1. 1-1 Chemistry 121, Winter 2015, LA Tech Introduction to Organic Chemistry and Biochemistry Instructor Dr. Upali Siriwardane (Ph.D. Ohio State) E-mail: upali@latech.edu Office: 311 Carson Taylor Hall ; Phone: 318-257-4941; Office Hours: MTW 8:00 - 10:00 am; ThF 9:00 - 10:00 am 1:00 - 2:00 pm. December 19, 2014: Test 1 (Chapters 12-13) January 26, 2015: Test 2 (Chapters 14-16) February 13, 2015: Test 3 (Chapters 17-19) March 2, 2015: Test 4 (Chapters 20-22) March 3, 2015: Make Up Exam: Chapters 12-22) Bring Scantron Sheet 882-E Chemistry 121(001) Winter 2015 1

2. 1-2 Chemistry 121, Winter 2015, LA Tech Chapter 16 and GHW#6 Questions Carboxylic Acids, Esters, and Other Acid Derivatives

3. 1-3 Chemistry 121, Winter 2015, LA Tech Chapter 16: Carboxylic Acids, Esters, and Other Acid Derivatives 16.1 Structure of Carboxylic Acids and Their Derivatives, 503 16.2 IUPAC Nomenclature for Carboxylic Acids, 506 16.3 Common Names for Carboxylic Acids, 508 16.4 Polyfunctional Carboxylic Acids, 510 16.5 Physical Properties of Carboxylic Acids, 512 16.6 Preparation of Carboxylic Acids, 514 16.7 Acidity of Carboxylic Acids, 514 16.8 Carboxylic Acid Salts, 515 16.9 Structure of Esters, 517 16.10 Preparation of Esters, 518 16.11 Nomenclature for Esters, 520 16.12 Selected Common Esters, 522 16.13 Isomerism for Carboxylic Acids and Esters, 524 16.14 Physical Properties of Esters, 526 16.15 Chemical Reactions of Esters, 526 16.16 Sulfur Analogs of Esters, 528 16.17 Polyesters, 529 16.18 Acid Chlorides and Acid Anhydrides, 531

4. 1-4 Chemistry 121, Winter 2015, LA Tech Bonding Characteristics of Carboxylic Acids A carboxylic acid has functional a carboxyl group. A carboxyl group is a carbonyl group (C=O) with a hydroxo group (—OH) bonded to the carboxyl carbon atom.

5. 1-5 Chemistry 121, Winter 2015, LA Tech Physical Properties of Carboxylic Acids Both polar molecules and hydrogen bonding makes: BP and MP are higher than alcohols, hydrocarbons and ether with comparable carbon numbers

6. 1-6 Chemistry 121, Winter 2015, LA Tech Acidity

7. 1-7 Chemistry 121, Winter 2015, LA Tech Physical Properties of carboxylic acids derivatives Esters, amides, acid chlorides and acid anhydride have lower boiling and melting points than parent acid, Except Carboxylic Acid Salts

8. 1-8 Chemistry 121, Winter 2015, LA Tech IUPAC Nomenclature of Carboxylic Acid and Esters The IUPAC system deals with functional groups two different ways. Modification of the hydrocarbon name to indicate the presence of a functional group. Acid – R-COOH oic Acid – R-COOH use -oic ending. oate Esters –R-COOR’ use -oate ending.

9. 1-9 Chemistry 121, Winter 2015, LA Tech Common Names of Carboxylic Acids

10. 1-10 Chemistry 121, Winter 2015, LA Tech IUPAC Nomenclature of Carboxylic Acid and Esters

11. 1-11 Chemistry 121, Winter 2015, LA Tech Carboxylic Acids

12. 1-12 Chemistry 121, Winter 2015, LA Tech Esters as Flavors

13. 1-13 Chemistry 121, Winter 2015, LA Tech Common/IUPAC Nomenclature of Esters

14. 1-14 Chemistry 121, Winter 2015, LA Tech Metal alkanoate (-oate suffix for anion) E.g. sodium salt of proponoic acid is named as sodium proponate Nomenclature of Carboxylate salts

15. 1-15 Chemistry 121, Winter 2015, LA Tech Alkanoic anhydride (-oic anhydride suffix) E.g. anhydride of propanoic acid is named as propanoic anhydride Mixed acid anhydride are name butanoic propanoic anhydirdes Nomenclature of Acid Anhydrides

16. 1-16 Chemistry 121, Winter 2015, LA Tech 1. Identify the carboxylic acids, esters, amides and acid from the following and give their common and/or IUPAC names. Carboxylic Acids, Esters, and Other Acid Derivatives a)Type:___________ Name:____________ b) Type:_________________ Name:__________________ c)Type:_________________ Name:__________________ d)Type:___________ Name:____________ e)Type:_________________ Name:__________________ f)Type:_________________ Name:__________________

17. 1-17 Chemistry 121, Winter 2015, LA Tech 1. Identify the carboxylic acids, esters, amides and acid from the following and give their common and/or IUPAC names. Carboxylic Acids, Esters, and Other Acid Derivatives g) Type:________________ Name:_______________ ___ h) Type:___________________ Name:__________________ i) Type:___________________ Name:__________________

18. 1-18 Chemistry 121, Winter 2015, LA Tech 2. Draw the condensed formula of following carboxylic acid and their derivatives. a) methyl propanoate b) ethyl pentanoate c) propanoyl chloride d) N-methyl propanamide e) N,N-dimethyl ethanamide f) 2-methyl pentanamide g) 2(  )- aminopropan oic h) butanoic ethanoic anhydride

19. 1-19 Chemistry 121, Winter 2015, LA Tech Polyfunctional Carboxylic Acids Dicarboxylic acids Oh my, such great apple pie!“ Oh my, such great apple pie!“ (oxalic, malonic, succinic, glutaric, adipic, pimelic) (oxalic, malonic, succinic, glutaric, adipic, pimelic) "Metabolic" Acids Propionic acid, (C3 mono acids): lactic, glyceric, and pyruvic acids Succinic acid (C4 diacid): fumaric, oxaloacetic, and malic acids Glutaric acid (C5 diacid):  -ketoglutaric and citric acids

20. 1-20 Chemistry 121, Winter 2015, LA Tech 3. Identify type and give name of each of the following poly functional carboxylic acids. a) Type:________________ Name:_______________ b) Type:______________ Name:_____________ c) Type:_______________ Name:______________ d) Type:________________ Nmee:_______________ e) Type:__________ Name:__________ f) Type:____________ Name:___________

21. 1-21 Chemistry 121, Winter 2015, LA Tech 3. Give common/IUPAC names of following dicarboxylic acids. Use "Oh my, such great apple pie!" (oxalic, malonic, succinic, glutaric, adipic, pimelic). a) Common:___________ IUPAC:_____________ __ b) Common:___________ IUPAC:_____________ __ c) Common:____________ IUPAC:_______________ d) Common:___________ IUPAC:_____________ e) Common:___________ IUPAC:_____________

22. 1-22 Chemistry 121, Winter 2015, LA Tech 3. Give common/IUPAC names of following dicarboxylic acids. f) Name:______________g) Name:__________h)Common:__________ IUPAC:______________

23. 1-23 Chemistry 121, Winter 2015, LA Tech Saturated Fatty Acids Saturated Fatty Acids Long chain even carbon atoms C >10

24. 1-24 Chemistry 121, Winter 2015, LA Tech Unsaturated Fatty Acids Unsaturated Fatty Acids Long chain even carbon atoms with C=C bonds

25. 1-25 Chemistry 121, Winter 2015, LA Tech 5. Give type/name of following fatty acids, and their derivatives. a)CH 3 (CH 2 ) 10 CO 2 H Type:_______________ Name:______________ b) CH 3 (CH 2 ) 14 CO 2 H Type:________________ Name:_______________ c) CH 3 (CH 2 ) 16 CO 2 H Type:________________ Name:_______________

26. 1-26 Chemistry 121, Winter 2015, LA Tech 5. Give type/name of following fatty acids, and their derivatives. d) CH 3 (CH 2 ) 7 CH=CH(CH 2 ) 7 CO 2 H Type:________________ Name:_______________ e) f) Type:________________ Name:________________ Type:_______________ Name:___________

27. 1-27 Chemistry 121, Winter 2015, LA Tech Triglycerides: Triesters of glycerol

28. 1-28 Chemistry 121, Winter 2015, LA Tech Preparation of Carboxylic Acids Oxidation of primary alcohol to carboxylic acid (described in reactions of alcohols) Tollen’s Oxidation using basic Ag(NH 3 ) 2+ or Bendict’s CuSO 4 /Na 2 CO 2 /Citrate (described in reactions of aldehydes) Oxidation of alkyl side chain of substituted aromatic hydrocarbons (reactions of aromatic alkyl compounds) Hydrolysis of esters. (Described in this chapter) Hydrolysis of acid, amides and cholrides etc.. )

29. 1-29 Chemistry 121, Winter 2015, LA Tech Non-aromatic carboxylic acids: Oxidation of primary alcohols or aldehydes, using an oxidizing agent such as K 2 Cr 2 O 7 Aromatic carboxylic acids: Oxidation of a carbon side chain (alkyl group) on a benzene derivative Examples: Oxidation of Alcohols to Carboxylic Acids

30. 1-30 Chemistry 121, Winter 2015, LA Tech Oxidation of primary alcohols

31. 1-31 Chemistry 121, Winter 2015, LA Tech Tollen’s and Benedict’s Oxidation of alkyl side chain substituted on a benzene ring Oxidation of Aldehydes

32. 1-32 Chemistry 121, Winter 2015, LA Tech Chemical Reactions of Carboxylic Acids Reduction to alcohols with reducing agents (LiAlH 4, NaBH 4 etc.) Reaction with halogen compounds to form acid chlorides(described below in preparation of acid chloride preparations) Reaction with strong bases to form acid salts (described below in preparation of acid salts) Reaction with strong alcohols to form esters (described below in preparation of esters) Reaction with ammonia and amine compounds to form amides (described in amides chapter 17)

33. 1-33 Chemistry 121, Winter 2015, LA Tech Carboxylic Acid Reduction: To alcohols

34. 1-34 Chemistry 121, Winter 2015, LA Tech Acid chloride Formation

35. 1-35 Chemistry 121, Winter 2015, LA Tech Preparation of esters. Esterification acid + alcohol ----> ester + H 2 O

36. 1-36 Chemistry 121, Winter 2015, LA Tech Amide Formation (Cl)

37. 1-37 Chemistry 121, Winter 2015, LA Tech 6) Name and complete following reactions 1) 2) 3) 4)

38. 1-38 Chemistry 121, Winter 2015, LA Tech 6) Name and complete following reactions 5) 6)

39. 1-39 Chemistry 121, Winter 2015, LA Tech Polymers are formed by reacting difunctional monomers Examples: dicarboxylic acids and dialcohols are used for the formation of polyesters Two important polymers: Poly(ethylene terephthalate) (PET) Lactomer Polyesters

40. 1-40 Chemistry 121, Winter 2015, LA Tech Poly(ethylene terephthalate) (PET): Prepared by reacting terephthalic acid (a diacid) and ethylene glycol (a dialcohol) Used for making textiles and other plastic applications Poly(ethylene terephthalate)Poly(ethylene terephthalate)

41. 1-41 Chemistry 121, Winter 2015, LA Tech Lactomer: Used in surgical staples because of its biodgradable nature It simply dissolves after several weeks and the by-products formed are lactic acid and glycolic acid both of which are part of human body Biodgradable PolymersBiodgradable Polymers

42. 1-42 Chemistry 121, Winter 2015, LA Tech 7) Name and complete following reactions. 1)Condensation Polymerization 2) Aspirin synthesis

43. 1-43 Chemistry 121, Winter 2015, LA Tech Cyclic Esters (Lactones) Hydroxy acids contain both a hydroxyl and a carboxyl group and such compounds have the capacity to undergo intermolecular esterification to form cyclic esters Takes place in situations where a five- or six-membered ring can be formed Cyclic esters are called lactones  -lactone  -lactone  -lactone  -lactone

44. 1-44 Chemistry 121, Winter 2015, LA Tech 7) Name and complete following reactions. 3) Cyclic ester formation 4) Decarboxylation of  - ketoacids

45. 1-45 Chemistry 121, Winter 2015, LA Tech Fatty acids and Glycerides Fatty Acids Glycerides

46. 1-46 Chemistry 121, Winter 2015, LA Tech 7) Name and complete following reactions. 5) Base hydrolysis of esters 6) Base hydrolysis of triglycerides

47. 1-47 Chemistry 121, Winter 2015, LA Tech Base hydrolysis of triglycerides Saponification-Soap formation