Organic Chemistry
A.Y. 2022/2023
Learning objectives
The aim of the course is to provide the basis for interpreting and predicting the structure, physical properties and chemical behavior of organic molecules. The course aims to present both synthetic and mechanistic aspects in order to lead students to an essential understanding of the principles and fundamental reactions of organic chemistry. The acquisition of the fundamental knowledge will be favored by classroom exercises.
The concepts learned in the course of Organic Chemistry represent the "basic code" to be able to deal with the appropriate cultural background courses of the following years, such as Biochemistry, Medicinal Chemistry, etc.
The concepts learned in the course of Organic Chemistry represent the "basic code" to be able to deal with the appropriate cultural background courses of the following years, such as Biochemistry, Medicinal Chemistry, etc.
Expected learning outcomes
At the end of the course the student will have acquired the following skills:
- know how to classify a molecule based on its functional groups, to attribute the IUPAC name to the molecule, be able to predict its Lewis structure, its geometry in the space, and know how to describe its stereochemical aspects;
- know how to predict the chemical-physical features of a compound based on its molecular structure;
- Know how to predict its reactivity based on its chemical properties (e.g. acidity or basicity, nucleophilicity or electrophilicity, etc.) and to describe the possible methodologies for its synthesis;
- know how to apply the acquired knowledge on the chemical behavior of organic molecules to the solution of problems both in a strictly chemical environment and in the broader context of life sciences (with particular reference to those concerning Medicinal Chemistry, Biochemistry and Pharmacology).
- know how to classify a molecule based on its functional groups, to attribute the IUPAC name to the molecule, be able to predict its Lewis structure, its geometry in the space, and know how to describe its stereochemical aspects;
- know how to predict the chemical-physical features of a compound based on its molecular structure;
- Know how to predict its reactivity based on its chemical properties (e.g. acidity or basicity, nucleophilicity or electrophilicity, etc.) and to describe the possible methodologies for its synthesis;
- know how to apply the acquired knowledge on the chemical behavior of organic molecules to the solution of problems both in a strictly chemical environment and in the broader context of life sciences (with particular reference to those concerning Medicinal Chemistry, Biochemistry and Pharmacology).
Lesson period: Activity scheduled over several sessions (see Course syllabus and organization section for more detailed information).
Assessment methods: Esame
Assessment result: voto verbalizzato in trentesimi
Single course
This course cannot be attended as a single course. Please check our list of single courses to find the ones available for enrolment.
Course syllabus and organization
Linea AL
Responsible
Lesson period
year
Course syllabus
- General part. The chemical bond. Ionic bond, pure covalent and polar covalent. Atomic, molecular and hybrid orbitals. Single double and triple bond. Methane, ethane, ethylene, acetylene, ammonia and water. The concept of resonance. Arrows in organic chemistry. How molecules are represented. Brute formulas, extended and shortened structural formulas. Structural isomers. Classification of organic compounds based on structure and functional groups. Intermolecular forces. Dipole-dipole interactions, van der Waals forces, hydrogen bond. Solubility. Organic solvents. Hydrophilicity and lipophilicity. Types of reactions. How organic reactions happen. Thermodynamic and kinetic aspects. Energy diagrams.
- Acids and bases. Acids and bases according to Arrhenius. Acids and bases according to Brønsted-Lowry. Acid dissociation constants, pKa and strength of acids and bases. Equilibrium positions in acid-base reactions. Molecular structure and acidity. Acids and bases according to Lewis. Factors affecting the acidity in organic molecules.
- Alkanes and cycloalkanes. Linear and branched alkanes, cycloalkanes. Nomenclature. Conformational analysis in alkanes: ethane and butane. Newman projections. Conformational analysis in cycloalkanes: cyclopropane, cyclobutane, cyclopentane, cyclohexane. Mono and disubstituted cyclohexanes. Cis-trans isomerism in cycloalkanes. Condensed cycloalkanes. Physical properties of alkanes. Radical reactions. What is a radical. Reactivity of alkanes: halogenation and oxidation. Methods of obtaining alkanes. Reduction of alkenes and alkynes and carbonyl compounds.
- Stereochemistry. Introduction to chirality. Asymmetrical objects and atoms. Chiral and achiral molecules. Enantiomers. Polarimetry. Specific rotary optical power. Enantiomeric excess and optical purity. Absolute configuration assignment. C.I.P. Convention (Cahn-Ingold-Prelog), system R, S. Prioritization rules. Fischer projections. Molecules with multiple stereocenters: diastereomers. Meso forms. Chirality in substituted cycloalkanes. Racemes (definition and resolution). Prochirality of sp2 and sp3 carbons. Chirality in atoms other than carbon. Dissymmetrical but not asymmetrical molecules: C2 symmetry in cluttered allen, spirani and biphenyls. Atropoisomerism. Importance of chirality in the biological world and in molecules with pharmacological activity.
- Alkenes. Nomenclature of structure and physical properties. Cis-trans isomerism in alkenes. The E / Z system. Reactivity. Carbocations. Nucleophilia and electrophilia. Electrophilic addition to alkenes: general information. Markovnikov rule. Addition of halogenhydric acids. Carbocation rearrangement. Stereochemical aspects. Addition of halogens: the halonium ion. Addition of acid catalyzed water, hydroboration / oxidation. Regio and stereochemical consequences. Double bond catalytic reduction reactions. Oxidation reactions: hydroxylations and oxidative demolitions. Stereochemical aspects. Preparation by elimination reaction from alcohols, alkyl halides and quaternary ammonium salts. Zaitsev and Hofmann rules. Preparation for partial reduction of alkynes.
- Alkynes. Nomenclature and physical properties. Acidity. Reactivity. Alkylation of acetylides. Electrophilic additions: addition of halogens, halogen acids, water and comparison of reactivity with alkenes. Reductions.
- Benzene and derivatives. Nomenclature of structure and physical properties. Reactivity. Electronic structure of benzene. Resonance of benzene and other important systems. Representations of benzene. Hückel's rule. Electrophilic aromatic substitution on benzene and monosubstituted derivatives. Nitration. Sulfonation. Halogenation. Friedel-Crafts alkylation and acylation. Activating and deactivating substituents. Inductive effect and mesomer. Orienting effects. SEAr on disubstituted benzenes: agonist and antagonist effects. Reduction of the aromatic ring. Oxidation in the benzyl position.
- Aliphatic halogen compounds. Nomenclature of structure and physical properties. Reactivity. Nucleophilic substitution reactions. SN1 and SN2 mechanisms, factors that influence their course and stereochemical aspects. E1 and E2 mechanisms, factors that influence their course and stereochemical aspects. Pseudohalides as alternative leaving groups. SN / E competition. Preparation of halogen compounds from alcohols. Aromatic nucleophilic substitution.
- Alcohols. Nomenclature, structure and physical properties. Classification. Acidity and basicity. Reactivity. Oxidation. Dehydration. Synthesis. Preparation by hydration of alkenes and by reduction of carbonyl compounds. Phenols. Nomenclature of structure and physical properties. Partial deactivation. Acidity of phenols. Synthesis of phenolic ethers.
- Ethers. Nomenclature of structure and physical properties. Synthesis. From alcohols for dehydration. Williamson's reaction. Addition of alcohols to alkenes. Split with HX. Epoxides. Nomenclature of structure and physical properties. Reactivity to nucleophiles in acidic and basic environments. Stereochemical implications. Synthesis. By dehydrohalogenation of halohydrines and by oxidation of alkenes.
- Sulfur compounds. Thiols and sulphides. Nomenclature of structure and physical properties. Acidity. Oxidation reactions. Preparation. Notes on the chemistry of thioethers, disulfides, sulfoxides, sulfones and sulphonic acids.
- Amines. Nomenclature of structure and physical properties. Basicity and acidity. Reactivity. Alkylation and acylation. Quaternary ammonium salts. Hofmann Elimination. Diazotation and reactions of diazonium ions of aliphatic amines. Synthesis. Synthesis of Gabriel. Reducing amination reactions. Hofmann rearrangement. Reduction of nitro compounds, nitriles, amides, azides. Aniline, basicity. Arendiazonium salts: synthesis and use. Preparation of phenol from diazonium salts.
- Organometallic compounds. Carbon-metal bond. Reactivity as a function of the nature of metals. Grignard and organo-lithium reagents. Basicity and nucleophilicity. Preparation of organometallic compounds. Reactions with aldehydes, ketones, esters, epoxides, carbon dioxide.
- Aldehydes and ketones. Nomenclature of structure and physical properties. Reactivity. Nucleophilic additions to the carbonyl: water, alcohols, ammonia and derivatives, thiols, cyanides. Reduction with hydrides. Wittig reaction. Oxidation. Alkane deoxygenation (Clemmensen, Wolff-Kishner). Synthesis. From compounds of Grignard and nitriles, by partial reduction of carboxylic acids (and derivatives) with hydrides and By oxidation of alcohols. Aldehydes and ketones of considerable importance: formaldehyde, acetaldehyde, acetone.
- Carboxylic acids. Nomenclature of structure and physical properties. Acidity. Effect of substituents on acidity. Salt formation. Reactivity. Reduction to alcohols. Methods of preparation of carboxylic acids: oxidative, carbonation of organometallic reagents, hydrolysis of derivatives. Reactions to hydroxyl H: carboxylate as nucleophile, formation of methyl esters with diazomethane. Reactions to hydroxyl OH: nucleophilic acyl substitution. Formation of halides, anhydrides, esters and amides. Fischer esterification. Decarboxylation of beta ketoacids. Esters of nitric and phosphoric acid.
- Derivatives of carboxylic acids (acyl halides, anhydrides, esters, amides and nitriles). Nomenclature of structure and physical properties. Reactivity. Nucleophilic acyl substitution: mechanism and applications. Hydrolysis. Transformations between carboxylic acid derivatives, allowed and not. Reduction. Lactones, lactams, imides and cyclic anhydrides: preparation and reactivity. Acidity of amides, sulfonamides and imides.
- Lipids. Fatty acids, triglycerides, oils and fats.
- Chemistry of enols and enolate ions. Formation of enols and enolates. Reactions via enol and via enolate. The role of the base. Halogenation of aldehydes and ketones via enol and enolate. Halogenation of Hell-Volhard-Zelinsky acids. Direct alkylation of enolates. Stork reaction. Malonic synthesis. Acetacetic synthesis. Condensation reactions: Aldol condensation and crotonization. Intramolecular and mixed aldolics. Knovenagel reaction. Condensation of Claisen and Dieckmann. Mixed Claisen. Mannich reaction.
- α, β-unsaturated carbonyl and nitrile compounds. Nomenclature of structure and physical properties. Conjugate addition reactions with nucleophiles. Addition of Michael and applications of him. Reactions with organometallic compounds. Robinson ringing. Reduction. Preparation with aldol type reactions.
- Carbohydrates. Nomenclature of structure and physical properties. Classification and properties. Fischer projections. Monosaccharide structures: stereochemistry and configuration, cyclic structures. Mutarotation. Reactions of monosaccharides: formation of glycosides. Reactions of monosaccharides: formation of ethers, esters and acetals. Selective hydrolysis. Oxidation and reduction reactions. Disaccharides: sucrose, maltose, lactose. Polysaccharides: starch, glycogen and cellulose. Nitrogen glycosides: necleosides and nucleotides of purine and pyrimidine bases.
- Amino acids, peptides, proteins. Natural amino acids. Biological role, stereochemistry and classification. Acid-base properties, titration, isoelectric point. Electrophoresis. Reactivity of the amino and carboxy group. Reactions of esterification and acylation. Oxidation of cysteine. Synthesis of amino acids: from alpha-halogen acids, malonic synthesis and Strecker synthesis. Resolution. Peptide synthesis. Nitrogen and carbon protective groups. Formation of the peptide bond with dicyclohexylcarbodiimide (DCC). Liquid and solid phase peptide synthesis (Merrifield). Secondary structure of proteins: alpha-helix, beta-sheet, beta-turn. Tertiary structure: fibrous and globular proteins. Quaternary structure: protein subunits.
- Aromatic heterocyclic compounds. Nomenclature of structure and physical properties. Acidity and basicity. Reactivity of furan, pyrrole, thiophene, indole and benzofuran. Electrophilic substitutions. Reactivity of pyridine and quinoline. Electrophilic and nucleophilic substitutions. Chichibabin reaction.
- Pericyclic reactions: Diels-Alder cycloaddition and 1,3-dipolar cycloaddition
- Acids and bases. Acids and bases according to Arrhenius. Acids and bases according to Brønsted-Lowry. Acid dissociation constants, pKa and strength of acids and bases. Equilibrium positions in acid-base reactions. Molecular structure and acidity. Acids and bases according to Lewis. Factors affecting the acidity in organic molecules.
- Alkanes and cycloalkanes. Linear and branched alkanes, cycloalkanes. Nomenclature. Conformational analysis in alkanes: ethane and butane. Newman projections. Conformational analysis in cycloalkanes: cyclopropane, cyclobutane, cyclopentane, cyclohexane. Mono and disubstituted cyclohexanes. Cis-trans isomerism in cycloalkanes. Condensed cycloalkanes. Physical properties of alkanes. Radical reactions. What is a radical. Reactivity of alkanes: halogenation and oxidation. Methods of obtaining alkanes. Reduction of alkenes and alkynes and carbonyl compounds.
- Stereochemistry. Introduction to chirality. Asymmetrical objects and atoms. Chiral and achiral molecules. Enantiomers. Polarimetry. Specific rotary optical power. Enantiomeric excess and optical purity. Absolute configuration assignment. C.I.P. Convention (Cahn-Ingold-Prelog), system R, S. Prioritization rules. Fischer projections. Molecules with multiple stereocenters: diastereomers. Meso forms. Chirality in substituted cycloalkanes. Racemes (definition and resolution). Prochirality of sp2 and sp3 carbons. Chirality in atoms other than carbon. Dissymmetrical but not asymmetrical molecules: C2 symmetry in cluttered allen, spirani and biphenyls. Atropoisomerism. Importance of chirality in the biological world and in molecules with pharmacological activity.
- Alkenes. Nomenclature of structure and physical properties. Cis-trans isomerism in alkenes. The E / Z system. Reactivity. Carbocations. Nucleophilia and electrophilia. Electrophilic addition to alkenes: general information. Markovnikov rule. Addition of halogenhydric acids. Carbocation rearrangement. Stereochemical aspects. Addition of halogens: the halonium ion. Addition of acid catalyzed water, hydroboration / oxidation. Regio and stereochemical consequences. Double bond catalytic reduction reactions. Oxidation reactions: hydroxylations and oxidative demolitions. Stereochemical aspects. Preparation by elimination reaction from alcohols, alkyl halides and quaternary ammonium salts. Zaitsev and Hofmann rules. Preparation for partial reduction of alkynes.
- Alkynes. Nomenclature and physical properties. Acidity. Reactivity. Alkylation of acetylides. Electrophilic additions: addition of halogens, halogen acids, water and comparison of reactivity with alkenes. Reductions.
- Benzene and derivatives. Nomenclature of structure and physical properties. Reactivity. Electronic structure of benzene. Resonance of benzene and other important systems. Representations of benzene. Hückel's rule. Electrophilic aromatic substitution on benzene and monosubstituted derivatives. Nitration. Sulfonation. Halogenation. Friedel-Crafts alkylation and acylation. Activating and deactivating substituents. Inductive effect and mesomer. Orienting effects. SEAr on disubstituted benzenes: agonist and antagonist effects. Reduction of the aromatic ring. Oxidation in the benzyl position.
- Aliphatic halogen compounds. Nomenclature of structure and physical properties. Reactivity. Nucleophilic substitution reactions. SN1 and SN2 mechanisms, factors that influence their course and stereochemical aspects. E1 and E2 mechanisms, factors that influence their course and stereochemical aspects. Pseudohalides as alternative leaving groups. SN / E competition. Preparation of halogen compounds from alcohols. Aromatic nucleophilic substitution.
- Alcohols. Nomenclature, structure and physical properties. Classification. Acidity and basicity. Reactivity. Oxidation. Dehydration. Synthesis. Preparation by hydration of alkenes and by reduction of carbonyl compounds. Phenols. Nomenclature of structure and physical properties. Partial deactivation. Acidity of phenols. Synthesis of phenolic ethers.
- Ethers. Nomenclature of structure and physical properties. Synthesis. From alcohols for dehydration. Williamson's reaction. Addition of alcohols to alkenes. Split with HX. Epoxides. Nomenclature of structure and physical properties. Reactivity to nucleophiles in acidic and basic environments. Stereochemical implications. Synthesis. By dehydrohalogenation of halohydrines and by oxidation of alkenes.
- Sulfur compounds. Thiols and sulphides. Nomenclature of structure and physical properties. Acidity. Oxidation reactions. Preparation. Notes on the chemistry of thioethers, disulfides, sulfoxides, sulfones and sulphonic acids.
- Amines. Nomenclature of structure and physical properties. Basicity and acidity. Reactivity. Alkylation and acylation. Quaternary ammonium salts. Hofmann Elimination. Diazotation and reactions of diazonium ions of aliphatic amines. Synthesis. Synthesis of Gabriel. Reducing amination reactions. Hofmann rearrangement. Reduction of nitro compounds, nitriles, amides, azides. Aniline, basicity. Arendiazonium salts: synthesis and use. Preparation of phenol from diazonium salts.
- Organometallic compounds. Carbon-metal bond. Reactivity as a function of the nature of metals. Grignard and organo-lithium reagents. Basicity and nucleophilicity. Preparation of organometallic compounds. Reactions with aldehydes, ketones, esters, epoxides, carbon dioxide.
- Aldehydes and ketones. Nomenclature of structure and physical properties. Reactivity. Nucleophilic additions to the carbonyl: water, alcohols, ammonia and derivatives, thiols, cyanides. Reduction with hydrides. Wittig reaction. Oxidation. Alkane deoxygenation (Clemmensen, Wolff-Kishner). Synthesis. From compounds of Grignard and nitriles, by partial reduction of carboxylic acids (and derivatives) with hydrides and By oxidation of alcohols. Aldehydes and ketones of considerable importance: formaldehyde, acetaldehyde, acetone.
- Carboxylic acids. Nomenclature of structure and physical properties. Acidity. Effect of substituents on acidity. Salt formation. Reactivity. Reduction to alcohols. Methods of preparation of carboxylic acids: oxidative, carbonation of organometallic reagents, hydrolysis of derivatives. Reactions to hydroxyl H: carboxylate as nucleophile, formation of methyl esters with diazomethane. Reactions to hydroxyl OH: nucleophilic acyl substitution. Formation of halides, anhydrides, esters and amides. Fischer esterification. Decarboxylation of beta ketoacids. Esters of nitric and phosphoric acid.
- Derivatives of carboxylic acids (acyl halides, anhydrides, esters, amides and nitriles). Nomenclature of structure and physical properties. Reactivity. Nucleophilic acyl substitution: mechanism and applications. Hydrolysis. Transformations between carboxylic acid derivatives, allowed and not. Reduction. Lactones, lactams, imides and cyclic anhydrides: preparation and reactivity. Acidity of amides, sulfonamides and imides.
- Lipids. Fatty acids, triglycerides, oils and fats.
- Chemistry of enols and enolate ions. Formation of enols and enolates. Reactions via enol and via enolate. The role of the base. Halogenation of aldehydes and ketones via enol and enolate. Halogenation of Hell-Volhard-Zelinsky acids. Direct alkylation of enolates. Stork reaction. Malonic synthesis. Acetacetic synthesis. Condensation reactions: Aldol condensation and crotonization. Intramolecular and mixed aldolics. Knovenagel reaction. Condensation of Claisen and Dieckmann. Mixed Claisen. Mannich reaction.
- α, β-unsaturated carbonyl and nitrile compounds. Nomenclature of structure and physical properties. Conjugate addition reactions with nucleophiles. Addition of Michael and applications of him. Reactions with organometallic compounds. Robinson ringing. Reduction. Preparation with aldol type reactions.
- Carbohydrates. Nomenclature of structure and physical properties. Classification and properties. Fischer projections. Monosaccharide structures: stereochemistry and configuration, cyclic structures. Mutarotation. Reactions of monosaccharides: formation of glycosides. Reactions of monosaccharides: formation of ethers, esters and acetals. Selective hydrolysis. Oxidation and reduction reactions. Disaccharides: sucrose, maltose, lactose. Polysaccharides: starch, glycogen and cellulose. Nitrogen glycosides: necleosides and nucleotides of purine and pyrimidine bases.
- Amino acids, peptides, proteins. Natural amino acids. Biological role, stereochemistry and classification. Acid-base properties, titration, isoelectric point. Electrophoresis. Reactivity of the amino and carboxy group. Reactions of esterification and acylation. Oxidation of cysteine. Synthesis of amino acids: from alpha-halogen acids, malonic synthesis and Strecker synthesis. Resolution. Peptide synthesis. Nitrogen and carbon protective groups. Formation of the peptide bond with dicyclohexylcarbodiimide (DCC). Liquid and solid phase peptide synthesis (Merrifield). Secondary structure of proteins: alpha-helix, beta-sheet, beta-turn. Tertiary structure: fibrous and globular proteins. Quaternary structure: protein subunits.
- Aromatic heterocyclic compounds. Nomenclature of structure and physical properties. Acidity and basicity. Reactivity of furan, pyrrole, thiophene, indole and benzofuran. Electrophilic substitutions. Reactivity of pyridine and quinoline. Electrophilic and nucleophilic substitutions. Chichibabin reaction.
- Pericyclic reactions: Diels-Alder cycloaddition and 1,3-dipolar cycloaddition
Prerequisites for admission
- Basic concepts of general chemistry and stoichiometry: atom, atomic number and mass number, atomic and molecular weight, mole and molar weight, structure of the atom, shells and atomic orbitals, rules for filling orbitals (Aufbau, Pauli, Hund), valence, electronic configuration, Lewis structures, octet rule, VSEPR theory, atomic and molecular orbitals, acids and bases (Arrhenius Broensted-Lowry and Lewis).
- Basic concepts of physical chemistry: chemical equilibrium, Keq, thermodynamics and kinetics of chemical reactions, free energy, enthalpy, entropy.
- Basic concepts of physical chemistry: chemical equilibrium, Keq, thermodynamics and kinetics of chemical reactions, free energy, enthalpy, entropy.
Teaching methods
- lectures in the classroom
- exercises in the classroom
- verification test, online through the Exam Manager app, or by carrying out at home exercises provided by the teacher and subsequently corrected in the classroom, for monitoring the level of learning.
- exercises in the classroom
- verification test, online through the Exam Manager app, or by carrying out at home exercises provided by the teacher and subsequently corrected in the classroom, for monitoring the level of learning.
Teaching Resources
Textbooks:
- Brown - Foote - Iverson, Organic Chemistry, EDISES
- Vollhardt - Schore, Organic Chemistry, ZANICHELLI
- Bruice, Organic Chemistry, EDISES
- Any full text of Organic Chemistry (no "introduction", "elements", "fundamentals" ...)
Workbooks:
- Iverson - Iverson, Guide to solving problems from organic chemistry by Brown, Iverson, Anslyn, Foote, EDISES
- D'Auria - Taglialatela Scafati - Zampella, Reasoned guide to carrying out organic chemistry exercises, LOGHIA
- Nicotra - Cipolla, Exercise Book of Organic Chemistry, EDISES
Digital material:
- Ariel website and/or Team with: slides of the lectures, exercises, examination texts, videos, websites of interest, forum, self-evaluation test.
- App Exam Manager from EDISES
- Brown - Foote - Iverson, Organic Chemistry, EDISES
- Vollhardt - Schore, Organic Chemistry, ZANICHELLI
- Bruice, Organic Chemistry, EDISES
- Any full text of Organic Chemistry (no "introduction", "elements", "fundamentals" ...)
Workbooks:
- Iverson - Iverson, Guide to solving problems from organic chemistry by Brown, Iverson, Anslyn, Foote, EDISES
- D'Auria - Taglialatela Scafati - Zampella, Reasoned guide to carrying out organic chemistry exercises, LOGHIA
- Nicotra - Cipolla, Exercise Book of Organic Chemistry, EDISES
Digital material:
- Ariel website and/or Team with: slides of the lectures, exercises, examination texts, videos, websites of interest, forum, self-evaluation test.
- App Exam Manager from EDISES
Assessment methods and Criteria
Written + oral examination, grades in thirtieth.
The written test will be divided into two parts. The first will include multiple choice exercises (20 questions of 0.75 points each; no answer: 0; wrong answer: -0.25) on the program carried out during the first smester (indicatively, acid-base reactions, resonance, stereochemistry, non-aromatic hydrocarbons, electrophilic addition, nucleophilic substitutions, reactivity / properties of aromatic rings, alcohols, thiols, ethers, epoxides and amines). The second part will consist of five open-ended exercises, possibly divided in subsections, and will focus on the program carried out in the second semester (indicatively, preparation and reactivity of carbonyl compounds; carbonyl condensation reaction; reactions / stereochemistry of carbohydrates; synthesis / properties of amino acids and peptides; reactivity of heterocycles). Each exercise will be worth 3 points. The student will have at least one hour to complete each part and at least two hours for the entire written test. Passing the exam requires the achievement of a score of at least 8/15 in each of the two parts and the overall grade of 18/30.
Oral exam: admission to the oral exam is subject to passing the written exam with a score of at least 18/30. The interview focuses mainly on concepts and principles of organic chemistry. The oral exam is normally held within 15 days from the written exam.
The written test will be divided into two parts. The first will include multiple choice exercises (20 questions of 0.75 points each; no answer: 0; wrong answer: -0.25) on the program carried out during the first smester (indicatively, acid-base reactions, resonance, stereochemistry, non-aromatic hydrocarbons, electrophilic addition, nucleophilic substitutions, reactivity / properties of aromatic rings, alcohols, thiols, ethers, epoxides and amines). The second part will consist of five open-ended exercises, possibly divided in subsections, and will focus on the program carried out in the second semester (indicatively, preparation and reactivity of carbonyl compounds; carbonyl condensation reaction; reactions / stereochemistry of carbohydrates; synthesis / properties of amino acids and peptides; reactivity of heterocycles). Each exercise will be worth 3 points. The student will have at least one hour to complete each part and at least two hours for the entire written test. Passing the exam requires the achievement of a score of at least 8/15 in each of the two parts and the overall grade of 18/30.
Oral exam: admission to the oral exam is subject to passing the written exam with a score of at least 18/30. The interview focuses mainly on concepts and principles of organic chemistry. The oral exam is normally held within 15 days from the written exam.
CHIM/06 - ORGANIC CHEMISTRY - University credits: 10
Practicals: 16 hours
Lessons: 72 hours
Lessons: 72 hours
Professor:
Contini Alessandro
Linea MZ
Responsible
Lesson period
year
Course syllabus
General part. The chemical bond. Ionic bond, pure covalent and polar covalent. Atomic, molecular and hybrid orbitals. Single double and triple bond. Methane, ethane, ethylene, acetylene, ammonia and water. The concept of resonance. Arrows in organic chemistry. How molecules are represented. Brute formulas, extended and shortened structural formulas. Structural isomers. Classification of organic compounds based on structure and functional groups. Intermolecular forces. Dipole-dipole interactions, Van der Waals forces, hydrogen bond. Solubility. Organic solvents. Hydrophilicity and lipophilicity. Types of reactions. How organic reactions happen. Thermodynamic and kinetic aspects. Energy diagrams.
Acids and bases. Acids and bases according to Arrhenius. Acids and bases according to Brønsted-Lowry. Acid dissociation constants, pKa and strength of acids and bases. Equilibrium positions in acid-base reactions. Molecular structure and acidity. Acids and bases according to Lewis. Factors affecting the acidity in organic molecules.
Alkanes and cycloalkanes. Alkanes, branched alkanes and cycloalkanes. Nomenclature. Conformational analysis in alkanes: ethane and butane. Newman's projections Conformational analysis in cycloalkanes: cyclopropane, cyclobutane, cyclopentane, cyclohexane. Mono and disubstituted cyclohexanes. Cis-trans isomerism in cycloalkanes. Condensed cycloalkanes. Physical properties of alkanes. Radical reactions. What is a radical. Reactivity of alkanes: halogenation and oxidation. Methods of obtaining alkanes. Reduction of alkenes and alkynes and carbonyl compounds.
Stereochemistry. Introduction to chirality. Asymmetrical objects and atoms. Chiral and achiral molecules. Enantiomers. Polarimetry. Specific rotary optical power. Enantiomeric excess and optical purity. Absolute configuration assignment. C.I.P. Convention (Cahn-Ingold-Prelog), system R, S. Priority assignment rules. Fischer projections. Molecules with multiple stereocenters: diastereoisomers. Meso forms. Chirality in substituted cycloalkanes. Racemes and resolution. Resolving reagents. Prochirality of sp2 and sp3 carbons. Chirality in atoms other than carbon. Dissymmetrical but not asymmetrical molecules: C2 symmetry in cluttered allenes, spirans and biphenyls. Atropoisomerism. Importance of chirality in the biological world and in molecules with pharmacological activity.
Alkenes. Nomenclature structure and physical properties. Cis-trans isomerism in alkenes. The E/Z system. Reactivity. Carbocations. Nucleophilia and electrophilia. Electrophilic addition to alkenes: general information. Markovnikov rule. Addition of halogenhydric acids. Carbocation rearrangement. Stereochemical aspects. Addition of halogens: the halonium ion. Addition of halogens and hypohalogen acids. Addition of acid catalyzed water, reduction and hydroboration / oxidation. Regio and stereochemical consequences. Double bond catalytic reduction reactions. Heat of hydrogenation and stability of alkenes. Oxidation reactions: hydroxylations and oxidative demolitions. Stereochemical aspects. Preparation by elimination reaction from alcohols, alkyl halides and quaternary ammonium salts. Zaitsev and Hofmann rules. Preparation for partial reduction of alkynes.
Alkynes. Nomenclature and physical properties. Acidity. Reactivity. Alkylation of acetylides. Electrophilic additions: addition of halogens, halogen acids, water and comparison of reactivity with alkenes. Reductions.
Conjugated systems. Nomenclature and physical properties. Reactivity. Heat of hydrogenation. Addition reactions 1,2 and 1,4. Addition of halogen and halogen acids. The Diels-Alder cycloaddition and azide-ene cycloaddition. Mechanism.
Benzene and derivatives. Nomenclature structure and physical properties. Reactivity. Heat of hydrogenation. Electronic structure of benzene. Resonance of benzene and other important systems. Representations of benzene. Hückel's rule. Electrophilic aromatic substitution on benzene and monosubstituted derivatives. Nitration. Sulphonation. Halogenation. Friedel-Crafts alkylation and acylation. Activating and deactivating substituents. Inductive effect and mesomer. Orienting effects. SEAr on disubstituted benzenes: agonist and antagonist effects. Reduction of the aromatic ring. Oxidation in the benzyl position.
Aliphatic halogen compounds. Nomenclature structure and physical properties. Reactivity. Nucleophilic substitution reactions. SN1 and SN2 mechanisms, factors that influence their course and stereochemical aspects. E1 and E2 mechanisms, factors that influence its course and stereochemical aspects. Pseudohalides as alternative leaving groups. SN / E competition. Preparation of halogen compounds from alcohols.
Alcohols. Nomenclature structure and physical properties. Classification. Acidity and basicity. Reactivity. Oxidation. Dehydration. Synthesis. Preparation by hydration of alkenes and by reduction of carbonyl compounds. Phenols. Nomenclature structure and physical properties. Partial deactivation. Acidity of phenols. Synthesis of phenolic ethers. Electrophilic aromatic substitution. Synthesis. Alkaline fusion.
Ethers. Nomenclature structure and physical properties. Synthesis. From alcohols for dehydration. Williamson's reaction. Addition of alcohols to alkenes. Split with HX. Epoxides. Nomenclature structure and physical properties. Reactivity to nucleophiles in acidic and basic environments. Stereochemical implications. Synthesis. By dehydrohalogenation of halohydrines and by oxidation of alkenes.
Sulfur compounds. Thiols and sulfides. Nomenclature structure and physical properties. Acidity. Oxidation reactions. Preparation. Notes on the chemistry of thioethers, disulfides, sulfoxides, sulfones and sulphonic acids.
Organometallic compounds. Carbon-metal bond. Reactivity as a function of the nature of metals. Grignard and organo-lithium reagents. Basicity and nucleophilicity. Preparation of organometallic compounds. Reactions with aldehydes, ketones, esters, epoxides, carbon dioxide.
Aldehydes and ketones. Nomenclature structure and physical properties. Reactivity. Nucleophilic additions to the carbonyl: water, alcohols, ammonia and derivatives, thiols, cyanides. Reduction with hydrides. Wittig reaction. Oxidation. Alkane deoxygenation (Clemmensen, Wolff-Kishner). Synthesis. From Grignard reactants and nitriles, by partial reduction of carboxylic acids (and derivatives) with hydrides and by oxidation of alcohols. Aldehydes and ketones of considerable importance: formaldehyde, acetaldehyde, acetone.
Carboxylic acids. Nomenclature structure and physical properties. Acidity. Effect of substituents on acidity. Salt formation. Reactivity. Reduction to alcohols. Methods of preparation of carboxylic acids: oxidative, carbonation of organometallic reagents, hydrolysis of derivatives. Reactions to hydroxyl H: carboxylate as nucleophile, formation of methyl esters with diazomethane. Reactions to hydroxyl OH: nucleophilic acyl substitution. Formation of halides, anhydrides, esters and amides. Fischer esterification. Decarboxylation of beta ketoacids. Esters of nitric and phosphoric acid.
Derivatives of carboxylic acids (acyl halides, anhydrides, esters, amides and nitriles). Nomenclature structure and physical properties. Reactivity. Nucleophilic acyl substitution: mechanism and applications. Hydrolysis. Transformations between carboxylic acid derivatives, allowed and not. Reduction. Lactones, lactams, imides and cyclic anhydrides: preparation and reactivity. Acidity of amides, sulfonamides and imides.
Chemistry of enols and enolate ions. Formation of enols and enolates. Reactions via enol and via enolate. The role of the base. Halogenation of aldehydes and ketones via enol and enolate. Direct alkylation of enolates. Malonic synthesis. Acetacetic synthesis. Condensation reactions: Aldol condensation. Intramolecular and mixed aldolics. Knovenagel reaction. Condensation of Claisen and Dieckmann. Mixed Claisen. Mannich reaction.
α,β-unsaturated carbonyl and nitrile compounds. Nomenclature structure and physical properties. Conjugate addition reactions with nucleophiles. Addition of Michael and applications of him. Reactions with organometallic compounds. Robinson ringing. Reduction. Preparation with aldol type reactions.
Amines. Nomenclature structure and physical properties. Basicity and acidity. Reactivity. Alkylation and acylation. Quaternary ammonium salts. Hofmann Elimination. Diazotation and reactions of diazonium ions of aliphatic amines. Synthesis. Synthesis of Gabriel. Reducing amination reactions. Hofmann rearrangement. Reduction of nitro compounds, nitriles, amides, azides. Aniline, basicity. Salts of arendiazonium: synthesis and use. Preparation of phenol from diazonium salts.
Carbohydrates. Nomenclature structure and physical properties. Classification and properties. Fischer projections. Monosaccharide structures: stereochemistry and configuration, cyclic structures. Mutarotation. Reactions of monosaccharides: formation of glycosides. Reactions of monosaccharides: formation of ethers, esters and acetals. Selective hydrolysis. Oxidation reactions: formation of aldonic acids. Essays by Tollens, Fehling and Benedict. Reducing and non-reducing sugars. Oxidation reactions: formation of aldaric acids and oxidation with periodic acid. Reduction reactions: formation of alditols.
Amino acids, peptides, proteins. Natural amino acids. Biological role, stereochemistry and classification. Acid-base properties, titration, isoelectric point. Electrophoresis. Reactivity of the amino and carboxy group. Reactions of esterification and acylation. Oxidation of cysteine. Reaction with ninhydrin. Synthesis of amino acids: fmalonic synthesis and Strecker synthesis. Resolution.of racemate. enantioselective synthesis: Scholkopf chiral auxiliary and the enantioselective idrogenation. Peptide synthesis. Nitrogen and carbon protective groups. Selective protection and deprotection. Liquid and solid phase peptide synthesis (Merrifield).
Aromatic heterocyclic compounds. Nomenclature structure and physical properties. Acidity and basicity. Reactivity of furan, pyrrole, thiophene, indole and benzofuran. Electrophilic substitutions. Reactivity of pyridine and quinoline. Electrophilic and nucleophilic substitutions. Chichibabin reaction.
Acids and bases. Acids and bases according to Arrhenius. Acids and bases according to Brønsted-Lowry. Acid dissociation constants, pKa and strength of acids and bases. Equilibrium positions in acid-base reactions. Molecular structure and acidity. Acids and bases according to Lewis. Factors affecting the acidity in organic molecules.
Alkanes and cycloalkanes. Alkanes, branched alkanes and cycloalkanes. Nomenclature. Conformational analysis in alkanes: ethane and butane. Newman's projections Conformational analysis in cycloalkanes: cyclopropane, cyclobutane, cyclopentane, cyclohexane. Mono and disubstituted cyclohexanes. Cis-trans isomerism in cycloalkanes. Condensed cycloalkanes. Physical properties of alkanes. Radical reactions. What is a radical. Reactivity of alkanes: halogenation and oxidation. Methods of obtaining alkanes. Reduction of alkenes and alkynes and carbonyl compounds.
Stereochemistry. Introduction to chirality. Asymmetrical objects and atoms. Chiral and achiral molecules. Enantiomers. Polarimetry. Specific rotary optical power. Enantiomeric excess and optical purity. Absolute configuration assignment. C.I.P. Convention (Cahn-Ingold-Prelog), system R, S. Priority assignment rules. Fischer projections. Molecules with multiple stereocenters: diastereoisomers. Meso forms. Chirality in substituted cycloalkanes. Racemes and resolution. Resolving reagents. Prochirality of sp2 and sp3 carbons. Chirality in atoms other than carbon. Dissymmetrical but not asymmetrical molecules: C2 symmetry in cluttered allenes, spirans and biphenyls. Atropoisomerism. Importance of chirality in the biological world and in molecules with pharmacological activity.
Alkenes. Nomenclature structure and physical properties. Cis-trans isomerism in alkenes. The E/Z system. Reactivity. Carbocations. Nucleophilia and electrophilia. Electrophilic addition to alkenes: general information. Markovnikov rule. Addition of halogenhydric acids. Carbocation rearrangement. Stereochemical aspects. Addition of halogens: the halonium ion. Addition of halogens and hypohalogen acids. Addition of acid catalyzed water, reduction and hydroboration / oxidation. Regio and stereochemical consequences. Double bond catalytic reduction reactions. Heat of hydrogenation and stability of alkenes. Oxidation reactions: hydroxylations and oxidative demolitions. Stereochemical aspects. Preparation by elimination reaction from alcohols, alkyl halides and quaternary ammonium salts. Zaitsev and Hofmann rules. Preparation for partial reduction of alkynes.
Alkynes. Nomenclature and physical properties. Acidity. Reactivity. Alkylation of acetylides. Electrophilic additions: addition of halogens, halogen acids, water and comparison of reactivity with alkenes. Reductions.
Conjugated systems. Nomenclature and physical properties. Reactivity. Heat of hydrogenation. Addition reactions 1,2 and 1,4. Addition of halogen and halogen acids. The Diels-Alder cycloaddition and azide-ene cycloaddition. Mechanism.
Benzene and derivatives. Nomenclature structure and physical properties. Reactivity. Heat of hydrogenation. Electronic structure of benzene. Resonance of benzene and other important systems. Representations of benzene. Hückel's rule. Electrophilic aromatic substitution on benzene and monosubstituted derivatives. Nitration. Sulphonation. Halogenation. Friedel-Crafts alkylation and acylation. Activating and deactivating substituents. Inductive effect and mesomer. Orienting effects. SEAr on disubstituted benzenes: agonist and antagonist effects. Reduction of the aromatic ring. Oxidation in the benzyl position.
Aliphatic halogen compounds. Nomenclature structure and physical properties. Reactivity. Nucleophilic substitution reactions. SN1 and SN2 mechanisms, factors that influence their course and stereochemical aspects. E1 and E2 mechanisms, factors that influence its course and stereochemical aspects. Pseudohalides as alternative leaving groups. SN / E competition. Preparation of halogen compounds from alcohols.
Alcohols. Nomenclature structure and physical properties. Classification. Acidity and basicity. Reactivity. Oxidation. Dehydration. Synthesis. Preparation by hydration of alkenes and by reduction of carbonyl compounds. Phenols. Nomenclature structure and physical properties. Partial deactivation. Acidity of phenols. Synthesis of phenolic ethers. Electrophilic aromatic substitution. Synthesis. Alkaline fusion.
Ethers. Nomenclature structure and physical properties. Synthesis. From alcohols for dehydration. Williamson's reaction. Addition of alcohols to alkenes. Split with HX. Epoxides. Nomenclature structure and physical properties. Reactivity to nucleophiles in acidic and basic environments. Stereochemical implications. Synthesis. By dehydrohalogenation of halohydrines and by oxidation of alkenes.
Sulfur compounds. Thiols and sulfides. Nomenclature structure and physical properties. Acidity. Oxidation reactions. Preparation. Notes on the chemistry of thioethers, disulfides, sulfoxides, sulfones and sulphonic acids.
Organometallic compounds. Carbon-metal bond. Reactivity as a function of the nature of metals. Grignard and organo-lithium reagents. Basicity and nucleophilicity. Preparation of organometallic compounds. Reactions with aldehydes, ketones, esters, epoxides, carbon dioxide.
Aldehydes and ketones. Nomenclature structure and physical properties. Reactivity. Nucleophilic additions to the carbonyl: water, alcohols, ammonia and derivatives, thiols, cyanides. Reduction with hydrides. Wittig reaction. Oxidation. Alkane deoxygenation (Clemmensen, Wolff-Kishner). Synthesis. From Grignard reactants and nitriles, by partial reduction of carboxylic acids (and derivatives) with hydrides and by oxidation of alcohols. Aldehydes and ketones of considerable importance: formaldehyde, acetaldehyde, acetone.
Carboxylic acids. Nomenclature structure and physical properties. Acidity. Effect of substituents on acidity. Salt formation. Reactivity. Reduction to alcohols. Methods of preparation of carboxylic acids: oxidative, carbonation of organometallic reagents, hydrolysis of derivatives. Reactions to hydroxyl H: carboxylate as nucleophile, formation of methyl esters with diazomethane. Reactions to hydroxyl OH: nucleophilic acyl substitution. Formation of halides, anhydrides, esters and amides. Fischer esterification. Decarboxylation of beta ketoacids. Esters of nitric and phosphoric acid.
Derivatives of carboxylic acids (acyl halides, anhydrides, esters, amides and nitriles). Nomenclature structure and physical properties. Reactivity. Nucleophilic acyl substitution: mechanism and applications. Hydrolysis. Transformations between carboxylic acid derivatives, allowed and not. Reduction. Lactones, lactams, imides and cyclic anhydrides: preparation and reactivity. Acidity of amides, sulfonamides and imides.
Chemistry of enols and enolate ions. Formation of enols and enolates. Reactions via enol and via enolate. The role of the base. Halogenation of aldehydes and ketones via enol and enolate. Direct alkylation of enolates. Malonic synthesis. Acetacetic synthesis. Condensation reactions: Aldol condensation. Intramolecular and mixed aldolics. Knovenagel reaction. Condensation of Claisen and Dieckmann. Mixed Claisen. Mannich reaction.
α,β-unsaturated carbonyl and nitrile compounds. Nomenclature structure and physical properties. Conjugate addition reactions with nucleophiles. Addition of Michael and applications of him. Reactions with organometallic compounds. Robinson ringing. Reduction. Preparation with aldol type reactions.
Amines. Nomenclature structure and physical properties. Basicity and acidity. Reactivity. Alkylation and acylation. Quaternary ammonium salts. Hofmann Elimination. Diazotation and reactions of diazonium ions of aliphatic amines. Synthesis. Synthesis of Gabriel. Reducing amination reactions. Hofmann rearrangement. Reduction of nitro compounds, nitriles, amides, azides. Aniline, basicity. Salts of arendiazonium: synthesis and use. Preparation of phenol from diazonium salts.
Carbohydrates. Nomenclature structure and physical properties. Classification and properties. Fischer projections. Monosaccharide structures: stereochemistry and configuration, cyclic structures. Mutarotation. Reactions of monosaccharides: formation of glycosides. Reactions of monosaccharides: formation of ethers, esters and acetals. Selective hydrolysis. Oxidation reactions: formation of aldonic acids. Essays by Tollens, Fehling and Benedict. Reducing and non-reducing sugars. Oxidation reactions: formation of aldaric acids and oxidation with periodic acid. Reduction reactions: formation of alditols.
Amino acids, peptides, proteins. Natural amino acids. Biological role, stereochemistry and classification. Acid-base properties, titration, isoelectric point. Electrophoresis. Reactivity of the amino and carboxy group. Reactions of esterification and acylation. Oxidation of cysteine. Reaction with ninhydrin. Synthesis of amino acids: fmalonic synthesis and Strecker synthesis. Resolution.of racemate. enantioselective synthesis: Scholkopf chiral auxiliary and the enantioselective idrogenation. Peptide synthesis. Nitrogen and carbon protective groups. Selective protection and deprotection. Liquid and solid phase peptide synthesis (Merrifield).
Aromatic heterocyclic compounds. Nomenclature structure and physical properties. Acidity and basicity. Reactivity of furan, pyrrole, thiophene, indole and benzofuran. Electrophilic substitutions. Reactivity of pyridine and quinoline. Electrophilic and nucleophilic substitutions. Chichibabin reaction.
Prerequisites for admission
- Basic concepts of general chemistry and stoichiometry: atom, atomic number and mass number, atomic and molecular weight, mole and molar weight, structure of the atom, shells and atomic orbitals, rules for filling orbitals (Aufbau, Pauli, Hund), valence, electronic configuration, Lewis structures, octet rule, VSEPR theory, atomic and molecular orbitals, acids and bases (Arrhenius Broensted-Lowry and Lewis).
- Basic concepts of physical chemistry: chemical equilibrium, Keq, thermodynamics and kinetics of chemical reactions, free energy, enthalpy, entropy.
- Basic concepts of physical chemistry: chemical equilibrium, Keq, thermodynamics and kinetics of chemical reactions, free energy, enthalpy, entropy.
Teaching methods
- lectures in the classroom
- exercises
- exercises
Teaching Resources
Textbooks:
- Brown - Foote - Iverson, Organic Chemistry, EDISES
- Bruice, Organic Chemistry, EDISES
- McMurry, Organic Chemistry, PICCIN
- Vollhardt, Organic Chemistry, ZANICHELLI
Workbooks:
- Iverson - Iverson, Guide to solving problems from organic chemistry by Brown, Iverson, Anslyn, Foote, EDISES
- D'Auria - Taglialatela Scafati - Zampella, Reasoned guide to carrying out organic chemistry exercises, LOGHIA
- Ariel website with: slides of the lectures, exercises, examination texts
- Brown - Foote - Iverson, Organic Chemistry, EDISES
- Bruice, Organic Chemistry, EDISES
- McMurry, Organic Chemistry, PICCIN
- Vollhardt, Organic Chemistry, ZANICHELLI
Workbooks:
- Iverson - Iverson, Guide to solving problems from organic chemistry by Brown, Iverson, Anslyn, Foote, EDISES
- D'Auria - Taglialatela Scafati - Zampella, Reasoned guide to carrying out organic chemistry exercises, LOGHIA
- Ariel website with: slides of the lectures, exercises, examination texts
Assessment methods and Criteria
Written + oral examination, grades in thirtieth.
The written test will be composed by 10 exercises.
Oral exam: admission to the oral exam is subject to passing the written exam with a score of at least 18/30. The interview focuses mainly on concepts and principles of organic chemistry. The oral exam is normally held within 15 days from the written exam.
The written test will be composed by 10 exercises.
Oral exam: admission to the oral exam is subject to passing the written exam with a score of at least 18/30. The interview focuses mainly on concepts and principles of organic chemistry. The oral exam is normally held within 15 days from the written exam.
CHIM/06 - ORGANIC CHEMISTRY - University credits: 10
Practicals: 16 hours
Lessons: 72 hours
Lessons: 72 hours
Professor:
Pellegrino Sara
Professor(s)