ORGANIC CHEMISTRY 2: FUNDAMENTALS
- Overview
- Assessment methods
- Learning objectives
- Contents
- Full programme
- Bibliography
- Teaching methods
- Contacts/Info
A deep knowledge of the topics tackled during the courses of General Chemistry and Organic Chemistry 1 is a pivotal prerequisite.
The final examination consists in a two-step procedure with written and oral tests. The former is usually structured in ten exercises on different topics, including nomenclature, guided synthesis by knowledge of reagents, planning of synthesis of aromatic compounds, acidity and basicity scale of different compounds, structure identification and separation of mixture of organic compounds. During the oral test, students will be examined on all the topics tackled during the lessons. The final mark is the average, weighted on the basis of the credits, of the partial mark of parts A and B of the course.
The course aims at increasing students’ knowledge of organic chemistry by these topics:
- nitrogen-containing functional groups: structure, conversion and reactivity;
- aromatic compounds: structure, reactivity, and synthesis.
At the end of the course, students will be able:
1) to knowledge properties and reactivity of aromatic and heteroaromatic systems, also taking into account possible functional groups;
2) to identify the reactivity of molecules in different conditions depending on their structures;
3) to plan a multi-step synthesis of aromatic molecules starting from assigned starting materials.
Amines and their derivatives (12 hours)
Naming the amines. Structural and physical properties. Basicity and acidity. Stereochemical aspects. Quaternary ammonium salts and N-oxide derivatives. Phase transfer catalysis (PTC). Alkylation reactions, reductive amination, acylation and sulfonation reactions. Imine and enamine formation, Mannich reaction. Diazotatization reaction. Synthesis of aliphatic amines.
Amides: naming of amides, properties, acidity. Reactivity toward acids, bases and reducing agents. Beckmann rearrangement.
Aminoacids, peptides and proteins: naming aminoacids and peptides. Stereochemistry of -aminoacids. Acid-base properties of aminoacids and peptides. Synthesis and resolution of -aminoacids. Synthesis of peptides: protecting groups, amidation reaction. Hydrolysis of peptides and proteins. Primary and secondary structure of proteins.
Aromaticity (6 hours)
Inductive, mesomeric, steric, and hyperconjugative effects. Hückel’s rule. Aromatic, antiaromatic and nonaromatic compounds. Hammond postulate. Kinetic and thermodynamic control. SEAr mechanism. Isomeric benzene compounds. Activation or deactivation by substituents (vs SEAr). Regioselectivity depending on the substituents.
Reactivity of aromatic compounds (10 hours)
SEAr reactions. C(arom)-N, C(arom)-S, C(arom)-alogeno, C(arom)-C bond formation. SEAr promoted by organometallated arenes (introduction).
Aromatic compounds (38 hours)
Alkylbenzenes and alkenylbenzenes: naming compounds, properties and reactivity of aromatic systems. Benzylic halogenation (Wohl Ziegler), benzylic hydroperoxydation, oxidation of the side-chain, Birch reduction.
Alcohols and benzylic halides: naming compounds, properties and reactivity. Synthetic methods.
Aromatic aldheydes and ketons: naming compounds, properties and reactivity. Reactivity vs oxygen, sulphur, nitrogen and carbon nucleophiles. SEAr reactions. Reduction and oxidation. Synthetic methods.
Aromatic carboxylic acids: naming compounds and general properties. Acidity of carboxylic acids. Acyl SN and SEAr reactions. Esterification and reduction. Synthetic methods.
Aromatic acyl chlorides: naming compounds and general properties. Reactivity vs nucleophiles.
Aromatic esters and anhydrides: naming compounds and general properties. Hydrolysis in acidic and basic medium. Reduction reactions by hydrides. Transesterifications. Reactivity vs nucleophiles. SEAr reactions. Synthetic methods.
Aromatic amides: naming compounds and general properties. Acidity. Acidic and basic hydrolysis. Reduction reactions. Reactivity vs nucleophiles. SEAr reactions. Synthetic methods.
Aromatic nitriles: naming compounds and general properties. Acidic and basic hydrolysis. Reduction reactions. Reactivity vs nucleophiles. SEAr reactions. Synthetic methods.
Aryl halides: naming compounds and general properties. SNAr reactions and reactions mediated by transition metal complexes. SEAr reactions. Synthetic methods.
Nitroarenes: general porperties. SEAr reactions. Synthetic methods.
Aromatic amines: naming compounds and general properties. SEAr reactions. Reactivity vs electrophiles and oxidation reactions. Synthetic methods.
Diazonium salts: general properties and reactivity.
Phenols: naming compounds and general properties. Acidity. Reactivity vs electrophiles. Rearrangements and SEAr reactions. Oxidation reactions. Synthetic methods.
Quinones: naming compounds and general properties. Redox equilibrium. Reactivity vs dienes and nucleophiles. Synthetic methods.
Polycyclic hydrocarbons: reactivity and synthesis.
Heteroaromatic compounds (6 hours)
Heteroaromatic systems: five-membered heterocyclic rings. Azines. Halogenopyridines and pyridines N-oxides. Benzofused heterocycles. Azoles and diazines.
Amines and their derivatives (12 hours)
Naming the amines. Structural and physical properties. Basicity and acidity. Stereochemical aspects. Quaternary ammonium salts and N-oxide derivatives. Phase transfer catalysis (PTC). Alkylation reactions, reductive amination, acylation and sulfonation reactions. Imine and enamine formation, Mannich reaction. Diazotatization reaction. Synthesis of aliphatic amines.
Amides: naming of amides, properties, acidity. Reactivity toward acids, bases and reducing agents. Beckmann rearrangement.
Aminoacids, peptides and proteins: naming aminoacids and peptides. Stereochemistry of -aminoacids. Acid-base properties of aminoacids and peptides. Synthesis and resolution of -aminoacids. Synthesis of peptides: protecting groups, amidation reaction. Hydrolysis of peptides and proteins. Primary and secondary structure of proteins.
Aromaticity (6 hours)
Inductive, mesomeric, steric, and hyperconjugative effects. Hückel’s rule. Aromatic, antiaromatic and nonaromatic compounds. Hammond postulate. Kinetic and thermodynamic control. SEAr mechanism. Isomeric benzene compounds. Activation or deactivation by substituents (vs SEAr). Regioselectivity depending on the substituents.
Reactivity of aromatic compounds (10 hours)
SEAr reactions. C(arom)-N, C(arom)-S, C(arom)-alogeno, C(arom)-C bond formation. SEAr promoted by organometallated arenes (introduction).
Aromatic compounds (38 hours)
Alkylbenzenes and alkenylbenzenes: naming compounds, properties and reactivity of aromatic systems. Benzylic halogenation (Wohl Ziegler), benzylic hydroperoxydation, oxidation of the side-chain, Birch reduction.
Alcohols and benzylic halides: naming compounds, properties and reactivity. Synthetic methods.
Aromatic aldheydes and ketons: naming compounds, properties and reactivity. Reactivity vs oxygen, sulphur, nitrogen and carbon nucleophiles. SEAr reactions. Reduction and oxidation. Synthetic methods.
Aromatic carboxylic acids: naming compounds and general properties. Acidity of carboxylic acids. Acyl SN and SEAr reactions. Esterification and reduction. Synthetic methods.
Aromatic acyl chlorides: naming compounds and general properties. Reactivity vs nucleophiles.
Aromatic esters and anhydrides: naming compounds and general properties. Hydrolysis in acidic and basic medium. Reduction reactions by hydrides. Transesterifications. Reactivity vs nucleophiles. SEAr reactions. Synthetic methods.
Aromatic amides: naming compounds and general properties. Acidity. Acidic and basic hydrolysis. Reduction reactions. Reactivity vs nucleophiles. SEAr reactions. Synthetic methods.
Aromatic nitriles: naming compounds and general properties. Acidic and basic hydrolysis. Reduction reactions. Reactivity vs nucleophiles. SEAr reactions. Synthetic methods.
Aryl halides: naming compounds and general properties. SNAr reactions and reactions mediated by transition metal complexes. SEAr reactions. Synthetic methods.
Nitroarenes: general porperties. SEAr reactions. Synthetic methods.
Aromatic amines: naming compounds and general properties. SEAr reactions. Reactivity vs electrophiles and oxidation reactions. Synthetic methods.
Diazonium salts: general properties and reactivity.
Phenols: naming compounds and general properties. Acidity. Reactivity vs electrophiles. Rearrangements and SEAr reactions. Oxidation reactions. Synthetic methods.
Quinones: naming compounds and general properties. Redox equilibrium. Reactivity vs dienes and nucleophiles. Synthetic methods.
Polycyclic hydrocarbons: reactivity and synthesis.
Heteroaromatic compounds (6 hours)
Heteroaromatic systems: five-membered heterocyclic rings. Azines. Halogenopyridines and pyridines N-oxides. Benzofused heterocycles. Azoles and diazines.
• P. C. Vollhardt, N. E. Schore Chimica organica, Zanichelli Editore 2016
• J. Clayden, N. Greeves, S. Warren Organic Chemistry , 2nd Edition, Oxford University Press 2012 (ISBN 978-0-19-927029-3)
• J. Clayden, S. Warren Solution Manual to Accompany Organic Chemistry , 2ndEdition, Oxford University Press 2013 (ISBN 978-0-19-966334-7)
The teaching activities are supplied by classroom lecturing. PPT slides will be used in classroom as support for the lessons. Exercises (which corrections will be made in the next lesson) are assigned at the end of each chapter.
Professor is available to meet the students any day by previous appointment