivity: radical reactions, halogenation and combustion reactions.
Alkenes and alkynes. Nomenclature, configurational isomerism of alkenes (cis-trans and E,Z notations), physical properties, naturally occurring alkenes (pheromones, terpenes). Electrophilic addition to alkenes: reaction mechanism. Transition state theory (overview), energy diagrams, intermediates, catalysts. Addition of hydrogen halides, molecular bromine, water (acid-catalyzed hydration). Markovnikov’s rule and carbocation stability. Reduction of alkenes: catalytic hydrogenation. Oxidation of alkenes: hydroxylation, epoxidation. Grignard reagents.
Stereochemistry. Chirality: stereogenic carbon atoms, enantiomers, racemic mixtures. R,S and D,L notations. Optical activity: observed and specific optical rotation. Compounds with two or more stereocenters: diastereomers, meso compounds. Chiral resolution of racemic mixtures.
Alkyl halides: nomenclature, properties and applications. Nucleophilic substitution reactions: SN1 and SN2 mechanisms (stereochemistry, role of the alkyl group, of the nucleophile, and of the solvent). beta-elimination reactions: E1 and E2 mechanisms. Saytzeff’s rule. The competition between substitution and elimination reactions.
Alcohols, phenols, and thiols: nomenclature, natural occurrence, physical properties, acid-base reactions. Preparation of alkoxides. Dehydration and oxidation of alcohols. Conversion of alcohols to alkyl halides. Ethers, thioethers. Epoxides: preparation from alkenes and conversion to glycols, stereochemistry.
Aromatic compounds. Arenes: nomenclature of substituted benzenes, polycyclic compounds. Heteroaromatic compounds. Hückel’s rule. Electrophilic aromatic substitution: mechanism, activation/deactivation and orientation effects in substituted benzenes (overview). Halogenation, nitration, sulfonation, Friedel-Crafts alkylation, Friedel-Crafts acylation. Oxidation of alkylbenzenes.
Amines: nomenclature, naturally occurrence, importance. Basicity of aliphatic, aromatic, and heterocyclic aromatic amines.
Carbonyl compounds. Aldehydes and ketones: nomenclature, natural occurrence, physical properties. Nucleophilic addition: hemiacetal, acetal, and imine formation. Reduction and oxidation of carbonyl compounds. Keto-enol tautomerism. Aldol reaction and condensation. Carboxylic acids: nomenclature, natural occurrence, physical properties. Conversion to acyl halides, anhydrides, esters, amides. Esters: nomenclature, natural occurrence, physical properties. Basic and acid hydrolysis. Reduction of esters, amides and carboxylic acids.
Lipids: triglycerides (fats, oils), soap and synthetic detergents, phospholipids, prostaglandins, waxes, terpenes, and steroids.
Carbohydrates: classification and naturally occurrence. Aldoses and ketoses: Fischer and Haworth formulas, conformational representations. Anomers, epimers. Mutarotation. D-glucose, D-fructose, D-ribose, D-mannose, D-galactose. Glycosides. Disaccharides: maltose, cellobiose, lactose, saccharose. Polisaccharides: starch, glycogen, cellulose.
Naturally occurring beta-amino acids: structure and chemico-physical properties. Isoelectric point. Peptides and proteins: structure and function. Primary, secondary, tertiary and quaternary structure of proteins. Peptide bond.
Nucleosides and nucleotides, nucleic acids (DNA, RNA). Structure

Adopted texts

- W.H. Brown, T. Poon “Introduction to organic chemistry”, any edition until V (2014); EdiSES, Napoli.
- J. McMurry “Foundamentals of Organic Chemistry” 3rd Ed., Zanichelli, Bologna 2011.
- B. Botta “Chimica Organica Essenziale” Edi. Ermes, Milano 2012.
- H. Hart, C. M. Hadad, L. E. Craine, D. J. Hart “Organic Chemistry”, VII Ed., Zanichelli, Bologna 2012.
- W. H. Brown, M. K. Campbell, S. O. Farrell “Elements of Organic Chemistry”, EdiSES, Napoli 2013
- L. G. Wade, Jr. “Foundamentals of Organic Chemistry” Piccin, Padova 2014

Exam modes

The written examination is about the following topics:
Isomerism, nomenclature, stereochemistry and reactivity
During the oral exam several questions can be asked to the students regarding all the course (see the program for further details)

Programme

SYLLABUS
Section 1.
Acids and bases (4 hours)
Arrhenius, Lowry-Brönsted e, and Lewis acids and bases. Factors influencing the strength of Lowry-Brönsted acids and bases: hybridization, polarizability, electronegativity, inductive effect, field effect, resonance, hydrogen bond, solvent.

Section 2. Hydrocarbons
Alkanes and cycloalkanes
Nomenclature, hybridization, structure, physical properties, structural isomers, conformation (torsional strain, angle strain), hybridization and bond angle (cyclopropane). Newman projections. Haworth projections. Reactivity: oxidation and radical halogenation [mention].
Alkenes
Nomenclature, hybridization, structure, stability, physical properties, geometric isomerism, E-Z rules. Reactivity: addition of HX (X = halogens) [ionic (carbocations: structure, stability) and radical (HBr)], water, halogens, epoxidation (reaction with peracids), palladium-catalyzed hydrogenation and hydrogenation heats,
Alkynes
Nomenclature, hybridization, structure, physical properties. Reactivity: palladium-catalyzed addition of hydrogen (mention), addition of HX (X = halogen) (vinylic cations: hybridization, stability), addition of halogens, addition of water (catalyzed by sulfuric acid and Hg(II) salts), acidity of terminal alkynes (addition and nucleohilic substitution reactions of acetylides).

Section 3. Stereochemistry (3 hours)
Fundamentals of stereochemistry
Stereoisomers. Chirality. Chiral and stereogenic center. Enantiomers and diastereoisomers. Symmetry elements: center, axis, plane. Enantiomers: nomenclature (Cahn, Ingold, and Prelog priority rules). Optical rotation. Racemates. Specific rotation. Enantiomeric excess. Compounds containing more than one chiral center (diastereoisomers and meso isomers). Fischer projections.

Section 4. Alkyl halides, alcohols, ethers and epoxides (6 hours)
Alkyl halides
Structure and IUPAC nomenclature, physical properties. Nucleophilic substitution (SN), nucleophilicity and basicity. SN1: mechanism, stereochemistry, ion pairs, factors influencing the SN1 reaction (alkyl halide, leaving group, nucleophile, solvent (protic solvents, polar aprotic solvents, apolar aprotic solvents). SN2: mechanism, stereochemistry, factors influencing the SN2 reaction (alkyl halide, leaving group, nucleophile, solvent). SN1 vs SN2 (influence of the alkyl group, solvent, and nucleophile). beta-Elimination (E). E1: mechanism, regiochemistry (Saitseff’s rule). E2: mechanism, regiochemistry, stereochemistry.. E1 vs E2: influence of the alkyl halide, solvent, and base. SN1 vs E1 and SN2 vs E2 Formation of alkylmagnesium compounds.
Alcohols
Nomenclature, physical properties. Reactivity: acidity, synthesis of esters, alkyl halides, tosylates, oxidation (mechanism with chromic acid and pyridinium chlorochromate).
Ethers and epoxides
Nomenclature, physical properties. Reactivity: reaction with con HX (X = halogens). Epoxides: nomenclature, ring opening (acid-catalyzed, with nucleophiles).

Section 5. Aldehydes and ketones, carboxylic acids and their derivatives (8 hours)
Aldehydes and ketones
Nomenclature, physical properties. Addition reactions: reaction with boron and aluminum hydrides, with terminal alkynes, Grignard reagents, HCN, water, alcohols (acetals as protecting groups). Addition-elimination reactions: reaction with primary and secondary amines.
Carboxylic acids
Nomenclature, physical properties. Reactivity: acid-base reactions, reactions with LiAlH4, with alcohols, with SOCl2, with PBr3 (mention).
Carboxylic acid derivatives
Acyl halides, anhydrides, esters, lactones, amides, lactames, imides, nitriles: Nomenclature, physical properties. Reactivity: reaction with water [acyl chlorides, anhydrides, esters, (esters from 1°, 2°, and 3° alcohols), amides, nitriles], with alcohols (acyl chlorides, anhydrides, esters), (acyl chlorides), with ammonia and amines [acyl chlorides, anhydrides, esters], with Grignard reagents (esters), with LiAlH4 (esters, amides, nitriles)..

Section 6. Enols, enolates (2 hours)
Enols and enolates
Keto-enol tautomerism (acid- and base-catalyzed), factors influencing the keto-enol equilibrium (hydrogen bond, resonance), Aldol condensation, Aldol condensation-dehydration (under acid and basic conditions), crossed aldol condensation.

Section 7. Aromatic compounds, phenols and amines
Aromatic compounds (5 hours)
Aromaticity. Huckel rule. Aromatic, antiaromatic and non aromatic compounds. Aromatic ions. Heteroaromatics. Nomenclature. Electrophilic aromatic substitution: mechanism, substituent effects, halogenation, nitration, sulfonation, Friedel-Crafts alkylation and acylation.
Phenols
Nomenclature. Reactivity: acidity, synthesis of esters and ethers.
Amines
Nomenclature. Chirality. Pyramidal inversion. Chirality of armonium salts. Reactivity: basicity of aliphatic and aromatic amines.

Section 8. Carbohydrates and amino acids (4 hours)
Carbohydrates
Carbohydrates: classification and naturally occurrence. Aldoses and ketoses: Fischer and Haworth formulas, conformational representations. Anomers, epimers. Mutarotation. D-glucose, D-fructose, Dribose, D-mannose, D-galactose. Glycosides. Disaccharides: maltose, cellobiose, lactose, saccharose. Polisaccharides: starch, glycogen, cellulose.
Amino acids
Structure and chemico-physical properties. Chirality. Acid-base property. Peptide bond.

Section 9. Summary and exercises (12 hours)


EXPECTED LEARNING OUTCOMES
Organic chemistry is a chemistry discipline involving the scientific study of the structure, reactivity, properties and applications of compounds which are formed mainly by carbon atoms, forming covalent bonds, both from natural and artificial sources The general objective, is to provide students with the knowledge and competences necessary to understand the structure, reactivity and synthetic methods of different functional groups, and the mechanisms of organic reactions. For a Natural Science student, this learning is essential, to understand physical or macroscopic properties of matter on molecular basis and to know the role and impact of organic chemistry in natural sciences, modern technology and society.
This knowledge will allow the student to be able to understand biochemistry, genetics and physiology, crucial topics in different next courses.

DUBLIN DESCRIPTOR
The Organic Chemistry course is devoted to provide students with the adequate knowledge to be independent in solving the examination problems or exercises.
This ability will be acquired by the means of frontal lesson and guided exercitations that will be organized in ascending order of the difficulties they pose.
Teaching materials, available on line will support students during the lessons even though studying the recommended text book is essential to acquire the skills and the competence that are necessary to perform the final exam.
In order to improve the exposure ability, students will be constantly encouraged to communicate their ideas to both specialists and non specialists audiences. The Erasmus programme will enable students to improve their communications skills, by exchanging informations, problems and solutions.
The specific objectives consist in acquiring the following knowledge and expertise:
1) to understand the importance of stereochemistry on the reactivity of organic compounds;
2) to understand the relationship between structure and reactivity for the different functional groups;
3) to acquire the basic knowledge of organic chemistry in order to understand the basic mechanism of organic reactions.
4) to acquire the basic knowledge of the organic synthesis
5) to apply the main concepts of stereochemistry to the reactivity of organic compounds.
6) to predict the reactivity and the physical properties of organic compounds.
7) to speculate about mechanistic aspect of the organic reactions.
8) to design the synthesis of organic molecules through their retrosynthetic analysis.

Adopted texts

B. Botta, CHIMICA ORGANICA ESSENZIALE, Edi-Ermes, 2° Ed.

alternative:
W. H. Brown, T. Poon “INTRODUZIONE ALLA CHIMICA ORGANICA” Terza Edizione, EdiSES, Napoli 2005
H. Hart, L. E. Craine, D. J. Hart, C. M. Hadad “CHIMICA ORGANICA” Sesta Edizione, Zanichelli, Bologna 2008
P. Y. Bruice “ELEMENTI DI CHIMICA ORGANICA” Prima Edizione, EdiSES, Napoli 2007
J. McMurry “FONDAMENTI DI CHIMICA ORGANICA” Terza Edizione, Zanichelli, Bologna 2005

Prerequisites

Students are expected to have basic knowledge of General and Inorganic Chemistry; in particular the following fundamentals of chemistry must be known: hybridization, resonance, aromaticity, fundamentals of thermodinamics (entalpy, Gibbs energy, entropy), chemical equilibria, fundamentals of chemical kinetics, reaction rate, transition state.

Exam modes

The acquisition of the CFU of the course is subject to passing the final exam that is planned according to Infostud information. Midterm exam are not provided.
In order to facilitate the student in their study planning, the date of the exam may be designated during the whole session. The final exam consists in a written examination followed by an oral one; its purpose is to certify the acquired knowledge about organic chemistry.
In order to be eligible for the oral examination students must pass the written examination. This latter has the duration of 60 minutes and consist in exercises which are prepared by the examination board. In order to get a positive results, students must correctly solve at least 3 of the 5 proposed exercise. The examination board reserves the right to consider eligible for the oral examination those students whose written test is considered adequate even if not completely responding to the previous request.
The oral examination result is expressed in thirtieths and depends on:
1) evaluation of written exam;
2) evaluation of general and specific knowledge about all the subject of the class;
3) clarity in exposure;
4) ability to create links between the studied topics.
Minimum to pass examination is (18/30). Students exhibiting a detailed knowledge will pass with first-class honours (30/30 cum laude).
The exam may be performed in every programmed session.