1

Practice Tests Answer Keys, Organic Chemistry I

Online Organic Chemistry I, Chem 350, Dr. Craig P. Jasperse, Minnesota State University Moorhead
For full class website, see
https://collaborate.mnstate.edu/public/blogs/jasperse/online-organic-chemistry-courses/online-organic-chemistry-i-350-fall-spring/

Test Page
Test 1 Version 1 3
Test 1 Version 2 9
Test 1 Version 3 15
Test 1 Version 4 21

Test 2 Version 1 27
Test 2 Version 2 33
Test 2 Version 3 39
Test 2 Version 4 43

Test 3 Version 1 49
Test 3 Version 2 55
Test 3 Version 3 61
Test 3 Version 4 67

Test 4 Version 1 73
Test 4 Version 2 79
Test 4 Version 3 85

Final Exam Version 1 93

Final Exam Version 2 101
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Answers, Test 1 Version 1
1

JASPERSE CHEM 350 TEST 1 VERSION 1 Organic Chemistry I - Jasperse

T Intro and Review
Structure and Properties of Organic Molecules
Structure, Nomenclature, and Conformation/Stereochemistry of Alkanes

1. Draw the correct Lewis structure of CH3CN. (Needn’t show 3-D geometry) (3pt)
1. Want normal bonding for all
2. C=O (or C=C in other cases) may help
3. If you have any formal charges (not here), they must sum
to net charge of molecule (zero, in this case)
4. Organization must match condensed formula sequence

2. Draw the correct Lewis structure for HOCH2CHO. (Needn’t show 3-D geometry). (3pt)

3. Draw a 3-dimensional picture for the atoms in CH3CO2CH2NHCH3, using the hash-wedge
convention. (You needn’t specify lone pairs, and orbitals need not be shown). (5pt)
1. The Nitrogen is tetrahedral, so the N-H hydrogen must
T either be wedged or hashed. (The lone pair doesn't need to
be drawn in, but it impacts the shape of the nitrogen)
2. Drawing the correct Lewis structure is essential! Do fifirst!

Fine if N-H is hashed

instead of wedged

4. For the structure shown, what is the hybridization, electron-pair geometry, and approximate
bond angle (90, 109, 120, or 180) relative to: (6pt)
1 3 4 7
5 6 N
HO 2 +
8

O H
9
electron-pair bond electron-pair bond
hybridization geometry angle hybridization geometry angle

O-1 C-5

C-2 N-7
T
C-3 O-9

5. Assign any formal charges to any apropriate atoms for proline, given the structure shown (one
of the body’s 20 monomers from which protein and enzyme biopolymers are constructred). (3pt)

O
O
NH 2

1
 4
2

6. Rank the acidity of the following, from 1 (most) to 4 (least). (4pt)

OH OH 3 Acidity Factors:
N 1. charge (not relevant here)
O H 2. Eneg
3. Resonance

7. Which of the following represent pairs of resonance structures? (4pt)

No atoms can move!

a.

b.

OCH 3 OCH 3
c.
Br Br

d. Both a and c

e. a, b, and c are all resonance structures.

8. Draw arrows to show electron-movement in the following two steps (draw arrows for each
step). Draw a circle around the atom that functions as nucleophile in step 1, and a square around
the atom that functions as nucleophile in step 2. (5pt)
Explain change in:
Br Step 1 Br 1. Bonds
O O Step 2 O + Br 2. Charge
+ OH
3. Lone Pairs
OH OH
(anion)

9. Rank the series on the basis of boiling point, 1 having highest boiling point, 3 having lowest.
(3pt)
O
OH
3 factors:
H-bonding No H-bonding No H-bonding Yes 1. H-bonding
Polar Yes Non-polar 2. London force (# of carbons)
-both RAISE BP
3. Polar vs nonpolar
10. Rank the series on the basis of water solubility, 1 having highest solubility, 3 having lowest.
(3pt)
OH OH

H-bonding Yes 2 factors:

1. H-bonding (raises solubility)
H-bonding Yes H-bonding No 2. London force (# of carbons)
-more C's reduces water
2 solubility
 5
3

11. For each of the following pairs of resonance structures, circle the one that would make a
greater contribution to the actual resonance hybrid. (4pt)

O O 2 Factors:
1. More bonds
OCH3 OCH3 (priority)
(anions) 2. Electronegativity
(if bonds are equal)

12. Cyclopropane is much more “strained” than cyclopentane. Why? (Short!) (3pt)
Angle strain. Bonds are forced to be 60º, far from the ideal ~109º angle.
Note: angle strain only appears in certain rings;
For acyclics, steric and torsional are the only strains available.
13. For the following acid-base reaction,
a. put a box around the weakest base in the reaction
b. put a circle around the weakest acid
c. draw an arrow to show whether the equilbrium goes to the right or left. (4pt)

O Base Stability factors:

O 1. charge
+ H 2O + NaOH
ONa 2. eneg
OH
3. resonance

1. Equilibrium favors the more stable base

2. More stable base is "weaker" base
3. "Weaker" acid + base on same side

14. Classify the relationship between the pairs of molecules as either: (8pt)
same compound structural isomers resonance structures
geometric isomers not isomers (different molecular formulas)

OH OH

CH3 CH3
H CH3 H H Br
Br H
OH H
H H H H CH3H H H OH

3
 6
4

15. Give the name for the following. (7pt)

T
1. cis/trans for di-subbed rings
1. Longest chain
H 2. Alphabetize substituents
2. Alphabetize substituents
3. Numbering
H CH3 3. Number from end near
4. Know isopropyl and t-butyl
substituent

cis-1-isopropyl-3-methylcyclohexane 4-ethyl-3-methylheptane

16. Identify all the funtional groups in the following molecules. (Do not include “alkane”, since
that isn’t “functional”.) (6pt)

O N O O
O O H

17. Which of the following pair will have the larger rotation barrier, relative to the bonds
T indicated? (3pt)

18. For the following Newman projections, rank them in stability from 1 to 4, 1 being most
stable. Identify the “anti” conformation, the “gauche” conformation, and the “totally eclipsed”
conformation. (6pt)
CH3 CH3 H3CCH H3C
3 H
H CH3 H H

H H3C HH
H H H H CH3H H HH H

T
19. Draw the Newman projection for the most stable conformation of 1,2-dichloroethane. (3pt)

Best: staggered Worst: Totally

and "anti" eclipsed
4
 7
5

20. Draw the two chair conformations of cis-1-ethyl-4-methylcyclohexane. (You don’t have to
T draw all the hydrogens). (5pt)
1. Make sure you've really
drawn "flflipped" chairs
2. What's "ax" in one chair flflip is
"eq" in the other.
3. Process cis-trans
4. Draw in H's on substituted
carbons (easier to see ax/eq).

21. Which is more stable, cis- or trans-1-t-butyl-2-methylcyclohexane? Draw the best

conformation of the more stable isomer. (4pt)

1. More stable chair has both

substituents equatorial
2. Process cis-trans

T 22. Draw as many structural isomers as you can for C6H14. Be careful not to draw the same
isomer twice! I will take off points for duplicating! (6pt)

Alkane Acyclic: CnH2n+2

Alkane Cyclic: CnH2n

Beware of drawing same

thing twice!

5
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 Answers, Test 1 Version 2 9
1

JASPERSE CHEM 350 TEST 1 VERSION 2 Organic Chemistry I - Jasperse

T Intro and Review
Structure and Properties of Organic Molecules
Structure, Nomenclature, and Conformation/Stereochemistry of Alkanes

1. Draw the correct Lewis structure of CH3CO2CH2COCH3. (Needn’t show 3-D geometry) (3pt)
1. Want normal bonding for all
2. C=O (or C=C in other cases) may help
3. If you have any formal charges (not here), they must sum
to net charge of molecule (zero, in this case)
4. Organization must match condensed formula sequence

2. Draw a 3-dimensional picture for the atoms in CH3CH2CHCHCH2NHCH2CHO, using the hash-
wedge convention. (You needn’t specify lone pairs, and orbitals need not be shown). (5pt)
Fine if N-H is hashed
instead of wedged

1. The Nitrogen is tetrahedral, so the N-H hydrogen must either be wedged or hashed.
(The lone pair doesn't need to be drawn in, but it impacts the shape of the nitrogen)
2. Drawing the correct Lewis structure is essential! Do fifirst!

T 3. For the structure shown, what is the hybridization, electron-pair geometry, and approximate bond
angle (90, 109, 120, or 180) relative to: (7pt, 2 points off for each error)

O
5
1 3 4 N
6
O H
2

electron-pair bond electron-pair bond

hybridization geometry angle hybridization geometry angle

C-1 C-4

O-2 N-5

C-3 C-6

T
4. Assign any formal charges to any appropriate atoms for the structure shown below. (4pt)

HO O
N CH 3
CH 3
 10
2

5. Rank the acidity of the following, from 1 (most) to 4 (least). (4pt) 3 Acidity Factors:
T 1. charge (not relevant here)
2. Eneg
HO OH NH 2 3. Resonance

6. For the following pairs, identify as “isomers” (“I”) or “resonance structures” (“R”). (6pt)
No atoms can move!

O O
OH
OH

T
7. Draw arrows to show electron-movement in the following reactions. (These are reactions, not
resonance.) (5pt)

H
O O H
+ Br + Br O H O O
a. + HO

Explain change in:

b.
1. Bonds
2. Charge
3. Lone Pairs
8. Rank the series on the basis of boiling point, 1 having highest boiling point, 3 having lowest. (3pt)
22 factors:
factors:
1.
1. H-bonding
H-bonding
T 2.
2. London
London force
force (#
(# of
of carbons)
carbons)
-both
-both RAISE
RAISE BP
BP NH 2 NH 2

9. Rank the series on the basis of water solubility, 1 having highest solubility, 3 having lowest. (3pt)

2 factors:
1. H-bonding (raises solubility) OH OH
2. London force (# of carbons)
-more C's reduces water
solubility H-bonding No
H-bonding Yes
Extra C's
reduce solubility
 Alkane Acyclic: CnH2n+2
11
Alkane Cyclic: CnH2n
3
Alkene: CnH2n (not expected to remember, but evident if you count)
Counting H's can always double-check on this!
10. Circle whichever of the following could fit the formula C5H10? (3pt)
T

11. For the following acid-base reaction,

a. put a box around the weakest base in the reaction
b. put a circle around the weakest acid
c. draw an arrow to show whether the equilibrium goes to the right or left. (4pt)

OH + NHNa ONa + NH 2
Base Stability factors:
1. charge O O
2. eneg
3. resonance

1. Equilibrium favors the more stable base

2. More stable base is "weaker" base
3. "Weaker" acid + base on same side

12. Classify the relationship between each pair of molecules as either: (10 pt)
same compound structural isomers resonance structures
T stereoisomers

H 3CO H 3CO

iPr iPr H H
Br Br
H H H H
H
H CH 3 H N
CH 3 H H Br HN
CH2CH 3 Br H

T
 4 12

14. Give the name for the following. (7pt)

1. cis/trans for di-subbed rings 1. Longest chain
H H 2. Alphabetize substituents 2. Alphabetize substituents
T 3. Numbering
3. Number from end near
4. Know isopropyl and t-butyl
substituent
trans-1-butyl-3-isopropylcyclopentane
5-ethyl-3-methyloctane
15.
16. Identify and write down the names for each of the functional groups in each of the following
molecules. (Do not include “alkane”, since that isn’t “functional”.) For each molecule, try to write
the names in order, as they appear from left-to-right in the molecules. (8pt)
O OH O O
O
H NH 2
O NH

17. Circle which of the following pair will have the larger rotation barrier, relative to the bonds
indicated? (2pt) Identify which reason explains why: steric strain, torsional strain, or angle strain?

T
Greater steric strain when totally eclipsed.
(Both will have equal torsional strain when totally eclipsed.)

18. For the following Newman projections: (6pt total)

a. rank them in stability from 1 to 4, 1 being most stable
b. identify the “anti”, “gauche”, and the “totally eclipsed” conformations.
CH 3 H
H H H H
H H H H H H
H H 3C

H H H 3C H
CH 3 H
CH2CH 3 H 3CH2C CH2CH 3 H 3CH2C

c. Is the energy difference between the gauche and the anti conformation based on steric strain,
torsional strain, or angle strain?

d. In the case of ethane (not shown), staggered conformations are better than eclipsed
T conformations. Is the difference based on steric strain, torsional strain, or angle strain?

19. Draw both the most stable and the least stable Newman projections for 1-bromopropane,
BrCH2CH2CH3, relative to C1-C2 bond. - (3pt)

Best: staggered Worst: Totally

and "anti" eclipsed
 13
5

20. Which of the following are correct Lewis structures, including formal charges, for nitric acid,
T HNO3. (3 pts)
O O O
H N O
H O N O H O N O
O
A B C
21.
a. A only
1. Do not exceed octet
b. B only 2. If formal charges, must sum to net charge
c. C only 3. As much "normal bonding" as possible, given
d. Both A and C the above constraints.
e. All of the above

22. Draw the two chair conformations of cis-1-isopropyl-4-methylcyclohexane. (You don’t have to
draw all the hydrogens). (5pt) (Use “iPr” as abbreviation). 1. Make sure you've really
drawn "flflipped" chairs
2. What's "ax" in one chair flip
fl is "eq" in
the other.
3. Process cis-trans
4. Draw in H's on substituted carbons
(easier to see ax/eq).

23. Draw the best chair conformation of the more stable isomer. Which is more stable, cis- or trans-1-
butyl-2-methylcyclohexane? (4pt)

1. More stable chair has both

substituents equatorial
2. Process cis-trans

24. Draw any 6 of the 9 possible structural isomers for alkanes with formula C7H16. When deciding
whether to draw cyclic or acyclic alkanes, make sure that you fit the formula! Be careful not to
draw the same isomer twice! I will take off points for duplicating! (You can try to show off by
getting more than 6, but if you do still be sure you don’t duplicate!) (6pt)

Alkane Acyclic: CnH2n+2

Alkane Cyclic: CnH2n

Beware of drawing same

thing twice!
14
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Answers, Test 1 Version 3

JASPERSE CHEM 350 TEST 1 VERSION 3 Organic Chemistry I - Jasperse

T Intro and Review
Structure and Properties of Organic Molecules
Structure, Nomenclature, and Conformation/Stereochemistry of Alkanes

1. (12 points) Give the relationship between the following pairs of structures. The possible
relationships are the following:
same compound structural isomers resonance structures
stereo isomers not isomers (different molecular formula)

H H Structural. 1. Resonance: No
Br Br atoms can move!
a. 1,2-dibromo vs
Br 2. Stereo: same
H 1,3-dibromo.
Br H condensed formula
3. Structural: different
H Br H H Same. condensed formula
b. H C C H H C C H Bond rotation around
Br H Br Br single bonds is
allowed.

T c. Br Br Structural.
CH3CHCHBr vs CH2CHCH2Br

d. Stereo. Trans-cis.
Double bond can't rotate.

e. Same. Both are 4-methylnonane

f. Resonance. Electrons and charge is

repositioned, but no atoms moved.

2. (8 points) Draw line-angle structures and names for 4 of the 5 structural isomers of C6H14.

T Alkane Acyclic: CnH2n+2

Alkane Cyclic: CnH2n

Beware of drawing same

thing twice!

butane

2,3-dimethylbutane
1
 2 16

O
T OH
H 2N 2
3
4
5
6
7 8
3. (10 Points) 1

a. For the above structure, what is the hybridization and approximate bond angles (109, 120, or
180) about:

C-2 sp2, ~120º

C-4 sp2, ~120º

C-6 sp3, ~109

O-8 sp3, ~109

b. In the above structure, N-1 is actually found to have 120º bond angles. (This may seem
unexpected to you at this point, but we’ll learn why later in the course.) What must be the
hybridization of the nitrogen?
sp2. Hybridization, bond angle, and electron geometry are all interlocked.
To know any one of them is to know the others.
4. (2 Points) Bond rotation around C6-C7 in the above structure has a 7 kcal/mol barrier, while
T rotation around the C4-C5 bond has a 70 kcal/mol barrier. Explain very briefly why it is so
much harder to rotate the latter bond?
Single bond versus double bond.
A double bond has overlapping p-orbitals.
To rotate a double bond, the p-p overlap would be lost. The full pi-bond would need
to break.
By contrast, no bonds are broken when you rotate around a single bond.
5. (4 points) For each of the pairs listed, circle the one with the higher boiling point.
2 factors:
CH3 H 1. H-bonding (raises solubility)
a. N N H-bonding 2. London force (# of carbons)
-more C's reduces water
solubility

b. OH OH
Extra carbons, hydrophobic

T 6. (6 points) Write a Lewis structure and assign any non-zero formal charges.
1. Want normal bonding for all: in absence of metal ions
a. [CH3NH3]+ 2. C=O (or C=C in other cases) may help
3. If you have any formal charges (not here), they must sum
to net charge of molecule (zero, in this case)
4. Organization must match condensed formula sequence

b. CH3CO2Na

c. CH3CHO

2
 3 17

7. (5 points) a) Draw the best resonance structure for anion A, and circle the resonance
T structure that would make the greater contribution to the resonance hybrid.

O 2 Factors:
1. More bonds
N
(priority)
A 2. Electronegativity
(if bonds are equal)

b. For the two resonance structures shown below, circle the resonance structure that would make
the greater contribution to the resonance hybrid.
+ NH
2 NH2
+

8. (6 points) Rank the acidity of the following molecules, 1 being most acidic, 4 being least
acidic. Hint: draw the anions!

T NH3 CH3CH2OH CH3CO2H HCl 3 Acidity Factors:

1. charge (not relevant here)
2. Eneg
3. Resonance

9. (6 points) Draw a line-angle picture for all of the atoms in the molecule
CH3CH2COCHClCH3, including the hydrogens. Use the hash-wedge convention to indicate
atoms that are not in the plane of the paper.

Cl could equally well be drawn in the

T hashed spot
10. (5 points) Rank the ring strain in the following, from 1(most) to 3 (least). Explain very
briefly the differences in strain.
A: has large angle strain (60º angles, not
109º angles)
A
C
B: By taking on chair conformation, there
B
is zero angle strain, and zero torsional (no
eclipsing)
C: If it has ideal angles, then some
eclipsing and torsional strain destabilizes it

3
 4 18

11. (6 points) Which of the following are capable of cis-trans stereoisomerism? (Yes/No).
T
a. 3-ethyl-1,1-dimethylcyclopentane

b. 3-pentene (name means a double bond is between carbons 3 and 4)

c. 1,3-dimethylcyclohexane

12. (9 points) Identify the functional groups in the following molecules. (Do not include
"alkane", since that is not "functional". And do not specify "cyclic".)
T
a. H 2N CO 2H
("GABA: brain neurotransmitter")

Amine Carboxylic Acid

OH
CH 3
H Alcohol
CH 3 H

b. H H
O
Testosterone
Ketone Alkene

CH 3 O O Ester
CH 3
N
T H
c.
O Arene or aromatic
H
Cocaine O
Amine Ester

4
 5 19

13. (5 points) Give the IUPAC name for the following compounds.
T
1. Longest chain
2. Alphabetize substituents H 1. cis/trans for di-subbed rings
3. Number from end near
CH 3 2. Alphabetize substituents
a. b. 3. Numbering
substituent
H 4. Know isopropyl and t-butyl
CH 2CH 2CH 3
4-ethyl-3,6-dimethyloctane cis-3-methyl-1-propylcyclobutane

14. (8 points) a. Draw Newman projections for the totally eclipsed, the gauch, and the anti
conformations of 2,5-dimethylhexane, relative to the C3-C4 bond. You may abbreviate the
isopropyl groups attached to C3 and C4 as "i-Pr" for convenience.
b. Explain very briefly why the rotation barrier around the C3-C4 bond of 2,5-dimethylhexane is
greater than the rotation barrier in butane.
4 4
b. Steric Strain. Larger
= i-Pr rotation barrier because
3 3 i-Pr greater steric strain in
total eclipse between two
larger isopropyl groups
compared to steric strain
T between two methyl
groups. Torsional stain is
common to both, to the
difference is the difference
in steric strain.

15. (8 points) a.) Draw the two chair conformations of cis-1-isopropyl-3-methylcyclohexane.

(You don't need to show the H's on carbons other than 1 and 3). For convenience, you may
abbreviate methyl as "Me" and isopropyl as "iPr"
b.) Circle the more stable conformation.
c) Would trans-1-isopropyl-3-methylcyclohexane be more stable or less stable than the cis
isomer? 1. Make sure you've really
drawn "flflipped" chairs
2. What's "ax" in one chair flflip is
"eq" in the other.
3. Process cis-trans
4. Draw in H's on substituted
T carbons (easier to see ax/eq).

5
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 1 21

JASPERSE CHEM 350 TEST 1 VERSION 4 Organic Chemistry I - Jasperse

Intro and Review
T Structure and Properties of Organic Molecules
Structure, Nomenclature, and Conformation/Stereochemistry of Alkanes

1. Order the following according to increasing electronegativity, 1 being highest, 4 lowest. (2pts)

N F O C

2. Write Lewis structures and assign any non-zero formal charges. (3pts each)

a. [CH3OH2]+ 1. Want normal bonding for all: in absence of metal ions

or overall charge
2. C=O (or C=C in other cases) may help
3. If you have any formal charges, they must sum to net
charge of molecule (zero, in this case)
4. Organization must match condensed formula
sequence
b. CH3CO2CH2ONa

c. CH3CHCHCONH2

3. For each of the following, a) draw its resonance structure, and for each pair b) circle the
structure that would make the greater contribution to the resonance hybrid. (2 pts each)

O
a. 2 Factors:
1. More bonds
H (priority)
b.
O+ 2. Electronegativity
(if bonds are equal)

4. Draw line-angle structures for 7 of the 9 structural isomers of C7H16. (5 pts)

Alkane Acyclic: CnH2n+2
Alkane Cyclic: CnH2n

Beware of drawing same

thing twice!
 2 22

5. For the following pairs of structures, identify them as either: Resonance Structures, Structural
Isomers, Stereoisomers, or Same. (2 pts each)
T
1. Resonance: No
OH O
a. atoms can move!
2. Stereo: same
condensed formula
3. Structural: different
H H H CH 3 condensed formula
b.
H 3C CH 3 H 3C H

c.

d.

e. CH3CH2CH2CH2CH3 (CH3)2CHCH2CH3

6. Rank the acidity of the following molecules, 1 being most acidic, 4 being least acidic. (3 pts)

CH3NH2 CH3OH HCO2H CH3CH3

3 Acidity Factors:
1. charge (not relevant here)
2. Eneg
3. Resonance
O O
+ CH 3 + CH4
7.

T
a) Put a box around the weakest base in the above reaction. (1pt)
b) Put a circle around the weakest acid in the above reaction. (1pt)
c) Draw an arrow to show whether at equilibrium the reaction will go left-to-right or right-to-
left. (2pt)
 3 23

8. Draw the line-angle structure for the following condensed structural formula: (CH3CH2)2CO
(3pt)
T

9
H 2N 2
3
4
5
6
7
8
9. 1
a. For the above structure, what is the hybridization, electron-pair geometry, and approximate
bond angles (109, 120, or 180) about: (6pt)

N-1

C-3

C-5

C-8

b. Rank the length of the following bonds, 1 being shortest, 3 being longest. (2pt)
T
C2-C3 C4-C5 C8-C9

10. For each of the pairs listed, circle the one with the higher boiling point. (4pt)

a. O 2 factors:
OH 1. H-bonding (raises bp +
solubility)
b. 2. London force (# of carbons)
-more C's raises bp but reduces
water solubility

c. O

11. Draw a 3-dimensional picture for all of the atoms (hydrogens included) in the molecule
CH3CHCHCOCH2CH2NHCH3. Your picture should use the hash-wedge convention to
T illustrate atoms that are not in the plane of the paper, and should reflect approximate bond
angles. (5pt)

Note: N-H
hydrogen is NOT
in the plane. But
it could be drawn
hashed or
wedged, either is
fifine.
 4 24

12. Draw a 3-D picture of CH2O showing the π bond as well as the four atoms. (3pt)

T p-orbitals used to make the pi-

bond are perpendicular to the
plane of the atoms. So if we draw
the pi-bond in the plane, the
attached H's must be out of plane.

13. For the following set, rank the solubility in water, from 1 (most soluble) to 4 (least soluble).
(3pt)

OH OH
O

14. Identify the functional groups in the following molecules. (8pt)

O
a. O
T

O
b.
HO N OH
H

15. Give the IUPAC name for the following compounds. (6pt)

a. 1. Longest chain
2. Alphabetize substituents
3. Number from end near
substituent

T
CH 3 H
b.
H CH 3 1. cis/trans for di-subbed rings
2. Alphabetize substituents
3. Numbering
4. Know isopropyl and t-butyl
 5 25

16. Draw the Newman projections for the best and worst conformations of butane, and give the
names for these conformations. Briefly explain what “strain factors” make the worst
T conformation worse than the best conformation. (6pt)
Torsional strain; any eclipsed conformation
has torsional strain, repulsion beween bond-
pair electrons.
Steric strain: atom are unnecessarily close,
and repel each other

17. a.) Draw both chair conformations of cis-1-methyl-2-isopropylcyclohexane. Draw the

substituents and H-atoms attached to carbons 1 and 2. (You don't need to show the H's on the
other carbons). (4pt)
b.) Circle the more stable conformation. (1pt)
1. Make sure you've really
drawn "flflipped" chairs
2. What's "ax" in one chair flflip is
"eq" in the other.
3. Process cis-trans
4. Draw in H's on substituted
carbons (easier to see ax/eq).
T

18. Draw the best chair conformation for 1,3-diethylcyclohexane, and identify whether it is “cis” or
“trans”. (3pt)

19. Use the arrow-pushing convention to show the electron-movement mechanisms for the follow
T two reactions. (5pt)

OH2
O O
a. + CH 3 b. + OH2
NH 2 NH 2
CH 3

Good mechanism must

explain changs in:
1. Bonds
2. Formal Charges
3. Lone pairs
26
 27
JASPERSE CHEM 350 TEST 2 VERSION 1
Ch. 4 The Study of Chemical Reactions; Ch. 5 Stereochemistry
Ch. 6 Alkyl Halides: Nucleophilic Substitution and Elimination
T
1. Predict the major organic product for each of the following. (3 points each)

Br2, hv

CH3SNa
Br

I
NaOCH2CH3

T 2. Show an alkyl bromide and some nucleophile that you could use to make the following by
SN2. (3 points)

OCH2CH 3

3. For the structure shown, (3 points each)

a. Draw the major elimination product
formed upon treatment with H2O/heat.

D H
Br
H CH3
H
T
b. Draw the major elimination product
formed upon treatment with CH3CH2ONa.

c. Draw the major substitution product

formed upon treatment with CH3CH2ONa.
 28
(3 points for each multiple choice question)
4. Which of the following is true regarding an SN1 reaction?
a. It would be faster at 25˚ than 50˚ Solvent polarity factor, good for cations
b. It would be faster in ethanol than in pentane
c. Keeping the moles of reactants constant but doubling the quantity of solvent would
decrease the rate by a factor of 4.
d. Stereochemical inversion occurs exclusively

6. Which of the following statements is true?

a. The rate determining step is always the last step in a reaction mechanism.
b. The stability/reactivity principle says that the more stable of two chemicals will be more
reactive
c. The reactivity/selectivity principle says that the more reactive of two chemicals will be less
selective.
d. The activation barrier for a reaction is the difference in energy between reactants and final
products.

7. Which of the following statements is true about the chlorination of methane?

a. In each propagation step a radical is produced Chain reaction.
23
b. 6.02 x 10 initiation events are needed to make one mole of chloromethane
c. Most chloromethane is made by combination of a methyl radical with a chlorine radical
d. The overall chlorination of methane is strongly endothermic.

8. Which of the following statements is FALSE?

a. Optically active solutions solutions always contain chiral molecules.
b. Two diastereomers always have identical melting points
c. Optically inactive solutions are either racemic or else contain no chiral chemicals at all
d. A solution with 60% optical purity would have an 80/20 mix of enantiomers

9. When the reactants shown undergo substitution, which of the products A-D will form? (3
points)
D H D H D H D OH D CH3
Br H2O OH H H H
???
H CH3 heat H CH3 H CH3 H CH3 H OH
H H A OH B H C H D

a. A only Carbocation rearrangement is

SN1, cationic, racemization results, two enantiomers form.
b. B only involved in this problem. *IF* I
c. A and B didn't really spend time discussing
d. A, B, and C carbocation rearrangements in
e. A, B, C, and D lecture, then don't bother with this
problem.
 29
10. Rank the reactivity of the structures shown toward the reactant(s) indicated on the left (1
being most, etc.) (3 points each)

T Br Br I
NaOCH2 CH3 Br

Br2/hv

O
CH3Br NHLi OLi OH

Br
H2O, heat, Br
T Br
Br

11. Carbocations often rearrange, as shown below. Draw in the hydrogens on the two carbons
involved in the rearrangement, and show formal arrow-pushing to illustrate the transformation.
(3 points)

+
+

T 12. Draw the mechanism for the following reaction, propagation steps only. (4 points)

Br2, hv Br
 30
13. Draw (3R,6R)-6-bromo-3-chloro-2-methyloctane (3 points)

14. Name the following: (3 points)

H
Br
(optically
active)
H
Cl

15. Classify each of the chiral carbons in the following structures as R or S (there may be more
than one in a molecule). (10 points)

H H CH3 H Cl
OH
CH3
H Br H

T
16. a. Classify each pair as diastereomers, enantiomers, or same. (12 points)
b. For the first structure of each pair, circle it if it is not chiral
c. For the first structure of each pair, write “meso” by it if it is meso

H
OH
HO OH
OH H H
H
H Br Br H H Br

H Br

T
Cl Br Br F

H F Cl H

17a. a) Draw all the unique stereoisomers of 2,3-dichlorobutane. Cross out any duplicates.
b) Identify which is meso. c) Identify a pair that are related as diastereomers. (5 points)
 31
18. Draw the mechanisms for the following reactions, using formal arrow pushing. Note: in
some case hydrogens that are not illustrated will be involved in bond changes. You would do
well to write them in at the beginning. (12 points total, 3/3/6 distribution)
T

Br NaOH OH

Br
NaOH

T
Br H2O OH

heat (identify the slow step)

T
32
 33

JASPERSE CHEM 350 TEST 2 VERSION 2

T Ch. 4 The Study of Chemical Reactions
Ch. 5 Sterochemistry
Ch. 6 Alkyl Halides: Nucleophilic Substitution and Elimination

1. Rank the reactivity of the following molecules toward Br2/hv. (1 most, 4 least) (3 points)

CH3-CH3

2. Rank the reactivity of the following molecules toward ethanol and AgNO3. (1 most, 4 least)
(3 points)

Br Cl Cl Br

T
3. Rank the reactivity of the following molecules toward NaOCH3. (1 most, 4 least) (3 points)

Br Br
I Br

4. Rank the reactivity of the following toward 1-iodopropane. (1 most, 4 least) (3 points)

CH3ONa CH3CO2H CH3CO2Na CH3SNa

5. What is the hybridization of a carbocation? (2 points)

 34

6. Predict the major organic product (1 major structure is all that is needed in each case) for each
T of the following reactions. (Minor products or inorganic side products need not be drawn.)
(3 points each)

Br + CH3CO2Na

hv
+ Br2

Br H Acetone
+ NaI Solvent

T
7. Draw the structures for intermediate A and final product B. (4 points)

Br2, hv NaOCH3
A B

8. Draw the product when the following substance undergoes E2 elimination. ("D" is deuterium,
basically just a labelled hydrogen). If the starting material is optically active, will the product by
optically active? (4 points)

H 3C Br
T H CH3 NaOCH3
H
D
 35

9. Show an alkyl bromide and some nucleophile that you could use to make the following by SN2.
T (3 points each)

CH3
O

H OCH3

10. Draw all possible elimination products that could form from the following reactant. Circle the
one that forms in greatest yield. (5 points)

O
Br

Error in problem: You

wouldn't be able to
choose between the two
tri-substitued alkenes
T
11. Which of the following would not increase the rate of an E1 reaction? (3 points)
a. an increase is temperature
b. an increase in the "activation energy"
c. an increase in the concentration of the alkyl halide
d. an increase in the stability of the carbocation intermediate

12. When comparing the reaction of 2-methylpropane with either Cl2/hv or Br2/hv, which of the
following statements is true? (3 points)
a. bromine is less reactive and more selective
b. chlorine is less reactive and more selective
c. bromine is more reactive and more selective
d. chlorine is more reactive and more selective

13. Which of the following statements is true relative to reactions I-III: (3 points)
I CH4 + Br• → CH3• and HBr
T II CH3CH3 + Br• → CH3CH2• + HBr
III CH3CH2CH3 + Br• → (CH3)2CH• + HBr
a. I has the smallest energy of activation and the highest energy transition state
b. II has the smallest energy of activation and I has the lowest energy transition state
c. III has the largest energy of activation and the highest energy transition state
d. III has the smallest energy of activation and the lowest energy transition state
 36

14. Classify each of the chiral carbons in the following structures as (R) or (S). (10 points)
T
Cl
HO H H CH3
Cl
H
H OH H CH3

15. a. Classify each pair of molecules as diastereomers, enantiomers, or same. (12 points)
b. Circle any molecules that are chiral
c. Write "meso" by any structures that are meso
.
Cl H
Cl
H Cl
H
H
Cl

F CH3 H 3C H
H Cl F Cl

O O
T

H Cl Cl H H Cl

Cl H

16. Which of the following statements is true? (3 points)

a. All solutions with chiral molecules are optically active
b. All molecules with chiral carbons are chiral
c. A solution that has 50% optical purity has a 50/50 mixture of enantiomers
d. Two enantiomers always have identical boiling points

17. Draw (2R,3S)-2-bromo-3-chlorohexane (3 points)

T
18. Name the following: (3 points)
Cl
Cl
H
 37

19. a) Draw all unique stereoisomers of 2,4-dibromopentane. Label each with a letter, A, B, etc..
T Cross out any duplicates. (8 points)
b) Identify any that are chiral
c) Identify any that are meso

20. a) Draw the mechanism for the following reaction. (Draw the propagation steps only.) (4
points)
b) Is your product chiral, and if so is it optically active? (1 points)

H 3C H Br2, hv H 3C Br

21. a) Draw the mechanism for the following reaction. (4 points)

b) Identify the slow step. (1 point)
Br OCH3
HOCH3

T
38
 39

JASPERSE CHEM 350 TEST 2 VERSION 3

T Ch. 4 The Study of Chemical Reactions
Ch. 5 Sterochemistry
Ch. 6 Alkyl Halides: Nucleophilic Substitution and Elimination

1. /4 6. /9 11. /6 16. /4
2. /4 7. /4 12. Removed 17. /6
3. /4 8. /6 13. /6 18. /16
4. /4 9. /10 14. /6
Total /100
5. /3 10. /6 15. /2

1. List the following radicals in order of increasing stability (from most stable 1 to least stable 4)

2. List the following alkyl halides in order of decreasing reactivity toward SN1/E1 reactions (from
T most reactive 1 to least reactive 4).

Br
Br Br

Br

3. List the following alkyl halides in order of decreasing reactivity toward SN2 reactions (from
most reactive 1 to least reactive 4).
Br
Br I
Br

4. Rank the bond strength of the following (from strongest 1 to weakest 4).

H-Br H-Cl H-F H-I

T
5a. Put a 1 by the reaction for which ∆H˚ = Eact. (Eact = activation energy)
b. Put a 2 by the reaction for which Eact = 0.
c. Put a 3 by the reaction for which Eact > ∆H˚.

Br-Br → Br• + Br•

H3C-H + Br• → H3C• + H-Br
H3C• + •CH3 → H3C-CH3
 40

6. Predict the major organic product for each of the following reactions. (Minor products or
T inorganic side products need not be drawn.)

hv
+ Br2

Br + NaOH

Br
+ NaOH

7. Show the Starting Alkyl Bromide which gave the following products.

H2O OH
+
heat

8. Show an alkyl bromide and some nucleophile that you could use to make the following. (I
don't care whether you specify a nucleophile just as the anion Z- or as NaZ with a metal
T counterion.)

OH

CN

9. Optically active (R)-2-bromobutane can be converted to 2-butanol under either conditions A or

conditions B. Describe the stereochemistry of the product solutions for the two different
conditions.

OH NaOH H Br H2O, heat OH

(Conditions A) (Conditions B)

T Conditions A Conditions B
a. Alcohol is Chiral or Achiral?
b. Optically Active or Not?
c. (R), (S), or both?
d. Reaction occured by Inversion,
Retention, or Racemization?
e. What happens to the rates if you double
the concentrations of all reactants?
 41

10. Draw the major product for the following reaction. Then draw the mechanism for its
T formation. (Draw the propagation steps only.) Is your product chiral? (You may need to add
relevant hydrogens.)

hv
+ Br2

11. Draw the major product for the following reaction. Then draw the mechanism for its
formation. (You may need to add relevant hydrogens.)

H 3C Br
+ NaOH
T

13. Draw the mechanism for the following reaction. (Don't worry about designating stereochem.)
H 3C Br H 3C OH
H2O
+ H-Br

T
 42

14. Classify each of the chiral carbons in the following structures as (R) or (S).
T
H
CH3
HO H
H
CH3

15. Draw (R)-2-bromopentane

16. Draw meso-1,3-dichlorocyclopentane, and mark the chiral C's as (R) or (S).

17. Draw all of the different isomers of 2,3-dichlorobutane, identify each as either chiral or meso,
and classify the relationship between each two as enantiotopic or diastereotopic. (You may use
Fischer projections or zig/zag/hash/wedge pictures, as you please. (If two are the same, cross one
of them off your list.)

18. Classify the pairs of molecules as diastereomers, enantiomers, or same. For the first molecule
in each pair, circle it if it is chiral. For the second molecule in each pair, put a * next to each chiral
C.
Br H HO Br
H H
H OH

H Cl Cl H

H CH3 H 3C H
T
H 3C H 3C
 43
1

JASPERSE CHEM 350 TEST 2 VERSION 4

Ch. 4 The Study of Chemical Reactions
Ch. 5 Alkyl Halides: Nucleophilic Substitution and Elimination
Ch. 6 Stereochemistry

1. Draw the mechanism for the following reaction, and write “slow” next to the rate-
determining step. Be sure to draw all intermediates, and to correctly draw “electron-
movement” arrows or half-arrows. (Show the propagation steps only.) (4 points)

H H hv H Br
+ Br 2 + H-Br

2. Draw the mechanism for the following reaction, and write “slow” above the rate-
determning step. Be sure to draw all intermediates, and to correctly draw “electron-
movement” arrows. (5 points)

Br OCH3
H+ (catalyst)
+ HOCH3 + H-Br
CH3 OH (solvent)
heat

3. Predict the major products for the following reactions. (4 points each)

Br + NaOCH CH3 OH (solvent)

a) 3

hv
+ Br 2
b)
 44
2

Br CH3 OH (solvent)
+ NaOCH 3
c)

hv
+ Br 2
d)

Br + CH SNa
e) 3

4. Draw the substitution products for the following reactions. (Do not draw the
accompnaying elimination products). Include stereochemistry in your answer, and if
two substitution products are formed draw them both. (4 points each)

H2O
+ NaOH
H Cl
a) H 3C H

cat. HCl
+ H2O
H Cl H2O
b) 3C
H CH3

5. Draw the E2 elimination product(s) [do not draw the substitution product(s)]. (4
points each)

H NaOCH3
CH3 CH3 OH
H
Br

6. Of the following alkyl halides, (3 points)

a) Circle the one that would be the most reactive toward SN2 substitution
b) Put a box around the one that would be the least reactive toward SN2 substitution

Cl I
I Br
Cl
 45
3

7. Of the following alkyl halides, (3 points)

c) Circle the one that would be the most reactive toward SN1 substitution
d) Put a box around the one that would be the least reactive toward SN1 substitution

Cl I I
Cl
Br

8. Rank the stability of the following carbocations, from 1 (most stable) to 4 (least
stable) (4 pts)

+ + + +

9. Rank the stability of the following radicals, from 1 (most stable) to 4 (least stable) (4
pts)
•
• • •

10. Classify as R or S (2 pts each)

H Br

a) Cl CH3

Br H

b)

c) H 3C H

d) H CH3
 46
4

11. Provide the structure and the IUPAC name for the following (3 pts each)

a) (R)-3-chloro-2-methylheptane

H
Br
b) CH3

12. Classify the paris of molecules as not isomers, structural isomers, diastereomers,
enantiomers, or identical, and circle any molecules that are achiral. (2 pts each)

Br H Br
H
a) H Cl H Cl

H Br Br H
b) Br H H Br

H Cl H CH3
c) H 3C Br Cl Br

13. For 1,2-dimethylcyclopentane, (8 pts)

a) How many stereocenters are present

b) Draw all the possible stereoisomers, and circle those that are chiral.
 47
5

Each of the following multiple choice problems is worth 3 points.

14. For the reaction shown below, with bond dissociation energies listed below each key
bond, the overall ∆H is:

(CH3) 3C-H + Cl-Cl → (CH3) 3C-Cl + H-Cl

∆H (kcal/mol) 91 58 78 103

a) +58 kcal/mol
b) -32 kcal/mol
c) +32 kcal/mol
d) -57 kcal/mol
e) +181 kcal/mol

15. Which factor would not increase the rate of an E1 reaction:

a) Use of a more polar solvent

b) Use of a 3˚ rather than a 2˚ alkyl halide
c) Doubling the concentration of the base
d) Using iodide rather than bromide as leaving group

16. Consider the SN2 reaction shown below. Assuming no other changes, what effect on
the rate would simultaneously doubling the concentrations of both 1-bromobutane
and KOH have?
CH3CH2CH2CH2Br + KOH → CH3CH2CH2CH2OH + KBr
a) No effect
b) It would double the rate
c) It would triple the rate
d) It would increase the rate by four times
e) It would increase the rate six times

17. Of the SN1/SN2/E1/E2 reactions, rearrangements are likely to occur in:

a) SN1 reactions only

b) SN2 reactions only
c) E1 reactions only
d) Both SN1 and E1 reactions
e) Both SN2 and E2 reactions
48
 49
1
JASPERSE CHEM 350 TEST 3 VERSION 1
Ch. 7 Structure and Synthesis of Alkenes
Ch. 8 Reactions of Alkenes

1. How many elements of unsaturation are in the formula C6H9NO2? (3 points)

a. 0 b. 1 c. 2 d. 3 e. 4 f. 5 g. 6

2. For the three structures shown, which of the statements is true? (3 points)

NO2
NO2
A B C D

a. A, C, and D are Z; B is E
b. A and B are the only Z compounds
c. A is the only Z compound; B is the only E compound
d. B, C, and D are Z; A is E
e. B is the only Z compound; A is the only E compound

3. Rank the reactivity of the following toward H2SO4/Î catalyzed dehydration. (3 points)
a. A is fastest; C is slowest heat
b. B is fastest; C is slowest
c. A is fastest; B is slowest
d. C is fastest; B is slowest
e. B is fastest; A is slowest
f. C is fastest; A is slowest

OH HO
OH
A B C

4. Which of the following reactants would give exaactly the same products from both (E)- and
(Z)-2-butene? (3 points)
If two chiral centers are produced, then
diastereomeric products are produced.

a. Br2 But if only one (or zero) chiral centers are

produced, then the two alkenes don't give
b. PhCO3H
different products. In this case, with H-OH
c. 1) BH3-THF 2) NaOH, H2O2 being added, only the carbon to which OH is
d. OsO4, H2O2 added ends up being chiral, so you get the
e. D2, Pt same racemic mix of 2-butanol either way.

5. Draw the alkene that gives the product shown, and specify its stereochemistry. (2 points)
The normal "E" alkene would
have given the wrong product OH
OsO4, H2O2
stereochemistry. If the cis/
trans sense of the addition and
the cis/trans appearance of the OH
product match, then "E" 1
alkene would have worked.
 50
2
6. Draw the major product for each of the following reactions or reaction sequences. You
needn’t bother to show side products or minor products. For chiral molecules that are racemic ,
you needn’t draw both enantiomers. BE CAREFUL TO SHOW THE CORRECT
ORIENTATION, AND THE CORRECT STEREOCHEMISTRY IN CASES WHERE
STEREOCHEM IS FACTOR. (3 points each)

1. Hg(OAc)2, H2O

2. NaBH4

Br
NEt3

OH
H2SO4, heat

H-Br

CH3CO3H

H2O

1. H-Br

2. NaOH

1. NaOCH2CH3 Skip This one. It involves

KMnO4, a reaction I covered in
Br 2. KMnO4, heat years past but not this year.

Br2, H2O

HBr, peroxides

2
 51
3
7. A single unknown reacts with O3/Me2S to give the following three products. What is the
structure for the unknown? (3 points)

O O O
1. O3
H H + +
2. Me2S
O

8. Provide the name or structure for the following. (3 points each)

Cl

(racemic, don’t do
R/S stuff)

or

9. Provide a possible structure for a compound with formula C5H8, given that it reacts with
excess H2/Pt to give C5H10. (3 points)

10. Fill in the blanks for the following reaction sequence: (6 points)

Br2, NaOCH3

hv CH3OH
PhCO3H

11. Consider how the Se-O bond would be polarized and predict the product which would result
when CH3SeOH adds to propene: (Selenium is located two rows directly below oxygen on the
periodic table). (3 points)

CH3Se-OH

Markovnikov's rule. Electronegativity/periodic

table shows Oyxgen more electronegative than
selenium, so the oxygen adds to the more 3
substituted end of the alkene.
 52
4
12. When the following isomeric alkenes are fully burned, rank the amount of heat produced in
the combustions, from most heat produced (1) to least heat produced (4). (3 points)

13. Provide structures for starting material A and reactions products B and C, given the formula
of starting material A and the stereochemical status of products B and C. (5 points)

Cl2 A PhCO3H
B C
racemic C 4H 8 meso
mixture compound

With (E)-but-2-ene, Cl2 would give meso

and PhCO3H would have given chiral.
But-1-ene would have given chiral with
both reactions.
14. Draw mechanisms for the following reactions, using formal arrow-pushing. Each
intermediate along the mechanism pathway must be shown. (6 points, 3 points, 6 points)

OH H2SO4

heat

HBr

Br

Br2, H2O HO Br

(be sure your mech. is consistent with

the observed stereochemistry)

4
 53
5
15. Provide reagents for the following transformations. (5 points each)

Br
OH

O I may or may not have had

time to discuss and require
OH the KMnO4 reaction.
OH
O
Skip This one. It involves
KMnO4, a reaction I covered in
years past but not this year.

H3C Br
Br

5
54
 55
1
JASPERSE CHEM 350 TEST 3 VERSION 2
Ch. 7 Structure and Synthesis of Alkenes
Ch. 8 Reactions of Alkenes

1. How many elements of unsaturation are in the formula C8H9N?

a. 0
b. 1
c. 2
d. 3
e. 4
f. 5

2. Provide the proper IUPAC name for the alkene shown below.
Br

CH 3

3. Provide the proper IUPAC name for the alkene shown below.
ClCH 2CH2 CH 3
C C
H H

4. Draw an acceptable structure for 4-phenyl-1-butene.

5. Draw the alkene of formula C4H8 which evolves the most heat per mole upon hydrogenation

6. Choose the most stable alkene among the following.

a. 1-hexene
b. (E)-2-hexene
c. (Z)-2-hexene
d. They are all of equal stability according to Saytzeff's rule.

1
 56
2

7. Draw the major product of the following reaction.

Br
+
(CH 3)3CO - K
CH
3 (CH 3)3COH

8. Draw the major product and the mechanism.

CH
3
H 2SO4
OH

heat

9. Which of the following best describes the geometry about the carbon-carbon double bond in the
alkene below?
CH3

Cl

a. E
b. Z
c. Neither E nor Z

10. Draw 3 examples of molecules with the formula C4H6O2.

11. Draw the major product.

H-Br

12. Draw the major product.

1. Hg(OAc)2, CH3OH
2. NaBH4

2
 57
3

13. Draw the major product.

1. BH3 • THF
2. H2O2, -OH

14. Draw the major product.

CH3 CH3
Cl2, H2O

H H

15. Draw the major product.

CH3
OSO4

H2O2

16. Draw the major product.

CH3 1. O3
2. (CH3)2S

17. Complete the following reaction and provide a detailed, step-by-step mechanism for the process.

H+, H2O

3
 58
4

18. Suggest a reasonable detailed, step-by-step mechanism for the reaction shown below.

Br
HO Br2 + HBr
O

19. Provide the reagents necessary to complete the following transformation. (2 steps minimum).

OH OH

OH

20. Both (E)- and (Z)-3-hexene can be treated with D2 in the presence of a platinum catalyst. How are
the products from these two reactions related to each other?

a. The (E)- and (Z)-isomers generate the same products in exactly the same amounts.
b. The (E)- and (Z)-isomers generate the same products but in differing amounts.
c. The products of the two isomers are related as diastereomers.
d. The products of the two isomers are related as enantiomers.
e. The products of the two isomers are related as structural isomers.

21. Consider how the I-Cl bond is polarized and predict the product which results when this mixed
halogen adds to 1-methylcyclohexene.

4
 59
5
22. β-Ocimene is a perfume. Suggest a possible structure for β-ocimene that is consistent with the
following information.

H2,Pt
ß-Ocimene 2,6-dimethyloctane
(C10H16)

1. O3 CH2O + CH3COCH3 + CH3COCHO

2. (CH3)2S + OHCCH2CHO

23. Fill in the starting reactant.

1. BH3-THF H OH

2. NaOH, H2O2 H CH3

24. Fill in the blanks for the following reaction sequence.

1. Hg(OAc)2 , H2 O H2 SO 4,
A B
2. NaBH4 heat

KMnO4

SkipCThis Last Step.

It involves KMnO4, a reaction I
covered in years past but not
this year.

25. Provide reagents to carry out the following transformation: (3 steps minimum)

Cl

Cl

or KOC(CH3)3
5
60
 61

JASPERSE CHEM 350 TEST 3 VERSION 3

Ch. 7 Structure and Synthesis of Alkenes
Ch. 8 Reactions of Alkene
The number of points per problem is indicated in parentheses following each problem.

1. Rank the following alkenes in order of stability, 1 being most stable, 4 being least stable. (4)

Trans-disubstituted Monosubstituted Trisubstituted Cis-disubstituted

2. Determine the number of elements of unsaturation for C5H7ClO. (3) Halogen is equivalent
to a hydrogen, both
use up one single-
bond.

3. Give the proper IUPAC name or the structure for the following compounds. (4 points each)

a. (E)-2-chloro-3-methyl-2-pentene
Cl > CH3 on left alkene carbon

b.

4. Rank the reactivity of the following alcohols towards HBr, 1 being the fastest reactant, 3
being the slowest reactant. (3 points)
Cation stability following protonation
(such that the best possible cation
can form.)

1
 62

5. Predict the major product for the following reactions. You needn't bother to show any side
products or minor products. Pay careful attention to orientation. (3 points each)

H2O, H+ Markovnikov

1. Hg(OAc)2, CH3OH
Markovnikov.
Ether not alcohol
2. NaBH4

potassium Bulky base, results in E2 not SN2, and results in

Hofmann orientation, not Zaytsev
Br tert-butoxide
(KOCMe3)

H2SO4, ! Zaytsev
HO

6. Predict the major product in each of the following reactions. Pay careful attention to
stereochemistry! (3 points each)

H2, Pt Cis Note: For chiral products, I’m

just drawing one of the two
enantiomers. Either is fine.
Understand that if chiral, both
enantiomers will form.
Br2
Trans

Cl2, H2O Trans, Markovnikov

OsO4, H2O2 Cis

2
 63

7. Fill in the starting reactant. (4 points each)

CH3CO3H H OH

H2O
H OH

Z, not E alkene.
The mechanism of addition is trans, so to result in the “cis look” of
the product as drawn, a bond rotation was required.
The product-look and the mechanism of addition are mismatched.

8. Provide the major product of the following reaction sequences. (4 points each)
OH Î
1. H2SO4, heat

2. Br
22

Br 1. NEt3, heat
2. HBr, peroxides

3. NaOCH3

9. What is a possible structure for a molecule A given the following: (6 points)

a. is has the formula C6H10
b. it reacts with H2/Pt to give a product with formula C6H12
c. upon ozonolysis (O3; Me2S) it gives two products, CH2=O and a product C5H8O.

Many answers possible.

But, must have the following:
1. One alkene
2. One ring
3. An alkene with CH2 on end

3
 64

10. Fill in the boxes. (6 points total)

O
Î
KMnO4, heat
OH

O
Ignore this part It involves KMnO4,
a reaction I covered in years past
1. O3 but not this year.
2. Me2S

11. Provide reagents to accomplish the following transformations. (6 points each)

Br

OH

CH3
H
Br
OH
H

4
 65

12. Draw the mechanisms for the following reactions. Be sure to draw all intermediates, and try
to correctly draw "electron-movement" arrows. (8 points for the first, 6 points for the second)
3 steps:
OH 1. Protonation
H2SO4, Î 2. Loss of neutral water
3. Deprotonation
heat
Note: identify of agent who grabs the H in step 3
Could be water or HSO4-anion. I don’t need that to be
specified.

HBr Br

CH2 CH3

13. Draw as many isomers as you can for alkenes with formula C5H10. (8 points. 2 points off
for each duplicate or each possible isomer not drawn.) EU = 1.
Problem wording specifies “alkene”

5
66
 67

JASPERSE CHEM 350 TEST 3 VERSION 4

Ch. 7 Structure and Synthesis of Alkenes
Ch. 8 Reactions of Alkenes

1. Rank the following alkenes in order of stability, 1 being most stable, 4 being least stable. (3
points)
Tri-subbed > di > mono
Trans > cis

2. Determine the number of elements of unsaturation for C5H8O. (2 points)

3. Give the proper IUPAC name or the structure for the following compounds. (3 points each)

a. 4-vinylcyclopentene

(E)-5-propyloct-2-ene
b.
Or trans-

4. Rank the reactivity of the following alcohols towards H2SO4/∆ catalyzed dehydration, 1
being
the fastest reactant, 3 being the slowest reactant. (3 points)
HO CH3 HO H HO CH3

Cation Stability
Explains

1
 68

5. Which of the following statements is true for the structures shown: (3 points)
a. A is Z and B is Z
b. A is Z and B is E
c. A is E and B is Z
d. A is E and B is E

Cl
A B

OCH3

6. Predict the major product for the following reactions. You needn't bother to show any side
products or minor products. Pay careful attention to orientation, which is important in many of
these problems. (3 points each)

HBr, no peroxides
a.

1. Hg(OAc)2, H2O
b.
2. NaBH4

H2, Pt
c.

d. PhCO3H

Br NaOCH3
e. Zaytsev

Br
potassium Bulky base, goes E2 over SN2
t-butoxide
f.
(KOCMe3)

2
 69

7. Predict the major product in each of the following reactions. Pay careful attention to
stereochemistry: stereochemistry is involved in each of these problems! (3 points each)

Note: For chiral products I just drew one

Br2, H2O of the two enantiomers. Either is fine.
a. You should be aware that both form, but
as time-saver we usually only draw one

b. OsO4

H2O2

1. BH3-THF
c.

2. H2O2, NaOH

CH3CO3H, H 2O
d.

8. Fill in the intermediates in the following transformation. (3 points each)

H2SO4, ! HBr,

OH Peroxides
A B
Î
NEt3, heat

OMe 1. Hg(OAc)2, MeOH

2. NaBH4
C

3
 70

9. For the following reactions, fill in the missing starting materials, reagents, or products. (3
points each)

Br2 H Br
a.

H Br

b.
OH

O Me O
1. O3
c.
Me H
2. Me2S

Î
KMnO4, heat
Skip This one. It involves
KMnO4, a reaction I covered
in years past but not this year.

d.

4
 71

10. Provide the major product of the following reaction sequences. (4 points each)
1. H2O, H+

2. H2SO4, !

1. HBr, peroxides

2. KOCMe3
3. Br 2

11. Provide reagents to accomplish the following transformations. (4 points each)

Br

CH3
OH
OH
OH
H

12. Provide the product for the following reaction. Be sure to show the stereochemistry of the
product. (3 points)
Br Me Very trick one! Notes:
NaOH 1. 3º R-Br required E2, not SN2.
OMe
Ph 2. But, E2 requires a trans H.
H Me 3. In the original figure, the H is cis, not
trans.
4. Bond rotation can happen to spin the H
into the trans position, enabling E2
elimination and leading to the resulting
stereochemistry.

5
 72

13. Draw the mechanism for the following reaction, and write "slow" next to the rate
determining step. Be sure to draw all intermediates, and to correctly draw "electron-movement"
arrows or half-arrows. (4 points)
Note: my answer doesn’t specify who actually grabs
OH H2SO4, ! the H in the final deprotonation step. One could
H imagine HSO4-anion doing that, to regenerate
catalytic H2SO4. Probably water does. I won’t be
points-picky on this, so long as you show an H
coming off from adjacent carbon.

14. Draw the mechanism for the following reaction. Be sure to draw all intermediates, and to
correctly draw "electron-movement" arrows or half-arrows. (4 points)
Br
Br2 Br In practice, the bromide does attack the more
substituted carbon of the bromonium ion ring,
because the more substituted carbon has
more partial-positive charge on it.

15. Formula: C4H8

Reactivity: reacts with H2/Pt to give C4H10
DRAW ALL POSSIBLE ISOMERS, INCLUDING STEREOISOMERS. (4 isomers are
possible!) (5 points)

6
 1 73

JASPERSE CHEM 350 TEST 4 VERSION 1

Conjugation, Diels-Alder, Aromaticity, Aromatic Reactions

1. Provide the Name or Structure for the Following (7 points)

m-nitroaniline

CH3

Br

2. Circle the aromatic molecules (6 points)

O +

3. For each nitrogen in the molecule, classify the hybridization of the nitrogen atom, the
hybridization of the nitrogen lone pair, and classify whether the basicity of the nitrogen is
“normal” or “low”. (5 points)

Nitrogen Lone-Pair Nitrogen

Hybridization Hybridization Basicity
Na

Nb H
a N N
Nc c NH2
N d
O
Nd b
H

4. Bromide B has normal reactivity (for a 2º bromide) toward SN1 substitution, but A has much
higher reactivity and C has much lower reactivity. a) Why is A more reactive toward SN1? b)
Why is C much less reactive toward SN1? (4 points)
Br >> Br >> Br Kinetic reactivity toward
A B SN1 reactivity (H 2 O, H +)
C
 74
2

5. Synthesis Reactions. Draw the feature product of the following reactions (need not show any
byproducts). (21 points, 3 points each)

HNO3 , H 2 SO4
HO SO3H

O
+

1. HNO3 , H 2 SO4

2. Cl 2 , AlCl 3
3. Fe, HCl

1. Br 2 , hv

2. NEt 3 , heat

+ CN
NC

1. SO3 , H 2 SO4
CH3O
2. Br 2 , FeBr 3
3. H 2 O, H 2 SO4

1. Cl AlCl3

2. Zn(Hg), HCl
3.
Cl, AlCl3
(1 equivalent)
 75
3

6. Design sequences for the designated conversions. (5 points each)

CH3 CH3

NH2

Br

7. Design a synthesis for the following molecule beginning with toluene. (6 points)

CH3 CO2H
NO2

Br

8. Draw the Reactants for the following (3 points)

Via Diels-Alder
O
CH3O
O
 76
4

9. a) Draw the major product for the following reaction, and b) draw the mechanism for its
formation. c) Identify the slow step. d) Draw all the resonance structures for the cation
intermediate. (7 points)

Cl2, AlCl3

Cl

10. (9 points total) a) Draw the mechanism for the following reaction, in which a common
intermediate gives rise to both products. SN1 mechanism:
1. Make cation
Br 2. Capture
H 2O OH 3. Deprotonate.
+
Ph Ph OH -asymmetric allylic cation
Ph A
optically active B results in two structure
isomers.

b) In the above reaction, is product A chiral or achiral? A is chiral (but would be racemic)

c) Which is the “thermodynamic” product (more stable, which builds up under equilibrating
conditions)? B is the thermodynamic product, due to conjugation with the phenyl

d) You probably already did this, but either re-draw or identify the two key resonance structures
for the intermediate in the mechanism above. (You can just circle the two of them, assuming you
already sketched them above.).
 77
5

11. Rank the following, with 1 being highest/most. (2 points each)

Heat of Hydrogenation
More stable, less heat.
Conjugated more stable than isolated
Higher substitution increases stability.
O

Cyclopentadiene is always “s-cis”

Reactivity Towards O Z-substituent retards reactivity

Reactivity toward
Br Br Br SN2 Substitution Allylic accelerates SN2
SN2 can’t do vinyl/aryl

Stability

aromatic conjugated Isolated

O O
HN
Stability
NH

conjugated Isolated

Reactivity toward
Br OCH3 HNO3 /H2 SO4

Deactivator Activator, cation stabilizer

Reactivity toward
HBr addition

Aromatic stability makes it less

reactive reactant. (Reactant stability/
reactivity principle.
78
 1 79

JASPERSE CHEM 350 TEST 4 VERSION 2

Conjugation, Aromatic Compounds, Reactions of Aromatic Compounds

1. Provide the Name of Structure for the following. (7 points)

a. 3-nitroaniline

b. o-isopropyltoluene

c. NH Pyrrole

2. Circle the aromatic molecules. (7 points)

NH •

3. The molecule has 3 different nitrogens. For each of them, classify the hybridization of the
nitrogen atom, the hybridization of the nitrogen lone pair, and whether the basicity of the
nitrogen is "normal" or "low". (6 points)

O
a Nc
N
H NH2
b
Nitrogen Lone-Pair Nitrogen
Hybridization Hybridization Basicity

Na

Nb

Nc
 2 80

4. Draw the major products of the following reaction (4 points).

H-Br

(no peroxides)

5. Draw the Major Product of the Following Reactions. Note: I want one major product in each
case. (3 points each) Note: This answer key is showing intermediates along the
pathway for multi-step reactions, so it’s easier for students to see
CH3 how the final product was formed. But for test grading, all I would
need is the final product.
Br2 , FeBr 3

1. HNO3 , H 2 SO4

2. Cl 2 , AlCl 3
3. Fe, HCl

1. Radical bromination on allylic spot

1. Br 2 , hv 2. Hydroxide does SN2 >>> E2.
-Small nucleophile, and SN2 is greatly
2. NaOH accelerated by being allylic

O
OMe

1. Cl , AlCl3

2. Zn(Hg), HCl

Br

Note: Either of two structural

OMe heat isomers is acceptable as
answer. First actually
+ predominates, but that
O wasn’t covered in class.

CH3 1. SO3 , H 2 SO4

2. HNO3 , H 2 SO4

3. KMnO4
4. H 2 O, H 2 SO4
 3 81

6. Rank the following, with 1 being highest/most. (2 points each)

Reactivity toward
OCH3 SO3H CH3
Br2 , FeBr 3

Strong donor/activator > weak donor/activator >

withdrawer/deactivator

Heat of
hydrogenation
More stable => less heat.
1. Conjugation.
2. Substitution level.

O O O

Stability
O O
O 1. Conjugated vs isolated.
2. Ring strain

Combined
+ + + Diels-Alder
Reactivity
1. Cyclopentadiene is always s-cis
O O 2. Electron withdrawing group activates dienophiile

H H H Cation
Stability
+ Br + Br + Br
NH2 NO 2 1. NH2 is a strong cation stabilizer
NO 2 2. NO2 is a strong cation de-stabilizer

Reactivity
Br Br Br toward NaOMe
For SN2,
1. vinyl/aryl is bad.
2. Allylic accelerates
 4 82

8. Treatment of an alkyl halide with methanolic AgNO3 often promotes ionization, via the
following:

R X Ag+ R+ + AgX

When 3-bromo-1-butene undergoes this reaction, two isomeric products A and B are formed.
Draw the structure for product B and the detailed mechanism for formation of product B. (7 pts)
Br OMe
AgNO3
+
MeOH
A SN1 mechanism,
B but since it
passes through
an asymmetric
allylic cation, the
second product is
available via the
second
resonance
structure.

9. Draw the product for the following reaction and draw the mechanism for its formation.
Identify the slow step. Draw all the resonance structures for the cation intermediate and circle
the most important contributor. (7 points)
NO 2

Br2 , FeBr 3

Me
 5
83
10. (3 pt) When comparing cyclopentadiene (A) versus 1,3-pentadiene (CH2=CH-CH=CH-
CH3, B), one is much more acidic. Circle the more acidic chemical, and explain why it is much
more acidic.

Since acidity involves donating a A B

proton and getting one charge unit
more negative, any neutral acid will
create an anion.
The cyclopentadiene anion is
aromatic.

11. Draw the Reactants for the Following Reactions (6 points)

NBS Cl Cl
+
peroxides

Via
O
Diels-Alder
CN

12. Provide reagents for the following transformations. (5 points each)

Notes:
1. For 1º alkyl, need to go in
via acyl group. 1º alkyl
cations have problems.
2. Sequence: must be as
Cl shown. The acyl group
(carbonyl) is a meta director.

NO 2 Sequence must be as
shown.
Need o/p-directing Br
Br first, prior to the meta-
directing NO2. And
need the sulfonation to
block the para position,
otherwise nitro would
mostly go para not
ortho.
84
 85
1

JASPERSE CHEM 350 TEST 4 VERSION 3

Conjugation, Aromaticity, Electrophilic Aromatic Substitution

1. Provide Either the Name or the Structure for the Following Chemicals. (6 points) (3
minutes)

a. Furan b. p-nitrobenzoic acid NH2

c.

3-ethylaniline
Or m-ethylaniline
Or meta-ethylaniline

2. For the following substituents, classify each as 1) electron-donating or electron-withdrawing

["D" or "W"], 2) as activating or deactivating ["Act" or "Deact"], and as 3) ortho-para directing
or meta directing ["o/p" or "m"]. (6 points) (2 minutes)

-OCH3 - CCH2CH 3 -CH3 -Cl

1. D or W
2. Act or Deact
3. o/p or m

3. The molecule below has 3 different nitrogens. For each of the nitrogens, classify the
hybridization of the nitrogen atom, the hybridization of the nitrogen's lone pair, and whether the
basicity of the nitrogen is "normal" or "low". (6 points, 2 min)

NH2
a N N c
b
.
Lone-Pair Hybridization
Double bonded
Na

Nb Conjugated

Nc Isolated
 2 86

4. Rank the reactivity (rates!) of the following sets of molecules toward the reagents shown, 1
being most reactive, 2 being middle, and 3 being least reactive. (10 points) (6 minutes)

Reagent Molecules Being Compared

a. H2 , Pt

Aromatic, Isolated, Conjugated

most stable least stable

Br

Br
b. H+, H 2 O (SN1/E1)

Carbocation is key Br

Allylic cation best 2º cation 1º cation worst

c.

Never s-cis Always s-cis

NO2 Cl CH3

d. HNO3 , H 2 SO4

deactivator
Activator

Br

f. NaOMe
(SN2 reactivity) Br Br

Allylic, fast 1º > 2º for SN2

 87
3

5. Draw the major product for each of the following reactions. (3 points each, 21 total, 7
minutes)

NO2

Cl2 , AlCl 3
a.

Br

1. SO3 , H 2 SO4
b.
2. HNO3 , H 2 SO4
3. H 2 O, H 2 SO4

OCH2 CH3
While both substituents are o/p
directors, the oxygen group is
1, HNO 3 , H 2 SO4 much strong activator and
c. dictates position.
2. Fe, HCl

Br

Br2 with Lewis acid adds to the ring. But

1. Br 2 , hv under radical conditions, radical
d. bromination occurs on the benzylic site.
2. NaOMe SN2 beats E2 because being allylic/
benzylic greatly activates SN2, plus
methoxide is pretty small.

O
Cl2 , FeCl 3
e. O2N C CH3

Nitro deactivates the left ring, so the methyl-activated right ring wins.

Many allylic brominations give isomers.

NBS, peroxides In this case, both allylic positions are
f. symmetry equivalent, and the allylic
radical is also symmetric.

CO2Me
heat
g. +
MeO 2C
 4 88

6. Provide reagents for the following transformations. (5 points each, 10 total, 6 minutes)

CH3 CO2H
a.

Cl

Note: Methyl is an o/p director, carboxylic acid is a meta director. So, you wanted
to install the Cl ortho prior to converting the methyl to carboxyl.
But direct chlorination would have come in predominantly para, *IF* the para
position was not blocked. Thus the use of sulfonation to block the para position.

b.

NH2

Notes: Direct install of 1º alkyl is problem, due to both instability of 1º carbocations

and carbocation rearrangement. So, you need to install the carbon as the
carbonyl, and convert it later. When the second group gets added, the first must
be a meta director. Nitro could have gone in first.
7. Daw the diene and dienophile from which the following Diels-Alder products would have
come. (3 points each, 6 total, 2 minutes)

CN
heat
a.
Me2N CH3

MeO O
H
heat
b. O

H O
 5 89

8. a. Draw the mechanism for the formation of the major product shown, and identify the
"slow" step in the reaction. (6 points, 5 minutes).
b. Also draw all 4 resonance structures for the cation intermediate in the reaction. (4 points)
O
O
AlCl3
+
Cl
MeO MeO

10. Circle the aromatic molecules: (6 points) (3 minutes)

+ N:

OH

HN
 6 90

9. Draw the major product or products that would result from the following reaction, and write
either "chiral" or "achiral" and "optically active" or "racemic" by each product. Draw a
mechanism for the reaction, and identify the "slow" step in the reaction. (8 points, 5 min)

+ 1.0 HBr

9. Provide a synthesis for the following molecule, starting from benzene and anything else you
like. (7 points, 5 min)

Br O

NO2
 91

Answers

JASPERSE CHEM 350 FINAL EXAM VERSION 1

150 points total

1. Provide names or structures for the following. 2 points each. Specify stereochemistry when
appropriate!
Note: Version 1 is relatively
trans-4-methyl-1- representative in terms of length.
Cl CH3 chlorocyclohexane Version 2 is longer than the real test
will be. But provides lots more
or trans-4-chloro-1- practice.
methylcyclohexane

Br
(R)-2-bromobutane

m-isopropylphenol

Cl

Z-2-chloro-2-hexene

HO
m-butylphenol
or meta-butylphenol
or 2-butylphenol

2. Identify the functional groups in the following molecule. (4 points)

O

OCH3

1
 92

3. Predict the major products for the following reactions. Pay careful attention when orientation
is a factor. Draw just one major product in each case. (3 points each)

CN
+
CN
OCH3

Br2 , hv

NaOCH3
Br

1. O3

2. Me2S

HBr

OsO4, H2O2

O 1. Br2, FeBr3
2. Zn(Hg), HCl

3. Br2, hv

1. H2O, Hg(OAc)2

2. NaBH4

2
 93

4. Classify the pairs of molecules as totally different, identical, structural isomers,

diastereomers, or enantiomers. (2 points each)

Br

Br Br Br

Br

Br Br Br

Cl CH3 Cl H

Br H Br CH3

5. Classify each chiral carbon as R or S. (2 points each)

HO H

H
CH3

6. Classify the hybridization and bond angles (109, 120, or 180) at the labelled atoms. (5 points)
O
4
2 OH
1 3

C-1 C-2 C-3 O-4

3
 94

7. Draw the mechanisms for the following reactions. For any radical reactions, draw
propagation steps only. 5 points each.

OCH3 OCH3
Cl2

AlCl3
Cl Draw the resonance structures for the cation intermediate.

H H H Br
Br2 , hv
Ph Ph

Br2 , H 2 O Br

OH

4
 95

8. Draw the products of the following multi-step sequences. (4 points each)

Me Br 1. NaOH

2. HBr, peroxides
Ph 3. NaOMe

CH3 1. SO3, H2SO4

2. 2-bromopropane, AlCl3

3. H2O, H+

OH 1. H2SO4
2. HBr, Peroxides

3. NEt3

9. Draw as many structural isomers as you can for C6H14. Circle any that are chiral. (Note: be
careful! You will lose points for any repeats!) (6 points)

None are chiral

5
 96

T
e 10. Rank the Following, from most to least. 2 points each.
Cl
x a. Reactivity toward S N2 Br
t

I Cl
T T
e e
x •
b. Stability x
• • t •
t

CH3 H
c. Stability H CH3
H
Me2CH H
CH3 1. Equatorial preferred
H Me2CH Me2CH 2. If forces to be axial,
H
worse for big group than for
smaller group

d. Acidity PhCO2 H (CH3 )2 NH HCl CH3 CH2 OH 1. Anion stability

2. HCl by memory is
strong
3. Electronegativity factor
4. Resonance factor
Me HMe Me Me
H H Me H Me
e. Stability 1. staggered vs eclipsed
H H H H
H H H 2. Anti > gauche
Me H H
H HH
Me 3. Eclipsed > total eclipsed

OH OH OH
f. Reactivity toward
H2 SO4 /Î catalyzed Cation stability is key
dehydration

OH
g. Boiling Point
OH

1. Hydrogen bonding
2. Molecular weight factor
6
 97

11. Provide reagents for the following transformations. You may use anything you like. Each
can be done within ≤3 steps. (4 points each)

Br
OH T
e
x Br
t

H2N Br

12. Provide the appropriate reactant for the following transformation. (3 points)

H OH
CH3 CO3 H, H 2 O

HO H

7
 98

13. Suggest a structure for X, given the following info: (5 points)

• Formula: C8H12O
• It Reacts With excess H2/Pt to produce C8H16O
• When it reacts with O3/Me2S, one of the products is CH2=O.

14. Which of the following are aromatic

H
N

15. Draw the products and mechanism for the following reaction:

1 H-Br

16. Rank the following:

O Combined
O O
Diels-Alder
+ O Reactivity
+ + O
O
O

Br Cl Br Combined
+ + O + O SN2
Reactivity
ONa ONa ONa

8
 1 99

JASPERSE CHEM 350 FINAL EXAM VERSION 2

Note: Good for practice, but significantly longer than the real one will be.

1. Rank the Following, from most to least. 2 points each.

a. Stability

•
b. Stability
• • •

c. Stability CH3 H H CH3

H H H CH3 H

d. Acidity CH3OH PhCO2H NH3 CH3CH3

Me HMe Me MeMe
H H Me H
e. Stability
H H H H
H H H
Me H
H HH
Me H
 2 100

f. Reactivity toward HBr

g. Reactivity toward Br 2 /hv

Cl
h. Reactivity toward SN2 Ph I Ph Br Ph Cl
Ph

OH
i. Boiling Point OH

j. Stability

2. Provide names or structures for the following. 3 points each. Note: don't forget to specify
stereochemistry!

a. CH3

H3 C

b.
 3 101

c. optically actve
OH

d.
Br

OH
e.

f. trans-1-bromo-3-isopropylcyclopentane

3. Classify the pairs of molecules as totally different, identical, structural isomers,

diastereomers, or enantiomers. (2 points each)

a.

Br Br Br Br

Br Br Br
b.

Br

Br Br
c.

Br Br
 4 102

3. (continued) Classify the pairs of molecules as totally different, identical, structural isomers,
diastereomers, or enantiomers. (2 points each)

d.

e.

f.

Br Br Br Br

OH OH
f.

4. Draw at least four different isomers for C5H10. (There are lots more than four…) (6 points)

5. (a) Draw the appropriate number of lone pairs on the oxygen atom,
(b) Assign a formal charge on oxygen if appropriate,
(c) Draw an additional resonance structure for the following, and
(d) Identify which of the two structures would make the greater contribution to the hybrid. (4
points)

O
 5 103

6. Draw resonance structures for each of the following:.

7. Identify the functional groups in the following molecule. (4 points)

HO OH
N
O H

8. Classify the hybridization and bond angles (109, 120, or 180) at the labelled atoms. (4 points)

2
O
1 3

C-1 O-2 C-3

9. Draw both chair conformations of trans-1-methyl-3-isopropylcyclohexane, and circle the

more stable one. (5 points.)
Note 1: It will simplify things if you abbreviate the isopropyl group as "R".
Note 2: Make sure that your second chair has the same "configuration" as the first, and is not an
enantiomer.
 6 104

10. Classify each chiral carbon as R or S. (Some structures may have more than one chiral
carbon!) (2 points each)

a.
H OH

O
b
H
CH3

11. Mechanisms Problem. Draw the mechanism for the following reactions, and write "slow"
next to the rate-determining step. Be sure to draw all intermediates, and to correctly draw
"electron-movement" arrows or half-arrows. For radical reactions, draw propagation steps only.
4 points each.

OH
a. H2O, H+

Br2 Br
b.
Br
 7 105

Mechs, continued

Br
Br2, hv
c.

H Br H+ (catalyst) H OH
d.
Ph Ph
H2O
 8 106

12. Predict the major products for the following reactions. In each case, pay careful attention to
orientation and stereochemistry. Draw just one product in each case. (3 points each)

HBr
a.

H2 O, H +
b.

H ONa CH3 CH2 I

c.

a. O3
d.
b. Me2S

e. Br2, hv

NaOCH3
f. Br

1. BH3-THF
g.
2. NaOH, H2O2

1. NEt 3
h.
Br 2. Cl2
 9 107

13. Draw the substitution products for the following reactions. (Do not draw any accompanying
elimination products.) Include stereochemistry in your answer, and if two substitution products
are formed, draw them both. Assume the starting material is optically active as drawn. (3 points
each)

H Br
NaOMe
a.
Ph

Me Br
H2 O,
b.
Ph cat. HBr

14. Draw the products of the following multi-step sequences. (4 points each)

1. H2SO 4
a.
OH 2. CH3 CO3H, H2O

1. Br2, hv
Me H 2. NEt3
b.
Ph 3. CH3CO 3H, H2 O
 10 108

15. Provide reagents for the following transformations. More than one step is needed in each
case. (4 points each)

Br Br

a. Br

H
OH
b. O

16. Provide the appropriate reactant for the following transformation. (3 points)

Br H
Br2, H 2O

HO H

17. Suggest a structure for A that is consistent with the following information. (There is more
than one possible solution, but you only need to provide one.) (5 points)
1. O3
A C + C2 H4 O
C7 H1 2 2. Me2 S C5 H8 O
achiral
achiral
H2 , Pt

B
C7 H1 4
achiral
 11 109

18. Draw the products for the following reactions:

Flawed problem.
Not clear which 1 H-Br
allylic cation youa.
should use.
Protonation on the
left gives allylic
where both + NBS,
carbons are 2º;
protonation on the b. peroxides
right gives a hybrid
of a 3º/1º cation.

O heat
+ O

c. O

H2O

Br Draw substitution
d. product(s) only

1. Br2, FeBr3

2. HNO3, H2SO4
e.

1. + AlCl3
Br

2. KMnO4
f.

1. SO3, H2SO4
O

Br 2. Cl + AlCl3

3. H2O, H+
g. 4. Zn(Hg), HCl

1. Br2, hv

2. NaOCH3
h.
 12 110

19. Which of the following are aromatic

20. Classify the lone pair hybridization on the three nitrogen atoms in the following molecule:

b Na
N
NCH3 Nb
H2N c
a Nc

21. Draw the major products and mechanism for the following reaction: Protonation occurs on the left-
most carbon, because that gives
1 H-Br by far the best cation. 3º allylic
Ph and conjugated to the phenyl as
well. The asymmetric allylic
cation gives two different
products (1,2 and 1,4 addition).

22. Draw the major product and mechanism for the following reaction. Draw all of the
resonance structures for the key carbocationic intermediate

HNO3,

O2N H2SO4
 13 111

23. Design a synthesis for the following:

O2N

24. Explain why A is more acidic than B, but C is less reactive than D towards SN1 reactivity
Br
Br
> Acidity SN1 Reactivity
<
A B
C D

25. Rank the following

O
CH3 OCH3 Reactivity
toward
Cl2, AlCl3

O O
O Combined
Diels-Alder
+ + + Reactivity

Stability
112