CHIMICA ORGANICA I E CHIMICA ORGANICA II

12 CFU - 1° and 2° Semester

Teaching Staff

VENERANDO PISTARA' - Module Organic Chemistry I - CHIM/06 - 6 CFU
ANTONIO RESCIFINA - Module CHIMICA ORGANICA II - CHIM/06 - 6 CFU

Learning Objectives

Organic Chemistry I
The course focuses on the fundamental chemistry of carbon compounds and an appreciation of its relevance to biology and toxicology. Topics will include nomenclature, structure, properties, synthesis, and reactions, of the major functional groups of organic compounds.
The fundamental objective is to stimulate the student to apply his reasoning skills in the study of matter, limiting the mnemonic effort to the learning of a restricted set of the basic principles of Organic Chemistry.
CHIMICA ORGANICA II
The course aims to provide a critical and scientific mentality and rational use of mnemonic abilities, favoring the ability to apply theoretical knowledge to problem-solving.

This means overcoming the limit of mere "mnemonic repetition" of concepts that, in doing so, would be aimed at simple learning. Critical and scientific mentality at the same time constitute a high-level objective; it requires a synthesis between mental operation and actual realization: the first is expressed in the design of an experiment, in the rational-intuitive control of the execution and calculation phases and the evaluation phase of the results; the second is expressed in the actual execution of the experiment, even at the virtual level.

Therefore, at the end of the course, the student must be able to:

D1 KNOWLEDGE AND UNDERSTANDING ABILITY

• Know in-depth the reactivity of new classes of organic compounds and the reaction mechanisms through which they react.

• Illustrate the criteria that allow to carry out processes with a pronounced chemical, positional, and stereochemical selectivity.

D2 ABILITY TO APPLY KNOWLEDGE AND UNDERSTANDING

• Identify the nature of the synthetic process to which the organic molecules are subjected based on the described reaction conditions.

• Correctly describe the reaction mechanism for the related processes.

• Discuss the nature of the selective processes that these mechanisms involve.

D3 AUTONOMY OF JUDGMENT

• Choose the most suitable reagents to carry out the required synthetic process with the desired selectivity degree.

• Use the most efficient method available to perform the synthesis of even multi-functionalized structures.

D4 COMMUNICATION SKILLS

• Communicate, using appropriate technical-scientific terminology, with the teacher and experts in the subject of study.

• Competently discuss, even in the context of an oral examination, the synthetic techniques learned.

D5 LEARNING SKILLS

• Find and learn the information, new compared to those provided during the training activity, necessary to broaden the knowledge on topics more or less correlated with those covered by the course.

• Understand and process the contents of scientific publications containing the results of new research.

• Use the knowledge acquired to make it easier to understand topics related to organic chemistry delivered in other educational activities.

Course Structure

Organic Chemistry I
The lectures for this course will be a combination of classic blackboard lectures and PowerPoint.

Should teaching be carried out in mixed mode or remotely, it may be necessary to introduce changes with respect to previous statements, in line with the programme planned and outlined in the syllabus.
CHIMICA ORGANICA II
The course activities consist of lectures and classroom exercises. To these will be added some "case studies" concerning molecules of chemical-pharmaceutical interest. The student is required to actively participate in the discussion of the topics presented and in particular, in the case studies.

Detailed Course Content

Organic Chemistry I
Introduction to Organic Chemistry:
- Review of general chemistry: atoms, molecules, bonding, polar and nonpolar molecules, intermolecular forces, solubilities, Lewis structures, preliminary ideas of resonance, arrow formalism, acids and bases. Orbitals, molecular orbital description of bonding, hybridization and molecular geometry. Acids and bases revisited: Electronegativity, resonance structures, definitions and strengths of acids and bases, organic acids and bases.
Alkanes
- Properties, conformational analysis, structural isomerism and nomenclature, alkyl groups. Cycloalkanes and their naming, stability, ring strain, polycyclic molecules.
Alkenes
- Structure and reactivity; nomenclature, cis/trans, E/Z notation; hydrogenation, relative stabilities. Reactions to carbon-carbon double bonds (electrophilic addition reactions): mechanism of hydrogen halide additions, regiochemistry, resonance effects, carbocation stabilities, addition of other reagents (hydroboration, addition of halogens, and water, epoxidation and chemistry of oxiranes, oxymercuration, cyclopropanation, carbenes, ozonolysis), dimerization and polymerization of alkenes. Carbocation rearrangements, alkene reduction and oxidations (permanganate and osmium tetroxide). Industrial preparation. Cycloalkenes.
Dienes
- conjugation, introduction to the concept of aromaticity. Diene polymers, natural and synthetic rubber, conjugation, color, and the chemistry of vision.
Alkynes
- Structure and reactivity; bonding and nomenclature, relative stabilities, triple bonds in rings. Addition reactions of alkynes (hydrogenation, hydrogen halide additions, water addition). Preparations.
Stereochemistry
- cis-trans isomerism, conformations and Newman projections, chirality, isomers: enantiomers, R/S notation, diastereomers, optical activity; Cahn-Ingold-Prelog rules; meso compounds, epimers; Fischer proiections.
Alkyl halides
- Physical and chemical properties; preparations, momenclature; reactions: substitution reactions of alkyl halides - S_N2 and S_N1 mechanisms. Elimination reactions: E1 and E2 mechanisms; Zaitsev’s Rule.
Alcohols
- Properties: Acidity, Alkoxides; Naming alcohols: - Preparation;Grignard Addition Reactions: Synthesis from Formaldehyde, from an Aldehyde, from a ketone; Synthesis from an Ester; Synthesis from an Epoxide; from haloalkane; Organolithium Alternative. Reduction: Synthesis from an Aldehyde, from a Ketone, from an Ester, from a Carboxylic Acid. Reactions: Conversion to haloalkanes; Oxidation; Ether and alkene formation.
Ethers, Epoxides, and Sulfides
- Nomenclature of Ethers, Epoxides, and Sulfides; Structure and Bonding in Ethers and Epoxides; Physical Properties of Ethers; Preparation of Ethers: The Williamson Ether Synthesis. Reactions of Ethers: A Review and a Preview; Acid-Catalyzed Cleavage of Ethers. Epoxides: Preparation: Conversion of Vincinal Halohydrins to Epoxides; Reactions of Epoxides: Nucleophilic Ring-Opening Reactions of Epoxides; Acid-Catalyzed Ring-Opening Reactions of Epoxides. Sulfides; Preparation; Reactions: Oxidation of Sulfides: Sulfoxides and Sulfones; Alkylation of Sulfides: Sulfonium Salts.
Dienes
- Classes of Dienes; Relative Stabilities; Electron Delocalization in Conjugated Diene; Preparation. Reactions: Addition of Hydrogen Halides to Conjugated Dienes, Halogen Addition; allylic bromuration; The Diels-Alder Reaction, Stereoselectivity.
CHIMICA ORGANICA II
MODULE 4. CARBONYL COMPOUNDS

15. REACTIONS OF CARBOXYLIC ACIDS AND CARBOXYLIC ACID DERIVATIVES

Nomenclature of carboxylic acids and carboxylic acid derivatives - Structure of carboxylic acids and carboxylic acid derivatives - Physical properties of carbonyl compounds - How carboxylic acids and carboxylic acid derivatives react - The relative reactivity of carboxylic acids and acid derivatives carboxylic acid - Reactions of acyl halides - Reactions of esters - Hydrolysis and transesterification of acid-catalyzed esters - Hydrolysis of esters favored by the hydroxide ion - Reactions of carboxylic acids - Reactions of amides - Hydrolysis and alcoholysis of amides catalysed by ions hydroxide of amides - Hydrolysis of an imide: Gabriel's synthesis of primary amines - Nitriles - Carboxylic acid anhydrides - Dicarboxylic acids - Chemical activation of carboxylic acids - Biological activation of carboxylic acids.

22. THE CATALYSIS IN ORGANIC REACTIONS

Catalysis in organic reactions - Acid catalysis - Basic catalysis - Nucleophilic catalysis - Catalysis with metal ions - Intramolecular reactions - Intramolecular catalysis.

16/23. REACTIONS OF ALDEHYDES AND KETONES • FURTHER REACTIONS OF DERIVATIVES OF CARBOXYLIC ACIDS

Nomenclature of aldehydes and ketones - Relative reactivity of carbonyl compounds - Reactivity of aldehydes and ketones - Reactions of carbonyl compounds with carbon nucleophiles - Reactions of carbonyl compost with hydride ion - Further information on reduction reactions - Chemoselective reactions - Reactions of aldehydes and ketones with nitrogen nucleophiles - Reactions of aldehydes and ketones with oxygen nucleophiles - Protecting groups - Reactions of aldehydes and ketones with sulfur nucleophiles - Reactions of aldehydes and ketones with a peroxy acid - Wittig reaction - SYNTHETIC STRATEGY IV: Disconnections, synthons and synthetic equivalents - Nucleophilic addition to de, -unsaturated aldehydes and ketones - Nucleophilic addition to unsaturated carboxylic acid derivatives - Conjugated addition reactions in biological systems.

17. CARBON REACTIONS

Acidity of hydrogen - Keto-enolic tautomers - Keto-enolic interconversion - Carbon halogenation de of aldehydes and ketones - Carbon halogenation of carboxylic acids - Formation of an enolate ion - Carbon alkylation  - Alkylation and carbon acylation  through an enzyme intermediate - Carbon alkylation  - An aldolic addition forms a -hydroxyaldehyde or a-hydroxyketone - The dehydration of an aldol additive product forms aldehydes and ketones ,-unsaturated - Cross aldol addiction - Claisen condensation : -ketoesters formation - Other crossed condensations - Condensation and intramolecular additions - Robinson's ring - -ketoacid decarboxylation - Malonic synthesis - Acetacetic synthesis - SYNTHETIC STRATEGY V: Formation of new carbon-carbon bonds - Carbon reactions  in biological systems.

MODULE 5. AROMATIC COMPOUNDS

18. REACTIONS OF BENZENE AND SUBSTITUTE BENZENES

Nomenclature of monosubstituted benzenes - General mechanism of reactions of electrophilic aromatic substitution - Benzene halogenation - Benzene nitration - Benzene sulphonation - Friedel-Crafts acylation of benzene - Friedel-Crafts alkylation of benzene - Alkylation of benzene by acylation-reduction - Use of coupling reactions in benzene alkylation - Chemical transformations of substituents on the benzene ring - Nomenclature of disubstituted and polysubstituted benzenes - Effect of substituents on reactivity - Effect of substituents on orientation - The ortho-para relationship - Further considerations on effects of the substituents - SYNTHETIC STRATEGY VI: Synthesis of mono and disubstituted benzenes - Synthesis of trisubstituted benzenes - Use of diazonium salts for the synthesis of substituted benzenes - Azobenzenes - Mechanism of the formation of a diazonium ion – Aromatic nucleophilic substitution - SYNTHETIC STRATEGY VII: Synthesis of cyclic compounds.

19. ADMINISTRATIONS

Nomenclature - Acid-base properties of amines - Amine reactivity as bases and as nucleophiles - Amine synthesis - Hofmann transposition - Curtius transposition - Cope elimination - Mannich synthesis - Heterocyclic amines of biological importance.

19/29/30. CHEMISTRY OF HETEROCYCLIC COMPOUNDS AND AROMATIC HETEROCYCLES

Classification of aromatic heterocycles - Heteroaromaticity - Electrophilic substitution: general aspects - Electronic systems: pentatomic heterocycles containing only one heteroatom - Preparation: Paal-Knorr synthesis of furan, pyrrole and thiophene - Synthesis of pyrrole Knorr - Synthesis of Feist-Bernary del furan and pyrrole Hantzsch synthesis - Reactivity: Acid-base, electrophilic substitution, addition and cycloaddition, oxidation and reduction reactions - Electron systems: benzocondensed pentatomic heterocycles containing only one heteroatom - Preparation: Fischer synthesis of indole - Reactivity: Acid-base, electrophilic substitution, oxidation and reduction reactions - Electron poor systems: exatomic heterocycles containing only one heteroatom - Preparation: Hantzsch synthesis of pyridine - Reactivity: Acid-base reactions, Nitrogen reactions with electrophiles , Electrophilic replacement reactions , of nucleophilic substitution, of oxidation and reduction - Pyridine N-oxide and electrophilic substitution - Electron-poor systems: benzocondensed heterocyclic heterocycles containing only one neutral heteroatom - Preparation: Skraup synthesis of quinoline, Bischler-Napieralski synthesis of isoquinoline - Reactivity: Main reactions.

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Textbook Information

Organic Chemistry I
P. Y. Bruice: Organic Chemistry – EdiSES (molecular models included), III Ed/2017 – ISBN 9788879599351
CHIMICA ORGANICA II
1. Organic Chemistry – P. Y. Bruice – 8ª Ed. Pearson.

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