CHIMICA ORGANICA I E LABORATORIO A - L

12 CFU - 2° Semester

Teaching Staff

ROSARIA SALETTI

Learning Objectives

Organic Chemistry I and Laboratory (Mod. 1)
Basic knowledge of organic compounds, of their three-dimensional structure and of their reaction mechanisms.

In particular, the specific training objectives of this course are:

- Understanding the chemical bond in organic compounds;

- Understanding the three-dimensional structure (stereochemical) of organic compounds;

- Understanding the relationship between structure and chemical reactivity;

- Understanding the reaction mechanisms of organic compounds;

- Understanding the kinetic and thermodynamic aspects of organic compounds;

- Know the reactivity of the main classes of organic compounds.

- Discussion of all the activities proposed with scientific method and appropriate language.

Furthermore, concerning to the so-called Dublin Descriptors, this course helps to acquire the following transversal skills:

Knowledge and understanding:
- Capacity of inductive and deductive reasoning;

- Ability to rationalize the property-structure-reactivity correlations of organic compounds.

Ability to apply knowledge:

- Ability to apply the acquired knowledge to rationally describe the chemical behavior of organic compounds, including stereochemical aspects;
- Ability to predict the chemical reactivity of organic compounds based on their molecular structure.

Autonomy of judgment:
- Critical reasoning skills;

- Ability to identify the most suitable conditions for the chemical modification of an organic structure.

Communication skills:

- Ability to describe the structure and chemical behavior of organic compounds in oral form, with properties of language and terminological rigor.

Learning skills:

- Ability to design the synthesis of an organic compound independently using the skills acquired during the course;
- Show to have developed good learning and in-depth skills to easily face subsequent courses in Organic Chemistry.
Organic Chemistry I and Laboratory (Mod. 2)
The course aims to provide the student with the fundamental notions of safety to be adopted in an Organic Chemistry laboratory and to provide the basic knowledge of the theoretical and practical aspects of the main laboratory techniques of Organic Chemistry.

In particular, the specific training objectives of this course are to provide the knowledge of the common techniques of purification of organic compounds and of the basic methodologies for their recognition and characterization.

The topics covered during the lectures will be put into practice in the laboratory hours. At the end of the course the student will be able to independently carry out the purification and characterization of an organic compound working in safe conditions and to prepare a scientific report.

Furthermore, concerning to the so-called Dublin Descriptors, this course helps to acquire the following transversal skills:

Knowledge and understanding:
- Knowledge of the equipment present in the Organic Chemistry laboratory and of the standard laboratory procedures for the preparation and purification of organic compounds;
- Knowledge of the concepts of safety and danger to the environment and health.

Ability to apply knowledge:
- Ability to handle organic compounds responsibly, knowing and respecting safety rules;
- Ability to assemble and use the main equipment present in an Organic Chemistry laboratory;
- Ability to recognize organic compounds on the basis of the knowledge acquired during the course;
- Ability to record and document experimental activities in a reliable and systematic way in the laboratory notebook.

Autonomy of judgment:
- Ability to interpret the data collected in a coherent, critical and correct way, correlating them with the appropriate theories;
- Ability to formulate hypotheses and discard incorrect ones;
- Be able to design and conduct experiments independently.

Communication skills:
- Ability to communicate in written and oral form, through the use of scientifically and technically appropriate language, experimental data, information, problems and solutions.

Learning ability:
- Ability to apply a standard technique used in Organic Chemistry laboratories independently;
- Ability to deal with a problem through the application of the skills gained during the course;
- Show to have developed good learning and in-depth skills to easily face subsequent chemistry laboratory courses.

Course Structure

Organic Chemistry I and Laboratory (Mod. 1)
Classroom Lectures (35 hours) and Classroom Exercises (12 hours).

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.

Learning assessment may also be carried out on line, should the conditions require it.
Organic Chemistry I and Laboratory (Mod. 2)
The course consists of 6 credits corresponding to 72 hours divided between hours of theoretical lessons and hours of laboratory exercises. The hours of theoretical lessons are preliminary to the development of laboratory exercises. The student will be engaged in laboratory exercises lasting 4 hours each.

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.

Learning assessment may also be carried out on line, should the conditions require it.

Detailed Course Content

Organic Chemistry I and Laboratory (Mod. 1)
1. Introduction to Organic Chemistry
Electronic configuration of atoms. Lewis representations. The octet rule. The chemical bond: ionic and covalent bonds. Pauling's electronegativity scale. Bond length and bond strength. Formal charge. Resonance theory. Quantum mechanics: shape of the atomic s and p orbitals; σ and π bonds. Hybrid orbitals sp3, sp2, sp. Structure of methane, ammonia and water. Double and triple bond. Main functional groups and related classes of compounds.

2. Acids and bases
Acids and bases according to Arrhenius, Brønsted-Lowry and Lewis. Definition of the pKa. Acid-base reactions: equilibrium position and relative strength of acids and bases.

3. Alkanes
Structure. Conformational isomerism. General principles of the IUPAC nomenclature and application in the case of alkanes. Classification of carbon and hydrogen atoms. Conformations of alkanes. Newman projections. Physical properties: dispersion forces. Natural sources and notes on oil processing. Reactivity: radical substitution and the combustion reaction.

4. Cycloalkanes
Structure, nomenclature and physical properties. Conformations and relative stability of cyclopropane, cyclobutane, cyclopentane, cyclohexane. Contributions to the ring tension: distortion of the bond angle, eclipsing tension and diaxial interaction. Axial and equatorial hydrogens in cyclohexane. Preferred conformations of the substituted cyclohexanes. Cis-trans isomerism in cycloalkanes.

5. Stereoisomerism
Stereoisomers: Enantiomers and Diastereoisomers. Chirality and Stereocenters. Absolute configuration. The R-S convention. Fischer projections. Meso compounds: the stereoisomers of tartaric acid. Optical activity: polarized light and polarimeter. Specific rotary power. Biological importance of chirality. Methods for resolving racemic mixtures.

6. Alkenes
Structure. Nomenclature. Isomerism: cis-trans and E-Z nomenclature. Addition reaction: halogenation; hydrohalogenation; acid-catalyzed hydration; Relative stability of carbocations and Markovnikov's rule. Rearrangement of carbocations. Hydroboration-oxidation. Oxidation reactions: with potassium permanganate; with osmium tetroxide and hydrogen peroxide; with ozone; with peracids. Catalytic hydrogenation, heats of hydrogenation and relative stability of alkenes. Preparations: Dehydrohalogenation of alkyl halides; Dehydration of alcohols; Wittig reaction.

7. Dienes
Classification. Structure of conjugated dienes according to the valence bond theory. Relative stability of boundary forms and their contribution to the resonance hybrid. Resonant energy. Electrophilic addition to conjugated dienes: -1,2 and -1,4 additions.

8. Alkynes
Structure. Nomenclature. Acidity of terminal alkynes. Addition reaction. Catalytic reduction to alkenes with Lindlar’s catalyst and to alkanes.

9. Halogenalkanes
Structure. Nomenclature. Nucleophilic substitutions. SN1 and SN2 mechanisms. Stereochemistry of nucleophilic substitutions. Effects of the structure of the substrate, the nucleophile, the leaving group and the solvent. Elimination reactions. E2 and E1 mechanisms. Competition between substitution and elimination reactions. Reaction with magnesium: formation of organometallic compounds. Grignard's reagents. Preparation: Halogenation of alkanes: mechanism of radical halogenation; homolytic cleavage of bonds. Relative stability and structure of primary, secondary and tertiary alkyl radicals. Relative reactivity of halogens in halogenation reactions. Chlorination of alkanes: relative reactivity of primary, secondary, tertiary hydrogens and relative stability of the respective radicals. Regioselective reactions (Hammond's postulate); stereochemistry of radical halogenation. Addition of halogen acids to alkenes and alkynes; addition of halogens to alkenes; halogenation of alcohols.

10. Benzene and derivatives

Structure. Nomenclature and properties of benzene and its derivatives. Aromaticity. Resonant energy. Huckel's rule. Aromatic electrophilic substitution reactions: halogenation; nitration; sulfonation; Friedel and Crafts alkylation and acylation. Activating and deactivating substituent groups. Reactivity and orientation.

11. Alcohols
Structure. Nomenclature. Hydrogen bond. Acidity and basicity. Reactions with active metals. Formation of halogenalkanes. Dehydration to form alkenes and Zaitsev's rule. Oxidation of primary and secondary alcohols with dichromate and with pyridinium chlorochromate . Oxidation of glycols with periodic acid. Esters formation. Formation of semiacetals and acetals. Preparation: Addition of H2O to alkenes; hydroboration-oxidation; hydrolysis of halogenalkanes; addition of organo-metals to aldehydes and ketones; reduction of carbonyl compounds; reduction of carboxylic acids and esters. Notes on: Ethers, epoxides, thiols and sulphides.

12. Aldehydes and Ketones
Structure. Nomenclature. Nucleophilic additions: addition of Grignard reagents, of HCN, of alcohols to form hemiacetals and acetals; addition of ammonia derivatives: formation of Schiff bases. Oxidations. Reduction to alcohols. Keto-enol tautomeria. Preparation: Oxidation of secondary alcohols; oxidation of primary alcohols with pyridinium chlorochromate.

13. Carboxylic acids and derivatives
Structure. Nomenclature. Acidity constants. Effect of substituents on acidity in aliphatic acids. Reduction with LiAlH4: formation of primary alcohols. Decarboxylation. Fischer esterification. Reaction with diazomethane: formation of methyl esters. Reaction with thionyl chloride: formation of acyl chlorides. Halogenation in alpha: reaction of Hell, Vholard, Zelinsky. Preparation: oxidation of primary alcohols and aldehydes; oxidation of methylketones with the halo-formal reaction; carbonation of Grignard reagents.
Esters: acid and basic hydrolysis (saponification). Halides of acids. Anhydrides. Amides. Nitriles. Hydroxy acids and keto acids. Fats and oils. Phospholipids.

14. Amines
Structure and classification: primary, secondary, tertiary amines and quaternary ammonium salts. Electronic structure of nitrogen. Physical properties. Reactivity: Basicity; nucleophilicity. Formation of imines; formation of amides. Reactions of amines with nitrous acid. Reactions of diazonium salts. Diazocopulation. Azo dyes. Hofmann elimination. Elimination of Cope. Preparation: Direct alkylation. .
Organic Chemistry I and Laboratory (Mod. 2)
Introduction to the organic chemistry laboratory:

Safety regulations; Laboratory equipment: risks and use; Use of laboratory solvents.Laboratory notebook.

Melting Point and Boiling Point Determination

Laboratory separation techniques:

Purification of solids and purity criteria; Filtration; Crystallization; Drying; Sublimation; Distillation techniques; Extraction techniques of organic compounds.

Chromatographic separations: thin layer chromatography and column chromatography.

Laboratory experiences
- Purification of an organic compound through recrystallisation;
- Distillation and boiling point determination;
- Separation of organic products through solvent extraction;
- Caffeine extraction from tea leaves;
- Thin-layer chromatography;
- Soap preparation;
- Pigment extractions from spinach leaves and chromatographic separation;
- Aspirin synthesis.

Textbook Information

Organic Chemistry I and Laboratory (Mod. 1)
1. W. H. Brown, C. S. Foote, B. L. Iverson. Chimica Organica, (EdiSES);

2. Streitwieser, C. H. Heathcock, E. M. Kosower, Chimica Organica (EdiSES);

3. Seyhan Ege, Chimica Organica, (Sorbona);

4. P. Vollhardt, Chimica Organica, (Zanichelli);

5. J. McMurry, Chimica Organica (Piccin);

6. B. Botta, Chimica Organica (edi-ermes)
Organic Chemistry I and Laboratory (Mod. 2)
1. D. L. Pavia, G. M. Lampman, G. S. Kriz. Il laboratorio di Chimica Organica. Ed. Sorbona
2. M. D’Ischia. La Chimica Organica in Laboratorio. Ed. Piccin
3. R. M. Roberts, J. C. Gilbert, S.F. Martin. Chimica Organica Sperimentale.Zanichelli
4. K. L. Williamson, K. M. Masters. Macroscale and Miscoscale Organic Experiments. Ed. K. Williamson, Houghton Mifflin

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