1. Chapter 18 Lecture Aldehydes & Ketones: Part I Organic Chemistry, 8 th Edition L. G. Wade, Jr.

2. Overview Classes of Carbonyl Compounds Structure of Carbonyl Group Nomenclature of Ketones & Aldehydes Physical Properties IR & NMR Spectroscopy Preparing Ketones & Aldehydes: A Review 2

3. © 2013 Pearson Education, Inc. Chapter 93 Classes of Carbonyl Compounds

4. © 2013 Pearson Education, Inc. Chapter 18 4 Structure of the Carbonyl Group Carbon is sp 2 hybridized. C ═ O bond is shorter, stronger, and more polar than C ═ C bond in alkenes.

5. © 2013 Pearson Education, Inc. Chapter 18 5 Resonance The first resonance is better because all atoms complete the octet and there are no charges. The carbonyl carbon has a partial positive and will react as an electrophile.

6. © 2013 Pearson Education, Inc. Chapter 18 6 Ketone Nomenclature Number the chain so that the carbonyl carbon has the lowest number. Replace the alkane -e with -one.

7. © 2013 Pearson Education, Inc. Chapter 18 7 Cyclic Ketone Nomenclature For cyclic ketones, the carbonyl carbon is assigned the number 1. When the compound has a carbonyl and a double bond, the carbonyl takes precedence.

8. © 2013 Pearson Education, Inc. Chapter 18 8 Aldehydes Nomenclature The aldehyde carbon is number 1. IUPAC: Replace -e with -al. If the aldehyde group is attached to a ring, the suffix carbaldehyde is used.

9. Carbonyl as Substituent On a molecule with a higher-priority functional group, a ketone is an oxo and an aldehyde is a formyl group. Aldehydes have a higher priority than ketones.

10. Common Names for Ketones Named as alkyl attachments to —C ═ O Use Greek letters instead of numbers.

11. © 2013 Pearson Education, Inc. Chapter 911 Historical Common Names

12. © 2013 Pearson Education, Inc. Chapter 18 12 Boiling Points Ketones and aldehydes are more polar, so they have a higher boiling point than comparable alkanes or ethers. They cannot hydrogen-bond to each other, so their boiling point is lower than the comparable alcohol.

13. © 2013 Pearson Education, Inc. Chapter 18 13 Solubility of Ketones and Aldehydes 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.

14. © 2013 Pearson Education, Inc. Chapter 18 14 Formaldehyde Gas at room temperature Formalin is a 40% aqueous solution. Trioxane is a cyclic trimer of formaldehyde. When trioxane is heated, it generates formaldehyde.

15. © 2013 Pearson Education, Inc. Chapter 18 15 Infrared (IR) Spectroscopy Very strong C ═ O stretch around 1710 cm -1 for ketones and 1725 cm -1 for simple aldehydes Additional C—H stretches for aldehyde: Two absorptions at 2710 cm -1 and 2810 cm -1

16. © 2013 Pearson Education, Inc. Chapter 18 16 IR Spectra Conjugation lowers the carbonyl stretching frequencies to about 1685 cm -1. Rings that have ring strain have higher C ═ O frequencies.

17. © 2013 Pearson Education, Inc. Chapter 18 17 Proton NMR Spectra Aldehyde protons normally absorb between  9 and  10. Protons of the α carbon usually absorb between  2.1 and  2.4 if there are no other electron- withdrawing groups nearby.

18. © 2013 Pearson Education, Inc. Chapter 18 18 1 H NMR Spectroscopy Protons closer to the carbonyl group are more deshielded. The , and  protons appear at values of  that decrease with increasing distance from the carbonyl group.

19. Industrial Importance Acetone and methyl ethyl ketone are common industrial solvents. Formaldehyde is used in polymers like Bakelite  and many other polymeric products. Also used as flavorings and additives for food.

20. © 2013 Pearson Education, Inc. Chapter 18 20

21. Preparing Aldehydes & Ketones: A Review of Past Reactions Grignards as Source for Aldehydes & Ketones Ozonolysis of Alkenes Friedel-Crafts Reaction Hydration of Alkynes Hydroboration-Oxidation of Alkynes Chapter 1821

22. © 2013 Pearson Education, Inc. Chapter 18 22 Grignards as a Source for Ketones and Aldehydes A Grignard reagent can be used to make an alcohol, and then the alcohol can be easily oxidized.

23. © 2013 Pearson Education, Inc. Chapter 18 23 Oxidation of Primary Alcohols to Aldehydes Pyridinium chlorochromate (PCC) is selectively used to oxidize primary alcohols to aldehydes. The Swern oxidation could also be used.

24. © 2013 Pearson Education, Inc. Chapter 18 24 Ozonolysis of Alkenes The double bond is oxidatively cleaved by ozone followed by reduction. Ketones and aldehydes can be isolated as products under these conditions.

25. © 2013 Pearson Education, Inc. Chapter 18 25 Friedel–Crafts Reaction Reaction between an acyl halide and an aromatic ring will produce a ketone.

26. © 2013 Pearson Education, Inc. Chapter 18 26 Hydration of Alkynes The initial product of Markovnikov hydration is an enol, which quickly tautomerizes to its keto form. Internal alkynes can be hydrated, but mixtures of ketones often result.

27. © 2013 Pearson Education, Inc. Chapter 18 27 Hydroboration–Oxidation of Alkynes Hydroboration–oxidation of an alkyne gives anti- Markovnikov addition of water across the triple bond.

28. © 2013 Pearson Education, Inc. Chapter 928 Show how you would synthesize each compound from starting materials containing no more than six carbon atoms. (a)(b) (a)This compound is a ketone with 12 carbon atoms. The carbon skeleton might be assembled from two six-carbon fragments using a Grignard reaction, which gives an alcohol that is easily oxidized to the target compound. Solved Problem 1 Solution

29. © 2013 Pearson Education, Inc. Chapter 929 An alternative route to the target compound involves Friedel–Crafts acylation. Solved Problem 1 (Continued) Solution (Continued) (b)This compound is an aldehyde with eight carbon atoms. An aldehyde might come from oxidation of an alcohol (possibly a Grignard product) or hydroboration of an alkyne. If we use a Grignard, the restriction to six-carbon starting materials means we need to add two carbons to a methylcyclopentyl fragment, ending in a primary alcohol. Grignard addition to an epoxide does this.

30. © 2013 Pearson Education, Inc. Chapter 930 Alternatively, we could construct the carbon skeleton using acetylene as the two-carbon fragment. The resulting terminal alkyne undergoes hydroboration to the correct aldehyde. Solved Problem 1 (Continued) Solution (Continued)