CHEM261, B2 Practice Questions for the MidTerm Exam, Answers 2009 02 25

HT
Review the Practice Questions for the Quiz as well as the Answer Keys for the actual Quiz.
( all available on my website).
Here are some more questions. Remember this is not an exhaustive compilation.
1. Define the following terms by description, example , sketch …
a. optical isomers : non-superposable mirror images
b. antiperiplanar : Can best be shown in a Newman projection. Let’s assume that X is the substituent of
interest on C1 and Y is the substituent of interest on C2. X and Y are antperiplanar if they form an
angle of 180°; in other words, they form a dihedral angle of 180°.
c. IR absorption : absorption of electromagnetic radiation (emr) in the infrared range
(approx. 4000 – 400 cm–1), causing transition from one vibrational level to a higher vibrational level
( increase in amplitude, but (ideally) not in frequency)
d. wavenumber: number of waves per unit length; customarily per cm
e. meso: refers to compounds that have “apparent stereogenic centers”( 4 different substituents at a C
atom), but have a plane of symmetry / superposable mirror images and that are consequently achiral
d. angle strain: results from geometric angle requirement (esp. in ring compounds) not allowing expression
of the normal bond angles; e.g., 60° vs. 109° in cyclopropane

H3C H
2. Consider (CH3)2C=CHCN.
C C
H3C C
N

a. Determine the number of bond types:

(sp3,sp3)σ 0 , (sp,sp2)σ 1 , (sp3,sp2)σ 2 , (sp2,sp2)σ 1 , (sp,sp)π 0 , (p,p)π 3
b. What other bond types are present? (s,sp3)σ, (sp,sp)σ, (s,sp2)σ
c. Which atoms lie in the same plane? Which ones are normally not in this plane.
all atoms are in the same plane, except the H atoms of the methyl groups
3. For this question ignore R/S designation.
a. Provide systematic (IUPAC) names for the following.

Br
Cl

1-chloro-3-ethyl-3,4-dimethylhexane
3-methylheptane trans-1-bromo-3-ethylcyclohexane
 -2-
b. Write a bond line structure for cis-1-sec-butyl-3-isopropylcyclopentane.

4. Sketch an IR chart with proper labeling of the x and y axes. Then indicate the relative positions
of C,C double and C,C triple bond peaks on this chart.

You don’t need to know the absolute positions of the peaks, but the C,C triple bond peak must be at a
larger wavenumber than the C,C double bond peak.
 -3-
5. For the halogenation reaction of ethane write an example for each of an initiation, a propagation
and a termination step. Use proper electron movement arrows.

I: Cl Cl Cl + Cl

H3C C H Cl H3C CH2 + HCl

P:
H

Cl Cl H3C CH2Cl + Cl
H3C CH2

Cl
T: H3C CH2 H3C CH2Cl

6. In the chlorination of pentane four (4) monochlorinated products are possible.

Show their bond line structure , incl. stereochemistry as required.
Cl Cl

Cl

enantiomers Cl

CH3 CH3
7. O O
Consider
*
*
H H
a. Is it chiral? Yes. Why? 2 stereogenic centers , no plane of symmetry
b. OK, it is. Now, indicate the stereogenic center(s) and identify them as R or S.
4
CH3 3 CH3
O O
2
1 *
1
3 * 2 "S" "R"
H4 H
 -4-
CH3 CH3
c. Draw its enantiomer. O O

or or ....

H H

d. Draw a diastereomer if there is any. There are two enantiomeric diastereomers.

CH3 CH3
O O

or or ....

H H
8. Rank the following groups in terms of C-I-P priority (highest first):

a.) -(CH2)2CH3, -CH2CH(OH)CH3, -(CH2)2CH2OH, -CH2CH=CH2, -CH(NH2)CH2CH3.

-CH-CH2-CH3 -CH3-CH-CH3 -CH2-CH CH2 -CH2-CH2-CH2OH -CH2-CH2-CH3
NH2 OH
1 2 3 4 5

b) -(CH2)2CH2Cl, -CH2C(=O)CH3, -(CH2)2CHO, -CH=CHCH3, - CH2CCl(CH3)2

-CH CH-CH3 -CH2-CH(CH3)2 -CH2-C-CH3 -CH2-CH2-CH2Cl -CH2-CH2-CHO

Cl O
1 2 3 4 5

9. a. Determine whether the substituents A, B, C and D in this steroidal compound are equatorial or
axial.(All rings are trans joined)
D (eq)

D
A CH3
CH3
(ax) A B
same as

C (ax) C

B (ax)
 -5-

b. If A, B, C and D are all -OH groups, what is the R/S designation of the carbon atoms that these -
OH groups are attached to.
1 CH3
1
A OH CH3 B OH
OH
4 3
H 3
2
2 H4
"S" "S"

CH3
C D
1
OH
2
3 2
H4
3
H4
1OH
"R" "R"
10. What positions ( ax. or eq.) do the -Cl and -CH3 groups occupy in the following molecules,
preferentially?

H
H CH3
CH3

Cl
Cl H
H cis = "mobile"
trans = "rigid" H
H CH3 H Cl
H CH3
"flip"
CH3
H Cl
Cl

H
cannot flip! preferred conformation!
-CH3 ax. -CH3 (more demanding) eq.
-Cl eq. -Cl ax.
 -6-
11. Consider the Fischer formula C1 CHO

C2 H OH

C3 H OH

C4 CH2OH

a. Show a Newman projection (looking from C3 to C2) of this molecule in the

conformation where the H’s at C3 and C2 are antiperiplanar.
CHO
OH
H OH
H OH

H rotate rear 180ο

HO H

CHO CH2OH
CH2OH
"staggered"
"eclipsed !" H's antiperiplanar
b. Determine R and S configuration at C2 and C3.
C
H 2 O
at C2 C at C3 H C
2
OH
4 1 4 1
H OH H OH

H C OH "R" H C OH
3 3
"R"
H
c. Show a 3-dimensionally correct “wedge and dash” structure of the above
with a horizontal zigzag line and the aldehyde group up and to the right.
OH

CHO
HOH2C

OH
 -7-
12. Consider Cl

CH3

Compare the following with the reference structure and apply the labels :
identical structure, different conformer, enantiomer, diastereomer, constitutional isomer.
Cl Cl
CH3
CH3 Cl CH3
H3C Cl

enantiomer diastereomer constit. isomer identical

a.) b.) c.) d.)

Cl
Cl
CH3 H3C

Cl CH3 CH3
Cl
identical identical diastereomer diastereomer
e.) f.) g.) h.)

13. Write the preferred conformation for the following:

iPr iPr iPr
Me

Me Me
a.) b.) c.)
Me
Me Me

iPr iPr iPr

 OH -8-
14. Consider
(which indicates 2 OH groups
OH attached to different C atoms on the ring)

Show two constitutional isomers, both meso, that have this general structure.
OH OH OH

HO

OH is also achiral, but not meso

OH
15. What feature of the substrate structure is critical that will determine whether
a substitution reaction will go by the SN1 or SN2 reaction mechanism? Why?
A primary substrate will favor SN2( the reaction site is more approachable, less hindered);
while a tertiary substrate favors SN1( the carbocation intermediate and, acc. to the Hammond
postulate, the transition state also) is more stable;
secondary substrates occupy the middle ground.
16. Attempt to draw the σ* antibonding orbital that is involved in the SN2 reaction of chloroethane.
The σ orbital responsible for the C–Cl bonding results from the in-phase overlap between the sp3
orbital of the C atom and the p orbital of a Cl atom.
The σ* orbital can then be imagined to be the result of opposite-phase overlap of the same atomic
orbitals.
Consider this to be a fairly crude approximation!

Atomic Orbitals
C atom Cl atom
in-phase

overlap

σ MO

opposite-phase

overlap
σ* MO

backside attack by the nucleophile

occurs here