ORGANIC CHEMISTRY II A - L

12 CFU - 2° Semester

Teaching Staff

COSIMO GIANLUCA FORTUNA - Module Organic Chemistry II - CHIM/06 - 6 CFU
CARMELA BONACCORSO - MODULO 2 - CHIM/06 - 6 CFU

Learning Objectives

Organic Chemistry II
The course aims to provide students with a more in-depth training in Organic Chemistry from the first basic course, particularly with regard to nomenclature, chemical properties and reactivity of multifunctional compounds; the main classes of organic compounds of biological significance: carbohydrates, lipids; the major heterocyclic systems. Students will gain further knowledge on advanced organic synthesis reactions, learning to develop simple synthetic sequences of polyfunctional organic compounds and to apply the principles of modern synthetic strategies for disconnection approaches, formation of carbon-carbon bonds, deprotection protection of functional groups.

The specific training objectives of the module are:

1)Knowing how to organize and assemble the laboratory glassware for the realization of a synthesis;

2)Knowing how to structurally characterize an organic molecule using one or more instrumental techniques;

3)Knowing how to interpret spectroscopic data to be able to trace the identity of an organic molecule

To acquire experience on the methodologies and techniques of organic synthesis through the preparation of some products and their structural determination. With reference to the Dublin Descriptors, this course aims to transfer the following transversal skills to the student:

Knowledge and understanding: Inductive and deductive reasoning skills;

Ability to rationalize and predict the reactivity of organic molecules; Ability to distinguish the different synthesis techniques;

Ability to distinguish the different laboratory instruments

Ability to apply knowledge:

Ability to design a synthetic path suitable for obtaining a precise organic molecule;

Ability to foresee the necessary instrumentation for the realization of the synthesis;

Ability to identify the optimal reaction conditions for a given reaction.

Autonomy of judgment: Critical reasoning skills;

Self-assessment of learning through interactions in the classroom with colleagues and with the teacher.

Communication skills: Ability to describe in oral and written form, with properties of language and terminological rigor, one of the topics covered, using both power point presentations and the blackboard

Course Structure

Organic Chemistry II
The teaching will take place through the discussion of the various topics reported in the program and will include days dedicated to the clarification of doubts and the simulation of the oral exam.

Detailed Course Content

Organic Chemistry II
Review of the main functional groups, of the concept of acidity and basicity.

Review of the main reactions of alcohols, amines, aldehydes and ketones and carboxylic acids and derivatives.

Enols, Enolates, enamines

Keto-enol tautomerism –Enolization catalysed by acids and bases – Enols stability - Acidity of a-hydrogens of carbonyl compounds – Enolate ions – Halogenation in a of carbonyl and carboxylic compounds –Haloform reaction –Alkylation of acarbons – Alkylation and acylation of acarbons by using enamines – The Aldol condensation: synthesis of b-hydroxyaldehydes – Dehydratation of aldols – Cross-condensation of aldols – The Claisen condensation: synthesis of -ketoesters – The Claisen ester condensation compared to the aldol condensation – Problems with acylation at carbon – Intramolecular Claisen ester and aldol condensations –Robinson annelation– b-ketoacids decarboxylation –Malonic synthesis –Acetoacetic synthesis

a,b- unsatured carbonyl compounds

Electron Delocalization and Resonance - Conjugation effects - Conjugate additions reactions – b-carbon alkylation – Michael reaction – Conjugate addition or direct addition to the carbonyl group - “hard” e “soft” nucleophiles - Conjugate addition of ammonia and amines– Conjugate addition of alcohols and thiols – Reactions with organometallic reagents – The Effect of the Cu(I) salts – Conjugate addition of enolates– Conjugate addition followed by cyclization in the ring synthesis

Benzene and the aromatic compounds

Review of some concepts: Linear and cyclic conjugated polyenes stability - Delocalized Electrons: the Structure of Benzene, the prototypic aromatic system - Identifying aromatic systems - Criteria for Aromaticity - Huckel's rule - Antiaromaticity- Aromatic polycyclic hydrocarbons - Nomenclature of Mono- and polysubstituted Benzenes - General Mechanism for Electrophilic Aromatic Substitution Reactions -

- Reduction - Reactions at the side chain - The Effect of Substituents on Reactivity - Inductive and Resonance Electron Donation and Withdrawal- Relative Reactivity of Substituted Benzenes - The Effect of Substituents on Orientation –, the Reimer-Tiemann formylation.

Aryl Halides

Nomenclature - Chemical properties compared to alkylic, vinylic and alleli alides- Nucleophilic Aromatic Substitution Reaction – The addition-elimination mechanism (S_NAr) - The elimination-addition mechanism (SNEA)- The benzyne

Phenols

Nomenclature – Physical and chemical properties – Preparation from aryl halides and from aryl diazonium salts – Acidity – Electrophilic aromatic substitution - Hydroxymethylation reaction- Phenolic resins- The Kolbe reaction – Polyphenols – Oxidation -
Quinone-hydroquinone redox equilibrium – Phenolic ethers – The Claisen rearrangement

Amines and their derivatives

Alkyl- and arylamines classification and nomenclature – Arylamines: structure and physical properties - Acidity and basicity– Enantiomeric pyramidal inversion – Quaternary armonium salts (properties, stereochemistry) - Synthesis of amines (alkylation, reducive amination, reduction of azides, nitriles, amides and nitro compounds, the Hofmann rearrangment , the Mannich reaction, the Hofmanndegradation – the Gabrielsynthesis – Preparation of arylamines – Reactions with carbonyl compounds – Reactions with nitrous acid - Imines, enamines – Diazoniun salts and their coupling reactions – Diazonium salts replacement reactions.

Sulfur compounds

Thiols : structure, nomenclature, physical properties – Acidity - Preparation reactions – oxydation reactions– Sulfides – Disulfides - Solfinic and Solfonic acids

Aromatic heterocycles
Heteroaromaticity – Five- and six membered aromatic heterocyclic rings - Furan, pyrrole, thiophene, pyridine. Synthesis starting from 1,3 and 1,4-dicarbonylic compounds – Heteroaromatic rings with two o more heteroatoms- Benzo-fused heterocycles- Electrophilic Aromatic Substitution Reactions, Nucleophilic Aromatic Substitution Reactions, oxidations, reductions –Pyridine N-oxyde.

Carbohydrates

Classification of Carbohydrates - The D and L Notation - Configurations of Aldoses and Ketoses - Redox Reactions of Monosaccharides – Oxidation - Chain Elongation: the Kiliani–Fischer Synthesis -

Chain Shortening: the Wohl and Ruff Degradation- Cyclic Structure of Monosaccharides: Hemiacetal Formation - Acylation and Alkylation of Monosaccharides -Formation of Glycosides - The Anomeric Effect - Reducing and Nonreducing Sugars – Mutarotation – Disaccharides - Polysaccharides

Solar energy, photosynthesis and the flow to Living Organisms- Some Eco Friendly Products Derived from cellulose fermentation

Lipids

Fatty Acids- Fats and Oils – Waxes – Triglycerides – Saponification –Micelles - detergent properties- Soaps and detergents - Prostaglandins – Steroids – Terpenes – Phospholipids –Phospholipid bilayers assembly- Liposomes - Cell membrane – Lecithins –Sphingolipids – Fat soluble vitamis

Textbook Information

Organic Chemistry II
- Required Texts
  
  1) § W.H.Brown, B.L.Iverson, E.V.Anslyn, C.S.Foote, CHIMICA ORGANICA, Edises 2015
  
  2) § D. Sica, F. Zollo, CHIMICA DEI COMPOSTI ETEROCICLICI, Edises 2011
  
  § Notes
  
  Recommended Readings:
  
  3)§ P.Y.Bruice, CHIMICA ORGANICA, Edises 2012
  
  4) § J. Claiden, N. Greeves, S. Warren, ORGANIC CHEMISTRY, Oxford University Press 2012

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