ORG2 (Chapter 21 - Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions)

Chapter 21 - Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions

58 flashcards · Other · by John Mark Webb

1. A _____ reactive derivative can be converted into a _____ one.

   more; less

2. In the conversion of acid anhydrides to esters, acetic anhydride forms _____ _____ from alcohols. This occurs in basic conditions = _____ / _____.

   acetate esters; NaOH / H2O

3. In the conversion of acid anhydrides to amides, acetic anhydride is used to prepare N-substituted _____ from amines. This occurs in basic conditions = _____ / _____.

   acetamides; NaOH / H2O

4. Esters are usually prepared from _____ _____.

   carboxylic acids

5. Acid chlorides are converted into esters by treatment with a(n) _____ in the presence of a(n) _____.

   alcohol; base (pyridine or NaOH)

6. What is the limitation when R–COOH is treated with 1. NaOH / 2. R'X to form R–COOR'?

   –R' can only come from a PRIMARY alkyl halide

7. Go step by step to form an ester from a carboxylic acid.

   R–COOH treated w/ SOCl2 ==> acid chlorideacid chloride treated w/ R'–OH / pyridine ==> R–COOR'

8. Esters are less reactive toward nucleophiles as compared to _____ _____ or _____.

   acid chlorides; anhydrides

9. Cyclic esters are called _____ and react similarly to _____ _____.

   lactones; acyclic esters

10. Hydrolysis of esters forms _____ _____.

    carboxylic acids

11. An ester is hydrolyzed by aqueous _____ or a aqueous _____ to yield a carboxylic acid and an alcohol.

    base; acid

12. What is saponification?

    ester hydrolysis in basic solution

13. Nucleophilic addition of -OH to the ester carbonyl group gives the usual _____ _____ intermediate which is then deprotonated to form a(n) _____ ion.

    tetrahedral alkoxide; carboxylate

14. Fischer esterification is a(n) _____-catalyzed ester hydrolysis reaction. It involves a _____ intermediate and the transfer of a proton to OR' to make it a better _____ _____.

    acid; tetrahedral; leaving group

15. Ammonia reacts with esters to form _____ because esters are _____ reactive.

    amides; more

16. A reduction (LiAlH4) of esters yields _____ _____.

    primary alcohols

17. A reduction (LiAlH4) of lactones yields a _____.

    diol

18. Esters react with 2 equivalents of a Grignard reagent (followed by H3O+) to yield a _____ alcohol

    tertiary

19. The aldehyde intermediate of ester reduction can be isolated if 1 equivalent of _____ is used as the reducing agent.

    DIBAH (DIBAL-H)

20. Amides are the _____ reactive of the common acid derivative.

    least

21. A cyclic amide is called a _____.

    lactam

22. You need at least _____ hydrogen(s) attached to nitrogen to make an amide.

    one

23. The conversion of amides into carboxylic acids is _____.

    hydrolysis

24. Order in increasing reactivity: thioester ester acid anhydride acid chloride amide

    amide ester thioester acid anhydride acid chloride

25. Nucleophiles react more readily with _____ carbonyl groups.

    unhindered

26. Carboxylic acid derivatives undergo _____ _____ _____ and does have a leaving group.

    nucleophilic acyl substitution

27. Acid chloride reacts with NH3 to yield _____.

    an amide (–Cl ==> NH2)

28. Acid chloride reacts with H20 to yield _____.

    a carboxylic acid (–Cl ==> –OH)

29. A tertiary amine (will / won't) react with acid chloride.

    won't

30. Acid chloride reacts with R'–OH to yield _____.

    an ester (–Cl ==> –OR')

31. Acid chloride reacts with R'–CO2– to yield _____.

    an acid anhydride

32. Acid chloride reacts with R'2–CuLi to yield _____.

    a ketone (–Cl ==> –R')

33. A carboxylate ion is formed from reacting a carboxylic acid with _____ or _____.

    NaOH; NaHCO3

34. What reagent would you use to convert a carboxylic acid to an acid chloride? Acid bromide?

    SOCl2 PBr3

35. With SOCl2, carboxylic acid is converted into a _____ _____ which then reacts with _____.

    chlorosulfite intermediate; chloride

36. Acid anhydrides can be derived from two molecules of _____ _____ by heating to remove _____.

    carboxylic acid; water

37. Fischer esterification reaction involves the synthesis of esters by an _____ _____ nucleophilic acyl substitution reaction of a carboxylic acid with an _____.

    acid-catalyzed (H–Cl); alcohol

38. Conversion of carboxylic acid into esters occur through a reaction of a _____ _____ with a primary _____ _____.

    carboxylate anion (RO-); alkyl halide (CH3–I) (RO- produced from reacting a carboxylic acid with NaOH or NaHCO3)

39. In a Grignard reaction, a(n) _____ reagent is used to make a(n) _____ or _____.

    organometallic; ketone; alcohol (R'MgX)

40. In a reduction reaction, a(n) _____ _____ is used to make a(n) _____ or _____.

    hydride source; aldehyde; alcohol (NaBH4, LiAlH4, H-)

41. The conversion of carboxylic acids into amides is difficult with a direct reaction. It is prepared by activating the carboxylic acid with _____ followed by the addition of the amine.

    DCC (amine = R–:NH2)

42. Carboxylic acids are reduced by _____ to give _____ _____.

    LiAlH4; primary alcohols

43. In aminolysis, _____ or a(n) _____ is used to make an _____.

    ammonia; amine; amide

44. Esters are produced in the reaction of acid chlorides with _____ in the presence of _____ or _____

    alcohols; pyridine; NaOH

45. When converting acid halides into esters, the _____ _____ alcohol attacks the _____ _____.

    less hindered; carbonyl carbon

46. In the conversion of acid halides into amides, _____ _____ cannot be used.

    trisubstituted amines (R3N)

47. LiAlH4 reduces acid chlorides to yield _____ and then _____ _____.

    aldehydes; primary alcohols

48. In alcoholysis, _____ is used as a reagent to make _____.

    alcohol; esters

49. In hydrolysis, _____ is used as a reagent to make _____ _____.

    water; carboxylic acids

50. Acid anhydride and water yield _____ _____.

    2 carboxylic acids

51. What mechanism does reduction occur?

    nucleophilic acyl substitution

52. Grignard reagents react with acid chlorides to yield _____ _____ with two identical substituents.

    tertiary alcohols (CH3MgBr/ether and then CH3MgBr/H3O+)

53. Grignard reagents react with acid chlorides to yield tertiary alcohols with _____ _____ _____.

    two identical substituents

54. The diorganocopper reaction (Gilman reagent) converts an acid chloride into a(n) _____.

    ketone

55. The diorganocopper reaction (Gilman reagent) converts an acid chloride into a ketone. There is an _____ _____ intermediate.

    acyl diorganocopper

56. In the preparation of an acid anhydride, there is a nucleophilic acyl substitution of a(n) _____ with a(n) _____.

    carboxylate; acid chloride

57. Acid chloride and water yield _____ _____.

    carboxylic acid

58. Acid halides and acid anhydrides react rapidly with _____.

    water