DEPARTMENT OF CHEMISTRY

CH 2104: ORGANIC CHEMISTRY II

REVIEW QUESTIONS - I

1. Assign the configuration of each of the following molecules:

CH3
Cl OH H

Cl C CH(CH3)2
H3C C C2H5 H3C C H H3C C CH2Cl

i. H ii. C2H5 iii. CO2H iv. CH3

H H CH2Br
CH2Br

H3C C CH2Cl H3C C CH2Cl H3C C CH2F H3C C CH2Br

v. CH2Br vi. H vii. CH2Br viii. CH2Cl

2. Circle each chiral molecule. Put a * next to each chiral carbon and label it as R or S

CCl3 CCl3
H3C CH3
C C
CHCl2 CH2Br H
H3C H3C H
i. CHCl2 ii. CHCl2 iii.
H3C H
Br H Cl H
H CH3
iv. v. Br H vi.

3. Assign a priority order to each of the following sets of groups:

i. CH3 , C(CH3)3 , H, OH

OCH3 , CH3 , CH2OH

ii. OH ,

iii. CN , NHCH3 , CH2NH2 , OH

iv. CH3 , CH2CH3 , CH2CH2CH3 , CH(CH3)2

C CH2
v. C CH and H

C O C CH2
vi. H , H , CH2CH3 , and OH

C CH2
vii. H and

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4. For each of the following pairs of structures, indicate whether the two compounds are
identical or enantiomers of each other.

CH2CH3 CH2CH3

C C
Br CH2CH3 H3CH2C Br

i. Cl and Cl

CH3 CH3

H C Cl C
Cl Br

ii. Br and H

CH3 OCH3

Cl C CF3 F3C C CH3

iii. OCH3 and Cl

H NH2

NH2 C COOH H C CH(CH3)2

CH(CH3)2
iv. and COOH

5. Which of the following compounds are chiral?

i. 2-Methylheptane
ii. 3-Methylheptane
iii. 4-Methylheptane
iv. 1,1-Dibromopropane
v. 1,2-Dibromopropane
vi. 1,3-Dibromopropane
vii. Ethene,
viii. Ethyne

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 HO CH(OH)CH2NHCH3

ix. HO

HO CHO

x. H3CO

6. Draw structural representations of each of the following molecules. Be sure that your
structure clearly shows the configuration at each stereocentre:
i. (R)-3-bromo-3-methylhexane;
ii. (3R,5S)- 3,5-dimethylheptane;
iii. (2R,3S)-2-bromo-3-methylpentane;
iv. (S)-1,1,2- trimethylcyclopropane;
v. (1S,2S)-1-chloro-1-trifluoromethyl-2-methylcyclobutane;
vi. (1R,2R,3S)-1,2-dichloro-3-ethylcyclohexane.

7. The optical rotation of a sample composed of only 2-butanol is determined. αobs=-0.45˚. [α]D
is known to be 13.52˚ ml/g dm for (+)-2-butanol. If the cell pathlength was 0.6 dm and the
concentration of 2-butanol in the sample was 0.15 g/ml what is the enantiomeric excess (EE)?
Calculate the percentage of the (+) and (-) isomers.

8. A sample of pure (d)-borneol is found to produce an αobs = 10.1˚. What must be the
concentration if [α]D = 37.7˚ ml/g dm?

9. A sample of an unknown enantiomerically pure compound produces an αobs = -120˚ when c =

1.0 g/ml. Upon diluting the sample to 0.5 g/ml the αobs =+120˚. Explain.

10. A sample has a 50% EE and αobs =20˚ for a concentration of 0.4g/ml and l = 0.5dm. What is
[α]D for the pure isomer?

11. The (+) enantiomer of compound A has an optical rotation of 125˚. If a pure sample of
compound A has an optical rotation of 100˚, what is the composition of the sample?

12. The (+) enantiomer of compound B has an optical rotation of 100˚. If a pure sample of
compound B has an optical rotation of 95˚, what is the composition of the sample?

13. The (+) enantiomer of compound C has an optical rotation of 18˚. If a pure sample of C
contains 30% of the (+) enantiomer and 60% of the (-) enantiomer, what is the optical
rotation value?

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14. The (+) enantiomer of compound D has an optical rotation of 25˚. If a pure sample of D
contains 80% of the (+) enantiomer and 20% of the (-) enantiomer, what is the optical
rotation value?

15. A pure sample of the naturally-occurring, chiral compound A (0.050 g) is dissolved in water
(2.0 mL) and the solution is placed in a 0.5 dm cell. Three polarimetry readings are recorded
with the sample: 0.625˚, 0.706˚, 0.682˚. What is α

16. A pure sample of the chiral compound B (0.540 g) is dissolved in ether (2.0 mL) and the
solution is placed in a 1.0 dm cell. Three polarimetry readings are recorded with the sample:
1.225˚, 1.106˚, 1.182˚. What is α

17. A pure sample of the (+) enantiomer of compound C shows [α] = 42˚. What would be the
observed a if a solution of the sample was made by dissolving 0.250 g in 2.0 mL of acetonitrile
and was then placed in a 0.5 dm cell?

18. A student has prepared compound D in lab. She is sure the compound contains no impurities;
a number of physical analyses have confirmed the structure and purity of the compound. A
sample of compound D (0.10 g) is dissolved in methanol (2.0 mL) and the solution is placed
in a 1.0 dm cell. Three polarimetry readings are recorded with the sample: 0.995˚, 0.904˚,
0.936˚.
i. What is α
ii. The optical rotation of D has previously been reported as 25˚. What is the optical
purity of this sample?
iii. What is the enantiomeric excess of this sample?
iv. What is the composition of this sample?
v. Why did the previous analyses show that there was only one compound present?

19. Suppose a student prepared a sample of a compound with known

α ˚ did not realize that her sample contained 10% (by mass)
of a non-chiral impurity. After correcting for c and l, what did she measure for α ?

20. Calculate the specific rotation of (2R,3R)-tartaric acid based on the following observation: A
0.856 g sample of the pure acid was diluted to 10.0 mL with water and placed in a 1.00 dm
polarimeter tube. The observed rotation using the 589 nm line of a sodium lamp at 20.0˚C
was +1.06˚.

21. What is the expected observed rotation of a 1.0 x 10-4 M methanol solution of the potent
anticancer drug paclitaxel (also called Taxol)? [α]D20 = -49˚ (c = 1, CH3OH). Paclitaxel has a
molecular weight of 853.93 gmole-1.

22. A certain compound has a specific rotation of -43.2˚ (c = 5, toluene). What is the observed
rotation of a sample of 1.24 g of the enantiomer of this compound when diluted to a
concentration of 1.00 g ml-1 in the same solvent?

23. In his classic studies of stereochemistry and optical activity in organic compounds, Pasteur
measured the optical activity of many solutions. For the naturally occurring enantiomer of

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 tartaric acid, [α]20 = +12.4˚ (c = 20, H2O). What can be concluded about the ratio of tartaric
acid enantiomers present in the solution if the observed rotation is (i) -6.0˚, or (ii) 0˚?

24. An organometallic chromium catalyst is developed that is able to perform the following
reaction stereo selectively. You isolate the product at 70% optical purity and you obtain
50mg of total product. How many milligrams of the desired (major) enantiomer do you
have?

25. For each pair of structures shown, indicate whether the two species are constitutional
isomers, enantiomers, diastereomers of one another, or identical molecules.

26. Draw and name all possible stereoisomers of (CH3)2CHCHBrCHClCH3

27. Natural epinephrine, [α]25D = -50˚, is used medicinally. Its enantiomer is medically worthless
and is, in fact, toxic. You, a pharmacist, are given a solution said to contain 1 g of epinephrine
in 20 mL of liquid, but the optical purity is not specified. You place it in a polarimeter (10-
cm tube) and get a reading of -2.5˚. What is the optical purity of the sample? Is it safe to use
medicinally?

28. The molecule in the margin is menthol, with the stereochemistry omitted. (a) Identify all
stereo-centers in menthol. (b) How many stereoisomers exist for the menthol structure? (c)
Draw all the stereoisomers of menthol, and identify all pairs of enantiomers.

29. Of the stereoisomers described in the problem above, (2)-menthol ([α]D = -51˚) and (1)-
neomenthol ([α]D = +21˚) are the major constituents in mentha oil, their main natural source.
The menthol – neomenthol mixture in a natural sample of mentha oil exhibits [α]D = -33˚.
What are the percentages of menthol and neomenthol in this oil?