CH 328N/3202N Due Tuesday, April 9th, 2024

Homework Problem Set 8

T R I
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Organic Chemistry II
Homework Problem Set 8 —Ch21 & 22-Aromaticity and Aromatic
Reactions
Prof. Zachariah Page– CH 328N/320N
Due: Tuesday, April 9, 2024

FranklinTrinh
Name: ____________________________

FT4543
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Grade: ________/ 2.0

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

1. Aromaticity
(A) For the following molecules, determine if it is aromatic, nonaromatic, or anti-aromatic

it aromatic aromatic
(i) nonaromatic (ii) nonaromatic
anti-aromatic e anti-aromatic

O aromatic - aromatic
(iii) nonaromatic (iv) nonaromatic
anti-aromatic anti-aromatic

aromatic aromatic
(v) nonaromatic (vi) E nonaromatic
& anti-aromatic anti-aromatic

S · aromatic aromatic
(vii) nonaromatic
anti-aromatic
(viii)
p O
nonaromatic
anti-aromatic

&
a

N O aromatic O aromatic
nonaromatic nonaromatic
(ix)
anti-aromatic
(x)
S anti-aromatic

(B) For thiophene, draw all arrows and formal charges that form the primary contributing structures. The
first and last structures are already drawn for you.

02
.. A
&
K
is
E & -

&S &

a & ⑦
S .
.
&S SE
·. S

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

(C) Rank the following phenolics (& thiophenol) in order of acidity (from the least acidic to the most
acidic).

OH OH SH OH

Cl Cl
A B C D

B < A < D < C

Least Acidic Most Acidic

2. Benzylic Reactions
For the following reactions, fill in the missing pieces (reactants, reagents, or products). Write racemic in
the product box if the reaction results in a racemic mixture.
(a)

H NBS, hν 17 Br

= I

(b)

H2CrOy
O OH

OH
O

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

(c)

H2, Pt

(d)

& -
so , S
SH Cl -
NaOH
- 3
IT
Cl -
Y

(e)

H2, Pd/C -
I
O
I HO
-

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

(B) Draw all starting materials of the following retrosynthesis assuming a single Williamson ether step
(note: more than one molecule can be possible starting materials and Williamson ether might be
impossible).

Naz(83
↑

OH +
- I
7

(a) O
I Br
↑

I
-

Naz(OS

%.
a

Ho
(b)
O
-

Nac CO3
↑

-Br
-
I
(c)
Hot
↑

O -

Na2[03

(d) CH
O By

Naz Coz
Br

O
-OH & -

I
-
(e)
I -
-

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

3. Electrophilic Aromatic Substitution

FeBrs
Brz

Br
(b)

Cl O
Benzene, AlCl3

OF
(c)

Halogenate 2x

a
O
Cl2 + FeCl3

OH

(d)
NO2
No2 ↓

E
HNO3 + H2SO4 H2SO4 (fuming) -
I
-
-
02H

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

(e)

BF-I NaOMe
O

- soste
SO3Me

(f)

I
-
H2 + Ni I
NO2 - NH2

(B) Circle the predicted product of the reaction.

O
ENG

NO2 NO2 NO2 NO2

O O
EDC
OH OH OH OH
H2SO4 (fuming) SO3H
(b)
SO3H
SO3H

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

00
Cl Cl Cl
Br2 + FeBr3 Br
(c)
Br
O O O

O O O O
HNO3, H2SO4 NO2
(d)
NO2
NO2

O O O O
O O O O
(e) HNO3, H2SO4 NO2

NO2
NO2

O OH O OH O OH O OH O OH
Br Cl2 + FeCl3 Br Br Br Cl Br
(f)
Cl Cl
Cl

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

(B) Propose a mechanism showing the formation of the indicated product via a Cope
rearrangement, using curved arrows to show the movement of electrons to go from the reactant
to product, and be sure to include ALL relevant lone pairs.

I 1. KOH, heat OH
2. H3O+ (acid workup)

: -v
H
E
+
-H A
G
NT
ne

:OI+ &
& :..
&
a

Ol+
>

..
-
-
&
Y I
-
- -OH
&a

&

I
-

-ot
L
...
-

I
-
S

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CH 328N/3202N Due Tuesday, April 9th, 2024
Homework Problem Set 8

6. Synthesis
Using the carbon-containing starting material(s), propose a synthesis the following
retrosynthesis scheme. Provide structures for all intermediates. The carbon atoms in the
product must originate from the starting material(s), but you may use as many equivalents of
each starting material as you would like, and any reagent/reaction you know. (Note: no
mechanisms are required).

O
Br
OH

NO2

C
Halroy O
Il Sol
CH >
- >
- Il
-
OH

~
T
G

9
!
+
↓ +a
-FT
=

&
-
HNOS
↓ HaSy

C G
I Febr II
-Br 2
1
I -I
-

The no

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