1. CHE 242 Unit VII The Physical and Chemical Properties, and Reactions of Ketones, Aldehydes, and Amines CHAPTER EIGHTEEN Terrence P. Sherlock Burlington County College 2004

2. Chapter 182 Carbonyl Compounds =>

3. Chapter 183 Examples 3-methyl-2-butanone 3-bromocyclohexanone 4-hydroxy-3-methyl-2-butanone =>

4. Chapter 184 Name as Substituent On a molecule with a higher priority functional group, C=O is oxo- and -CHO is formyl. Aldehyde priority is higher than ketone. 3-methyl-4-oxopentanal 3-formylbenzoic acid =>

5. Chapter 185 Historical Common Names acetone acetophenone benzophenone =>

6. Chapter 186 Aldehyde Common Names Use the common name of the acid. Drop -ic acid and add -aldehyde.  1 C: formic acid, formaldehyde  2 C’s: acetic acid, acetaldehyde  3 C’s: propionic acid, propionaldehyde  4 C’s: butyric acid, butyraldehyde. =>

7. Chapter 187 Boiling Points More polar, so higher boiling point than comparable alkane or ether. Cannot H-bond to each other, so lower boiling point than comparable alcohol. =>

8. Chapter 188 Solubility Good solvent for alcohols. Lone pair of electrons on oxygen of carbonyl can accept a hydrogen bond from O-H or N-H. Acetone and acetaldehyde are miscible in water. =>

9. Chapter 189 Formaldehyde Gas at room temperature. Formalin is a 40% aqueous solution. trioxane, m.p. 62  C formaldehyde, b.p. -21  C formalin =>

10. Chapter 1810 IR Spectroscopy Very strong C=O stretch around 1710 cm -1. Conjugation lowers frequency. Ring strain raises frequency. Additional C-H stretch for aldehyde: two absorptions at 2710 cm -1 and 2810 cm -1. =>

11. Chapter 1811 1 H NMR Spectroscopy =>

12. Chapter 1812 McLafferty Rearrangement Loss of alkene (even mass number) Must have  -hydrogen =>

13. Chapter 1813 UV Spectra,    * C=O conjugated with another double bond. Large molar absorptivities (> 5000) =>

14. Chapter 1814 UV Spectra, n   * Small molar absorptivity. “Forbidden” transition occurs less frequently. =>

15. Chapter 1815 Synthesis Review Oxidation  2  alcohol + Na 2 Cr 2 O 7  ketone  1  alcohol + PCC  aldehyde Ozonolysis of alkenes. =>

16. Chapter 1816 Synthesis Review (2) Friedel-Crafts acylation  Acid chloride/AlCl 3 + benzene  ketone  CO + HCl + AlCl 3 /CuCl + benzene  benzaldehyde (Gatterman-Koch) Hydration of terminal alkyne  Use HgSO 4, H 2 SO 4, H 2 O for methyl ketone  Use Sia 2 BH followed by H 2 O 2 in NaOH for aldehyde. =>

17. Chapter 1817 Ketones from Nitriles A Grignard or organolithium reagent attacks the nitrile carbon. The imine salt is then hydrolyzed to form a ketone. =>

18. Chapter 1818 Aldehydes from Acid Chlorides Use a mild reducing agent to prevent reduction to primary alcohol. =>

19. Chapter 1819 Ketones from Acid Chlorides Use lithium dialkylcuprate (R 2 CuLi), formed by the reaction of 2 moles of R-Li with cuprous iodide. =>

20. Chapter 1820 Nucleophilic Addition A strong nucleophile attacks the carbonyl carbon, forming an alkoxide ion that is then protonated. A weak nucleophile will attack a carbonyl if it has been protonated, thus increasing its reactivity. Aldehydes are more reactive than ketones. =>

21. Chapter 1821 Wittig Reaction Nucleophilic addition of phosphorus ylides. Product is alkene. C=O becomes C=C. =>

22. Chapter 1822 Addition of HCN HCN is highly toxic. Use NaCN or KCN in base to add cyanide, then protonate to add H. Reactivity formaldehyde > aldehydes > ketones >> bulky ketones. =>

23. Chapter 1823 Other Condensations =>

24. Chapter 1824 Addition of Alcohol =>

25. Chapter 1825 Acetals as Protecting Groups Hydrolyze easily in acid, stable in base. Aldehydes more reactive than ketones. =>

26. Chapter 1826 Selective Reaction of Ketone React with strong nucleophile (base) Remove protective group. =>

27. Chapter 1827 Oxidation of Aldehydes Easily oxidized to carboxylic acids. =>

28. Chapter 1828 Tollens Test Add ammonia solution to AgNO 3 solution until precipitate dissolves. Aldehyde reaction forms a silver mirror. =>

29. Chapter 1829 Reduction Reagents Sodium borohydride, NaBH 4, reduces C=O, but not C=C. Lithium aluminum hydride, LiAlH 4, much stronger, difficult to handle. Hydrogen gas with catalyst also reduces the C=C bond. =>

30. Chapter 1830 Catalytic Hydrogenation Widely used in industry. Raney nickel, finely divided Ni powder saturated with hydrogen gas. Pt and Rh also used as catalysts. =>

31. Chapter 1831 Deoxygenation Reduction of C=O to CH 2 Two methods:  Clemmensen reduction if molecule is stable in hot acid.  Wolff-Kishner reduction if molecule is stable in very strong base. =>

32. Chapter 1832 Clemmensen Reduction =>

33. Chapter 1833 Wolff-Kisher Reduction Form hydrazone, then heat with strong base like KOH or potassium t-butoxide. Use a high-boiling solvent: ethylene glycol, diethylene glycol, or DMSO. =>

34. Chapter 1834 POWER POINT IMAGES FROM “ORGANIC CHEMISTRY, 5 TH EDITION” L.G. WADE ALL MATERIALS USED WITH PERMISSION OF AUTHOR PRESENTATION ADAPTED FOR BURLINGTON COUNTY COLLEGE ORGANIC CHEMISTRY COURSE BY: ANNALICIA POEHLER STEFANIE LAYMAN CALY MARTIN