ORGANIC CHEMISTRY II A - L

Learning Objectives

• Organic Chemistry 2

  This course extends the knowledge of organic chemistry and chemical reactivity that students have already acquired. The course will focus on a deeper understanding of the structure and reactivity of organic molecules with emphasis on aromatic compounds, enols, enolates and conjugated compounds. Moreover, it will provide a introductive knowledge on heterocyclic aromatic compounds as well as two families of natural molecules such as carbohydrates and lipids

• MODULO 2

  Acquire experiences on the methodologies and techniques on the organic synthesis through the preparation of some products and their identification.

Course Structure

• Organic Chemistry 2

  lectures

• MODULO 2

  Frontal lessons.

  Laboratory exercises. Use of spectroscopies for the characterization of organic compounds (UV-Vis, IR, ¹H- , ¹³C-NMR).

Detailed Course Content

• Organic Chemistry 2

  Enols, Enolates, enamines

  Keto-enoltautomerism–Enolizationcatalysed by acids and bases – Enols stability - Acidity of a-hydrogens of carbonyl compounds – Enolateions –Lithiumenolates- Halogenation in aof carbonyl and carboxylic compounds –Haloform reaction –Alkylation of acarbons – Alkylation and acylationofacarbons 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 – Problemswith acylation at carbon – Intramolecular Claisen ester and aldolcondensations –Robinson annelation– b-ketoacidsdecarboxylation –Malonic synthesis –Acetoacetic synthesis

  alpha,beta- 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

  Linear and cyclic conjugatedpolyenes stability -Delocalized Electrons: the Structure of Benzene, the prototypic aromatic system - Identifying aromatic systems - Criteria for Aromaticity - Huckel's rule - Antiaromaticity- Aromaticpolycyclic hydrocarbons - Nomenclature of Mono- and polysubstituted Benzenes - General Mechanism for Electrophilic Aromatic Substitution Reactions -Halogenation – Nitration - Sulfonation - Friedel–Crafts Acylation -Friedel–Crafts Alkylation of Benzene-Alkylation of Benzene by Acylation - 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 Ortho–Para Ratio– Chloromethylation -The Gattermann-Koch ,the Gattermann , the Vilsmeyer ,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 –TheLepetit-Bucherer reaction– Polyphenols – Oxidation -
  Quinone-hydroquinone redox equilibrium – Natural antioxydants – Phenolic ethers – The Claisenrearrangement

  Aminesand their derivatives

  Alkyl- and arylamines classification and nomenclature – Arylamines: structure and physical properties - Acidityand basicity– Enantiomeric pyramidal inversion – Quaternary armonium salts (properties, stereochemistry) - Synthesis of amines (alkylation, reducive amination, reduction of azides, nitriles, amidesand 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

  Heterocyclic compounds

  The Hantzsch-Widman nomenclature – The replacement nomenclature - Common nomenclature - Synthesis reactions –Retrosynthetic analysis– Cyclization reactions - The Baldwin rules– Arylnitrene ring-expansion and ring-contraction – Modern synthetic methods (combinatorial synthesis , microwaves assisted synthesis).

  Aromatic heterocycles
  Heteroaromaticity – Five- and six membered aromatic heterocyclic rings - Furan, pyrrole, thiophene, pyridine. Synthesis starting from1,3 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

• MODULO 2

  Introductive ideas on common identification techniques as: ¹H - e ¹³C-NMR, UV-Vis, GC, GC/MS e HPLC.

  Practical execution of electrophilic aromatic substitution, carbonyl addition-elimination reactions, local anesthetic multistage synthesis.

  Isolation, purification and characterization of the products obtained in the experiences through: : p.f., UV-Vis, IR, ¹H- e ¹³C-NMR.

Textbook Information

• Organic Chemistry 2

  • W.H.Brown, B.L.Iverson, E.V.Anslyn, C.S.Foote, CHIMICA ORGANICA, Edises 2015

  • D. Sica, F. Zollo, Chimica dei Composti Eterociclici, Edises 2011

  • P.Y.Bruice, CHIMICA ORGANICA, Edises 2012

  • notes

  RecommendedReadings

  J. Claiden, N. Greeves, S. Warren,ORGANIC CHEMISTRY, Oxford University Press 2012

  T.W. G. Solmons, C. B. Fryhle, Chimica Organica, Zanichelli

• MODULO 2

  1. D.L. Pavia, G.M. Lampman, G.S. Kritz, Introduction to Organic Laboratory, Saunder College Pubblishing.

  2. R.M. Silverstein, F.X. Webster, Identificazione Spettroscopica di Composti Organici,

  Ambrosiana.