Prof. Janina E. Kamińska Łódź University of Technology Faculty of Biotechnology and Food Sciences

1. ORGANIC CHEMISTRY 2 Prof. Janina E. Kamińska Łódź University of Technology Faculty of Biotechnology and Food Sciences Institute of General Food Chemistry ul. Stefanowskiego 4/10 Room no 209 (Consultation hours: Tue. 13:15-14:00, Wed. 14:15-15:00) Phone: 42 6313412 E-mail: janina.kaminska@p.lodz.pl

2. ORGANIC CHEMISTRY 2 sem. III. 2018/19 Lecture 15 h Tutorials 15 h Laboratory 45 h Prof. J.E. Kamińska, dr Ewa Maciejczyk Workload outside classroom 90 h ECTS credits: 6

3. Textbooks John McMurry, “Organic Chemistry”, 5th ed. Brooks/Cole Publishing Co., Pacific Grove, California 2000 (or later editions) K. P. C. Vollhardt, N. E. Schore, “Organic Chemistry, Structure and Function”, 3rd ed. W. H. Freeman and Co., New York 1999(or later editions) J. Clayden, N. Greeves, S. Warren, P. Wothers, “Organic Chemistry”, Oxford University Press 2000 (or later editions) Laboratory textbooks: J.R. Mohrig, C. Noring-Hammond, P.F. Shatz ”Techniques in Organic Chemistry” W.H. Freeman and Company 2010 J.C. Gilbert, S.F. Martin ”Experimental Organic Chemistry” 5th ed. Brooks/Cole 2011 L. M. Harwood, C. J. Moody, J. M. Percy, “Experimental Organic Chemistry”, 2nd ed., Blackwell Science Ltd., Oxford 1999

4. Textbooks Organic Chemistry with Biological Applications Organic Chemistry Fundamentals of Organic Chemistry

5. McMurry in Polish

6. Laboratory textbook

7. Final grade consist of: Written exam test 50% Laboratory grade 30% Organic chemistry 1 20%

8. Lectures • An overview of carbonyl group chemistry • Aldehydes and ketones – preparation and chemical reactions: nucleophilic addition to carbonyl group; -substitution reactions, carbonyl condensation reactions (aldol condensation). • Carboxylic acids and their derivatives (acyl chlorides, anhydrides, esters, amides, nitriles) – preparation and chemical behaviour (nucleophilic acyl substitution, -substitution reactions). • Aliphatic and aromatic amines - preparation and chemical properties.

9. Biomolecules • -Amino acids – structure and properties. Isoelectric point, analytical reactions of amino acids. • Peptides and proteins. Peptide structure determination. Chemical synthesis of peptides. Protein structure (general). • Monosaccharides(pentoses and hexoses) – structure and properties. • Disaccharides (sucrose, lactose, maltose, cellobiose) and polysaccharides (cellulose, starch, glycogen) – structure and properties. • Lipids– structure and properties of glycerides, isoprenoids, terpenes. • Heterocyclic compoundscontaining oxygen, sulphur and nitrogen. Pyrimidine and purine bases – structure and properties. Nucleotides, nucleosides and nucleic acids structure.

10. An overview of carbonyl group chemistry

11. CARBONYL GROUP sp2      sp2 sp2      sp2 C=O bond length 1.22 A C=C bond length 1.33 A

12. CARBONYL GROUP ELECTRONIC STRUCTURE Lone-pair electrons - Lone-pair electrons π-bond + Carbon or Hydrogen Carbon or Hydrogen

13. CARBONYL GROUP ORBITALS

14. POLARIZATION OF CARBONYL GROUP AND ITS REACTIVITY Nucleophilic oxygen reacts with acids and electrophiles - + Electrophilic carbon reacts with bases and nucleophiles

15. TYPES OF CARBONYL COMPOUNDS ALDEHYDES Hydrogen or carbon cannot stabilize negative charge and therefore cannot act as leaving group KETONES

16. TYPES OF CARBONYL COMPOUNDS Carboxylic acid Carboxylic acid chloride Carboxylic acid anhydride Carboxylic acid ester Carboxylic acid amide Electronegative atom (oxygen, halogen, nitrogen) bonded to acyl group R-CO- can stabilize a negative charge, therefore groups –OH, -Cl, -OCOR’, -OR’, -NH2 can serve as leaving groups in substitution reactions.

17. TYPES OF CARBONYL COMPOUNDS Cyclic acid anhydride Cyclic ester (lactone) Cyclic amide (lactam)

18. POLARITY OF CARBONYL COMPOUNDS

19. TYPES OF CARBONYL COMPOUNDS REACTIONS GENERAL MECHANISMS • Nucleophilic addition • Nucleophilic acyl substitution • -Substitution • Condensation reactions

20. Nucleophilic addition to carbonyl group 1st step Carbonyl carbon rehybridizes from sp2 to sp3

21. Nucleophilic addition to carbonyl group 2nd step Two ways of stabilization of tetrahedral intermediate

22. Nucleophilic addition to carbonyl group EXAMPLE 1 – addition of methylmagnesium bromide to cyclohexanone Synthesis of tertiary alcohol from ketone

23. Nucleophilic addition to carbonyl group EXAMPLE 2 – cyclohexanone imine formation Net effect – replacing C=O by C=NR

24. Nucleophilic acyl substitution Net effect – replacing of group Y with nuclephile. -Y is called leaving group Y = -OR (ester) -OCOR (anhydride) -Cl (acid chloride) -NH2, -NHR, -NR2 (amide)

25. Nucleophilic acyl substitution EXAMPLE – ester synthesis from acid chloride and alkoxide Net effect – replacing of Cl by OR

26. -Substitution reactions -carbon -substituted carbonyl compound Intermediates

27. -Substitution reactions Net effect – extending of carbonyl compound hydrocarbon framework by –CH2R fragment at -carbon

28. -Substitution reactions EXAMPLE – -methylation of cyclohexanone

29. Carbonyl condensation reactions New C-C bond Two aldehydes Aldol product (aldehyde + alcohol)

30. Carbonyl condensation reactions Carbonyl condensation reaction is a combination of -substitution step and nucleophilic addition step acetaldehyde By condensation of acetaldehyde 3-hydroxybutanal is prepared 3-hydroxybutanal

31. Nucleophilic addition reactions of carbonyl compounds Alcohol Alcohol Cyanohydrin Alkene Imine Alkane Acetal Enamine

32. Negatively charged nucleophiles Neutral nucleophiles Hydroxide ion Hydride ion A carbanion An alkoxide ion Cyanide ion Water An alcohol Ammonia An amine