Homework Assignments

Chapter-6: Alkyl Halides- Substitution and Elimination reactions

1. Which of the following is a vicinal dihalide?
A) cis-1,2-dibromocyclopentane B) 3,3-dichloropentane

C) trans-1,4-diiodocyclohexane D) isobutyl chloride

E) 1,3-dibromoheptane

2. The flame retardant below has been found to be an androgen agonist and may have a
contribution to an increasing rate of occurrence of prostate cancer (J. Med. Chem. 2006, 7366).
What is the correct term that describes the relative position of the bromides in this structure?

A) germinal B) vinyl C) vicinal D) aryl

3. Which of the following alkyl chlorides will undergo SN2 reaction most readily (Hint: draw
structure and answer)?
A) 1-chloro-4-methylpentane B) 2-chloro-4-methylpentane

C) 2-chloro-3-methylpentane D) 3-chloro-2-methylpentane

E) 2-chloro-2-methylpentane

4. Provide a detailed, stepwise mechanism for the reaction below.

(CH3)2CHCH2CH2CH2I + CN- → (CH3)2CHCH2CH2CH2CH2CN + I-

5. Arrange the following species in order of increasing nucleophilicity:
CH3CH2S-, CH3CH2O-, (CH3)3CO-, (CH3)3COH.

6. Which of the following alkyl bromides undergoes solvolysis in aqueous methanol most rapidly?
A) PhCHBrCH3 B) (CH3)2CHCH2CH2Br
C) (CH3)2CHCH2CHBrCH3 D) CH3CH2CH2CH2Br
E) PhBr

7. Provide the major organic product of the reaction below and a detailed, stepwise mechanism
which accounts for its formation.

8. For of the following reactions, assume the concerted process is taking place and draw a
mechanism.

9. For of the following reactions, assume the concerted process is taking place and draw a
mechanism.
10. Identify which of the following substrate will undergo SN1 reaction more rapidly? Explain your
choice.

11. Draw the product for each of the following SN2 reactions:

12. When(S)-1 bromo-1 fluoroethane reacts with sodium methoxide, an SN2 reaction takes place in
which the atom is replaced by a methoxy group (OMe). The product of this reaction is (S) - 1
fluoro-1-methoxyethane. How can it be theat the starting material and the product both have
the S- configuration? Shouldn’t SN2 involve the change in configuration? Draw the starting
material and the product of inversion, and then explain the anomaly.
13. Draw the mechanism of the following SN1 process:

14. Rank the following molecules in order of increasing relative rate of SN1 solvolysis with methanol
and heat (slowest to fastest reacting).

A) 3 < 2 < 4 < 5 < 1 B) 2 < 3 < 4 < 1 < 5 C) 5 < 4 < 3 < 2 < 1
D) 2 < 3 < 4 < 5 < 1 E) 1 < 2 < 5 < 4 < 3

15. List the following bromides in order of their increasing reactivity as substrates in SN1 reactions:
1-iodo-1-ethylcyclopentane, chlorocyclopentane, and iodocyclopentane (draw the structure and
answer the question).
16. Draw the products that you expect in each of the following SN1 reaction:

17. Draw the mechanism for the following SN1 processes.

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18. Draw the two products that you expect in each of the following SN1 reaction and describe their
stereoisomeric relationship:

19. Treatment of (2R, 3R)-3 methyl-2 pentanol with H3O+ affords a compound with no chirality
centers. Predict the product of this reaction and draw the mechanism of its formation. Use
your mechanism to explain how both chirality centers are destroyed?

20. For each of the following substrate, determine whether an SN1 process is likely to involve a
carbocation rearrangement or not?

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 Carbocation Rearrangement with proton transfer process:

Energy diagram for carbocation rearrangement with proton transfer

21. Draw the mechanism of each of the following solvolysis reactions:

22. Identify whether each of the following substrate favors SN2, SN1, both, or neither?

23. Does each of the following nucleophile favor SN2 or SN1?

Important notes: Leaving group comparison
24. Determine whether the following reaction proceeds via an SN1 or an SN2 mechanism and
product(s) of the reaction

25. Determine whether the following reaction proceeds via an SN1 or an SN2 mechanism and
product(s) of the reaction

26. For each of the following pairs of compounds, identify which compound would react more
rapidly in an SN2 reaction. Explain your choice in each case.
27. For each of the following pairs of compounds, identify which compound would react more
rapidly in an SN2 reaction. Explain your choice in each case.

28. classify the following solvents as protic or aprotic

29. When the following optically active alcohol is treated with HBr, a racemic mixture of alkyl
bromide is obtained.

30. List the following carbocations in order of increasing stability.

31. consider the following reaction:

32. consider the following substitution reaction:

33. Arrange each set of compounds in order of reactivity towards the E2 process.

34. Identify the major and minor products for each of the following E2 reactions:

35. Identify the major and minor products for each of the following E2 reactions:
Things to memorize and understand.

36. Propose the mechanism for each of the following transformations: