202-DCP-05 Organic Chemistry 1 – Problem Set 6 M.

Hachey
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1. Explain why alkanes are generally considered unreactive compounds.

2. Rank each group of radicals in order of increasing stability:

a)

b)

c) Abstraction of a hydrogen atom from 3-ethylpentane can yield three different radicals,
depending on which hydrogen atom is abstracted. Draw all three radicals and rank them
in order of increasing stability.

3. Provide the full mechanism (initiation, propagation and termination) to account for the
following reaction:

4. How many products are formed from the monochlorination of ethylcyclohexane? Draw
the structures of all products and identify the major product. If bromine, more selective
reagent, is used to react instead, how many products are expected?

5. Draw four dibromo products that could be obtained by radical bromination of propane.
Show the reaction pathway or mechanism for the compound that you think would be the
major product. Also, which of the four dibromo products are chiral?

6. Provide the full mechanism for the radical chlorination of 2,2-dichloropropane to produce
1,2,2-trichloropropane.

7. In practice, the chlorination of methane often produces many by-products. For example,
ethyl chloride (CH3CH2Cl) is obtained in small quantities. Can you suggest a mechanism
for the formation of ethyl chloride?

8. The relative rates of termination of methyl and isopropyl radicals are quite different. Give
two possible reasons for this difference.

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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9. For each radical, draw all resonance structures using curved-arrow. For resonance
structures involving radicals, single barbed arrows are used.

a) b) c)

d) e) f)

10. 5-methylcyclopentadiene, shown to the right, undergoes homolytic bond

cleavage of a C-H bond to form a radical that exhibits five resonance
structures. Determine which hydrogen is abstracted and draw all five
resonance structures of the resulting radical.

11. Draw the structure of the major product upon radical monobromination of each of the
following compounds:

a) b) c)

12. Compound A has molecular formula C5H12 and undergoes monochlorination to produce
four different constitutional isomers.

(a) Draw the structure of compound A

(b) Draw all four monochlorinated products
(c) If compound A undergoes monobromination (instead of monochlorinaion), one product predominates.
Draw that product.

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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13. Using the steps provided below, calculate the theoretical percent yields of the four
monochlorinated products that result when 2- methylbutane is subjected to free radical
chlorination. Assume that the relative ease of hydrogen abstraction in the chlorination
process is 5 for 3°; 3.8 for 2°; and 1 for 1°hydrogens.

Step 1 Draw out the structures and label (ex. A, B and so on) all
- monochlorinated products, and identify them as primary (1°), secondary
(2°) and tertiary (3°) alkyl halides.

Step 2 Determine the total number of hydrogen atoms from the starting
- alkane that are potentially subject to the radical substitution to yield a
monochlorinated product you labeled in step 1. Then, identify the
hydrogens as primary (1°), secondary (2°) and tertiary (3°). Repeat this
process for all other monochlorinated products.

Step 3 For each monochlorinated product, multiply the number of the

- hydrogens you determined from step 2 by their corresponding rate of
abstraction. (i.e. if the hydrogens identified in step 2 are primary,
multiply the number of hydrogens by rate 1).

Step 4 Sum up all results from the multiplication involving all monochlorinated
products. Then divide each multiplication result for each
monochlorinated product by the sum, followed by x 100. There, it gives
the theoretical percent yield for each product.

14. For the free radical reaction below, answer the following
questions for the monochlorination of 1,3-
dimethylcyclohexane:

a) Draw the structures of the five monochlorinated constitutional isomers. (ignore

stereoisomers)
b) For chlorination, the relative reactivities of the hydrogens in this reaction are 1 : 3.9 :
5.2 for 1o (Primary) : 2o (Secondary) : 3o (Tertiary), respectively. Calculate the
percentage yield for the five products drawn in question (a) above. (i.e. please refer to
the guideline in Q13 for calculation)

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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Solutions
1. Explain why alkanes are generally considered unreactive compounds.

Alkanes are unreactive because they only have very strong, non-polar C-H and C-C  (sigma) bonds.
These bonds are extremely difficult to break unless a large amount of heat or light is provided.

2. Rank each group of radicals in order of increasing stability:

a)

b)

c)

3. Provide the full mechanism (initiation, propagation and termination) to account for the
following reaction:

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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4. How many products are formed from the monochlorination of ethylcyclohexane? Draw
the structures of all products and identify the major product. If bromine, more selective
reagent, is used to react instead, how many products are expected?

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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5. Draw four dibromo products that could be obtained by radical bromination of propane.
Show the reaction pathway or mechanism for the compound that you think would be the
major product. Also, which of the four dibromo products are chiral?

6. Provide the full mechanism for the radical chlorination of 2,2-dichloropropane to produce
1,2,2-trichloropropane.
See answer for question 3 for mechanism pattern

7. In practice, the chlorination of methane often produces many by-products. For example,
ethyl chloride (CH3CH2Cl) is obtained in small quantities. Can you suggest a mechanism
for the formation of ethyl chloride?

In the termination step of the chlorination of methane, ethane is produced as a by-product, which can
undergo a propagation step with chlorine radical to generate ethyl chloride

8. The relative rates of termination of methyl and isopropyl radicals are quite different. Give
two possible reasons for this difference.

1) The less stable methyl radical recombines faster than the more substituted, more stable, and thus
longer lived isopropyl radical (i.e. hyperconjugation). 2) The bulkier (meaning more branching; hence,
more electron repulsion due to steric strain) isopropyl radical has more difficulty in recombining than does
the smaller methyl radical.

9. For each radical, draw all resonance structures using curved-arrow. For resonance
structures involving radicals, single barbed arrows are used.

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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a)

b)

c)

d)

e)

f)

10. 5-methylcyclopentadiene, shown to the right, undergoes hemolytic bond

cleavage of a C-H bond to form a radical that exhibits five resonance
structures. Determine which hydrogen is abstracted and draw all five
resonance structures of the resulting radical.

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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11. Draw the structure of the major product upon radical monobromination of each of the
following compounds:

a)

b)

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 202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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c)

12. Compound A has molecular formula C5H12 and undergoes monochlorination to produce
four different constitutional isomers.

(a) Draw the structure of compound A.

(b) Draw all four monochlorinated products

(c) If compound A undergoes monobromination (instead of monochlorinaion), one product predominates.

Draw that product.

13. Using the steps provided below, calculate the theoretical percent yields of the four
monochlorinated products that result when 2- methylbutane is subjected to free radical
chlorination. Assume that the relative ease of hydrogen abstraction in the chlorination
process is 5 for 3°; 3.8 for 2°; and 1 for 1°hydrogens.

Step1 and 2

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202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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Step 3 and 4

The rate of hydrogen abstraction

Class of Relative Rate of
hydrogen Abstraction
1° 1
2° 3.8
3° 5

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Product of Theoretical Yield

# of Hydrogens x Relative for each product
Rate

A 6x1=6 (6 / 21.6)*100 = 27.8%

B 1x5=5 (5 / 21.6)*100 = 23.1%
C 2 x 3.8 = 7.6 (7.6 / 21.6)*100 = 35.2%
D 3x1=3 (3 / 21.6)*100 = 13.9 %
Sum = 21.6

14. For the free radical reaction below, answer the following
questions for the monochlorination of 1,3-
dimethylcyclohexane:

a) Draw the structures of the five monochlorinated constitutional isomers. (ignore

stereoisomers)

b) For chlorination, the relative reactivities of the hydrogens in this reaction are 1 : 3.9 :
5.2 for 1o (Primary) : 2o (Secondary) : 3o (Tertiary), respectively. Calculate the
percentage yield for the five products drawn in question (a) above. (i.e. please refer to
the guideline in Q13 for calculation)

Product of Theoretical Yield

# of Hydrogens x Relative for each product
Rate

A 6x1=6 (6 / 47.6)*100 = 12.6%

B 2 x 3.9 = 7.8 (7.8 / 47.6)*100 = 16.4%
C 2 x 5.2 = 10.4 (10.4 / 47.6)*100 =
21.8%
D 4 x 3.9 = 15.6 (15.6 / 47.6)*100 = 32.8
%

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202-DCP-05 Organic Chemistry 1 – Problem Set 6 M. Hachey
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E 2 x 3.9 = 7.8 (7.8 / 47.6)*100 = 16.4

%
Sum = 47.6

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