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Chapter 06 - An Overview of Organic Reactions

Exhibit 6-1
Classify each reaction below as a(n):
a. addition
b. elimination
c. substitution
d. rearrangement
Place the letter corresponding to the correct answer in the blank to the left of the reaction.

1. _____

2. _____

3. _____

Exhibit 6-2
Identify the functional groups present in each compound below and predict the direction of polarity in each.

4. mustard gas ClCH2CH2SCH2CH2Cl


ANSWER:

5.

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Chapter 06 - An Overview of Organic Reactions

Exhibit 6-3
Classify each structure below as a nucleophile or electrophile and briefly explain your choice.

6.
ANSWER: Azide is a nucleophile since it has a net negative charge (and lots of electron pairs!).

7.

8.

Exhibit 6-4
Identify the nucleophile and electrophile in each reaction below and label them.

9.

10.

11.

Exhibit 6-5
Add curved arrows to the following reactions to indicate the flow of electrons in each.

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Chapter 06 - An Overview of Organic Reactions

12.
ANSWER:

POINTS: 1

13.

14.

15. Acidic ether cleavages are typical substitution reactions. Use the information in Table 6.3 of the textbook to calculate
H for the reaction of ethyl methyl ether with hydrogen chloride and hydrogen iodide.

a.
b.

Which acid would you predict to be most effective at ether cleavage?


CH
CH3CH2OH
a.3CH2OCH3 +
HCl + CH3Cl
Bonds Bonds
broken formed
CH3CH2OC CH3CH2O 436
339 kJ/mol
H3 H kJ/mol
351
HCl 432 kJ/mol CH3Cl kJ/mol
787
771 kJ/mol
kJ/mol
= H bonds broken
H H bonds formed =
771 787 kJ/mol
= 16 kJ/mol

Complete the
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Chapter 06 - An Overview of Organic Reactions
analysis to answer
this question

Exhibit 6-6
MATCH each definition to one of the terms below. Place the letter of the term in the blank to the left of the definition.
a. polarization f. substitution
b. addition reaction g. nucleophile
c. homolytic bond breakage h. radical reaction
d. electrophile i. elimination reaction
e. polar reaction j. heterolytic bond breakage

16. _____ A process involving symmetrical bond breaking and bond making.

17. _____ This occurs when both bonding electrons remain with one product fragment.

18. _____ A reaction where two reactants exchange parts to give two new products.

19. _____ A general term for species which have electron rich sites that can form a bond by donating a pair of electrons to
an electron poor site.

Exhibit 6-7
Consider this reaction when answering the following question(s):

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Chapter 06 - An Overview of Organic Reactions

20. Refer to Exhibit 6-7. This reaction is an example of:


a. a substitution reaction.
b. a rearrangement reaction.
c. an addition reaction.
d. an elimination reaction.
ANSWER: b

21. Refer to Exhibit 6-7.


The structures below show the step-wise bond making and bond breaking in this reaction.
a.
Draw curved arrows to show the electron flow that has occurred in each step.

b. Calculate Keq for the reaction in part a @ 25 degree centigrage

c. Calculate G for the reaction in part a.


ANSWER:

a.

b. Keq = [products]/[reactants] = 76/24 = 3.17

c. G= RT ln Keq = 8.314 J/(K mol)(298) ln 3.17 = 2.86 x 103 J/mol = 2.86 kJ/mol

23. Refer to Exhibit 6-7. Draw a qualitative energy diagram for the reaction (assume that the first step is slower than the
second step). Label fully.
ANSWER:

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Chapter 06 - An Overview of Organic Reactions

POINTS: 1

Exhibit 6-8
MATCH each definition to one of the terms below. Place the letter corresponding to the term in the blank to the left of the
definition.
a. transition state d. standard Gibbs free energy change
b. endergonic reaction e. exergonic reaction
c. activation energy f. reaction intermediate

24. _____ A species that lies at an energy minimum between steps on a reaction.

25. _____ The energy needed by reactants to reach the transition state.

26. _____ A reaction where G is negative.

27. _____ G = RT ln Keq

Exhibit 6-9
Use the reaction energy diagram below to answer the following question(s).

28. Refer to Exhibit 6-9. The reaction depicted in this reaction energy diagram can best be described as:
a. a slow exothermic reaction
b. a fast exothermic reaction
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Chapter 06 - An Overview of Organic Reactions
c. a slow endothermic reaction
d. a fast endothermic reaction

29. Refer to Exhibit 6-9. The transition state is found at point _____ on the diagram.

30. Refer to Exhibit 6-9. The products are found at point _____ on the diagram.

31. Refer to Exhibit 6-9. The free-energy change for the reaction is indicated at point _____ on the diagram.

32. Refer to Exhibit 6-9. The reactants are found at point _____ on the diagram.

Exhibit 6-10
Consider the reaction of 2-bromo-2-methylpropane with water, shown below, to answer the following question(s).

Diagram 1: The first step of this reaction is shown below.

Diagram 2: The second and third steps of the reaction are shown below.

33. Refer to Exhibit 6-10. This reaction is an example of:


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Chapter 06 - An Overview of Organic Reactions
a. a substitution reaction.
b. a rearrangement reaction.
c. an elimination reaction.
d. an addition reaction.

34. Refer to Exhibit 6-10. In Diagram 1, Species B is:


a. a carbene
b. a carbanion
c. a carbocation
d. a radical

35. Refer to Exhibit 6-10. In Diagram 1, add curved arrows to indicate electron flow.

36. Refer to Exhibit 6-10. In Diagram 2, label the nucleophile, Nu, and the electrophile, E+, in the blanks provided under
the structures.
ANSWER:

37. Refer to Exhibit 6-10. In Diagram 2, draw arrows on the structures showing electron flow.

38. Refer to Exhibit 6-10. The reaction in Diagram 2 is an example of:


a. a pericyclic reaction.
b. a radical reaction.
c. a concerted reaction.
d. a stepwise reaction.
ANSWER: d

39. Refer to Exhibit 6-10. Using the bond dissociations values in the table below, calculate the H for the reaction in
Diagram 2. Show your calculations for full credit.
Bond D (kJ/mol)
(CH3)3CBr 263
(CH3)3COH 380
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Chapter 06 - An Overview of Organic Reactions
HOH 498
HBr 366
ANSWER: H = H bonds broken H bonds formed
= 761 kJ/mol 746 kJ/mol
= +15 kJ/mol
Bonds Broken Bonds Formed
(CH3)3CBr 263 kJ/mol (CH3)3COH 380 kJ/mol
HOH 498 kJ/mol HBr 366 kJ/mol
761 kJ/mol 746 kJ/mol

40. Refer to Exhibit 6-10. Based on all of the data presented in Exhibit 6-10, draw a qualitative reaction energy diagram
for the reaction of 2-bromo-2-methylpropane with water. The first step is the slowest step of the reaction. Fully label the
diagram, including the coordinates.
ANSWER:

POINTS: 1

Exhibit 6-11
In each reaction below:
a. Label the nucleophile (Nu) and the electrophile (E).
b. Draw arrows on the structures showing electron flow in the reaction.

41.

42.
ANSWER:
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Chapter 06 - An Overview of Organic Reactions

43. The following represents the carbocation intermediate in the reaction of an alkene with HBr.

Draw the skeletal structure of the possible products and reactants.


ANSWER: Two possible reactants:

One product:

POINTS: 1

44. What are the major differences between a reaction occurring in flask in the laboratory compared to a reaction
occurring in a biological system?
ANSWER: Solvent: Laboratory reactions occur in nonpolar solvents whereas biological reactions occur in an aqueous
environment.
Temperature: Laboratory reactions can be carried out at very low temperatures or very high temperatures or
anywhere in between whereas biological reactions are limited to the organisms body temperature which for
warm-blooded species is a very narrow range.
Catalysis: Laboratory reactions can occur with or without catalysts and the catalysts can be acids, bases, metal
surfaces, etc. Biological reactions are catalyzed by large protein molecules called enzymes, that often require
coenzymes or cofactors to function. Laboratory catalysts in general are nonspecific, an acid or Pt surface can
catalyze many different reactants or reactions. Enzymes are highly specific - a given enzyme may only be able
to catalyze the reaction of one reactant (substrate) or one class of reactions.
pH: Laboratory reactions can occur at a variety of pHs whereas biological reactions must function within
narrow physiological pH limits.

45. The alkane formed by hydrogenation of (S)-4-methyl-1-hexene is optically active while the one formed by
hydrogenation of (S)-3-methyl-1-pentene is not. Explain. Draw the structures of reactants and structures to understand this
question and the answer below.
ANSWER: Each starting alkene is optically active because it contains a chiral center a carbon with four different groups
bonded to it. The alkane formed by the hydrogenation of (S)-4-methyl-1-hexene is optically active because
carbon four is still chiral. The product of hydrogenation of (S)-3-methyl-1-pentene is not optically active
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Chapter 06 - An Overview of Organic Reactions
because two of the groups on carbon three are the same now they are ethyl groups.

46. The enzyme aconitase catalyzes the hydration of the alkene functional group of aconitic acid to give two products,
citric acid and isocitric acid. Isocitric acid is optically active; citric acid is not optically active. Based on your knowledge
of alkene hydration and optical activity, the structure of citric acid is:

a. b.

c. d. cannot be determined

47. Which of the following could act as an electrophile?


a. CN b. NH2
c. NH3 d. H3O+

48. Which of the following could act as a nucleophile?


a. HCl b. CH3NH2
c. BF3 d. CH3Br

49. Consider the following grayscale electrostatic potential map. The regions are labeled as to color.

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Chapter 06 - An Overview of Organic Reactions

Which atom is the most electron poor?


a. 1 b. 2
c. 3 d. 4

50. Consider the following grayscale electrostatic potential map. The regions are labeled as to color.

Which atom is the most likely to be attacked by a nucleophile?


a. 1 b. 2
c. 3 d. 4

51. In a polar reaction mechanism, the atom that gives away electrons in a neutral nucleophile will end up as a(n):
a. cation b. anion
c. radical d. neutral molecule

52. Consider the following.

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Chapter 06 - An Overview of Organic Reactions
This process would result in the formation of:
a. a positive ion and negative ion.
b. two neutral species.
c. two radicals.
d. two negative ions.
e. a positive ion and a neutral species.
f. a negative ion and a neutral species.

53. Consider the following process.

Which of the following correctly applies?


a. termination step b. unsymmetrical bond formation
c. polar reaction d. produces a radical
ANSWER: a

54. A reaction that establishes equilibrium with almost no reactants present:


a. is exergonic.
b. has a negative G.
c. has a large Keq.
d. all of the above.
ANSWER: d

55. A reaction has H = 14.7 kJ and S of 35.7 J/(K mol), will


a. be exergonic. b. have a positive G.
c. have a very small Keq. d. will proceed rapidly.

58. Consider the following energy diagram for an enzyme-catalyzed reaction.

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Chapter 06 - An Overview of Organic Reactions

How many transition states are involved?


a. 2 b. 3
c. 4 d. 5

59. Consider the following energy diagram.

Which step has the least endergonic G?


a. A - C b. C - E
c. E - G d. G - I

POINTS: 1

60. Consider the following energy diagram for an enzyme-catalyzed reaction.

Which step is probably the slowest?


a. A - C b. C - E
c. E - G d. G - I
ANSWER: c

61. Consider the following energy diagram for an enzyme-catalyzed reaction.

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Chapter 06 - An Overview of Organic Reactions

Which step has the least energetic transition state?


a. A - C b. C - E
c. E - G d. G - I

62. Write the mechanism of the reaction of trans-2-butene with hydrogen bromide.

63. Write the mechanism of the reaction between water and ammonia.

64. Write the mechanism of the reaction between hydroxide ion and methyl chloride.

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