Lebanese University

Lebanese University Faculty of Sciences

Faculty of Sciences

C1102
Introduction to
Organic Chemistry
Exercises
Department of Chemistry and Biochemistry

Spring Semester
2020 - 2021

©opyright Reserved
 Table of contents

Chapter I : Electronic structure of organic molecules

Chapter II : Electronic effects

Chapter III : Alkanes-Cycloalkanes

Chapter IV : Stereochemistry

Chapter V : Substitution and elimination reactions of alkyl halides

(SN + E)

Chapter VI : Alkenes

Chapter VII : Alkynes

Chapter VIII : Dienes

Chapter IX : Alcohols

Chapter X : Electrophilic aromatic substitution of benzene (EAS)

1
 Chapter I
Electronic structure of organic
molecules

2
 Electronic structure of organic molecules
1) What is the hybridization of carbon atoms in each of the following structures:

CH3Cl ; CH3OH ; CH2 = CH2 ; HC ≡ CH ; CH3CHO

2) Consider the following compound:

C2H5 CH3
(1) (2) (3) (4)
CH CHOH CH C
(5) (6) (7)
H3C C CH CHO
O
CH3
Indicate the hybridization of carbon atoms starting from (1) to (7).

3) Lynestrenol has the following structure: H

O

In the above structure, indicate:

a) A very polar covalent bond
b) A covalent bond almost not polar
c) Carbon atom of sp hybridization
d) Carbon atom of sp2 hybridization
e) Carbon atom of sp3 hybridization
f) A bond between atoms of different hybridization
g) Primary carbon atom
h) Secondary carbon atom
i) Tertiary carbon atom
j) Quaternary carbon atom

4) Starting from the condensed formula below; write the developped formula:

NH2

(CH3)2CHCHCOOH CH3CH(OH)CH2COCH2CH3 HOCH(CH3)CH(CH3)CHO

3
5) Transform the developped structures below into condensed structures:

H H
H H O H O H
H C C
H
H C C C C C O H C O H
H
H O H C
H
N

6) Use the symbols δ+ and δ– to show the direction of polarity of the indicated bond in each of the
following compounds:

a) H3C Cl ; b) HO Br ; c) I Cl

7) Which bond would be stronger?

a) C Cl or C I ; b) C Cl or C C ; c) H Cl or H H

4
 Choose the correct answer (A, B, C or D) (one choice only):

1) Predict which bond is the most polar in ethanol, CH3CH2OH?

A. C—C B. C—H C. C—O D. O—H

2) Identify the condensed formula of the following structure:

Cl

A. (CH3)2CHCHClCH(CH3)2 B. CH3CH(CH3)CHClCH(CH3)2

C. (CH3)2CHCHClC(CH3)3 D. (CH3)3CCHClC(CH3)3

3) How many hydrogen atoms are there on carbon atoms (1) and (2), respectively, in the structure below?
(1)
(2)

A. 4, 1 B. 4, 0 C. 3, 1 D. 3, 0

4) How many C3H8O constitutional isomers are possible?

A. one B. two C. three D. four

5) How many constitutional isomers of C4H9Br are possible?

A. one B. two C. three D. four

6) How many constitutional isomers of C3H6Cl2 are possible?

A. three B. four C. five D. six

7) The carbon-carbon sigma bond in ethane is formed by overlap of which two orbitals?

A. 2p-2p B. sp-sp C. sp2-sp2 D. sp3-sp3

5
 Chapter II
Electronic effects

6
 Electronic effects
1) Draw curve arrows in order to convert the structures on the left into the structures on the right.

CH3 CH3

a)

.. .. .. ..
: O: O: :O : O:
b) H3C H
H3C H
..
Br S
.. Br S
c)

..
NH2 NH2

d)
.. ..
:O
.. N : ..O N
:O.. : ..:
O
.. ..
N N
e)
.. N ..N
..
..

2) Draw resonance contributors for each of the following species. Indicate the most stable resonance
contributor. Justify your answer.
..
.. NH2
H3C O
..

..
a) H3C CH2 CH C C H b) HO N N c)
NO2
.. O
O
..

.. e) :
d) H3C C CH CH CH2 f)

.. ..
g) h)
..

O2N ..S ..NH

CH3
O

3) Rank the following acids from strongest to weakest acid.

a) CH3 – CO2H ; b) CH3 – HN – CH2 – CO2H ; c) CH3 – CH2 – CO2H ;
d) H2N – CH2 – CO2H ; e) CH3 – CH(CH3) – CH2 – CO2H

7
4) In each of the following pairs, indicate the strongest acid. Briefly justify your answer.

a) CH3-CH2-CH2-OH or (CH3)2CH-OH
b) m-NO2-C6H4-OH or p-NO2-C6H4-OH
c) p-CHO-C6H4-OH or p-CH3O-C6H4-OH

5) In each of the following pairs, indicate the strongest base. Briefly justify your answer.

a) C6H5-NH2 or C6H11-NH2
b) CH3-CO-CH2-NH2 or CH3-CH2-CO-NH2
H2N COCH3 H2N
c) or
COCH3

6) Rank the following compound from least acidic to most acidic and attribute to each its pKa value.
Approximate pka values: 5- 7- 9 and 10.

O2N O2N OH OH COOH

a) b) c) d)
OH

7) In each of the following pairs, identify the molecule having the smallest pKa. Justify briefly your
answer.

H H H
N N
a) Or
H3C CH3 H3C CH3

O
H H C
N N CH3
b) CH3 Or
CH3 CH3
O O
c) CH2 CH CH C CH3 Or CH3 CH2 CH C CH3
Ha Hb

8) Rank the following molecules from strongest to weakest acid. Justify your answer briefly.

a) CH3CH2 CH2 CH2 OH ; CH3O CH2 CH2 OH ; O2N CH2 CH2 OH

b) CH3HN CH2 CH2 OH ; CH3HN CH2 CH2 CH2 OH ; (CH3)3N CH2 CH2 OH

O O O O
c) CH3 C OH ; ClCH2 C OH ; Cl2CH C OH ; Cl3C C OH

8
9) Rank the following molecules from least basic to most basic. Justify your answer briefly.

a) H3C CH2 CH2 NH2 ; NH3 ; NH(CH2CH2CH3)2

b) CH3OOC CH2 CH2 NH2 ; CH3 CH2 CH(CH3) NH2 ; H3N CH2 CH2 NH2

NH2 NH2 NH2

c) ; ;

10) Compare the acidity of the following compounds:

a) O2N – CH = CH – CH = CH – CH = CH – CH2OH
b) O2N – CH2 – CH2 – CH2 – CH2 – CH2 – CH2OH
c) O2N – CH2 – CH2 – CH2OH

11) Rank the following anions by increasing order of basicity. Justify your answer briefly.

a) (CH3)2CH O ; CH3O ; (C2H5)3C O

.. ..
b) CH3CH2O ; ;
..F
..

HC C
..

..
..

..
.. ..
c) CH3(CH2)3 C C ; CH3(CH2)4CH2 ; CH3(CH2)3 CH CH
..

O O O
d) H3C C O ; H3C C NH ; H3N CH2 C O

12) Identify the most acidic hydrogen in each compound and briefly explain your answer.

HbO
Ha
O Hb HcO O O
a) Ha O C C O Hc ; b)
H HdO OHe
Vitamin C

13) Identify the most acidic proton in each of the compound below and justify briefly your answer.

CO2H CO2Et
a) ; b) ; c) H3C CH2 CHO ; d) C2H5O C CH2 CN
CO2H CO2Et O

e) H3C CH2 CH2 NH3 ; f) NC CH2 CH2 OH

9
14) Compare the basicity of the following compounds:
NH2 NH2 NH2 NH2

a) ; ; ; ; H3C NH2
NO2
NO2 OCH3

NHCH3 NHCH3 NHCOCH3 N(CH3)3 NH2

b) ; ; ; ;

CN SCH3 COCH3 CN

15) Explain why?

a) is less basic than

N N
H ..
N
b) the electron pair of one of the these two nitrogen atom is not a part of the- ..
conjugated system (cannot be delocalized). N
H

16) Discuss the value of pKa values, of benzoic acid PhCOOH, p-hydroxybenzoic acid and p-
methoxybenzoic acid.
COOH COOH COOH

OH OCH3
pka = 4.19 pka = 4.47 pka = 4.58

17) Rank the following carbocations in order of increasing stability.

a) C H b) H3C C H c) H C CH d) H C CH CH e) H3C CH2

2 2 2
CH3

18) Classify the compound below as : acid, base, nucleophile (and) or electrophile:

a) CH3 – NH2 b) CH3 – C ≡ C – H c) CH3 – C ≡ C –

d) H – CN e) CN– f) BF3

10
19) In each of the following pairs specify the most stable species?

a) CH3 CH2 CH2 Or CH3 CH CH3

O
b) CH3 C CH2 Or H2C CH2OH

. .
c) C6H5 CH CH3 Or C6H5 CH2 CH2

d) CH3 COH CH3 Or CH3 CH CH3

e) CH3 CH2 Or ClCH2 CH2

f) CH3 CH2 Or F3C CH2

g) CH3 CHOH Or CH3 CH CH3

O
h) CH3 C CH2 Or C2H5 CH2

20) In each of the following pairs specify the most stable species?

a) CH2 Or CH2 CH2

O CH3
b) C Or H3C C C
CH3

CH CH CH2 CH3 CH CH CH2

c) Or

d) N Or N
H3C CH3
CH3

Or
e) R C NH R C O
O NH

f) CH2 Or CH2

g) EtOOC CH2 Or EtOOC CH COOEt

11
 Choose the correct answer (A, B, C or D) (one choice only):

1) Which of the following best describes the relationship between the following two structures?

Br
and
Br

A. identical compounds B. resonance structures

C. constitutional isomers D. different compounds with different constitutions

2) Which of the following describes the relationship between the following two structures?

OH OH
and

A. identical structures B. resonance forms

C. constitutional isomers D. different compounds with different constitutions

3) Which one of the following is the strongest base?

– – – –
A. OH B. CH3 A. F B. NH2

4) Which is the conjugate base of NH3?

A. NH4+ B. H+ C. N3- D. NH2–

5) Which one of the following is the strongest acid?

A. FCH2CO2H B. ClCH2CO2H C. BrCH2CO2H D. ICH2CO2H

6) Which one of the following has the largest acid equilibrium constant, Ka?

A. CH3CO2H B. ClCH2CO2H C. Cl2CHCO2H D. Cl3CCO2H

7) Identify the resonance structure which results from the following "electron pair movements".

..
?
..

..

N C O
..

..
A. B. C.
..N C O
..

..

..N C O ..N C O D.
..

..

..

..

..N C O
..

..

.. .. .. ..

12
8) a, b and c represent the length of the bond C-C in the following molecule:

a b c O
H3C CH CH C H

Classify the bonds by decreasing bond length:

A. c ˂ a ˂ b B. b ˂ c ˂ a C. b ˂ a ˂ c D. c ˂ b ˂ a

9) Given the following 4 molecules:

NH2
H3C CH2 OH H3C CH3 H3C O CH3
CH3
(a) (b) (c) (d)

Choose the correct answer:

A. There is hydrogen bond between (b) and (c)
B. There is hydrogen bond between two molecules of (d)
C. There is hydrogen bond between (a) and (d)
D. There is hydrogen bond between two molecules of (b)

10) Which of the following carbocations is the most stable?

A) CH3 CH2 C CH2 B) CH2 CH CH2 CH2

C) CH3 CH CH CH2 D) CH3 CH CH2 CH3

11) Rank the following carbocations in decreasing order of stability.

(CH3)2C CH CH2 CH3 CH CH CH2 CH2 CH CH2

I II III

A. I > II > III B. III > II > I C. II > I > III D. They are of equal stability

12) Which of the following cannot act as a nucleophile?

A. NH3 B. H2O C. I- D. CH4

13) Which of the following is a conjugate base of CH3NHOH?

A. CH3NH B. CH3NHO C. CH3NH3 D. CH2=NHO

13
 Chapter III
Alkanes-Cycloalkanes

14
 Alkanes-Cycloalkanes
1) Name the following compounds:

a) b) c) d)

e) f) g) h)

2) Correct (if necessary) the systematic names of the following compounds and write their structures
respectively:
a) 4-butyl-2,3,4-trimethylheptane
b) 4-(2-Ethylbutyl)decane

3) Which one of the following compounds, is the most stable: cis-1,2-dimethycyclopropane or trans-1,2-
dimethylcyclopropane? Explain.

4) Draw the two chair confomers for each of the following and indicate which conformer is more stable.
a) cis-1-tert-butyl-3-methylcyclohexane.
b) trans-1-tert-butyl-3-methylcyclohexane.
c) trans-1-tert-butyl-4-methylcyclohexane.
d) cis-1-tert-butyl-4-methylcyclohexane.

5) Which compound in each pair has the highest heat of combustion?

a) cis- or trans- 1,2-dimethylcyclohexane.
b) cis- or trans- 1,3-dimethylcyclohexane.
c) cis- or trans- 1,4-dimethylcyclohexane.

6) a) Draw the most stable conformer of cis-1-ethyl-2-methylcyclohexane.

b) Draw the most stable conformer of trans-1-ethyl-2-methylcyclohexane.
c) Which one is the more stable stereoisomer, the cis- or trans-1-ethyl-2-methylcyclohexane?

15
7) Represent each of the following compounds A and B in its most stable chair comformation. Deduce
which compound is the most stable (A or B).

CH3 CH3

C(CH3)3 ; C(CH3)3

A B

8) Draw the most stable Newman projection of each of the following compound:
a) 3-methylpentane, viewed along the C2-C3 bond.
b) 3-methylhexane, viewed along the C3-C4 bond.
c) 3,3-dimethylhexane, viewed along the C3-C4 bond.

9) Bromination of isopentane in presence of light can give four products.

Write their structures. Which one is the major product?

10) How many products can be formed from monobromination of each of the following compounds?

CH3
CH3 CH3 CH3 CH3 CH3
a) H3C C C CH3 b) H3C C CH2 CH CH3 c)
CH3 CH3 CH3

11) How many products can be formed from monochlorination of each of the following compounds?

CH3 CH3
a) b) H3C C CH CH CH3
CH3 CH3

12) Draw the two chair conformations for each of the following compounds and indicate the most stable
form in each case.

CH3 Cl Cl
a) b)
CH3
C(CH3)3 Cl

16
13) Which two structures represent the same compound?

H3C CH3
CH3 CH CH3
H CH3 H H C2H5 H

H3C C2H5 H CH2CH3 H CH3

CH3 CH3 CH2CH3

A B C

14) Indicate the relationship between the two structures in each of the following pairs:

Br H
H
a) H ; CH3
H3C
Br
H
H H
H CH3
b) CH3 ; Br

Br
H
Cl H H
Br
c) H ; Cl
Br

15) Which of the following represent a cis isomer? a trans isomer?

H
H H
a) ; d) Br
Br CH3
Cl

H
Br H

b) H ; e) Cl
CH3
H3C

H H
H H
H CH3
c) CH3 ; f) CH3

Br H

17
16) Represent the different conformations of the two compounds shown below and complete the schemes to
the right. Indicate in each case the most stable conformers.

H3C CH3

H3C OH

CH3
OH HO

17) Give the different conformations of the cis and trans isomers of cyclohexa-1,3-diol.

18
 Choose the correct answer (A, B, C or D) (one choice only):
1) The correct IUPAC name of the following compound is:

A. 2-ethyl-3,5-dimethylheptane B. 6-ethyl-5,5-dimethylheptane
C. 3,4,4-trimethyloctane D. 5,5,6-trimethyloctane

2) Which one of the following is 2,2,5-trimethylhexane?

A. (CH3)2CHCH2C(CH3)3 B. (CH3)2CHCH2CH2C(CH3)3
C. CH3CH2CH(CH3)C(CH3)3 D. (CH3)2CHCH2CH2CH2C(CH3)3

3) The correct IUPAC name of the following is:

CH3
H3C CH CH2 CH CH2 CH2 CH CH3
CH3 CH2
CH3

A. 2,4,7-trimethylnonane B. 3,6,8-trimethylnonane
C. 7-ethyl-2,4-dimethyloctane D. 2-ethyl-5,7-dimethyloctane

4) What is the IUPAC name of the following?

A. 1-ethyl-4.4-dimethylcyclopentane B. 1-ethyl-3,3-dimethylcyclopentane
C. 3-ethyl-1,1-dimethylcyclopentane D. 4-ethyl-1,1-dimethylcyclopentane

5) The correct name of the following compound is

A. (1-methylpropyl)cyclohexane B. (2-methylpropyl)cyclohexane
C. (2,2-dimethylethyl)cyclohexane D. (2,2-dimethylpropyl)cyclohexane

19
6) Carbon atoms 1, 2, and 3 in the following structure are classified, respectively, as

1 H3C CH3

2
3
CH3

A. tertiary, primary, secondary B. quaternary, primary, tertiary

C. quaternary, secondary, secondary D. quaternary, secondary, tertiary

7) The correct IUPAC name of the following compound is:

A. (1-methylhexyl)cyclopentane B. (1-pentylethyl)cyclopentane
C. 2-cyclopentylheptane D. 1-cyclopentyl-2-heptane

8) Which of the following are constitutional isomers?

CH3 CH3 CH3 CH3

H3C

I II III IV

A. I, II and III B. I, III and IV C. I and III D. I, II, III and IV

9) Arrange the following isomeric alkanes in order of increasing boiling points.

I. n-heptane II. 2,3-dimethylpentane III. 2,2,3-trimethylbutane

A. I < II < III B. II < III < I C. III < I < II D. III < II < I

10) Identify the conformation of butane shown below.

CH3
H3C H

H H
H

A. anti B. gauche C. skewed D. eclipsed

20
11) Which of the following are the chain propagation steps in the free radical chlorination of methane?

I. Cl2 2 Cl
.

II. Cl2 + H
. 2 HCl + Cl
.

. .
III. CH4 + Cl CH3 + HCl

. .
IV. CH4 + H CH3 + H2

. .
V. CH3 + Cl2 CH3Cl + Cl

. .
VI. CH3 + Cl CH3Cl

A. I and III B. II and VI C. III and IV D. III and V

12) What is the IUPAC name of the compound shown in the following Newman projection?

CH3
H3C H

H3C H
CH3

A. 1,1,2,2-tetramethylethane B. 1,2-dimethylethane
C. 2,2,3,3-tetramethylbutane D. 2,3-dimethylbutane

13) Which statement is correct concerning the relative stabilities of the two conformations, A and B, below?
CH3
H
H
H3C H
CH3
H A CH3 B

A. A is more stable. B. B is more stable. C. A and B are equal in stabilities.

D. A and B are not equal in stability, but the preferred conformation cannot be determined.

14) Which of the following can have cis-trans stereoisomers?

A. 1,1-dimethylcyclobutane B. 1,3-dimethylcyclobutane
C. 1,1,3-trimethylcyclobutane D. 1,1,3,3-tetramethylcylclobutane

21
15) Identify the relationship between the following two structures.
CH3 CH3
H
H H
H3C and H CH3
H3C
H CH3 H

A. constitutional isomers B. stereoisomers

C. different conformations of the same compound D. identical

16) The most stable conformation of the compound shown has:

1 CH3

H3C 4 2 CH3

A. all methyl groups equatorial.

B. equatorial methyl groups at C-1 and C-2, axial at C-4.
C. equatorial methyl groups at C-1 and C-4, axial at C-2.
D. equatorial methyl groups at C-2 and C-4, axial at C-1.

17) What is the IUPAC name of the following compound?

CH3

CH3CH2CH2 C CH3

CH3

A. 4,4-dimethylpentane B. 1-tert-butylpropane
C. 2,2-dimethylpentane D. 1,1,1-trimethylbutane

18) Alkanes are characterized by the general molecular formula:

A. CnH2n-2 B. CnH2n C. CnH2n+2 D. CnH2n+4

19) Cycloalkanes are characterized by the general molecular formula:

A. CnH2n-2 B. CnH2n C. CnH2n+2 D. CnH2n+4

20) Which one of the following gives a single monochlorination product?

A. 2,2-dimethylpropane B. 2,2-dimethylbutane
C. 2,3-dimethylbutane D. 2-methylpropane

22
21) Identify the correct stereoisomer and the most stable conformation of the following compound.

CH(CH3)2

CH3
H H

CH(CH3)2 CH(CH3)2
A. B.
H3C H

H CH3
CH(CH3)2 CH(CH3)2

H H
C. D.
H3C H

H CH3

22) The common name of the following group is:

CH3CH2 CH

CH3

A. n-butyl B. sec-butyl C. isobutyl D. tert-butyl

23) What is the IUPAC name of the following?

CH2CH3

CH3CH2CH2CH2 CH CH CH3

CH2CH3

A. 5,6-diethylhexane B. 2,3-diethylhexane
C. 5-ethyl-6-methylheptane D. 4-ethyl-3-methyloctane

24) The tert-butyl group can also be called :

A. 1,1-dimethylpropyl B. 1,1-dimethylethyl
C. 2,2-dimethylpropyl D. 2,2-dimethylethyl

25) Identify the isomer of C6H14 that only has primary and tertiary carbons.

A. hexane B. 2,2-dimethylbutane
C. 3-methylpentane D. 2,3-dimethylbutane

23
26) Identify the relationship of the two chlorine atoms.

Cl

H
H
Cl

A. gauche B. anti C. eclipsed D. twist

27) What is the IUPAC name of the following compound?

CH3
H3C

A. trans-1,4-dimethylcyclohexane B. cis-1,4-dimethylcyclohexane
C. trans-1,3-dimethylcyclohexane D. cis-1,3-dimethylcyclohexane

28) Identify the relationship between the following two Newman projections.

CH3 H
H3C H H3C H
and
H H H3C H
CH3
CH3

A. identical B. stereoisomers
C. different conformations of the same compound D. constitutional isomers

29) Cyclohexane adopt the chair conformation in order to:

I. minimize the angular II. make the C—C—C bond III. minimise the 1,3-diaxial
tensions closer 109.5o. interactions

A. only I B. only II C. I and III D. I and II

24
 Chapter IV
Stereochemistry

25
 Stereochemistry
1) Indicate the asymmetric carbons in each of the following molecules:

a - CH3 – CH2 –CHOH – CH2 – CH2 – CH3 b - CH3 – CH = CH – CO2H

CH3
HO CH3 OH
c- d- OH e- f-
H H H
OH

g - HOCH2 – CH2 – CH(CH3) – CH2 – CH2OH h - CH2Br – CH2 – CH3

i – CH3 – CH(Br) – CH(CH3) – CH2CH3 j – 1-methylcyclopropanol

k – CH3 – CH2 – CH(CH2CH3) – CH(CH2CH3) – CH2–CH3

OH O
H3C CH3 H3C
HO O
l- m- H H3C
H O n- o-
HO H H3C OH OH
CH2OH
H3C
HO O

O
O
p- O
CH3 CH3

H3C

2) Assign relation priorities to each set of substituents.

a - – OCH2CH3 ; - CH2OH ; - CH2OCH3 ; - CHBr – CH3 ; - CONH2 ; - NHCH3

b - - C6H5 ; - C(CH3)3 c - - CCl3 ; - CH2Br ; - CHBrCl

OCH3 O O H CH3 CH3

d- C CH2CH3 ; C CH3 ;
e- C CH ; C C ; C C ; C N
C OH H H
CH3 H

f- –CH3, –OH, –CH2Cl, –CH2OH g- –CONH2, –NHCH3, –CH2OH, –CH3

h- –CH=CH2, –CN, –CH2NH2, –CH2Br i- CH CH2 ; CH2CH3 ; CH3

;
j- –CH3, –CH2CH2Br, –C(CH3)3, –OH

26
3) Which of the following are chiral?

H3C H3C

a) b) c) d)
H3C CH3 H3C CH3
CH3 CH3

H3C Cl H3C Cl H3C Cl

e) f) g) h)
Cl CH3
CH3 Cl CH3 Cl CH3
Cl
OH
H CH3
i) j) k) l) CH C CH
COCH3 H3C H OH
Cl OH

4) What is the configuration of the asymmetric carbons in the following molecules?

BrH2C CH2
H
HO
a) C CH3 b) C C(CH3)3 c) D C
H BrH2C CH2OH
Cl H CH3

H3C H H3C H3C

C C OH
H C H H3CH2C
d) C C e) C CH2OH f) H
H H Cl CH3
H3C H3C

CHO
CH(CH3)2
H OH
g) h) CH3CH2 CH2Br i)
H OH
OH CH3
CH2OH
H
OCH3
Cl HO CH3 H3C
Cl H H OH
H
j) k) HO H l) H m)
H OH
H3C H H3C H
CH3CH2 CH3
CH3
OH

27
5) Name each of the following compounds:

Br Cl
H3CH2C
CH3

H
Cl CH3
H

6) Draw the Fisher projection of each of the following compounds:

a) (3R,4R)-CH2=CHCH(CH3)CH(CH3)CH2CH3
b) meso-2,4-dichloropentane

CH2OH
H2N H
7) Given is the following Fisher projection:
H OH
C6H5

a) Give the Newman representation of this molecule, in staggered conformation.

b) Assign the absolute configurations of asymmetric carbons.
c) Draw the enantiomer of this molecule according to Fisher and Newman projections.

8) Consider the following perspective representation:

C 2H 5 C3H7
(1) (2)
H H
Cl CH3

a) Give the absolute configurations of asymmetric carbons.

b) Draw the Newman projection following the C1-C2 axis.
c) Draw the perspective and Newman representations of the stereoisomer (1R, 2S).
d) Represent using the Newman projection the other stereoisomers of the above molecule showing
the absolute configuration of each one.

9) The (S)-ibuprofene is an anti-inflammatory drug; however its (R) enantiomer is inactive.

Give a perspective representation of the biologically active enantiomer.

OH
O

28
10) Complete the representation B and C of the molecule A.

H Ph Ph Me
Me
H Me OH
Ph OH

A B C

11) Complete the following representations of the compound below:

(2R,3S) H3C CH CH COOH

Ph NH2

COOH
HOOC

H
H

12)
a) Complete the following Newman representation of the compound shown in perspective.

H OH
HO H

CH2OH CHO

b) Starting from the Newman representation, give its corresponding Fisher projection.

CH2OH
H CHO
H

OH
OH

13) Draw a diastereomer for each of the compounds below:

CH3 Cl
Cl
H OH H H H
a) b) c)
H OH H HO CH3
H3CH2C CH3
CH3

29
14) The following product is given: (2S, 3S)-CH3CBr(OH)-CCl(OH)CH3
Complete each of the following structures of the same compound:
Br
Cl Br Cl
Cl

HO Cl
OH

15) Each of the following four molecules below is represented in the Newman projection and in the most
stable conformation. Explain the reason behind this conformation in each case.

C2H5 OH OH
H H H OH H NH2

H H H 3C H H H
H C2H5
C2H5

16) Consider the following chiral compound (A):

H OCH3
OH
H3C
H3C OC(CH3)3
(A)

a) Determine the geometric configuration of the double bond and absolute configureation of the
asymmetric carbon.
b) Indicate all possible isomer of this compound.

17) Consider compound (A) the following:

H3C CHO
(3) (2)
Br H
H CH3
(A)

a) Draw the Newman projection of (A) following C2C3 axis.

b) Give respectively the stereochemical relationship in each of the following couples. (A1, A2) ; (A1,
A3) ; (A1, A4) and (A2, A3) of the compounds shown below.

CHO CHO CHO

H3C CHO H Br Br CH3
H3C H
Br CH3 H CH3 H3C H H Br
H H CH3 H CH3

A1 A2 A3 A4

c) What relationship exists between A and A4.

30
18) Specify the relationship between the compounds of each of the following pairs:

H3C H3C H3C Br

H H H H
a) and ; b) and
C CH2Br C CH2OH C Br C CH3
HO Br H3CH2C H3CH2C

CH2OH CH2OH
H3C CH2CH3
H H OH HO H
c) and Br CH3 ; d) and
C Br
H H H H
H3CH2C H
OH OH
CH3
H Br Br Br CH3
HO H H3C
OH H3C CO2H HO2C Br
e) and ; f) and
HO
H OH
H CH2OH H H H H
CH2OH
OH CH3
H CH3
HO2C CH3 HO2C OH
g) and ; h) HO2C NH2 and H2N CO2H
H3C CO2H HO CO2H
CH3 H
OH CH3

CH3 CH3
CH3 OH
H OH HO H
i) and ; j) H and
H OH CH3
H OH HO CH3CH2CH2
CH2CH2CH3 H
CH2OH CH2OH

Cl CH3 CHO CHO

k) ; l)
OH and OH and
H CH2CH2OH
H Cl HOCH2CH2 CH3CH2
CH3 H CH2CH3 OH
OH CH3 OH
H OH Ph OH
m) ; n)
H3C and and
CH2CH3 H H
OH Ph H H
H CH3CH2 Ph
HO
Ph

31
 Choose the correct answer (A, B, C or D) (one choice only):

1) Which of the molecules below are chiral?

Cl
H3C CH2 CH CH2 CH3 H3C CH2 CH CH CH3 H3C CH2 CH2 C CH3
OH OH OH F
I II III

A. only II B. only III C. I and III D. II and III

2) Which of the molecules below are chiral?

HO OH HO OH HO Br
I II III

A. only I B. I and III C. II and III D. I, II and III

3) How many stereogenic centers are there in the following molecule?

H3C CH CH2 CH CH2 CH2 CH CH3

OH CH3 CH3

A. one B. two C. three D. four

4) Give the configurations, respectively, of the following two molecules.

CH3
HO H
H and
Cl
Br

A. R and R B. R and S C. S and S D. S and R

5) Give the configurations of carbons 1 and 2, respectively, in the structure shown below.

H 1 2 H
H3C CH3

A. R and R B. R and S C. S and S D. S and R

32
6) Which one of the following groups has the highest rank as assigned by the Cahn-Ingold-Prelog system?

A. –CH=CH2 B. –CH2OH C. –CH=O D. –CH2SH

7) What is the IUPAC name of the following compound?

H Br
H

H3C
Br CH2CH3

A. (2S, 3S)-2,3-dibromopentane B. (2S, 3R)-2,3-dibromopentane

C. (2R, 3S)-2,3-dibromopentane D. (2R, 3R)-2,3-dibromopentane

8) What is the relationship between the following two compounds?

H3C H Br H
OH H3C
and
H CH3
Br CH3 H OH

A. different conformations of the same compound B. enantiomers

C. diastereomers D. constitutional isomers

9) Which of the following has a meso stereoisomer?

I. 2,4-dichloropentane II. 1,3-dimethylcyclopentane III. 2,3-dichloropentane

A. only I B. only II C. I and III D. I and II

10) How many stereoisomers are there of D-fructose(including D-fructose), shown below?
CH2OH

HO H

H OH

H OH

CH2OH

A. four B. six C. eight D. twelve

11) Which one from the following molecules does not have stereoisomers:

A. 1,2-dichlorobutane B. 1,3-dichlorobutane C. 1,4-dichlorobutane D. 2,3-dichlorobutane

33
12) Which of the following Fischer projections corresponds to the compound shown below?

H3C H
OH

Br
H CH3

CH3 CH3 CH3 CH3

H OH H OH HO H HO H

H Br Br H H Br Br H

CH3 CH3 CH3 CH3

A. B. C. D.

13) The four isomeric dimethylcyclopropanes are shown below. Identify two of the isomers which are
related as diastereomers.

H3C H H H3C H CH3 H H CH3 H H CH3

H CH3 H H H3C H H CH3

H H H H
I II III IV

A. I and III B. I and IV C. II and III D. III and IV

14) How many different stereoismores are there for the following compound?

CH3
H3C CH CH CH CH CH2 CH3
Ph

A. 3 B. 4 C. 5 D. 8

15) If a chiral molecule has an absolute configuration of R, which direction does it rotate the plane of
polarized light?

A. clockwise (dextroratory)
B. counterclockwise (levarotatory)
C. it doesn’t rotate the plane of polarized light
D. can’t be determined from the information given

34
16) Which two Fischer formulas represent a pair of enantiomers?

CH3 CH3 C2H5 CH3

HO H H Cl Cl H HO H
H Cl HO H HO H Cl H
C2H5 C2H5 CH3 C2H5
I II III IV

A. I & II B. III & IV C. I & IV D. II & III

17) Which two of the following compounds represents a pair of enantiomers?

HO OH HO OH

HO OH HO OH
I II III IV

A. I & II B. II & III C. III & IV D. II & IV

18) Which of the following is properly classified as a meso compound?

CH3 C2H5
H CH3 C2H5
H OH HO H H OH
OH OH H H
H OH
HO H
C2H5 H OH
CH3 H CH3
CH3
I II III IV

A. I B. II C. III D. IV

19) Which of the following statements is true for a pair of diastereomers?

A) they will have identical physiological properties.

B) they will have specific rotations of opposite sign.
C) they will have identical chemical properties (e.g. reactivity)
D) they will have different physical properties.

35
 Chapter V
Substitution and elimination
reactions of alkyl halides
(SN + E)

36
 Halogenoalkanes:
Nucleophilic substitution and elimination (SN + E)
1) (3R,4R)-3-bromo-4-methylhexane was reacted with NaCN (good nucleophile).
a) Write the semi-developed formula of the product?
b) Write the detailed mechanism of the reaction and give the reaction rate.
c) Specify the stereochemistry of the final product. Is it optically active?

2) Consider the following substitution reaction:

(CH3)3C – CHOH – CH3 + HBr 2 products

Based on the detailed mechanism of this reaction, write the semi-developed formula of the two products
obtained and specify the major product.

3) When (A) 2R,3R-CH3CH2CH(Ph)CH(OH)CH3 is treated with HBr, it yields three substitution products
one of which major.
a) Name compound (A) and draw the perspective representation.
b) The rate of the reaction is independent on the concentration of HBr. Write the detailed mechanism
and precise the stereochemistry of the products (B) and (C).

4) Which alkyl halide would you expect to be more reactive in an SN2 reaction with a given nucleophile?

a) H3C CH Cl Or H3C CH Br b) CH3CH2 CH Br Or CH3CH2 CH Br

CH3 CH3 CH3 CH2CH3

c) CH2CH2Br Or CH2 CH CH3 d) CH2Br Or Br

Br

e) CH3CH C CH3 Or CH3CH CH CH CH3

Br Br

5) What will be the product of each of the following reactions:

a) H3C CH CH CH2Br + CH3O

b) H3C CH CH CH2Br + CH3OH

37
6) Classify the following compounds by decreasing order of reactivity in an ethanolysis reaction
(solvolysis in ethanol). Justify briefly.

CH2Br CH2Br CH2Br CH2Br

OCH3 Cl NO2 CH3

(I) (II) (III) (IV)

7) Which alkyl halide, in each of the following pairs, would you expect to be more reactive in an S N1
solvolysis reaction? Justify your choice.

.. ..
a) CH3O
.. CH CH CH2Br Ou CH3..
OCH2 CH CH CH2Br

CH3 CH3
b) C Cl Ou C Cl
O O
CH3 CH3

H CCl3 H CH3
c) C C Ou C C
H3C CH2 CH H H3C CH2 CH H
Br Br

8) Determine the major product that would be formed from the SN1 hydrolysis reaction of the followings:

CH3 Br CH3 Br
a) H3C CH CH CH CH3 b) CH3CH2 C CH CH3 CH
CH3
c)
CH3 CH3 Br

CH3 Cl CH3 CH3

d) H3C CH CH2 C CH3 f) Br
e)
Cl
CH3

9) Reaction of (2R,3R)-2-bromo-3-phenylbutane (X) with CH3ONa (strong base) at high temperature gives
two alkenes.
a) Write the structural formula of the products obtained and precise the major compound.
b) What is the configuration of the major product? (Utilize the mechanism of the reaction in order to
justify you answer).
c) Determine (without mechanism) the configuration of the major alkenes obtained in the case where
the stereochemistry of (X) is: i) 2S,3S; ii) 2R,3S.

38
10) Consider the following compound (A):

H3 C H

H C 6H 5
Br CH3

a) Give the systematic name of (A) and determine the absolute configuration of each asymmetric
carbon in compound (A).
b) Draw the perspective structure of the enantiomer of (A).
c) Complete the following representations of (A):
CH3
CH3

CH3 CH3

d) Compound (A) is treated with NaI in appropriate solvent. One step reaction was observed, and it
gives one product B. Write the detailed mechanism of this reaction and precise the stereochemistry
of B.

e) Treatment of (A) with EtO- yields two elimination products C and D. D is the major product.
i) Give the structures of C and D.
ii) Write the detailed mechanism of the reaction that leads to the formation of D, and indicate
its the configuration.
iii) Precise the stereochemistry of C.

11) Consider the following compound (A):

Br CH3
CH3 C CH CH2CH3
H

a) Give the Fisher representation, and Newman representation following C2-C3 axis, of stereoisomer
(2R,3R) of (A).
b) The stereoisomer (2R, 3R) of (A) was treated with C2H5O– Na+ (strong base) in ethanol. The rate
of the formation of major alkene (B) is increased when the concentration of base is increased.
i) Give the type of this reaction?
ii) Give the rate equation.
iii) Give the detailed mechanism, and deduce the configuration of alkene (B). What is the
configuration of the alkene product if the starting stereoisomer is (2S, 3R) ?
c) The reaction of stereoisomer (2R, 3R) of (A) with CH3S– (strong nucleophile) gives, in the
appropriate solvent, a unique product (C). Write the detailed mechanism of the reaction and
precise the absolute configuration of the asymmetric carbons in (C).

39
12) Consider the following compound (W):
H H
C2H5
C C
H3C
Cl

a) i) Determine the absolute configuration of each asymmetric center in compound W.

ii) Complete the following representations of Newman.

Cl

b) Treatment of (W) by sodium ethoxide, at high temperature, gives two alkenes T (major) and T’
(minor).
i) Write the structural formula of T and T’.
ii) Write the detailed mechanism of formation of T’ showing all the stereochemistry.
iii) Indicate the stereochemistry of the major compound T.

c) Hydrolysis of (W) yields four substitution compounds: (X and X’) major products, (Y and Y’)
minor products.
i) Write the detailed mechanism of hydrolysis.
ii) Indicate the stereochemistry of compounds X, X’, Y and Y’.
iii) Justify the formation of the major products.
iv) Deduce the relationship (enantiomers, diastereoisomers, meso compound …) between X, X’,
Y, and Y’

13) Consider the following compound (A):

H H
H CH
3
C C
C
H3 C C
H Br
H3 C

a) Give a systematic name for (A) including the configurations (E/Z; R/S).
b) Complete the following representations of (A):

CH=CHCH3

c) Compound (A) is treated with sodium ethoxide [NaOCH2CH3] in ethanol. What are the types of
the possible reactions? Write their detailed mechanism. Give the structure and the stereochemistry
of the product(s) in each reaction.

40
14) Give the major elimination product that is obtained when each of the following alkyl halides is treated
with potassium tert-butoxide [(CH3)3COK]. Explain your reasoning.

OCH3
a) 1-chloro-1-methylcyclohexane b) Br c) CH CH2I

15) Which alkyl halide would you expect to be more reactive in an E2 reaction?

CH3 CH3 Br
a) H3C CH CH CH2 CH3 Or H3C CH CH2 CH CH3
Br

b) Or
Br
Br

16) Give the structural formula(s) with stereochemistry of the substitution product(s) that will be formed
from the following reactions:

CH2CH3
a) C + CH3CH2CH2O
H3C H
Br conc.

CH2CH2CH3
b) C + NH2
H3C H
Cl
H
CH3
c) + CH3O
Cl conc.
H
H
CH3
d) + CH3OH
Cl
H

17) A solution of (R)-2-iodooctane in acetone is reacted with sodium iodide loses its optical activity. Why?

18) Complete the following reactions and write their mechanisms. Precise the stereochemistry and
the optical activity in each case.

a) (R)-2-chloro-3-methylbutane + CN-
b) trans-1-bromo-3-methylcyclohexane + CN-
c) trans-1-bromo-3-methylcyclohexane + (CH3)3CO-

41
19) Polarimetric study follows the rotation of each of the reaction mixture below:

H OCH3
CH3OH KCN KCN
a) b) c)
H I H I H I

i) For the reaction (a) we observe a decrease of specific rotation  to reach zero. For (b) and (c) the
specific rotation changes to stabilize at a new value not zero. What conclusion could you deduce
related to the mechanism?
ii) Other studies deduce that the product of (b) and (c) have configuration of S and (R,R)
respectively. Write the complete mechanism and give your conclusions.

20) Which alkyl halide X should be used to prepare E-3-methyl-2-pentene in good yield by an E2
elimination? Specify the stereochemistry of X.

21) Which isomer reacts more rapidly in an E2 reaction, cis-1-bromo-4-tert-butylcyclohexane or trans-1-

bromo-4-tert-butylcyclohexane? Explain your answer by drawing the chair conformation of both
isomers.

22) Comment on the proportions of obtained products in the following reactions where alcohol is used as
a solvent at low temperature.

a) H3C CH2 O + (CH3)2CH Br CH2 CH CH3 + (CH3)2CH OC2H5

87 % 13 %

b) H3C CH2 O + CH3 CH2 CH2 Br CH2 CH CH3 + CH3 CH2 CH2 OC2H5

9% 91 %

c) (CH3)3C O + (CH3)2CH Br CH2 CH CH3

> 98 %

23) When potassium hydroxide was used, and in the appropriate operating conditions, on the (2R, 3R)-2-
chloro-3-phenylbutane, a mixture of 3-phenyl-2-butene and 3-phenyl-2-butanol was obtained.
The alcohol isolated from the reaction was optically active and was in a unique configuration.
a) What is the configuration of the alcohol? Draw its structure and name it.
b) What do you expect for the alkene stereochemistry? Do you expect to get one configuration and
what is it, or would you expect to get a mixture of stereoisomers? Draw and name the
configuration.

42
24) Explain why only a substitution and no elimination product is obtained when the following compound
is treated with sodium ethoxide (CH3CH2ONa): use its chair conformation.

CH3
Br

CH3

25) Give a detailed stepwise mechanism that explains the following transformations.

HBr
1) (CH3)3CCH2OH (CH3)2C(Br)CH2CH3 (maj. product)

Br
H2O
2) OH
O

Br
OH
CH CH H2O
3
3) CH3

26) When 2R,3S-2-bromo-3-deuterobutane CH3-CHBr-CHD-CH3 A is treated with sodium ethoxide in

ethanol, we obtain (E)-2-butene and (Z)-2-deuterio-2-butene.
a) Represent A following perspective.
b) Write the mechanism of the reaction.
c) Give and justify the rate of the reaction.

27) Synthesis Iodo-methane starting from methane.

43
 Choose the correct answer (A, B, C or D) (one choice only):

1) Identify the nucleophile in the following reaction.

H2O
CH3Br + NaOH CH3OH + NaBr

A. CH3Br B. OH- C. H2O D. Br -

2) What is the nucleophile in the following substitution reaction?

(CH3)3COH + HBr (CH3)3CBr + H2O

A. (CH3)3COH B. (CH3)3C+ C. Br - D. H+

3) Which of the following undergoes a substitution reaction with sodium cyanide in DMSO at the fastest
rate?

A. CH3CH2F B. CH3CH2Cl C. CH3CH2Br D. CH3CH2I

4) Which of the following reacts the fastest by the SN2 mechanism?

A. CH3Br B. CH3CH2Br C. (CH3)2CHBr D. (CH3)3CBr

5) Which of the following reacts fastest with methanol by the SN1 mechanism?

A. CH3CH2CH2CH2CH2Br B. H3C CH2 CH2 CH CH3 C. (CH3)2C CH2 CH3 D. (CH3)3CCH2Br

Br Br

6) Which compound is the most reactive via hydrolysis reaction?

Br CH2Br CHBrCH3 CH2CH2Br

A. B. C. D.

7) Which compound is the most reactive compound via SN1 solvolysis reaction in ethanol/water?
OTs F Cl Br
A) B) C) D)

44
8) Which compound could not be considered as a nucleophile?

A. NH3 B. H2O C. I- D. CH4

9) Which of the following mechanistic steps is the most likely route for the formation of the cyclic ether
shown?
.. CH3ONa O
..
:Cl ..OH
.. CH3OH

.. .. .. .. ..
A. : .. ..OH B. ..OH C. :Cl ..O: D. ..O
:
Cl
.. ..

10) Which halide ion reacts the fastest with cyclopentyl p-toluenesulfonate in ethanol/water?

OTs

- - - -
A. I B. Br C. Cl D. F

11) Based on Zaitsev's rule, which of the following is the major product of the reaction below?

CH3
CH3ONa
H3C CH C CH2CH3
CH3OH
CH3 Br

H3C CH3 CH2 H3C CH3 CH3

A. C C B. H3C CH C CH2CH3 C. C C D. H3C CH C CH2CH3
C2H5 CH3 CH3 (CH3)2CH H CH3 OCH3

12) Identify the substitution product(s) in the following reaction.

Br

CH3 CH3OH
H3C
H

OCH3 CH3
CH3
A) CH3 B) OCH3 C)
H3C H3C H3C
H H H

A. A) B. B) C. C) D. a mixture of A) and B)

45
13) In the solvolysis of t-butyl chloride, a minor product is 2-methylpropene, which results from the:

(CH3)3CCl + H2O (CH3)3COH + (CH3)2C CH2

Maj. Min.

A. E2 mechanism with OH¯ acting as the base. B. E2 mechanism with H2O acting as the base.
C. E1 mechanism with OH¯ acting as the base. D. E1 mechanism with H2O acting as the base.

14) The species shown below represents the transition state for the

CH2CH3
- -
HO C Br
H H

A. reaction of 1-propanol with HBr. B. reaction of 1-bromopropane with OH–.

C. elimination of HBr from 1-bromopropane. D. addition of HBr to propene with peroxides.

15) Identify the mechanistic pathways, respectively, for the products in the following reaction.

Br CH3OH OCH3
+

A. E1, SN1 B. E1, SN2 C. E2, SN1 D. E2, SN2

16) Considering the SN1, SN2, E1, and E2 mechanisms, the energy diagram shown below corresponds to:

A. only the SN1 mechanism. B. only the SN2 mechanism.

C. both the SN1 and E1 mechanisms D. SN2 or E2 mechanisms.

46
17) Identify the tertiary halide(s).
CH3
CH2Br Br H3C Br CH3 C Br

I II III IV

A. I and II B. II and III C. III and IV D. only IV

18) What is the major product of the following reaction?

Br

CH3 NaOCH2CH3
H3C CH3CH2OH
H

OCH2CH3 CH3

A) CH3 B) OCH2CH3
H3C H3C
H H
CH3 CH2
C) D)
H3C H3C
H H

47
Chapter VI
Alkenes

48
 Alkenes
1) Give the detailed mechanism for the reaction of the following compound with Br2/H2O.

H3CO CH3
C C
H3CH2C H
C

2) Consider the following reaction:

Alkene (B) + Br2 (C) (2S,3R)-2,3-dibromo-3-methylpentane

a) Give the Fisher representation of (C).

b) Write the semi-developed formula of alkene (B).
c) Write the detailed mechanism of the reaction; deduce the geometry of alkene (A).

3) Consider the following alkene (D):

C2H5 C2H5
C C
H CCl3
(D)

a) Give the systematic name of (D) and precise its geometry.

b) Write the detailed mechanism of (D) with Br2/H2O and indicate the stereochemistry of the
product (s) obtained.

4) Consider the following reaction:

2-Butene + Br2 product (A) (meso compound)

a) Give the structure of (A) according to Fisher and Newman.

b) Deduce the geometry of the alkene (2-butene) starting material.

49
5) Give the structure of the ;qjor product in each of the following reactions:

H3C CH3
H2 , Pd
a) C C

H3CH2C CH2CH3
H3C CH2CH3
H2 , Pd
b)
C C

H3CH2C CH3
CH3
1) CH3CO3H
c) CH2 C
2) H+ , H2O
CH2OH
H3CH2C H
1) O3
d) C C
2) (CH3)2S
H CH2CH2

OH
HBr , ROOR
e) (CH3)2CCH CH2

1) O3
f)
2) Zn / H2O

6) What stereoisomer of alkene was used in the following reactions?

a) Alkene A (CH3)2CHCH(OH)CH3

KMnO4
b) RCH CHR RCH(OH)CH(OH)R
OH meso
c) C3H7CH CHC3H7 + Br2 C3H7CH(Br)CH(Br)C3H7 racemic mixture 4R,5R / 4S, 5S

7) Which of the following alcohols can be synthesized relatively free of structural isomers and
diastereomers from methylcyclopentene by hydroboration-oxidation reaction?

CH3 CH3 CH3

OH H H
H OH H
A H B H C OH

8) Write a detailed mechanism for the addition of HBr to the following compounds:

a) H2C CH OCH3 b) H3C HC CH NO2

50
9) From what alkene and by which method would you prepare each of the following compounds ?

CH2OH
CH3 OH
a) H3C CH CH CH2Br b) c) H3C CH CH CH3
CH3 CH3
Br CH3
CH3 Br
d) e) f) CH3CH2 CH CH CH3
OH Br

10) For each of the following reactions, provide the following information.

i) Give the structure of major product(s) (including stereoisomers).

ii) If more than one major product is formed, give the stereochemical relationship (if any) of each
pair of products.

a) (S) CH3 CH2 CH C CH2 + HBr

CH3 CH2CH3
BH3 H2O2
b) (R) CH3 CH2 CH C CH2
THF NaOH
CH3 CH3
BH3 H2O2
c) (E)-3-ethyl-2-hexene
THF NaOH

d) Catalytic hydrogenation of (Z)-2,3-dichloro-2-butene

11) In each case, give the structure of an alkene that would yield each of the following compounds after
treatment with ozone followed by dimethyl sulphide or zinc in H2O.

O
O O
a) CH3 CH2 CH2 CH O b) c) H C CH2 CH2 C H

12) Identify the compounds A, B, C, etc…

a) A + H2/cat → 2-methylpropane (isobutane)

b) CH2=CH-(CH2)8-COOH + HBr  B
c) CH2=CH-(CH2)8-COOH + HBr (in presence of peroxide) C
d) 3-Hexene + Br2  D
e) 2-methylpropene (isobutene) + H2O (in acidic medium)  E
f) 1-methylcyclohexene + HCl  F
g) 2-methyl-2-pentene + Cl2/H2O  G
h) H + O3  CH3-CO-(CH2)4-CO-CH3

51
13) Complete, without mechanism, the following reactions:

a) CH3-CH=CH-CCl3 + HCl →
b) CH2=CH-OCH3 + HBr →
c) C6H5-CH=CH2 + ICl →
d) CH2=CH-CO2C2H5 + HBr →
e) (CF3)(CH3)C=CHCH3 + HBr →
f) (CH3)2C=CHCH3 + Br2/H2O →

14) Compound A has the following structure:

CH3

H3 C H
A
a) Name A.
b) Precise the product (or the products) obtained, when A reacted with: Br2, HCl, Cl2/H2O, ICl,
Br2/H2O.

15) If we have the compound A: the 1-chloro-2-butene.

a) How many structure of A have stereochemistry?
b) Draw them and indicate their configurations?
The Z isomer of A have addition of Br2
c) Write the detailed mechanism.
d) What are the obtained products?
e) Indicate the configuration of each asymmetric carbon, and conclude.

16) Hydration of trans-1-chloro-2-butene at room temperature in presence of diluted sulfuric acid gave two
products C1 (major) and C2.
a) Write the mechanism and explain the role of sulfuric acid.
b) Identify C1 and C2 and justify.
c) Why hydration of styrene under the same conditions is faster then that of trans-1-chloro-2-
butene.

17) Consider the compound A:

a) Name A.
b) A is treated with Br2 in CH2Cl2 as a solvent.
i) Write the mechanism.
ii) How many products are obtained?
iii) Represent them in perspective.
iv) They are obtained in equal amount or not?
c) The same reaction was done using CH3OH as solvent. We obtained two product of formula
C8H15BrO. Write the mechanism of this reaction.
18) An alkene A gives by ozonolyze one ketone B of formula C4H8O.

52
 a) Give the formula of B and deduce the formula of the alkene A.
Addition of Br2 to compound A gave one optically inactive product.
b) Write the mechanism of this reaction and deduce the configuration of A.

19) Hydrogenation of compound A is achieved in presence of Pt as catalyst.

H H Cl

A
a) Name A.
b) How many products are obtained?
c) The mixture obtained is optically active? Justify.
d) What is the relationship between the products obtained?

20) Complete the following scheme using the suitable conditions:

CH2-CHBr-CH2Br

CH2-CH2-CH2OH CH2-CH2-CH3

CH2-CHOH-CH3 CH2-CH=CH2 CH2-CHOH-CH2Br

CH2-CH-CH3 CH2-CH2CH2Br
OCH3

CH2-CHBrCH3

21) Propose a synthesis of each of these compounds from the given starting material and any needed
inorganic reagent.

Br
a) from
OH

b) from
OH

53
 Choose the correct answer (A, B, C or D) (one choice only):

1) What is the IUPAC name of the following compound?

A. 2-methyl-3-propylpent-2-ene B. 3-ethyl-2-methylhex-2-ene
C. 4-ethyl-4-methylhex-4-ene D. 4-methyl-3-propylpent-3-ene

2) How many isomeric alkenes of formula C4H8, including stereoisomers, are possible?

A. two B. three C. four D. five

3) What is the IUPAC name of the following compound?

CH3

Br

A. 3-bromo-2-methylcyclohexene B. 1-bromo-2-methyl-2-cyclohexene
C. 6-bromo-1-methylcyclohexene D. 2-bromo-1-methylcyclohexene

4) Which of the following alkenes exhibit E-Z isomerism?

I. CH3CH2CH CHCH2CH3 II. (CH3)2C CHCH3

III. CH3CH2CH CHBr IV. H2C CHCH2CH(CH3)2

A. I and II B. I and III C. II and IV D. I, II, and III

5) Which of the following carbocations is(are) likely to undergo a rearrangement?

CH3 CH3
CH3 CH2 CH2 CH2 CH3 CH C CH3 H3C CH2 CH CH CH3
I. II. CH3 III.

A. only I B. I and III C. II and III D. I, II, and III

54
6) The product(s) in the following reaction is(are)

CH2
H2 / Pd

H3C

A. only trans-1-4-dimethylcyclohexane B. only cis-1-4-dimethylcyclohexane.

C. both trans and cis-1-4-dimethylcyclohexane. D. methylcyclohexane.

7) What is the major product of the following reaction?

HBr

Br
A) B) C) D)
Br Br
Br

8) What is the intermediate in the following reaction?

(CH3)2C CH2 + HCl

H Cl
A) CH3 C CH3 B) CH3 C CH2 C) CH3 C CH2Cl D) CH3 C CH2
CH3 CH3 CH3 CH3

9) What is the major product of the following reaction?

1) B2H6 / THF
2) H2O2, NaOH

OH
A) B) C) D)
OH OH
OH OH

10) What is(are) the product(s) of the following hydroboration-oxidation reaction?

CH3
1) B2H6 / THF
2) H2O2, NaOH

A. 1-methylcyclobutanol B. trans-2-methylcyclobutanol
C. cis-2-methylcyclobutanol D. equal amounts of B and C

55
11) Which of the following alkenes gives 1-bromo-2-methyl-2-pentanol upon reaction with Br2/H2O?

A) CH3CH CHCH(CH3)2 B) CH3CH2 CH CH CH2

CH3

C) CH3CH2CH C(CH3)2 D) CH3CH2 CH2 C CH2

CH3

12) A compound is treated with ozone followed by zinc in water to give the following three products.
Which structure below best fits the data?

O O H
O
H3C CH3 H3C H O
H

A) CH3CH CHCH2CH2CH2CH C(CH3)2 B) (CH3)2C CHCH2CH2CH CHCH3

C) CH2 CCH2CH2C CHCH3 D) CH2 CHCH2CH2C C(CH3)2

CH3 CH3 CH3

13) What is(are) the major product(s) of the following reaction?

NBS, CCl4
H2C CHCH(CH3)2

Br Br
Br

Br
I II III IV

A. only II B. only III C. I and III D. II and IV

14) Which of the following does not give 1-bromo-1-methylcyclopentane as the major product?

CH3 CH3
HBr Br2
A) B)
ROOR h

CH2 HO CH3
HBr HBr
C) D)

56
15) Which of the following gives acetone, (CH3)2C=O, as one of the products of its ozonolysis?

A) B) C) D)

16) What are the required reagents in order to do the following transformation?

?? OH
CH CH CH2 CH CH CH3
CH3 CH3

A. H2O/H2SO4 B. 1. Hg(OAc)2/H2O C. H2SO4/  D. 1. BH3

2. NaBH4 2. H2O2/ NaOH

17) Propylbenzene reacts following the sequence below. Identify the final product.
Br2 Base HBr
CH2CH2CH3
h peroxides

A) CHCH2CH2Br B) CH2CHCH3
OH Br

C) CH2CH2CH2Br D) CHCH2CH2Br
Br

57
Chapter VII
Alkynes

58
 Alkynes
1) Name the following molecules:

a) CH3C CCH2CH2Br b) ClCH2C CCH2CH3

c) CH3CH2 CH C C CH2 CH CH3 d) CH3CH2 CH C CH

Br Cl CH2CH2CH3
HC CH2
e) H3C CH CH C CH2 CH2 CH2 CH3

CH2 C C CH2 CH3

2) Complete the following tree of reactions by giving the major products:

2 HCl 2 equiv. H2/Pt

1 mole
Br2/CCl4

NaNH2 H2 Lindlar
H3C C C H

H2O 2 HBr 1) BH3

H2SO4, HgSO ROOR
4 2) H2O2, OH-

3) Complete without mechanism the following reaction:

a) Cylopentylacetylene + H2O/H+ → A
b) 1-pentyne + 2 HCl → B
c) Propyne + Br2 → C
d) Phenylacetylene + NH2- → D

4) Which alkyne would be the best starting material to use for the synthesis of each of the following
ketones?

O O
a) H C C b) CH3CH2 C CH(CH3)2
3

5) Which reagent is the best choice to complete the following transformation?

59
6) What is the major product in the following reactions?

HBr Br2
a) CH3C CH d) CH3C CCH3
peroxide CH2Cl2

HBr HBr
b) CH3C CH e) CH3C CCH3
excess
HBr HBr
c) CH3C CH f) CH3C CCH2CH3
excess excess

7) Give the principal organic product, including (if any) its stereochemistry, formed in each of the
following reactions.

HBr
a)
excess
H2 Lindlar
b) CH3CH2CH2C C(CH2)4CH CH2

c) CH3C C: Na + CH3CH2 I

d) Br Br + HC C: Na
excess

8) Explain why in the following reaction results in the product that is shown:

Br2 O
CH3CH2CH2C CH CH3CH2CH2 C CH2Br
H2O

9) Starting with acetylene, how could each of the following compounds be synthesized?

H3C CH3 Et H O
a) C C b) C C c) H3C CH2 CH2 CH2 C H
H H H Me

Cl
d) e) H3C C CH3 f) CH2 g)
Cl O
OH H

60
10) Show how each of the following compounds could be prepared using the given starting material.

??
a) HC CH CH3CH2CH2CH CH3
Br
??
b) C CH CH2 CH2OH

O
??
c) HC CH C C
H H
CH3CH2 CH2CH3
??
d) H2C CH2 HC CH

??
e) H3C CH3 HC CH

61
 Choose the correct answer (A, B, C or D) (one choice only):

1) What is the IUPAC name of the following compound?

CH3CH2 C C CH CH2CH3
CH2CH2CH3

A. 5-propylhept-3-yne B. 5-isopropylhept-3-yne
C. 5-ethyloct-3-yne D. 4-ethyloct-5-yne

2) Predict the major product(s) in the reactions below.

1)NaNH2 1)NaNH2
HC CH
2) CH3Br 2) 1-iodohexane

A. 1-nonyne B. 2-nonyne C. cis-2-nonene D. trans-2-nonene

3) Which sequence of reactions below works best in carrying out the following conversion?

??
CH CH C C

A. (1) HBr, (2) excess NaNH2 B. (1) Br2, (2) excess NaNH2
C. (1) Br2/ H2O, (2) excess NaNH2 D. (1) H2O/H2SO4(cat.), (2) excess NaNH2

4) Which of the following is the enol intermediate in the acid-catalyzed addition of water to propyne?

H2O, H2SO4
CH3 C CH
HgSO4

H CH3 H CH3 H CH3 H CH2OH

A) C C B) C C C) C C D) C C
H OH HO H HO OH H H

5) Select the best method to carry out the following conversion.

??
HC C CH2 CH2CH(CH3)2 HOCH2 CH2 CH2 CH2CH(CH3)2

A. 1) H2O, H2SO4/HgSO4 B. 1) HBr C. 1) H2, Lindlar Pd D. 1) HBr, ROOR

2) H2, Pt 2) H2, Pt 2) BH3/THF 2) NaOH
3) NaOH 3) H2O2,NaOH 3) H2, Pt

62
6) Identify compound Y.

H2 Br2
CH3 C C CH3 X Y
Lindlar Pd

A. 2-bromobutane B. meso-2,3-dibromobutane
C. racemic (2R,3R) and (2S,3S)-2,3-dibromobutane D. 2,3-dibromo-2-butene

7) What is the product of the following reaction sequence?

1)NaNH2/NH3 H2 1) BH3 / THF

HC CH
2) CH3CH2CH2CH2Br Lindlar Pd 2) H2O2, NaOH

A. 1-hexanol B. 2-hexanol C. 1,2-hexanediol D. 1-hexene

8) What is the product of the following reaction?

2 HCl
CH3CH2C CH

A. 1,1-dichlorobutane B. 1,2-dichlorobutane C. 2,2-dichlorobutane D. 1,1,2,2-tetrachlorobutane

9) Which of the following ketones cannot be made by the acid-catalyzed hydration of an alkyne?
O O O O
A) B) C) D)

63
Chapter VIII
Dienes

64
 Dienes

1) Draw the major product of the following Diels-Alder reactions.

H3C CO2CH3
a) ; b) +
+ H2C C
CO2CH3 O

O CO2CH3
c) + CH2 CH C OCH3 ; d) + H2C C
CO2CH3

e) + HC C CO2CH3 ; f) + O

Ph H
CN C C H O O
g) + ; h) C C + CH3O C CH CH C OCH3
H
H Ph

2) Give the structural formulas of A and B.

O
20°C
a) + A B

O

b) 2,3-dimEthyl-,3-butadiene + H2C CH CN C

3) Give the structures of the starting materials that would yield each of the following compounds in Diels-
Alder reactions.

CN
a) b)

4) Identify all the products obtained in the following reaction, and write the detailed mechanism and show
all the stereoisomers obtained.

CH3 HBr

CH3 1 equiv.

65
 Choose the correct answer (A, B, C or D) (one choice only):

1) Which of the following is the product of the intramolecular Diels-Alder reaction shown below?
O


O O O O

A) B) C) D)

2) What is the product of the following Diels-Alder reaction?

CH3 CH3O2C CO2CH3 

+
H H

H3C CO2CH3 H3C CO2CH3 H3C CO2CH3 H3C CO2CH3

A) B) C) D)
CO2CH3 CO2CH3 CO2CH3 CO2CH3

3) Identify the diene and dienophile needed to make the following Diels-Alder adduct.
H O

H
O

O
O O O O

A) + O B) + O C) + O D) + O

O O O O

4) How many stereoisomers are possible for the following diene?

CH3CH=CHCH2CH2CH=CHCH2CH2CH3

A. only 1 B. two C. three D. four

5) Identify the diene needed for the following reaction.

O CH3 O

diene + O O

O O
A. 1,3-pentadiene B. 1,4-pentadiene C. 2-methyl-1,3-butadiene D. 1-methyl-1,3-cyclohexadiene

66
Chapter IX
Alcohols

67
 Alcohols
1) Give the systematic name for each of the following compounds.

OH
HO Cl OH H3C CH3
a) b) e) CH3 CH CH CH CH3 d) C C
H3C OH CH2 H CH CH2Cl
OH
CH2 CH2 CH3

2) Write the formula of the product (s) upon reaction of 1-pentanol with each of the following reagents:

a - (CH3)3CO-K+ b- metallic sodium (Na) c- CH3Li

d- HI concentrated e - HCl + ZnCl2 f- PBr3
o
g- SOCl2 h- H2SO4 concentrated at180 C

3) Give the structure of the major organic product obtained in each of the following reactions:

O
H3O+
a) (CH3)2CHCH2OH + PBr3 ; b) CH CH2 + H2O

OH CH3
c) CH3 CH CH3 + HBr ; d) CH3 CH CH CH3 + HBr
OH
CH3
OH CH3
CH3OH
e) + HBr ; f) + H2SO4
OH
OH
g) + HCl
CH3

4) Which of the following alcohols would dehydrate the most rapidly when heated with acid?

CH3 CH3 CH2OH CH3

OH OH
OH
A B C D

68
5) Explain the following transformation :

H3C CH3 CH3

OH H+ CH3
a)

H2SO4
b) CH2OH CH3 +

CH3 CH3
H2SO4
c) CH2 C CH2 CH CH2OH
O

6) Identify A through H.

HBr B
a) CH3CH2CH2CH2OH A CH3CH2CH2CH2OCH3

TsCl D
b) CH3CH2CH2OH C CH3CH2CH2CH2OCH2CH3

potassium metal CH3I
c) (CH3)3COH E F

OH CN
pyridine H
d) + SOCl2 G


7) Which compound in each pair, after removing a proton from the OH group, would form a cyclic
compound more rapidly?

a) HO Br Or HO Br

Br
b) HO Br Or HO

8) Give the major product which is formed when heating each of the following compounds in presence of
H2SO4.
OH
CH3 CHCH2CH3
a) CH3CH2 CH C CH3 b) c)
OH CH3 CH2OH

CH3 OH
d) CH3CH2 C CH CH3 e) f) CH3CH2CH2CH2CH2OH
OH CH3

69
9) Outline a synthesis of each of the following compounds from the indicated starting material.
a) 2-methylpentan-3-ol from 2-methylpentan-2-ol
b) 2-methoxy-2-methylbutane from 2-methylbutan-2-ol

10) If a pure enantiomer of 2-butanol was reacted with traces of H2SO4. A decrease of the optical activities
was observed for this alcohol and after a certain time the optical activities disappear completely.
Explain this observation.

11) Explain why the ether obtained by treating an optically active alcohol with metal sodium followed by
reaction with methyl chloride has the same configuration as the alcohol, whereas the ether obtained by
treating the alcohol with tosyl chloride followed by sodium methoxide has a configuration opposite that
of the alcohol.

CH3 CH3
1) Na
C C same configuration as the alcohol
OH 2) CH3Cl OCH3
R R
H H
CH3 CH3
1) TsCl / pyridine
C C configuration opposite to that of the alcohol
OH 2) CH3O R
R CH3O
H
H

12) Explain the above transformations by writing the mechanism of each reaction?

H3C OH H3C Br H3C OH

HBr H2SO4 conc.
a) b)

13) Write the major product of each of the below reactions:

KOH / 

Br KOC(CH3)3 / 

14) Complete (without mechanism) the following reaction sequence.

A C O
B
OH C9H17OBr

70
 Choose the correct answer (A, B, C or D) (one choice only):

1) What is the IUPAC name of the compound below?

CH3 CH CH2CH2C(CH3)3
OH

A. 5,5-dimethylhexan-2-ol B. 2,2-dimethylhexan-5-ol
C. 5,5-dimethylpentan-2-ol D. 2,2-dimethylpentan-5-ol

2) What is the IUPAC name of the compound below?

CH2CH2CH(CH3)2
CH3CH2CH2 CH CH CH3
OH

A. 3-isobutylhexan-2-ol B. 2-methyl-5-(1-hydroxyethyl)octane
C. 2-methyl-5-propylheptan-6-ol D. 6-methyl-3-propylheptan-2-ol

3) What is the IUPAC name of the compound below?

CH3 CH3
CH3CH2 CH2 C CH2 CH2 CH CH CH3
CH(CH3)2 Cl

A. 8-chloro-4-isopropyl-4,7-dimethylnonane B. 2-chloro-6-isopropyl-3,6-dimethylnonane
C. 2-chloro-3,6,7-trimethyl-6-propyloctane D. 6-sec-butyl-2-chloro-3,6-dimethyloctane

4) Rank the following three compounds in order of increasing boiling point.

I. CH3CH2CH3 II. CH3CH2OH III. CH3OCH3

A. I < II < III B. I < III < II C. II < III < I D. II < I < III

5) What is the major product of the following reactions?

H2SO4
CH3CH2 CH CH2OH
CH3


A) CH3CH2 C CH2 B) CH3CH CH CH2CH3 C) CH3CH C CH3 D) (CH3)2CH CH CH2

CH3 CH3

71
6) What is the IUPAC name of the following compound?

CH3 H

H OH

A. cis-3-methylcyclohexanol B. trans-3-methylcyclohexanol
C. cis-5-methylcyclohexanol D. 6-sec-butyl-2-chloro-3,6-dimethyloctane

7) Which of the following is isobutyl alcohol?

A. CH3CH2CH2CH2OH B. CH3CH2CH(OH)CH3
C. (CH3)2CHCH2OH D. (CH3)3COH

8) Identify the tertiary alcohol(s).

CH3
CH3 CH CH2CH(CH3)2 CH3CH2 CH CH(CH3)2 CH3CH2CH2 C CH3
OH OH OH
I II III

A. only I B. only II C. only III D. both I and III

9) What is the nucleophile in the following substitution reaction?

(CH3)3COH + HBr (CH3)3CBr + HBr

A. (CH3)3COH B. (CH3)3C C. Br D. H

10) What are the products of the following reaction?

CH3CH2CH2CH2OH + HBr

A. 1-bromobutane and water B. 1-bromobutane + H2(g)

C. butane and HOBr D. CH3CH2CH2CH2OBr + H2(g)

11) Which of the following is not a good method to make bromocyclopentane?

A. cyclopentanol + HBr B. cyclopentanol + NaBr

C. cyclopentanol + PBr3 D. cyclopentane + Br2 with light

72
12) Arrange the following carbocations in order of their decreasing stabilities (most stable first).

CH3 CH2 CH3

I II III

A. I > II > III B. III > II > I C. I > III > II D. II > III > I

13) What is the product of the following reaction?

BrCH2CH2CH2CH2OH + SOCl2

A. ClCH2CH2CH2CH2OH B. BrCH2CH2CH2CH2SH
C. BrCH2CH2CH2CH2Cl D. ClCH2CH2CH2CH2SOCl

14) The acid-catalyzed dehydration of the alcohol shown below gives a major product which results from a
carbocation rearrangement. Identify this major product.

H3C CH3
OH H2SO4

CH3 CH3 H3C CH3 CH2CH3

CH3 CH3

A. B. C. D.

15) Consider the following reaction.

RO Na
+
Br ROH
X Y
R = –CH3 or –C(CH3)3
Which statement(s) below is(are) correct?

I. X is the major product based on Zaitsev's rule.

II. The X:Y ratio is greater when R = –CH3 than when R = –C(CH3)3.
III. The X:Y ratio is greater when R = –C(CH3)3 than when R = –CH3.

A. I and II B. I and III C. only II D. only III

73
16) Which one of the following reactions makes the cyclic ether shown below?

NaOH H2SO4
A. HO OH B. HO OH

NaOH H2O, H2SO4

C. HO D. Br

17) Which one of the following mechanistically depicts the protonation of methanol by hydrogen bromide?

.. .. .. ..
..

..
A) CH3..
OH H Br
.. B) CH3..
OH H Br
..

.. .. .. ..
..

CH3..
OH H Br CH3..
OH

..
C) .. D) H Br
..

18) Which alcohol is dehydrated first in acidic medium?

CH2OH OH OH HO CH3
A) B) CH3 C) D)

CH3

19) What condition is the most suitable in order to do the reaction below?

CH2OH CH2

??

A. H2SO4, heat B. NaOCH2CH3 C. (1) PBr3 (2) NaOH D. (1) PBr3 (2) KOC(CH3)3

20) Which compound below does not form 1,2-dimethylcyclohexene by catalytic dehydration in acidic
medium?

CH2OH H3C CH3 H3C OH H3C CH2OH

CH3 OH CH3
A) B) C) D)

74
 Chapter X
Electrophilic aromatic
substitution of benzene (EAS)

75
 Electrophilic aromatic substitution of benzene
(EAS)
1) Indicate the aromatic compounds:

a) b) CH2 CH2 c)

HN N
d) e) f)

H2N N N
H

2) Write a mechanism of formation of (1,1-dimethylethyl)benzene (tert-butylbenzene) starting from 2-

Chloro-2-methylpropane (tert-butyl chloride) and benzene in presence de AlCl3.

3) Cumene, (1-methylethyl)benzene, is an important intermediate in the industrial synthesis of benzenol

(phenol). Propose a mechanism of its synthesis starting from propene, benzene and phosphoric acid.

4) Alkylation of benzene using 1-chlorobutane and AlCl3 give, not only butylbenzene, but also as a major
product (1-methylpropyl)benzene. Explain using mechanism.
How is it possible to prepare butylbenzene without formation of secondary products?

5) Explain using mechanism the following transformation:

Cl AlCl3

6) Justify the stability of cyclopentadienyl anion and of cation tropylium (cycloheptatrienyl cation).

76
7) Which compound is aromatic? Explain your choice.

..

..
.. N
..

8) Indicate whether each of the following compounds is aromatic. Explain your choice.

..
:N N
..

a) .. N: b) c) ..
..O ..N
N
H

9) Classify each substituent group in the following compounds as an ortho, para director or a meta
director and explain your reasoning.

O
..
a) NH C CH3 b) CF3 c) .. :
O

d) N(CH3)3 e) C(CH3)3 f)

10) Arrange the following compounds in order of increasing reactivity toward HNO3 in H2SO4.
a) chlorobenzene, benzene, nitrobenzene, toluene, phenol
b) chlorobenzene, p-chloroanisole, anisole
c) dichloromethylbenzene, difluoromethylbenzene, chloromethylbenzene

11) Rank the following compounds in order of increasing reactivity in monobromination.

..
CH2N(CH3)3 N(CH3)3 N(CH3)2 CH3

A B C D

12) Give the products expected (if any) when ethylbenzene reacts under the following conditions.

a) Br2 in CCl4 b) HNO3, H2SO4 c) conc. H2SO4

d) CH3Br, AlCl3 e) Br2, FeBr3 f) C2H5COCl, AlCl3, then water

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13) Give the products expected (if any) when nitrobenzene reacts under the following conditions.

a) Cl2, FeCl3, heat b) fuming HNO3, H2SO4 c) CH3COCl, AlCl3, then water

14) Which can lose a proton more readily, a methyl group bonded to cyclohexane or a methyl group
bonded to benzene?

15) Give the product(s) obtained from the reaction of each of the following with one equivalent of Br2 and
employing the catalyst, FeBr3.

O
a) O C b) CH2O

16) Give a curved-arrow mechanism for the following reaction.

H2SO4
+
5-10°C

17) What product is formed when 2-methylpropene is added to a large excess of benzene containing HF
and the Lewis acid BF3? By what mechanism is it formed?

18) Complete the following reactions.

O AlCl3
a) CH3 CH2CH2 C Cl ketone C10H10O

AlCl3
b) O CH2CH2 CH Cl a compound with ten carbon
CH3

19) Give the products of vigorous KMnO4 oxidation of the following compounds.

CH3

a) 1-butyl-4-tert-butylbenzene b)

20) Using benzene, or toluene and any other reagents, outline a synthesis of each of the following
compounds.

a) p-chloroacetophenone b) m-bromonitrobenzene c) tert-butylcyclohexane

d) 1-bromo-4-butylcyclohexane

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21) Complete the following scheme in identifying A, B and C

A + O3 (then Zn, H2O)  CH3COCH3 + CH2=O

A + HCl  B

B + C6H6 (AlCl3)  C + HCl

22) Classify the following compounds by decreasing order of reactivity via electrophilic aromatic
substitution.

CH3 NH2 NH3 NO2

A B C D E

23) How is it possible to do the following transformation?

COOH

a) from

Br

b) from

HO

c) from

d) from

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 Choose the correct answer (A, B, C or D) (one choice only):

1) What is the IUPAC name of the following compound?

OH

Cl
C(CH3)3

A. 4-tert-butyl-3-chlorophenol B. 4-tert-butyl-5-chlorophenol
C. ortho-tert-butylchlorophenol D. 2-tert-butyl-meta-chlorophenol

2) Which of the following ions are aromatic species?

..
..
I II III IV

A. I and III B. II and III C. II and IV D. III and IV

3) Identify the aromatic compounds.

N
H N

I II III IV

A. I and II B. III and IV C. I, II and IV D. all of them

4) Rank the following compounds in order of decreasing reactivity to aromatic electrophilic bromination.

I. benzene II. toluene III. benzoic acid IV. phenol

A. IV > II > I > III B. IV > III > II > I C. II > I > IV > III D. II > III > IV > I

5) Which of the following groups are ortho/para directors?

I. –NO2 II. –OCH3 III. –CO2CH3 IV. –CH3

A. I and III B. II and III C. II and IV D. III and IV

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6) What is the product of the reaction shown below?

C(CH3)3
Br2 , h
CCl4
CH3

CH3
C(CH3)3 C(CH3)3 H3C C CH2Br C(CH3)3

CH3 Br CH3 CH3 CH2Br

Br Br
A B C D

7) What is the product of the following reaction?

H
+ H2C C(CH3)2

A. isobutylbenzene B. 2-methyl-1-phenylpropene
C. sec-butylbenzene D. tert-butylbenzene

8) Which of the following is the best method to make n-butylbenzene?

AlCl3
A) + CH3CH2CH2CH2Cl

H2SO4
B) + CH3CH2CH CH2

O AlCl3
C) + CH3CH2CH2 C Cl
then NH2NH2/KOH, 

H2SO4
D) + CH3CH2CH2CH2OH

9) Identify the major product(s) of the reaction sequence shown below.

O
H3C C Cl Cl2
AlCl3 FeCl3

A. ortho and para-chloroacetophenone B. meta-chloroacetophenone

C. ortho and para-chlorobenzaldehyde D. meta-chlorobenzaldehyde

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10) From the following proposition choose the one corresponding to the aromatic compound :

A. Cyclic compound with conjugated -electrons B. Cycle with 4n -electrons

C. All the atoms of the cycle are carbons D. Cycle with conjugated (4n + 2) -
electrons

11) Identify the preferred site(s) of electrophilic attack on the following compound.

CH2 O

ring 1 ring 2

A. ortho/para positions on ring 1 B. meta position on ring 1

C. ortho/para positions on ring 2 D. meta position on ring 2

12) Where would the compound shown below undergo bromination with Br2/FeBr3?
O
NH C

ring 1 ring 2

A. ortho/para positions on ring 1 B. meta position on ring

C. ortho/para positions on ring 2 D. meta position on ring 2

13) Choose the correct method in order to synthesis the meta-bromoethylbenzene starting from benzene?

A. (1) benzene + CH3CH2Cl/AlCl3 (2) Br2/FeBr3

B. (1) benzene + Br2/FeBr3 (2) CH3CH2Cl/AlCl3

C. (1) benzene + CH3COCl/AlCl3 (2) Zn(Hg), HCl (3) Br2/FeBr3

D. (1) benzene + CH3COCl/AlCl3 (2) Br2/FeBr3 (3) Zn(Hg), HCl

14) Which combination of reagents used in the indicated order with benzene will give m-
nitropropylbenzene ?

A. (1) HNO3/H2SO4 (2) CH3CH2CH2Cl/AlCl3

B. (1) CH3CH2CH2Cl/AlCl3 (2) HNO3/H2SO4

C. (1) CH3CH2COCl/AlCl3 (2) HNO3/H2SO4 (3) NH2NH2/NaOH

D. (1) HNO3/H2SO4 (2) CH3CH2COCl/AlCl3 (3) NH2NH2/NaOH

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15) Which will be the main product upon bromination of phenyl benzoate with Br2/AlBr3 ?

O
Br2 / AlBr3
C O

Br
O O
A. C O B. Br C O

Br
O O
C. C O Br D. C O

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