00148 - Organic Chemistry

Learning outcomes

At the end of the course, the student acquires the basic notions on the structure and properties of organic compounds, with particular regard to natural organic substances and those of biochemical interest. Based on the reactivity of the main functional groups, it is able to trace the synthesis of new compounds. It deepens the topics covered through exercises, applied experimentally in the course of practical exercises in the laboratory. At the end of the laboratory, the student has the technical-practical knowledge to perform synthesis reactions, including the recognition of organic compounds.

Course contents

Introduction. Review of the following concepts: Lewis bond model. Formation of a chemical bond. Electronegativity and chemical bonds. Lewis structures of ions and covalent molecules. Formal charge. Exceptions to the octet rule. Bond angles and shape of molecules. Functional groups. Structural isomers. resonance theory. The shape of atomic orbitals. Valence bond and covalent bond. Formation of a covalent bond by overlapping of atomic orbitals. Hybridization of atomic orbitals. Molecular orbital approach to covalent bonding. Formation of molecular orbitals. Alkanes and cycloalkanes. Alkane structure. Structural isomerism of alkanes. Nomenclature of alkanes. The IUPAC system. Common names. Classification of carbon and hydrogen atoms. Cycloalkanes. Structure and nomenclature. Bicyclic alkanes. Steroids. Conformations of alkanes and cycloalkanes. Cyclohexane. Cis-trans isomerism in cycloalkanes and bicycloalkanes. Physical properties of alkanes and cycloalkanes. Reactions of alkanes. Oxidation. Halogenation. Chlorination and bromination. Regioselectivity. Acids and bases. Bronsted-Lowry acids and bases. Quantitative measure of the strength of acids and bases. Equilibrium position in acid-base reactions. Lewis acids and bases. Alkenes. Nomenclature. IUPAC names. Common names. Structure. Valence bond approach. The lengths and bond strengths of alkanes, alkenes and alkynes. Description of the molecular orbital of a carbon-carbon double bond. Cis-trans isomerism. The EZ system. Cis-trans isomerism in cycloalkenes. The cis-trans isomerism in dienes, trienes, (etc.). Physical properties. Preparation: dehydrohalogenation of alkyl halides. The reaction mechanisms. Electrophilic additions. Bromination. Addition of halogen acids. Addition of water: acid-catalyzed hydration of alkenes. Mechanism of electrophilic addition to alkenes. Formation of carbocation intermediates. Regioselectivity and stability of carbocations. Radical additions. Allyl halogenation. The structure of the allyl radical. Hammond's postulate. Oxidation. Catalytic reduction. Alkynes. Outline of the following concepts. Structure. Nomenclature. IUPAC names. Common names. Physical properties, acidity. Preparation. reactions. You are married. Nomenclature. Stability. Structure. Valence bond model. Model of the molecular orbital. Electrophilic additions. Conjugate addition: addition-1,2 and addition-1,4.

Chirality. Isomerism. Chirality. Chirality due to a tetrahedral stereocenter. Chirality due to stereocenters other than carbon atoms. Chirality in the absence of a stereocenter. Classification of enantiomers: the R-S system. Fisher projection formulas. Optical activity. The polarimeter. Raceme blend. Optical purity and enantiomeric excess. Relationship between configuration and rotation sign. Acyclic molecules with two or more stereocenters. Enantiomers and diastereoisomers. Meso compounds. Cyclic molecules with two or more stereocenters. Properties of stereoisomers. Separation of enantiomers by resolution. Alcohols and thiols. Structure of alcohols and thiols. Nomenclature. Alcohols. Thiols. Physical properties. Preparation of alcohols. Acid-catalyzed hydration of alkenes. Reactions of alcohols. Acidity of alcohols. Basicity of alcohols. Conversion to alkyl halides. Dehydrations of alcohols to alkenes. Oxidation of primary and secondary alcohols. Thiol reactions. Acidity. Alkyl halides. Structure. Nomenclature. IUPAC system. Common names. Physical properties. Polarity. Preparation. Conversion of an alcohol into an alkyl halide. Halogenation of alkanes. Addition of HX to alkenes. Reactions with bases and nucleophiles. Aliphatic nucleophilic substitution. Mechanisms of aliphatic nucleophilic substitution. Relative nucleophilicity. Nucleophilicity in aprotic polar solvents. Nucleophilicity in polar protic solvents. Stereochemistry. SN1 reactions. SN2 reactions. Structure of the alkyl halide. The outgoing group. The solvent. E1 reactions. E2 reactions. Ethers and epoxides. Structure of the ethers. Nomenclature of ethers. Physical properties of ethers. Preparation of ethers. Synthesis of Williamson ethers. Acid-catalyzed addition of alcohols to alkenes. Acid-catalyzed dehydration of alcohols. Reactions of thiols and sulphides. Epoxides. Structure and nomenclature. Synthesis. Reactions of epoxides. Acid-catalyzed opening of the ring. Nucleophilic ring opening. Aromatic. The structure of benzene. Kekulé's model of benzene. The valence bond model. The resonance energy of benzene. The concept of aromaticity. Huckel's rule. Heteroaromatic compounds. Phenols. Structure and nomenclature. Acidity of phenols. Acid-base reactions of phenols. Electrophilic aromatic substitutions. Bromination and chlorination. Nitration and sulfonation. Friedel-Crafts alkylation and acylation. Effect of a substituent on further substitution. Activating/deactivating, and orienting effect.

Aldehydes and ketones. Structure. Structural features. The covalent bond. IUPAC nomenclature. Common names. Physical properties. Preparation. Oxidation of primary and secondary alcohols. Friedel-Crafts acylation of aromatic rings. Oxidation of alkenes: cleavage of the carbon-carbon double bond. reactions. Addition of carbonucleophiles. Formation and structure of organometallic compounds. Addition of Grignard reagents. Addition of organolithium compounds. Addition of hydrogen cyanide. Addition of oxygenated nucleophiles. Addition of water. Addition of alcohols: formation of hemiacetals and acetals. Acetals as carbonyl protecting groups. Addition of nitrogenous nucleophiles. Ammonia and its derivatives. Hydrazine and related compounds. Keto-enol tautomerism. Acidity of hydrogens in alpha. Reactions at the alpha carbon. The aldol reaction. Oxidation of aldehydes. Oxidation of ketones. Reduction. Catalytic reduction. Reduction with metal hydrides. Carbohydrates. Monosaccharides. Structure. Nomenclature. Stereoisomerism. The cyclic structure of monosaccharides. Fisher projections. Haworth projections. mutarotation. Physical properties. Reactions of monosaccharides. Formation of glycosides. Reduction. Oxidation. Disaccharides and oligosaccharides. Nucleosides and nucleotides in biochemistry.

ATP, NADH. Notes on RNA and DNA. Notes on gluconeogenesis. Carboxylic acids. Structure. Nomenclature. IUPAC system. Common names. Physical properties. Acidity. Acid ionization constants. Reactions with bases. Preparation. Oxidation of primary alcohols. Oxidation of aldehydes. Reduction. Lithium aluminum hydride. Reduction with diborane. Esterification. Fisher esterification. Transformation into acyl halides. Decarboxylation. Functional derivatives of carboxylic acids. Structure and nomenclature. Acid halides. Acid anhydrides. Foreign. Amides and imides. nitriles. characteristic reactions. Reaction with water: hydrolysis. Acyl chlorides. Reaction with alcohols. Acyl halides. Reactions with ammonia and amines.

Enolate anions. Claisen condensation. Acetoacetic synthesis. Malonic synthesis. Amines. Structure and classification. Nomenclature. Common names. IUPAC names. Chirality of amines and quaternary ammonium ions. Physical properties. Basicity. Preparation of amines. Alkylation of ammonia and amines. Reduction of nitro groups to primary amino groups. Alkylation of the azide ion to prepare primary amines. Gabriel's synthesis of primary alkylamines. Reductive amination of aldehydes and ketones. Reduction of nitriles to primary amines. Reduction of amides. Reactions of amines. Reactions of tertiary aliphatic amines. Reactions of tertiary aromatic amines. Reactions of aliphatic and aromatic secondary amines. Lipids. Fatty acids, soaps and detergents. the structure of fatty acids. Structure and preparation of natural soaps. Prostaglandins. Steroids. Phospholipids. Notes on fatty acid biosynthesis. Amino acids and proteins. Amino acids. Structure. Chirality of amino acids. The amino acids derived from proteins. Acid-base properties of amino acids. Amino acids, proteins and nutrition. Asymmetric synthesis of amino acids. Polypeptides and proteins. Primary structure of polypeptides and proteins. Synthesis of polypeptides. Enzymes Lipids: structure, nomenclature, physical properties, preparation, chemical reactions, mechanisms, synthesis and basicity. Nucleic acids. Nucleotides and nucleosides. DNA structure. Ribonucleic acids. Main aspects of protein synthesis.

 

Readings/Bibliography

Both Introduction or Fundamentals texts (which are reduced versions) and complete texts can be utilized, which can also be useful continuing with biochemistry; some texts contain very useful molecular models for free for studying molecules in 3D; for those who feel like it, I would recommend the English versions. Introduction to Organic Chemistry with Molecular Models, William H. Brown - Thomas Poon, EDISES Organic Chemistry - with molecular models W.H. Brown – B.L. Iverson-E.V. Anslyn–C.S. Foote, EDISES Fundamentals of organic chemistry John McMurry, Zanichelli Organic Chemistry by John McMurry, Piccin Organic Chemistry, T W Graham Solomons, Craig B Fryhle, Zanichelli, Organic chemistry. With Digital Content (Provided Electronically) Paperback, Peter C. Vollhardt, Neil E. Schor, Zanichelli

Teaching methods

Frontal lessons, with ongoing checks and group work on exercises Partial written assignments with correction in the classroom Tutorials. 30 hours (2 credits) consist of practical exercises in the laboratory and frontal lessons of introduction to the laboratory. The practical exercises are related to general chemistry and organic chemistry and are carried out in the laboratories of the Department of Chemistry “G. Ciamician” in groups of 2 or 3 students divided over two shifts.

Assessment methods

The exam includes an oral test relating to both modules that make up the course. The interrogation begins with a synthesis exercise to be carried out on the blackboard, based on shared support teaching material and made available through the portal. The second part of the test provides for the deepening of the theoretical knowledge that is linked to the exercise just carried out. For the laboratory module, a synthetic work (report) relating to one of the experiences carried out in the laboratory is required, which must be delivered in good time before the exam is carried out. The document will be viewed by the teacher and any comments will be communicated to the student. During the exam, the report is discussed to ensure that the concepts underlying the operations carried out in the laboratory have been fully understood. The final grade of the exam consists of 40% from the discussion of the exercise, 40% from the outcome of the deepening of the theory, 20% from the discussion of the tests carried out in the laboratory. On average, each query takes 30 minutes. At the request of the student, the test can be written, in the form of a paper.

Teaching tools

power point projections, handouts and laboratory exercises guide available on unibo's "Online Teachings" platform. Solid molecular models of atoms and molecules and virtual models. Presentation of movies, animations, 3D simulations

Office hours

See the website of Luca Gentilucci

See the website of Giulio Bertuzzi

See the website of Giulio Bertuzzi