2. CARBOXYLIC ACIDS Properties and Synthesis

3. NOMENCLATURE

4. -oic acid IUPAC ending -carboxylic acid IUPAC ending for ring compounds IUPAC NOMENCLATURE

5. 3-Methylbutanoic acid  -Methylbutyric acid Isovaleric acid 2-Chloropentanoic acid  -Chlorovaleric acid Naming

6. 2-Methylpropanoic acid  -Methylpropionic acid Isobutyric acid 4-Aminobutanoic Acid  -Aminobutyric Acid “GABA” Naming

7. Benzoic acid Benzenecarboxylic acid Cyclohexanecarboxylic acid More Naming

8. Common Names

9. SYNTHESIS OF SYNTHESIS OF CARBOXYLIC ACIDS

10. Oxidation of Primary Alcohols with KMnO 4 with KMnO 4 two  -hydrogens + MnO 2 precipitate

11. Oxidation of Primary Alcohols with K 2 Cr 2 O 7 with K 2 Cr 2 O 7

12. Oxidation of Side Chains Example KMnO 4 

13. Carbonation of Grignard Reagents ( or Alkyllithium Compounds ) ( R-Li )

14. Formation of Nitriles and Hydrolysis DMSO H 2 SO 4 H2OH2O heat SN2SN2

15. or CO 2 CrO 3 H 2 SO 4 KMnO 4 H 2 SO 4 KMnO 4 NaCN acetone DIBAL or Rosenmund KMnO 4 Li or Mg H2OH2O H2OH2O H 2 SO 4 H2OH2O or KMnO 4 SYNTHESIS OF CARBOXYLIC ACIDS ( DUE TO LACK OF SPACE REACTION CONDITIONS ARE ABBREVIATED) KMnO 4 ( benzene = R sidechain = R’ ) This is all stuff you know! SOCl 2 Chap 19

16. ACIDITY

17. Carboxylate Ion Formation They are acids, ya know ! pK a   5 carboxylate ioncarboxylic acid

18. + +.. : : H 2 SO 4.. : + Protonation and Deprotonation of a Carboxylic Acid.. : NaOH.. : - equivalent structures due to resonance

19. Electron-withdrawing Groups: –strengthen acids –weaken bases Electron-releasing Groups: –weaken acids –strengthen bases

20. Substituents with Electron-Withdrawing Resonance ( - R ) Effects -R substituents strengthen acids and weaken bases X Y

21. +R substituents weaken acids and strengthen bases Substituents with Electron-Releasing Resonance ( + R ) Effects hydroxy mercapto methyl amino fluoro bromo alkoxy acyloxy dialkylamino alkyl chloro iodo Y..

22. Substituents with Electron-Withdrawing ( - I ) Inductive Effects ( - I ) Inductive Effects -I substituents strengthen acids and weaken bases carboxyl alkoxycarbonyl acyl hydroxyl mercapto amino chloro nitro cyano sulfonic acid alkoxy dialkylamino trimethylammonium fluoro bromo iodo X

23. Substituents with Electron-Releasing Inductive ( + I ) Effects +I substituents weaken acids and strengthen bases methyl alkyl oxide carboxylate R

24. increasing acidity

26. Benzoic Acid: pK a = 4.19 ortho meta para ortho meta para

27. Benzoic Acid: pK a = 4.19 2.97 4.06 4.48 4.08 4.46

28. Benzoic Acid: pK a = 4.19