Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

1. From the choices below, circle the only molecule that is not aromatic (this means it doesn’t fit Hückel’s
rules for aromaticity). Explain your choice.

O O H
N N
N
N
O H N

Explanation:

2. Rank the following compounds from 1-4, where 1 has the lowest pKa/highest acidity and 4 has the
highest pKa/lowest acidity.
OH
OH
OH NH2

NO2 NO2
___________ ____________ ___________ __________

3. Rank the following amines from 1-4, where 1 is the most basic (easiest to protonate) and 4 is the least
basic (hardest to protonate).

NH2 NH2

NH2 NH2

OMe NO2

___________ ____________ ___________ __________

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

4. Fill in the boxes with the missing products.

F O
LiAlH4
a)
N
H

O 1) NaN3
b)
(R) (R) 2) LiAlH4

NH2
O 1) Ph
c)
2) NaBH3CN

excess CH2N2
d) HOOC COOH

1) EtONa
2) Br Ph

1) NaOH
2) HCl

3) heat

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

5. Fill in the boxes with the missing reactants, reagents and products.

NO2

a)

NH2 NH2

(E) (E) heat

b) CN + (Z)
NC

ONa O
c) +

1) HN

d) O
O Br
(R)
2) NaOH, H2O
O

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

6. Provide an arrow-pushing mechanism for the following transformation. Make sure to include side
products in each step, to indicate all formal charges and to draw lone-pairs where relevant. Explain the
regioselectivity observed!
HNO3
H2SO4 O2N

O O

Explanation:

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

7. Provide an arrow-pushing mechanism for the following transformation. Make sure to include side
products in each step, to indicate all formal charges and to draw lone-pairs where relevant. Explain the
regioselectivity observed!

CF3 FeCl3, Cl2 Cl CF3

Explanation:

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

8. Provide an arrow-pushing mechanism for the following transformation. Make sure to include side
products in each step, to indicate all formal charges and to draw lone-pairs where relevant. Explain the
regioselectivity observed!

NH2 1) NaNO2, HCl N2

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

b) The phenyl-diazonium cation created in this reaction can be used to create a variety of benzene
derivatives. Fill in the missing reagents for each transformation below.

Cl I

OH N2 Br

CN

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

9. Provide a synthetic route to the desired compound using toluene and phenol as the starting materials.
You don’t have to draw the mechanisms. (If you get ortho- and para- mixture at a key step or steps, you
may choose the isomer that you need to move forward.)
O
OH O2N
MeOH + +
OMe

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

10. Provide a synthetic route to the desired compound using toluene and phenol as the starting materials.
You don’t have to draw the mechanisms. (If you get ortho- and para- mixture at a key step or steps, you
may choose the isomer that you need to move forward.)
Br

O Cl
H
+ N
OH

HO3S

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Organic Chemistry 2: Sessler CH320N Homework Set 11 Due Thursday, May 03, 2018

11. Provide a synthetic route to the desired compound using toluene and phenol as the starting materials.
You don’t have to draw the mechanisms. (If you get ortho- and para- mixture at a key step or steps, you
may choose the isomer that you need to move forward.)

HINT: If you have trouble introducing the right regio-chemistry, bare in mind that sulfonate groups
(SO3H) and amino (NH2) groups can be introduced and removed again. One of these groups might help
you to achieve the intended stereochemistry.

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