Organic Chemistry I

Structures of molecules: Theory of covalent bonding, explanations of chemical bonds. Atomic orbitals, molecular orbitals, hybridization, delocalized chemical bonding.

Stereochemistry, configuration, conformation: Constitutional, geometric and configurational isomerisms. Chirality, symmetry elements, enantiomers, diastereomers. The CIP system. Inversion, retention and recemization. Conformation of  aliphatic and alicyclic hydrocarbons.

Theory of reactions, theories of acid and bases, HSAB and FMO theories: Types of organic reactions: substitutions, additions, eliminations and rearrangements. Nature of the reactions: multistep, concerted, ionic and radical reactions. The energy profile of  reactions: transition state, parameters for activation, intermediates, concept of  kinetic and thermodynamic control. Acid-base equilibria. Bronsted-, Lewis-, HSAB-and FMO theories. The concept of electrophilicity and nucleophilicity.

Theory of redox and radical reactions, chemistry of  paraffins. Rationalizing the oxidation number. The SET mechanisms. Preparation of paraffins and cycloparaffins by reduction, methods for producing carbon-carbon single bonds. Physical properties, radical reactions and oxidation of paraffins and cycloparaffins.

Reactivity of olefines and acetylenes, electrophilic addition, oxidation and polymerization: Electrophilic addition, radical, substitution and cycloaddition reactions of olefine- and  acetylene-derivatives. Rationalization of Markovnikov’s rule. Hammond’s postulate. Reactions of 1,3-dienes. Substitution and adddition reactions of conjugate bases of  acetylene-derivatives.

Reactivity of monocyclic aromatic compounds, electrophilic substitution: The structure of benzene. Aromatic character and aromaticity. The mechanism of electrophilic substitution, halogenation, nitration and sulphonation. Friedel-Crafts alkylation and acylation. Orientation rules, and their rationalization by FMO theory and by Hammond’s postulate.

The theory of substitution and elimination: The mechanisms of nucleophilic substitutions (S_N1 and S_N2) and eliminations (E₁, E₂ and E₁cB), their regio- and stereochemistry, their rationalization by FMO and HSAB theories. Ambident nucleophiles. Factors influencing these reactions, catalysis and solvation. Addition-elimination and elimination-addition mechanisms of aromatic nucleophilic substitution.

The chemistry of halogen compounds, alcohols, phenols and ethers: The physical properties of halogen compounds, alcohols, phenols and ethers. The acidity and basicity of these compounds. The rationalization of their acidic strength. Reactions of halogen compounds with metals. Reactions of alcohols, phenols and ethers. Complexing properties of ethers.

The chemistry of  nitro compounds and amines: Tautomerism of nitro compounds. Preparation and reduction of nitro compounds. The structure, physical and bacic properties of amines. The rationalization of their basic strength. Preparation and nucleophilic reactions of amines.

Reduction and oxidation of alcohols, oxo compounds and carboxylic acid derivatives: Preparation of oxo compounds and carboxylic acids by oxidation. Preparation of alcohols and oxo compounds by reduction. Using Grignard and related reactions for the preparation of alcohols and oxo compounds. The mechanism of Grignard reaction.

Reactivity of oxo compounds, carboxylic acids and carboxylic acid derivatives: The electron structure of carbonyl group. The theories of  nucleophilic addition and addition-elimination reactions. Comparison of the reactivities of aliphatic and aromatic oxo compounds, carboxylic acids and carboxylic acid derivatives. Reactions of α,β-unsaturated oxo compounds and carboxylic acids. Factors influencing Ad_N reactions. Inverse reactions. Rationalization of  Cannizzaro reaction and the conjugate addition reactions of α,β-unsaturated oxo compounds.

Oxo-enol tautomerism: Comparison of the reactivities of tautomers. Reactions taking place with the conjugate bases of oxo compounds and carboxylic acid derivatives (at α-position). The chemistry of dioxo and related compounds. Malonate ester syntheses.

Chemistry of carboxylic acids: Physical and chemical properties of carboxylic acids, structure and acidity. Decarboxylation reactions. Reactions of dicarboxylic acids.

Chemistry of  carboxylic acid derivatives: Carboxylic acid derivatives: ketene, acyl halides, acid anhydrides, esters, amides, imid acid esters, nitriles. Mechanisms of the reactions of carboxylic acids and carboxylic acid derivatives, rationalization of the reactivity order. Nucleophilic addition and addition-elimination reactions.