CHIMICA ORGANICA I E CHIMICA ORGANICA II

Learning Objectives

• Organic Chemistry I

  The course aims to provide students with the basic instruments of Organic chemistry necessary to understand the other chemical and biological disciplines. The study will develop by comparing the synthesis and reactivity of the main functional groups present in organic molecules.

• Organic Chemistry II

  FRONTAL LESSONS

Course Structure

• Organic Chemistry I

  The course structure will be developed following the items reported in the books, make attention to the chemistry of functional groups.

Detailed Course Content

• Organic Chemistry I

  MODULE 1

  PRINCIPLE OF CHEMICAL BASE

  Electronic configurations of elements and the Octet rule. Electron spin, Pauli exclusion principle and principle of maximum multiplicity.

  Chemical bonds: ionic and covalent (homopolar, polar, and dative). Bond Polarity and polarized molecules. Force and energy to bond.

  Length and bond angle. Formal charge and Oxidation number of atoms in organic compounds. Atomic and molecular orbitals. HOMO and LUMO orbitals. Hybrid orbitals sp³, sp², and sp. σ e л bonds.

  Molecular interactions: inter-and intramolecular forces: dipole-dipole interactions, dipole-induced dipole, hydrogen bonds and van der Waals forces. Physical relief of organic molecules: melting and boiling points, solubility.

  Definition of resonance and rules for writing correct resonance structures of organic molecules. Inductive and mesomeric effects.

  Definition of acid and base according to the theories of Arrhenius, Bronsted-Lowry and Lewis.

  Scale of acidity and basicity.

   

  FUNCTIONAL GROUPS, CLASSES OF ORGANIC COMPOUNDS AND NOMENCLATURE

  Description of the functional groups. Classes of organic compounds. Nomenclature and chemical-physical characteristics.

   

  STUDY OF STEREOCHEMISTRY

  Classification: constitutional isomerism and stereoisomerism. Diastereomers and enantiomers. Conformational differences (Newman projections) and configurations. Stereoisomerism and geometrical optics. Centers, stereogenic axes and planes.

  Molecular chirality and ways to determine it (centers, axes and planes). Racemic and scalemic mixtures. Descriptors of cis / trans, E / Z, R / S configurations. Priority rules of Cahn-Ingold-Prelog. Representation of structures using Fischer projections (rules for their proper writing and manipulation). Epimers. Ooptical activity, enantiomeric excess, optical purity). Relative configuration of asymmetric centers: Descriptors of D / L, erythro / threo, sin / anti, exo / endo configurations. Notes on the resolution of enantiomers.

  REACTIONS OF ORGANIC CHEMISTRY.

  Thermodynamic quantities involved in the reactions: changes in free energy, enthalpy and entropy, Gibbs equation. Energy diagrams that describe the variations of these quantities as a function of the reaction coordinate.

  Kinetic variables involved in organic reactions: rate constants and activation energies. Reaction order. Relationship between the rate constants and equilibrium constant.

  Cleavage of bonds by homolytic and heterolytic processes.

   

  MODULE 2

  HYDROCARBONS

  Alkanes and Cycloalkanes:

  Conformational analysis and heat of combustion.

  Stereochemistry of cycloalkanes.

  Synthesis of alkanes and cycloalkanes: hydrogenation of alkenes, reduction of alkyl halides, Synthesis of Corey-House.

  Radical reactions: homolytic dissociation energy and enthalpy of reaction. Geometry and stability of alkyl radicals. Halogenation reactions of methane and higher alkanes: selectivity and Hammond-Leffler postulate.

   

  Alkyl halides:

  Reactions

  Nucleophilic Substitution: SN1, SN2.

  Elimination Reactions: E2, E1 and E1cb mechanisms.

  Competition between substitution and elimination reactions.

  Geometry and stability of carbocations and carbanions.

  Allylic halides and benzylic in nucleophilic substitution reactions.

  Synthesis of alkyl halides ( see reactions of other functional groups)

   

  Alkenes:

  Reactions

  Addition of: hydrogen halides, sulfuric acid, water, halogens (reaction mechanisms and stereochemistry). Stereospecific and stereo selective reactions: Formation of halohydrins. Ozonolysis. Hydroxylation. Oxidation and reduction (Heat of hydrogenation). Stability of alkenes.

  Radical addition of hydrogen bromide. Allyl radical and allyl cation: description, stability and resonance. Allylic chlorination and bromination.

  Preparation of Alkenes: dehydrohalogenation of alkyl halides, dehydration of alcohols, dehalogenation of vicinal dibromine, Wittig reactions.

   

  Alkynes

  Acidity and replacement of the acetylenic hydrogen of terminal alkynes.

  Reactions: Hydrogenation: Addition sin and anti. Addition of: halogens, hydrogen halides and water (keto-enol tautomerism). Oxidation reactions.

  Preparation of Alkynes: dehydrohalogenation of alkyl dihalides. Reactions of metal acetylides with primary alkyl halides.

   

  MODULE 3

  Dienes and polyenes:

  Conformations and stability. Addition 1.2 and 1.4 (kinetic versus thermodynamic control). Diels-Alder reaction.

   

  Aromaticity and electrophilic aromatic substitution:

  Structure and stability of benzene. Hückel's Rule: aromatic annulenes and ions. Aromatic compounds, antiaromatic and non-aromatics. Polycyclic aromatic compounds: naphthalene, anthracene, phenanthrene.

  Electrophilic substitution reactions: halogenation, nitration, sulfonation, Friedel-Crafts alkylation and acylation. Substituents effects on the reactivity and orientation. Alkyl benzenes: Radicals and benzylic cations. Halogenation in the side chain and oxidation.

   

  Alcohols:

  Acid-base properties.

  Reactions: with hydrohalic acids, with thionyl chloride, with methanesulfonyl chloride, with tosyl chloride, with trimethylsilyl chloride, with phosphorus tribromide. Dehydration. Synthesis of esters. Mitsunobu reaction. Oxidation reactions.

  Preparation of alcohols: Hydration of alkenes, hydromercuration-demercuration, hydroboration-oxidation, nucleophilic substitution with hydroxyl, Grignard synthesis, hydrolysis of acid derivatives, reduction of: carbonyl compounds, acids and esters.

   

  Ethers:

  Reactions: acid cleavage.

  Preparation: Intra-and Intermolecular Dehydration of alcohols. Alkoxymercuration-Demercuration. The Williamson ether synthesis.

   

  Epoxides:

  Reactions: Acid and base-catalyzed ring opening. Reaction with Organometallic compounds.

  Preparation: Oxidation of alkenes with peroxy compounds. Dehydrohalogenation of halohydrins.

   

  Diols:

  Preparation: Hydroxylation of alkenes and epoxide ring opening: mechanistic and stereochemical aspects.

  Reactions: oxidation with periodic acid. Formation of acetals and ketals.

   

  Aryl halides:

  Reactions :Aromatic nucleophilic substitutions: addition-elimination, elimination-addition.

  Preparation: direct Halogenation. Reactions of aryldiazonium ions.

  Phenols:

  Reactions: Acid-base properties. Replacing the ring (Reimer and Tieman, Kolbe, nitrosation, and copulation reaction). Synthesis of esters. Claisen transposition. Synthesis of ethers.

  Preparations: Cumene Synthesis. Dow process. Alkaline fusion of sulfonates; hydrolysis of aryldiazonium ions.

   

   

   

   

  Books recommended: a) Organic Chemistry by Bruno Botta, Authors: hanger. Botta, Cacchi, Chiacchio, Corsaro, ... Taddei. Ed Edi-Ermes 2011 (Milan) ISBN 978-88-7051-327-1. b) W. H. Brown c) P. Y. Briuce d) K. And Peter C. Vollhardt, e) A. Streitwieser, C. H. Heathcock f) Norman and Coxon;

   

  Prerequisites: General Chemistry

   

  Evaluation procedure:

   

  XX written test: The written test will be based on the nomenclature of simple organic compounds, on the acidity and basicity, on the synthesis of organic compounds.To access the oral examination must have passed the written test

  XX oral test: The oral test is based on the discussion of the written test and on the basic knowledge . and basic understanding of the functional groups studied during the course of study

• Organic Chemistry II

  ALDEHYDES AND KETONES;CARBOXYLIC ACID, NITRILES AND CARBOXYLIC ACID DERIVATES; CARBONYL ALPHA-SUBSTITUTION REACTIONS; CARBONYL CONDENSATION REACTIONS; AMINES; HETEROCYCLES.BIOMOLECULES: CARBOHYDRATES; AMINO ACIDS,PEPTIDE AND PROTEINS;LIPIDS; NUCLEIC ACIDS.

Textbook Information

• Organic Chemistry I

  Books recommended: a) Organic Chemistry by Bruno Botta, Authors: hanger. Botta, Cacchi, Chiacchio, Corsaro, ... Taddei. Ed Edi-Ermes 2011 (Milan) ISBN 978-88-7051-327-1. b) W. H. Brown c) P. Y. Briuce d) K. And Peter C. Vollhardt, e) A. Streitwieser, C. H. Heathcock .

• Organic Chemistry II

  a) CHIMICA ORGANICA a cura di Bruno Botta, Autori: Appendino. Botta, Cacchi, Chiacchio, Corsaro, … Taddei. Ed. Edi-Ermes (Milano) ISBN 978-88-7051-327-1. b) W. H. Brown; c) P. Y. Briuce; d) K. Peter e C. Vollhardt; e) A. Streitwieser, C. H. Heathcock;