University of Nairobi Chemistry of Benzene Derivatives Questions Please answer all the questions in the problem set as indicated, follow instructions as wr

University of Nairobi Chemistry of Benzene Derivatives Questions Please answer all the questions in the problem set as indicated, follow instructions as written. Problem Set #4 (Chapter 18)
Chemistry 322b Summer 2020
Prof. Rebecca M. Broyer
1. Given the general reaction below:
R
+
AlCl3
R-Cl
Circle the compound or compounds below that could effectively play the role of “R-Cl” to
generate the product shown above.
Cl
Cl
Cl
Cl
1
2. Draw the complete “electron-pushing” reaction mechanism for the transformation
below. Make sure to show all steps.
Br
Br
HNO3
H2SO4
NO2
2
3. Draw the complete “electron-pushing” reaction mechanism for the transformation
below.
O
A.
Cl
+
O
2. H2O
O
O
B.
1. AlCl3 (1 eq.)
NaOH
3
4. Circle the compound or compound that would react in a Friedel-Crafts reaction to
give a substitution product.
NH2
Cl
O
CF3
5.
C(CH3)3
+
(CH3)3COH
excess
6.
O
O
O
O
O
O
7. Circle the condition or conditions below that yield exclusively a single monosubstituted
product.
Cl
Cl
AlCl3
AlCl3
excess
O
Cl
AlCl3
1.
Cl
AlCl3, 1 eq.
2. H2O
4
8. Circle the reactive electrophile or electrophiles below that will lead to an
electrophilic aromatic substitution reaction with benzene (do not assume the
presence of any other reagents).
HO
N
O
O
KNH2
O
S
O
O
BF3
5
9. Draw the complete “electron-pushing” reaction mechanism for the transformation below.
Make sure to show all steps.
A
Br
Br2
H3C
NO2
FeBr3
H3C
NO2
6
10. Circle the correct order of reactivity for the following compounds toward nitration
(HNO3/H2SO4).
O
NO2
Cl
CH3
I
II
III
HN
IV
IV
>
III
>
II
>
I
II
>
III
>
IV
>
I
III
>
II
>
IV
>
I
III
>
II
>
I
>
IV
11.
A
O
A
O2N
7
12.
Cl
N
AlCl3
H 3C
13.
O
1. AlCl3, 1 equivalent
+
2. H2O
F 3C
CH3
14.
Cl
H3C
NO2
Br2
FeBr3
8
15.
NH2
NH2
NH2
Br
+
Br
16.
Compound A
NO2
Compound A
Br
17. Give the major tri-substituted benzene product(s). (The product or products will
have three substituents on the benzene ring).
Cl
Cl2
CN
FeCl3
9
18. Outline an efficient synthesis for the product below using the indicated starting
material and any compound of 2 carbons or fewer as the only carbon sources.
Cl
O
10
19. Outline an efficient synthesis for the product below using the indicated starting
material as the only carbon source.
O
+
O
O
O
11
20. Outline an efficient synthesis for the product below using the indicated starting
material and any compound of 1-2 carbons as the only carbon sources.
COOH
Br
NO2
12
21. Circle the compound or compounds below for which the substituent is an orthopara director.
O
O
O
O
S
NH2
22. Circle the order (from most reactive to least reactive) that corresponds to the order
of reactivity of the compounds below toward nitration.
O
NO2
HN
NO2
F
F
F
CF3
I
II
III
IV
IV
>
II
>
I
>
III
III
>
I
>
II
>
IV
I
>
III
>
II
>
IV
I
>
II
>
IV
>
III
13
23.
Cl
O
AlCl3
24.
OH
1. H2SO4 / Heat
2. HBr
25.
NO2
O
1.
Cl
AlCl3 (1 eq.)
2. H2O
F
A
1. LiAlH4
A
2. H2O
14
26. Circle the order that correctly ranks the following compounds from most reactive to
least reactive towards bromination (Br2 / FeBr3).
CF3
NH2
O
N(CH3)3
I
O
II
III
IV
III
>
IV
>
II
>
I
II
>
III
>
I
>
IV
III
>
II
>
IV
>
I
IV
>
II
>
III
>
I
27. Circle the order (from most reactive to least reactive) that corresponds to the order
of reactivity of the compounds below in the Friedel-Crafts Acylation reaction.
O
OH
OCH3
CH3
CH3
OCH3
F
I
II
HN
III
F
IV
III
>
II
>
I
>
IV
IV
>
II
>
I
>
III
III
II
>
>
II
IV
>
>
IV
I
>
>
I
III
15
28.
O
1. KMnO4 / KOH / Heat
2. H3O+
O
29.
CN
NO2
F
Br2
FeBr3
16
30.
O
O
1.
O2N
O
OCH3
O
AlCl3 (1 eq.)
2. H2O
A
SOCl2
A
B
17
31. Circle the order that correctly ranks the following compounds from most acidic to
least acidic.
OH
O
OH
OH
OH
O2N
NO2
NO2
CH3
I
III
II
IV
III
>
IV
>
I
>
II
IV
>
III
>
I
>
II
IV
>
III
>
II
>
I
III
>
I
>
IV
>
II
18
32.
Br
A
Br
Zn(Hg)
A
HCl, HOAc, Heat
B
B
C
Br
O2N
OH
C
19
33.
F
CN
NH3
Cl
20
34.
Cl
OMe
NO2
CF3
& any 1 carbon source
CF3
21
35. Circle the order that correctly ranks the following compounds from most acidic to
least acidic.
OH
OH
OH
OH
NO2
H
N
O
NO2
NO2
I
NO2
II
III
IV
II
>
III
>
IV
>
I
II
>
I
>
III
>
IV
IV
>
I
>
II
>
III
III
>
II
>
I
>
IV
22
36.
O2N
Br2
FeBr3
NO2
A
A
NBS
hν
B
B
NaOH
C
23
37. Outline an efficient synthesis for the product below using the indicated starting material
and any two or three carbon compounds as the only carbon sources.
OH
O
O
O2N
24
38. Circle the reaction condition or conditions that would selectively lead to the
transformation below.
O
OH
1. KMnO4, KOH, heat
OH
PCC
2. H3O+
H2CrO4
1. LiAlH4
H2SO4
2. H2O
25
39. Outline an efficient synthesis for the product below using the indicated starting material
and any one or two carbon compounds as the only carbon sources. Note that HCOCl is not a
viable carbon source.
H
O
Br
NO2
26
27

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