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Chapter 17

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  1. Chapter 17 Carboxylic Acids and Their Derivatives Nucleophilic Addition–Elimination at the Acyl Carbon

  2. About The Authors These PowerPoint Lecture Slides were created and prepared by Professor William Tam and his wife, Dr. Phillis Chang. Professor William Tam received his B.Sc. at the University of Hong Kong in 1990 and his Ph.D. at the University of Toronto (Canada) in 1995. He was an NSERC postdoctoral fellow at the Imperial College (UK) and at Harvard University (USA). He joined the Department of Chemistry at the University of Guelph (Ontario, Canada) in 1998 and is currently a Full Professor and Associate Chair in the department. Professor Tam has received several awards in research and teaching, and according to Essential Science Indicators, he is currently ranked as the Top 1% most cited Chemists worldwide. He has published four books and over 80 scientific papers in top international journals such as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem. Dr. Phillis Chang received her B.Sc. at New York University (USA) in 1994, her M.Sc. and Ph.D. in 1997 and 2001 at the University of Guelph (Canada). She lives in Guelph with her husband, William, and their son, Matthew.

  3. Introduction • Carboxylic Acid Derivatives

  4. Nomenclature and PhysicalProperties • Nomenclature of Carboxylic Acids and Derivatives • Rules • Carboxylic acid as parent (suffix): ending with “–oic acid” • Carboxylate as parent (suffix): ending with “–oate”

  5. Most anhydrides are named by dropping the word acid from the name of the carboxylic acid and then adding the word “anhydride” • Acid chloride as parent (suffix): ending with “–oyl chloride” • Ester as parent (suffix): ending with “–oate” • Amide as parent (suffix): ending with “amide” • Nitrile as parent (suffix): ending with “nitrile”

  6. Examples

  7. Examples

  8. 2C. Acidity of Carboxylic Acids pKa ~ 4-5 • Compare • pKa of H2O ~ 16 • pKa of H2CO3 ~ 7 • pKa of HF ~ 3

  9. When comparing acidity of organic compounds, we compare the stability of their conjugate bases. The more stable the conjugate base, the stronger the acid

  10. The conjugate base B1 is more stable (the anion is more delocalized) than B2 due to resonance stabilization • Thus, A1 is a stronger acid than A2

  11. Acidity of Carboxylic Acids, Phenols and Alcohols

  12. Acidity of Carboxylic Acids, Phenols and Alcohols

  13. Acidity of Carboxylic Acids, Phenols and Alcohols

  14. Acidity of Carboxylic Acids, Phenols and Alcohols (NO resonance stabilization)

  15. Question • If you are given three unknown samples: one is benzoic acid; one is phenol; and one is cyclohexyl alcohol; how would you distinguish them by simple chemical tests? • Recall: acidity of

  16. Stability of conjugate bases > > > > > >

  17. > > > > > > > > >

  18. 2D. Dicarboxylic Acids

  19. 2J. Spectroscopic Properties ofAcyl Compounds • IR Spectra • The C=O stretching band occurs at different frequencies for acids, esters, and amides, and its precise location is often helpful in structure determination • Conjugation and electron-donating groups bonded to the carbonyl shift the location of the C=O absorption to lower frequencies

  20. IR Spectra • Electron-withdrawing groups bonded to the carbonyl shift the C=O absorption to higher frequencies • The hydroxyl groups of carboxylic acids also give rise to a broad peak in the 2500-3100-cm-1 region arising from O–H stretching vibrations • The N–H stretching vibrations of amides absorb between 3140 and 3500 cm-1

  21. 1H NMR Spectra • The acidic protons of carboxylic acids are highly deshielded and absorb far downfield in the d 10-12 region • The protons of the a carbon of carboxylic acids absorb in the d 2.0-2.5 region

  22. 13C NMR Spectra • The carbonyl carbon of carboxylic acids and their derivatives occurs downfield in the d 160-180 region (see the following examples), but not as far downfield as for aldehydes and ketones (d 180-220) • The nitrile carbon is not shifted so far downfield and absorbs in the d 115-120 region

  23. 13C NMR chemical shifts for the carbonyl or nitrile carbon atom

  24. Preparation of Carboxylic Acids • By oxidation cleavage of alkenes • Using KMnO4 • Using ozonolysis

  25. By oxidation of aldehydes & 1o alcohols • e.g.

  26. By oxidation of alkyl benzene

  27. By oxidation of benzene ring • e.g.

  28. By hydrolysis of cyanohydrins and other nitriles • e.g.

  29. By carbonation of Grignard reagents • e.g.

  30. Acyl Substitution: Nucleophilic Addition-Elimination at the Acyl Carbon • This nucleophilic acyl substitution occurs through a nucleophilic addition-elimination mechanism

  31. This type of nucleophilic acyl substitution reaction is common for carboxylic acids and their derivatives

  32. Unlike carboxylic acids and their derivatives, aldehydes & ketones usually do not undergo this type of nucleophilic acyl substitution, due to the lack of an acyl leaving group A good leaving group Not a good leaving group

  33. Relative reactivity of carboxylic acid derivatives towards nucleophilic acyl substitution reactions • There are 2 steps in a nucleophilic acyl substitution • The addition of the nucleophile to the carbonyl group • The elimination of the leaving group in the tetrahedral intermediate

  34. Usually the addition step (the first step) is the rate-determining step (r.d.s.). As soon as the tetrahedral intermediate is formed, elimination usually occurs spontaneously to regenerate the carbonyl group • Thus, both steric and electronic factors that affect the rate of the addition of a nucleophile control the reactivity of the carboxylic acid derivative

  35. Steric factor • Electronic factor • The strongly polarized acid derivatives react more readily than less polar ones

  36. Thus, reactivity of • An important consequence of this reactivity • It is usually possible to convert a more reactive acid derivative to a less reactive one, but not vice versa

  37. Acyl Chlorides 5A. Synthesis of Acyl Chlorides • Conversion of carboxylic acids to acid chlorides • Common reagents • SOCl2 • (COCl)2 • PCl3 or PCl5

  38. Mechanism

  39. Nucleophilic acyl substitution reactions of acid chlorides • Conversion of acid chlorides to carboxylic acids

  40. Mechanism

  41. Conversion of acid chlorides to other carboxylic derivatives

  42. Carboxylic Acid Anhydrides 6A. Synthesis of Carboxylic AcidAnhydrides

  43. 6B. Reactions of Carboxylic AcidAnhydrides • Conversion of acid anhydrides to carboxylic acids