1. Name or draw structures for the following compounds.

(b) 2-methyl-1-phenyl-2-butene

Ph

(c) o-bromophenol
OH

Br

(d) 4-hydroxy-2-methylbenzaldehyde
CH3

CHO

HO

NO 2
(e) m-fluoronitrobenzene

F
(f) (3R, 4R)-4-methyl-3-phenylnonane CH 3

CH 2CH 3 Ph

(g) p-Ethylphenol

NH 2

(h) aniline OH

2. Predict the major organic product(s) of each of the following reactions. If no reaction will occur, write “N.R.”

NO2
 CH3Cl
(a) N.R.
Al C l 3

Cl Cl

Cl Cl
C l2
(b)
FeCl3
Cl Cl

Cl Cl

3. Provide reagents by each arrow below to complete the following reaction scheme.

Br

CH3Cl Br2
AlCl3 h

1. CH3CH2C(O)Cl 1. Mg, Et2O

2. H2, Pt 2. CH3CHO
3. H3O+

Zn(Hg) PCC
HCl O OH
4. (i) Draw the major product of the following reaction.
NO 2

HNO3
H2SO4

(ii) Draw the major product formed from the reaction of the compound you drew in part (i)
with another electrophile (E+).

NO 2

(iii) Draw the intermediate of the reaction described in part (ii). Include all valid, contributing
resonance structures of this intermediate in your answer.

NO 2 NO 2 NO 2

H H H

E E E
H H H

(iv) Explain why the isomer you drew in part (ii) is the major product of this reaction (rather
than any other isomers).

A resonance structure for the ortho,para substitution have a positive charge on the carbon bearing
the nitro group. This is very unstable because two positive charges are adjacent to one another.
The resonance structures for the meta substitution are more stable, so the meta product is more
likely to form.
5. Circle the letter that corresponds to the correct answer for each question. There is only one correct
answer for each question.

(i) Which of the statements is TRUE regarding the nitration reaction of

isopropylbenzene?
A. A 50:50 mixture of ortho and para products will be formed.
B. A greater amount of the para product will be formed.
C. A greater amount of the ortho product will be formed
D. Only the meta product will be formed.

(ii) Which of the following sets of substituents are ALL ortho/para directing
groups in electrophilic aromatic substitution?
A. Cl, CN, NO2
B. CH3, OCH3, C(O)CH3
C. Cl, NH2, CH3
D. CN, NO2, C(O)CH3

6. Aniline reacts with nitrous acid, HNO 2, to yield a stable diazonium salt.

This diazonium salt undergoes electrophilic aromatic substitution on activated aromatic rings to yield brightly
colored azo compounds that are widely used as dyes. The intermediate structures for the mechanism of this
reaction are given below. Show all electron flow with arrows for this mechanism on the structures provided.
7. Name or draw structures for the following compounds.

OH

(a) (R)-1,3-butanediol
OH

HO Cl
(b) trans-3-chlorocyclohexanol

OH
(c) 3-isopropyl-1-hexanol

(d) 4-penten-2-ol

OH

(i) isobutyl alcohol OH

(j) (E)-2-buten-1-ol
OH

OH OH
(k) (2R, 4R)-2,4-hexanediol

(l) cis-3-ethylcyclobutanol HO

CH 2CH 3
8. Consider the following reaction.

HO CH3
HBr

0°C

(a) What is the stereochemistry of the starting material? S

(b) What is the solvent in this reaction? Water

(c) Draw the first step of the reaction mechanism.

HO CH 3 H2O CH 3

H OH2

(d) Why is this step necessary? To make the –OH a better leaving group

(e) What type of reagent must be present for this step to occur in any reaction? Why? Strong acid to
protonate the weak base.

(f) Draw the second step of the reaction mechanism.

H2O CH 3

+ H2O

(g) Does the carbocation intermediate rearrange? Why or why not? No. It is stable as a 3° carbocation.

(h) Draw the final step of the reaction mechanism.

Br CH 3

Br

(i) What is the stereochemistry of the major organic product? Why? Racemic mixture. Bromide ion
is equally likely to attack either side of planar carbocation.
9. Draw the major organic products formed in the following reactions, clearly showing all appropriate
regio- and stereochemistry.

PBr3
(a) HO
Br

OH
OTs

TsCl
(b) pyridine

H2SO4
(c) OH 

OH
O excess
MgBr
H3O+
(d)
O ether

Cl
OH

SOCl2
(e)
dioxane

O O OH O

OH OH
1. NaBH4
(f)
2. H3O+

O O
OH

(g) OH 1. LiAlH4 OH
+
2. H3O

CH 2OH
(h) PCC H
CH2Cl2

(i) Na2Cr2O7
H2SO4
OH O
10. The following alcohol can be synthesized by three different combinations of a Grignard reagent and a
ketone. Show all three possible combinations. (You do not need to show any mechanisms).

HO CH3

+ CH3MgBr

+ CH3CH2MgBr

+ CH3CH2CH2MgBr

11. Provide starting materials in the boxes below to complete the following reactions.

CH2OH
O
1. PhMgBr
(a)
C 2. HCl, H2O
H H

OH
O

1. PhMgBr
(b) H
2. HCl, H2O

O
OH
1. PhMgBr
(c)
2. HCl, H2O
12. Each of the following conversions requires more than one step. Show reagents and experimental
conditions necessary to bring about each conversion.

OH
OH
(a)

OH
OH H2SO4,  H2O, H2SO4

(b)

Br2
h

OH
Br MgBr
Mg 1. CH3CHO

ether 2. HCl/H2O

PCC

O
13. Name the following compounds

CHO
(a) (R)-3-hydroxy-2-methylpropanal
H
CH2OH
H3C

(b) 2-methyl-3-pentanone

CHO

(c) (2S)-2-ethyl-3-methylpentanal

O CH3
(d) (R)-3-methylcyclopentanone

14. Draw structures for the following compounds.

(m) 5-oxohexanal
O O

O
(n) 3-methyl-3-buten-2-one

O
(o) isopropyl methyl ketone

CHO

(p) trans-4-hydroxycyclohexanecarbaldehyde

OH
15. Identify any nucleophilic and/or electrophilic atoms in the following molecules.

(a) Ph3P CH2

E N

ON

E
(b)

N E
(c) CH3CH2 MgBr

16. Give the major organic product(s) for the following reaction.

O
O O

HOCH2CH2CH2OH
HCl
Br
Br

17. Provide structures in the empty boxes below to complete the following reaction scheme.

O H H H
H+ N H2 N
+ NH3
Ni

18. The following alkene can be synthesized using the Wittig reaction. Show both possible routes,
including formation of the phosphonium ylide. O
1. PPh3
CH3CH2Br CH3CH-PPh3 +
2. BuLi

O
1. PPh3
(CH3)2CHBr (CH3)2C-PPh3 +
2. BuLi
H
 19. Show reagents and experimental conditions necessary to bring about each of the following conversion.

Et
N

OH

(a)

O
PCC
OH
CH2Cl2
H

1. (CH3)2CHMgBr
2. H3O+

OH O
N
H2CrO4 H2NCH2CH3

H+

(b) OH OH

OH O
1. CH3MgBr PCC
OH
CH2Cl2
2. H3O+
H

H+

OH
1. BH3-THF OH H2CrO4
2. H2O2, NaOH
O
20. Name the following compounds.

Cl
(a) propanoyl chloride
O

(b) isopropyl acetate

O

N
(c) N-ethyl-N-methylacetamide

C O
(d) phenyl benzoate

CH3

(e) H (S)-3-hydroxybutanoic acid

CH2CO2H
HO

(f) E-2-methyl-2-butenoic acid

HO

(g) 2-ethyl-4-methylhexanoic acid

CO2H

O O

(h) acetic butanoic anhydride

O
21. Draw structures for the following compounds.
O
(q) Octanoyl chloride
Cl

OH O
(r) Ethyl 3-hydroxybutanoate
O

(s) N-Cyclohexylpentanamide O

N
H

(t) Propanoic anhydride

O O

(u) Formic propanoic anhydride

O O

H O

22. Each of the following conversions requires more than one step. Show reagents and
experimental conditions necessary to bring about each conversion.

CH3 CH2CO2CH2CH3

(a)

CH 3 CH 2Br
CH 2MgBr
Br2 Mg
h Et2O

1. CO2
2. H3O+

CH2CO 2CH 2CH 3 CH 2CO 2H

CH3CH2OH

H+
 CH3 O
(b) C NO2

H2N

Cl
CH 3 CH3 CH 3

Cl
HNO3 Cl2

H2SO4 FeCl3

NO 2 NO 2

1. KMnO4, OH-, 
2. H+

C(O)NH 2 CO 2H
C(O)Cl

Cl Cl
Cl
2 NH3 SOCl2

NO 2 NO 2
NO 2

23. What is the order of decreasing activity (most reactive = 1, least reactive = 4) towards
nucleophilic acyl substitution for the following carboxylic acid derivatives?

O O O O O

H3C C O C CH3 H3C C N(CH3)2 H3C C O CH3 (CH3)2CH C O CH3

1 4 2 3

24. Draw the major organic products formed from the following reactions or sequences of reactions.
 O
OH

1. LiAlH4, ether
(a)
2. H3O+

C
CH 2OH
O O

O
O

OH
OCH3 HCl
(b) + CH3OH
H2O

O excess
OH
MgBr
(c) H3O+
CH3CH2 C CH 2CH 2CH3
Cl ether
CH 2CH 2CH3

H
N

SOCl2 LiAlH4 H3O+ N

(d) CO2H

25.)

26.)

27.)
28.)

29.)

30.)

31.)
32.)

33.)

34.)
35.)