Description of subjects

Classification of sugars. The constitution of chain varieties of aldoz and ketoz. Perspective patterns, Fischer patterns, Newman throws. Principles of the D,L configuration nomenclature (Rodan concept). Configuration isomeria of sugar chain varieties - enantiomeria, diastereisomeria, epimeria. Families of sugar diastereomers. Create more configuration members in pairs of epileptic patients. Common and systematic names, three-letter symbols, names of configuration members of non-anomeric carbon atoms. Nomenclature of higher and modified sugars. Cyclic varieties of sugars. Formation by rearrangement of oxo-cyclo aldoz and ketoz (hemiacetals). Patterns of Fischer-Tollens and Haworth. Nomenclature. Configuration of the anomeric carbon atom. Principles of the nomenclature of the anomeric configuration of pyranoz, furanoz and sugars about NC>6. Set an anomeric configuration. Boric acid complexes and conductivity measurements. Mutation and anomerization - polarimetric measurements. Basic reactions of sugars. Comparison of the anomeric properties of the hydroxyl group and other hydroxyl groups. Formation of O-glycosides (acetals) and ether and ester systems. The mechanism of acid and alkaline acetylation of sugars. Reducing properties of sugars. Carbonyl-endiol Tautomeria. Isomeria of simple sugars in aqueous solution. Construction and nomenclature of selected sugar derivatives. O- and N-glycosides, acylsugars, deoxysugars, anhydrides, unsaturated sugars, glycosyl halides, disaccharides, oligosaccharides, alditole, uronic and aldonic acids and their derivatives. Vitamin C. Conformation Isomeria. Factors determining the durability of conformation. Conformations of acyclic sugar derivatives. Conformations of cyclohexane and substituted cyclohexane. Conformations of pyranose rings. Sterile and electron interactions in pyrannoses. Determination of the energy values of the destabilizing effects. Anomeric effect. Factors determining its value. Effect on the stability of sugar formation.

Physical methods of testing the structure of the sugar molecule. Infrared spectroscopy. Features of IR spectra of free sugars and their derivatives. Tracking the completeness of the response. Nuclear magnetic resonance spectroscopy. Examination of the structure of the furanozoic and pyrannotic ring, the anomeric configuration, the sugar ring conformation, the composition of the balance mixture. 1H-NMR single- and two-dimensional spectra, 13C-NMR broadband and two-dimensional heteronuclear). Spectropolarimetry. ORD and CD spectra in anomeric configuration studies. Conformations of furanose rings and cyclic unsaturated systems and some ways of their testing.

Skills and competences: Description of the structure, chemical and physico-chemical properties of sugars and their derivatives.

Distribution of electron density in the molecule: Polarization, polarization, induction effect, mesomeric effect, aromaticity, the effect of overcoupling. Acidity and alkalinity of organic compounds: Acidity theories; factors affecting the power of acids and bases. Intermediate products of organic reactions: Carbonates, carbonates, free radicals, carbenes, nitrites - construction, durability, ways to generate. Reaction kinetics and thermodynamics: Mechanism types, thermodynamic and kinetic requirements for reaction, kinetic and thermodynamic response control, Hammond postulate, reversibility of reaction. Methods for testing reaction mechanisms: Identification of products and intermediate products, analysis of catalysis, isotopic labeling, stereochemical certification, kinetic evidence, isotope effects. Nucleophilic substitution on sp³ carbon: S_N2, S_N1 - factors affecting reactivity, ionic pairs, mixed mechanisms, participation of the neighboring group, S_NI mechanism, S_N on allyl carbon. Nucleophilic substitution on carbon sp2: SN on acyl carbon: Tetraedric mechanism, carboxylic acid derivative reactivity, catalysis, reaction reversibility; SN on vinyl carbon; aromatic nucleophilic substitution. Aromatic electrophilic substitution: Mechanisms; orientation and reactivity in mono- and more substituted benzene ring, in other rings. Aliphatic electrophilic substitution: SE2, SEI, SE1, with double binding shift; aldehyde and ketone halogenation, carboxylic acid halogenation and acyl halides. Free radical substitution: Mechanisms, neighboring group participation, reactivity; halogenation on alkyl, allyl and benzyl carbon; diazo salt reactions, Kolbe reaction, Hunsdiecker reaction, decarbonylation of aldehydes. Electrophilic addition: For double binding C=C - mechanism, regioselectiveness stereochemistry; addition of water, hydrogen halide, halogen, alcohols and phenols, carboxylic acids, carbenes; addition in the conjugate system, addition to the rings cyclopropane; addition to triple-binding C≡C. Nucleophilic addition: To the carbonyl group: Water, HCN, alcohols, amines, anions, Ylides; addition to binding carbon-heteroatom: Hydrolysis of imines, nitrile compounds, nitrils, alcoholism and aminoliza of isocyanates and nitrils; addition to the double binding C=C in the conjugate system. Addition of free radical to double binding C=C: Addition of halogen, halogen (competition with substitution in the allyl position), addition of carbines. Elimination reactions: Mechanisms, orientation of the double bond, reaction stereochemistry, factors affecting reactivity, examples of reactions. Regroupings: Nucleophilic, electrophilic, free radical, through a cyclic transition state; transpiring of pinacol, regrouping with a change in ring size, synthesis of Arndt-Eistert, the insertion of methylene into aldehyde or ketone, the rearrangement of Hofmann, Curtius, Lossen. Cyclic reactions: Molecular orbitals of coupled electron π systems; electrocyclical reactions: Thermal and photochemical; cycloadditionals reactions; sigmatropic regroupings. Oxidation and reduction reactions: Types of mechanisms; oxidation reactions: By elimination of hydrogen, by rupture of the C-C bond, by substitution of hydrogen by oxygen, by addition of oxygen, by oxidative coupling; reduction reactions: By substitution of oxygen by hydrogen, removal of oxygen by the substrate, reducing bond rupture, reducing coupling; reduction selectivity.

Skills and competences: Description of mechanisms of reaction in organic chemistry, understanding of issues concerning various regroupations, knowledge of methods of testing reaction mechanisms, ability to interpret oxidation and reduction processes in organic chemistry.

Particle architecture, basic issues and concepts related to stereochemistry. Nature of spatial isomers; barriers to the transformation between spatial isomers. Symmetry: Symmetry elements, symmetry operators; point groups of symmetry containing chiral particles, point groups containing only achiral particles, symmetry and molecular properties (spillover, dipole moment). Configuration: Relative and absolute, methods for determining absolute configuration. The properties of stereoisomers and their differentiation: the nature of racemates and their enantiomeric components; the biological properties of stereoisomers, the origin of enantiomeric uniformity in nature, chiral drugs. Separation of the stereosomes. Racemisation. Prostereoisomer and prochirality: Meaning, homophobic and heterotopic ligands and parties (homophobic ligands and parties, enantipotic ligands and parties, diasteretopic ligands and parties), heterotopic and NMR, heterotopic and reactions catalyzed by enzymes, heterotopic versus stereoselective synthesis. Stereochemistry of alkenes: the nature of CIS-trans isomeries, double bonds C= N and N = N, determination of CIS-trans isomeric configurations (chemical and physical methods), mutual transformation of CIS-trans isomers. Conformation of chain molecules: Conformation of alkanes and their derivatives substituted with polar substituents, formation of unsaturated acyclic compounds, equilibrium of diastereomers in acyclic systems, physical and spectral properties of diastereisomers and conformers, conformation and reactivity. Ring molecules of different sizes - conformation and configuration: Determination of the configuration of substituted ring compounds, conformation aspects of the chemistry of ring compounds, stress in ring molecules, conformation and physical properties, conformation and reactivity, conjugated and bridge polycyclic molecules. Stereo-selective and stereospecific synthesis: A diastereselective synthesis based on chiral substrates of natural origin, enantiselective synthesis. Spectropolarimetry: Optical activity, dispersion of optical rotation of the ORD, circular dichroism of the CD, applications of the ORD and CD (determination of configuration and conformation). Chirality in molecules without centers of chirality: Allen (cumulation); spirants; biphenyls, helicens, particles with planar chirality (cyclophane, annulenes, trans-cycloalkene, metallocene).

Skills and competences: Knowledge of stereochemistry issues, use of stereochemistry terminology, ability to determine relative and absolute configuration, distinguish stereoisomers and determine their properties, use of spectropolarimetry.

 

SEMESTER 4 (summer)

 

Lecture 30
Lecturer: dr hab. Janusz Madaj, prof. UG