Benzene Additions

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Organic Chemistry › Benzene Additions

Questions 1 - 10
1

Which of the following are electron withdrawing substituents?

Screen shot 2015 10 24 at 10.14.50 am

1, 4 and 5

2 and 4

4 and 5

3, and 4

1 and 2

Explanation

Carbonyls (as in 4 and 5) are always electron withdrawing due to the Oxygen's electronegativity. Similarly, the oxygens on the nitrate (1) are electron withdrawing.

2

Which of the following are electron withdrawing substituents?

Screen shot 2015 10 24 at 10.14.50 am

1, 4 and 5

2 and 4

4 and 5

3, and 4

1 and 2

Explanation

Carbonyls (as in 4 and 5) are always electron withdrawing due to the Oxygen's electronegativity. Similarly, the oxygens on the nitrate (1) are electron withdrawing.

3

Which position will be most favored when adding chlorine to tert-butylbenzene?

Para

Ortho

Meta

Ortho and para

Meta and para

Explanation

A tert-butyl functional group is electron donating and will therefore activate the ortho and para positions. However, the ortho positions are sterically hindered by the bulky tert-butyl group. Therefore, the para position will be favored.

4

Which position will be most favored when adding chlorine to tert-butylbenzene?

Para

Ortho

Meta

Ortho and para

Meta and para

Explanation

A tert-butyl functional group is electron donating and will therefore activate the ortho and para positions. However, the ortho positions are sterically hindered by the bulky tert-butyl group. Therefore, the para position will be favored.

5

Which of the following substituents is electron-withdrawing when added to a benzene ring?

None of these substituents are electron-withdrawing

Explanation

is the only electron-withdrawing substituent because it contains two electronegative oxygen atoms which pull electrons from the benzene ring towards itself. This effect is electron-withdrawing and makes the ring slightly positive in charge. All the other substituents are electron-donating groups, which activate the ring for electrophilic addition.

6

Which of the following substituents is electron-withdrawing when added to a benzene ring?

None of these substituents are electron-withdrawing

Explanation

is the only electron-withdrawing substituent because it contains two electronegative oxygen atoms which pull electrons from the benzene ring towards itself. This effect is electron-withdrawing and makes the ring slightly positive in charge. All the other substituents are electron-donating groups, which activate the ring for electrophilic addition.

7

Which of the following groups would be added on the para position to phenol?

Explanation

is the only electron-donating group listed. Therefore, it will add to the ortho and para positions on phenol. The rest of the substituents are highly electron-withdrawing groups and will add to the meta positions on phenol.

8

If the molecule nitrobenzene were to undergo an electrophilic aromatic substitution, on which carbon(s) will the incoming substituent likely be directed to? (When numbering carbons on the benzene ring, label the carbon containing the nitro group as carbon number , the one immediately next to it as carbon number , and continue around the ring in that direction.

and

and

, , and

All carbons are equally likely to be substituted.

Explanation

Several resonance structures can be drawn for the molecule nitrobenzene. These are shown below.

Screen shot 2015 12 26 at 9.11.16 pm

From these resonance structures, an overall molecular electronic distribution can be determined:

Screen shot 2015 12 26 at 9.11.29 pm

Because the overall charge distribution puts partial positive charges on carbons , , and , these carbons have an increased electrophilic character. Therefore, these carbons are less likely than the other carbons to accept an incoming electrophilic substituent, making these positions less likely to be substituted. By default, carbons , and , known as the meta positions are the only ones nucleophilic enough to carry out this reaction.

9

If the molecule nitrobenzene were to undergo an electrophilic aromatic substitution, on which carbon(s) will the incoming substituent likely be directed to? (When numbering carbons on the benzene ring, label the carbon containing the nitro group as carbon number , the one immediately next to it as carbon number , and continue around the ring in that direction.

and

and

, , and

All carbons are equally likely to be substituted.

Explanation

Several resonance structures can be drawn for the molecule nitrobenzene. These are shown below.

Screen shot 2015 12 26 at 9.11.16 pm

From these resonance structures, an overall molecular electronic distribution can be determined:

Screen shot 2015 12 26 at 9.11.29 pm

Because the overall charge distribution puts partial positive charges on carbons , , and , these carbons have an increased electrophilic character. Therefore, these carbons are less likely than the other carbons to accept an incoming electrophilic substituent, making these positions less likely to be substituted. By default, carbons , and , known as the meta positions are the only ones nucleophilic enough to carry out this reaction.

10

Which of the following groups would be added on the para position to phenol?

Explanation

is the only electron-donating group listed. Therefore, it will add to the ortho and para positions on phenol. The rest of the substituents are highly electron-withdrawing groups and will add to the meta positions on phenol.

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