69074 - Organic Chemistry I

Learning outcomes

At the end of the course, the student is able to predict the chemical behavior of monofunctional organic compounds and to solve problems related to the practical application of synthesis and transformation methodologies for simple organic molecules.

Course contents

Prerequisites

Students are expected to have a solid understanding of the fundamental principles of general chemistry, with particular emphasis on: atomic structure and the Periodic Table; nature of chemical bonding; principles of chemical equilibrium and basic kinetics/thermodynamics of chemical reactions; acid-base reactions. Intermediates and transition states; reaction energy diagrams. Meaning of activation energy and the concept of catalysis.

Course Content

Introduction
Definition, relevance, and limitations of Organic Chemistry. Review of chemical bonding. Bonding and antibonding molecular orbitals. Bond energy and bond length. Resonance. Electronegativity, bond polarity, and molecular dipoles. Carbon as the central element of Organic Chemistry.

ALKANES and CYCLOALKANES
Structure: Hybrid orbitals and molecular geometries. Sigma bonds (C-H and C-C) and structure of alkanes. Concept of isomerism. Nomenclature of alkanes. Cycloalkanes. Physical properties. Sources and significance. Conformations of linear alkanes. Structure and conformations of 3-, 4-, 5-, and 6-membered rings. Chair and boat conformations of cyclohexane: axial and equatorial bonds. Ring flip. Substituted cyclohexanes. Cis/trans isomerism in cyclic compounds.
Reactivity: Combustion and energy use; greenhouse gases and climate change; brief mention of environmental issues in chemistry. Halogenation of alkanes: mechanism and selectivity. Radical stability and hyperconjugation. Allylic halogenation.

ORGANIC REACTIVITY
Elementary reaction mechanisms. Bond formation and cleavage via one- or two-electron processes. Nucleophiles, electrophiles, radicals. Types of reactions: substitution, addition, elimination, rearrangement. Oxidation and reduction in organic chemistry. Concept of "functional group oxidation state." Brønsted and Lewis acids/bases. Mechanistic representation in organic chemistry.

STEREOCHEMISTRY
Molecular chirality and enantiomerism. Representations and Fischer projections. C.I.P. system. Enantiomerism and optical rotation. Racemic mixtures. Compounds with one or more stereocenters. Diastereomerism and meso forms. Importance of chirality.

ALKENES, CYCLOALKENES, DIENES, AND POLYENES
Structure and properties: C=C π bonds. Structure and nomenclature. Physical properties. E/Z isomerism. Types of polyenes (isolated, conjugated, cumulated). Stability of polyenes. Structure of allenes. Electronic structure of conjugated dienes: HOMO and LUMO. Interaction of alkenes with electromagnetic radiation; brief mention of the visual process.
Reactivity: Electrophilic addition to C=C double bonds; mechanism, regioselectivity, carbocation stability and rearrangements. Addition of hydrogen halides. Acid-catalyzed hydration and alcohol addition; oxonium ions. Halogenation and halohydrin formation. 1,2- and 1,4-addition to conjugated dienes. Allylic resonance. Kinetic vs. thermodynamic control. Hydroboration and oxidation. Catalytic hydrogenation. Radical addition of HBr. Oxidations: epoxidation and dihydroxylation (mechanism, stereochemistry). Ozonolysis: mechanism and ozonide conversion.

ALKYNES
Structure and properties: C≡C triple bonds, structure and nomenclature.
Reactivity: Electrophilic additions: single and double addition of HX, alcohols, and halogens. Acid-catalyzed hydration and keto-enol tautomerism. Hydrogenation and partial hydrogenation. Reduction with solvated electrons. Hydroboration, protonolysis, and oxidation of alkenylboranes. Acidity of C-H bonds. Acetylide anions and their reactivity.

ALKYL/ARYL HALIDES
Structure and properties: C–X sigma bonds. Nomenclature and physical properties.
Reactivity: Nucleophilic substitution and β-elimination: SN2 and SN1 mechanisms. Nucleophile examples. Leaving groups (halides, sulfonates, sulfates, phosphates). Influence of substrate structure and reaction conditions. Carbocation stability. Stereochemistry of substitution. E2 and E1 eliminations. Alkene stability and regioselectivity.

AROMATIC COMPOUNDS
Structure and properties: XXXXX (You can provide this section and I’ll translate it as well.)

ALCOHOLS/ETHERS and THIOLS/THIOETHERS
Structure and properties: Sigma bonds (C–O and C–S). Structure of alcohols, thiols, ethers, sulfides. Nomenclature. Hydrogen bonding. Physical properties of alcohols and ethers. Solvents in organic chemistry.
Reactivity: Acidity/basicity of alcohols and thiols. Alkoxides and their reactivity. Nucleophilic substitutions on alcohols. Conversion of alcohols to alkyl halides. Formation and substitution of sulfonates. Alcohol dehydration to alkenes. Oxidation of alcohols and diols. Chemoselectivity in primary alcohol oxidation. Toxicity of reagents and an introduction to Green Chemistry. Oxidation of thiols. Williamson ether synthesis and its limitations. Acid-catalyzed ether synthesis. Silyl ethers. Nucleophilic substitutions on ethers. Nucleophilic additions to epoxides under SN1 and SN2 conditions. Sulfide oxidation.

AMINES
Structure and properties: C–N sigma bonds. Nomenclature and physical properties of amines and ammonium ions.
Reactivity: Basicity and nucleophilicity. Alkylation with alkyl halides and epoxides. Quaternary ammonium salts. Hofmann and Cope eliminations. Synthesis of amines via azides.

CARBONYL COMPOUNDS
Structure and properties: C=O π bonds and structure of the carbonyl group. Nomenclature and physical properties of aldehydes and ketones. C=N π bonds and imine structure. Structure of acyl-containing compounds. Nomenclature and properties of carboxylic acids, carboxylates, acyl halides, anhydrides, esters, thioesters, and amides. C≡N triple bond: structure, nomenclature, and properties of nitriles.
Reactivity: General reactivity of carbonyl compounds. Nucleophilic addition mechanisms. Basicity and acid catalysis of carbonyls. Organometallic compounds of Mg and Li: structure and addition to C=O and C=N. Complex hydride addition and hydroboration. Catalytic hydrogenation. Addition of weak nucleophiles: water, alcohols, amines. Acetal formation. Imine synthesis. Imine reduction and reductive amination. Enamine, hydrazone, and oxime formation. Aldehyde oxidation.

Reactivity of acyl compounds and nitriles.

CARBOXYLIC ACID COMPOUNDS
Structure and properties: C=O(X) π bonds and carboxyl group structure. Nomenclature and physical properties of carboxylic acids and derivatives.
Reactivity: Acidity of carboxylic acids. Nucleophilic acyl substitution mechanisms and relative reactivity/stability. Reactions of acyl halides and anhydrides. Conversion of acids to acyl chlorides. Acid esterification. Acidic/basic hydrolysis of esters. Transesterification. Reactivity of thioesters. Ester aminolysis. Amination of carboxylic acids. Acidic/basic hydrolysis of amides. Nitrile synthesis and hydrolysis. Reduction of acids, esters, amides, nitriles. Organometallic addition to esters and nitriles.

Readings/Bibliography

Most comprehensive university-level Organic Chemistry textbooks are generally valid. Below are some suggested texts.

1. K. Peter, C. Vollhardt, N.E. Schore, "Chimica Organica", Zanichelli, Bologna, (IV edition).

2. W.H. Brown, B.L. Iverson, E.V. Anslyn, C.S. Foote, "Chimica Organica" EdiSES, Napoli (VI edition).

3. T.W.G. SOLOMON, C.B. Fryhle, "Chimica Organica", Zanichelli, Bologna (III edoition).

Teaching methods

Lectures with video projection.
Classroom exercises carried out collectively.

Assessment methods

Written and Oral exam

The exam consists of a written test (in person) with 10 open-ended questions (duration: 1.5 hours). Students who score at least 15 out of 30 on the written test will be eligible to take an oral exam consisting of a single question (approximate duration: 10 minutes, grade out of 30). The final grade will be a weighted average of the written and oral exams, with the written part accounting for 3/4 and the oral part for 1/4. The exam is considered passed if the overall score is at least 18 out of 30.

The exam is intended to assess the achievement of the following learning objectives:
(i) familiarity with the logic, concepts, and tools of organic chemistry;
(ii) ability to write, recognize, name, and predict the properties and reactivity of organic molecules;
(iii) ability to rigorously and clearly describe the mechanisms of organic reactions;
(iv) ability to apply the above concepts to solve basic problems related to synthesis strategies, reactivity, and the structure of organic molecules.

An overall failing evaluation (score < 18/30) is due to major gaps in course content, resulting in unanswered or inadequately answered questions in the written/oral tests.

An overall sufficient to fair evaluation (18–24/30) indicates an acceptable level of preparation, although with significant knowledge gaps or topics that have not been adequately studied.

An overall good evaluation (25–28/30) indicates that the student has acquired a solid understanding of the course content and is able to make meaningful connections between different parts of the program.

An excellent evaluation (29–30/30 with honors) indicates a complete and in-depth understanding of the entire course material, demonstrating a clear and coherent overall grasp of the subject.

 

Students with learning disorders and\or temporary or permanent disabilities: please, contact the office responsible (https://site.unibo.it/studenti-con-disabilita-e-dsa/en/for-students ) as soon as possible so that they can propose acceptable adjustments. The request for adaptation must be submitted in advance (15 days before the exam date) to the lecturer, who will assess the appropriateness of the adjustments, taking into account the teaching objectives.

Teaching tools

The slides will be provided to the students. There are no comprehensive monographs available on the market that cover all the topics of the course. Course organization: all hours, both theoretical lessons and practical exercises, will be held in person in the classroom. 

 

Office hours

See the website of Marco Bandini