200  C h a p t e r 5 Alkenes

PR OBL EMS
21. What is each compound’s systematic name?
CH3 Cl
HC 3
a. b. c.
CH3 CH3

22. Draw the structure of a hydrocarbon that has six carbon atoms and
a. three vinylic hydrogens and two allylic hydrogens.
b. three vinylic hydrogens and one allylic hydrogen.
c. three vinylic hydrogens and no allylic hydrogens.

23. Which of the following compounds is the most stable? Which is the least stable?

3,4-dimethyl-2-hexene; 2,3-dimethyl-2-hexene; 4,5-dimethyl-2-hexene

24. Draw the condensed structure for each of the following:

a. (Z)-1,3,5-tribromo-2-pentene c. (E)-1,2-dibromo-3-isopropyl-2-hexene e. 1,2-dimethylcyclopentene
b. (Z)-3-methyl-2-heptene d. vinyl bromide f. diallylamine

25. Draw the skeletal structures for the compounds in Problem 24.

26. a. Draw the condensed structures and give the systematic names for all the alkenes with molecular formula C6H12, ignoring
­stereoisomers. (Hint: There are 13.)
b. Which of the alkenes have E and Z isomers?
c. Which of the alkenes is the most stable?

27. Draw curved arrows to show the flow of electrons responsible for the conversion of the reactants into the products:
Cl
N N
+
+ Cl−

28. Name the following:

Cl Cl
a. c. e.
Cl

b. d. f.

Br
29. Which is more stable?

a. or b. or c. or

30. By following the curved red arrows, draw the product(s) of each of the following reaction steps. For each reaction, indicate which
reactant is the electrophile and which is the nucleophile.

O CH3 CH3
a. CH3CH2 Br b. C c. CH3C CCH3
CH3 CH3 H Cl
NH3
−
HO

31. How many of the following names are correct? Correct the incorrect names.
a. 3,4-dimethylpentane d. 2,8-dimethyl-4-ethylnonane g. (3Z,6Z)-3,6-dimethyl-3,6-decadiene
b. 3,6,8-trimethyldecane e. 3-methyl-6-ethyloctane h. 2-chloro-1-pentene
c. 4-ethyl-6-methyloctane f. 3-methyl-5-ethyloctane i. 3,3,4-trimethyl-1-decene
 Problems    201

32. Draw a reaction coordinate diagram for a two-step reaction in which the products of the first step are less stable than the reactants,
the reactants of the second step are less stable than the products of the second step, the final products are less stable than the initial
reactants, and the second step is the rate-determining step. Label the reactants, products, intermediates, and transition states.

33. Using curved arrows, show the mechanism of the following reaction:

O H O+ H +
OH H2O OH OH
C H C R C R R C R
R R R R +
OH OH
+
H H2O H3O

34. a. How many alkenes could you treat with H2, Pd/C in order to prepare methylcyclopentane?
b. Which of the alkenes is the most stable?
c. Which of the alkenes has the smallest heat of hydrogenation?

35. Given the reaction coordinate diagram for the reaction of A to form G, answer the following questions:
a. How many intermediates are formed in the reaction?
b. Which letters represent transition states? D
c. What is the fastest step in the reaction? B F
d. Which is more stable, A or G?

Free energy
e. Does A or E form faster from C? E
f. What is the reactant of the rate-determining step?
C
g. Is the first step of the reaction exergonic or endergonic? A
h. Is the overall reaction exergonic or endergonic?
i. Which is the more stable intermediate? G
j. Which step in the forward direction has the largest rate constant?
k. Which step in the reverse direction has the smallest rate constant? Progress of the reaction

36. a. Draw a reaction coordinate diagram for a reaction that is very slow and slightly exergonic.
b. Draw a reaction coordinate diagram for a reaction that is very fast and slightly endergonic.
c. Draw a reaction coordinate diagram for a reaction that is very slow and slightly endergonic.
d. Draw a reaction coordinate diagram for a reaction that is very fast and very exergonic.

37. Name each of the following:

Cl
Cl
a. b. c.
F Cl

38. a. Which of the following reactions will have the larger ∆S° value?
b. Will the ∆S° value be positive or negative?
Br OH Br
A + HO− + Br− B + HO− + H2O + Br−

39. Given that the twist-boat conformer of cyclohexane is 5.3 kcal/mol higher in free energy than the chair conformer, calculate the
percentage of twist-boat conformers present in a sample of cyclohexane at 25 °C. Does your answer agree with the statement made
on page 131 about the relative number of molecules in these two conformations?

The ∆G° for conversion of “axial” fluorocyclohexane to “equatorial” fluorocyclohexane at 25 °C is - 0.25 kcal>mol. Calculate
40. a. 
the percentage of fluorocyclohexane molecules that have the fluoro substituent in an equatorial position at equilibrium.
b. Do the same calculation for isopropylcyclohexane (its ∆G ° value at 25 °C is - 2.1 kcal/mol).
c. Why is the percentage of molecules with the substituent in an equatorial position greater for isopropylcyclohexane?