Reactions of Aromatic Compounds Flashcards

1
Q

How is aromaticity regained?

A

By the loss of a proton.

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2
Q

Name 5 reactions of electrophilic aromatic substitution.

A

Halogenation
Nitration
Sulfonation
Friedel-Crafts alkylation
Friedel-Crafts acylation

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3
Q

Explain halogenation.

A

Replacement of H (on benzene) by Br or Cl.

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4
Q

Explain nitration.

A

Replacement of H (on benzene) by NO2.

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5
Q

Explain sulfonation.

A

Replacement of H (on benzene) by SO3H.

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6
Q

Explain Friedel-Crafts alkylation.

A

Replacement of H (on benzene) by R.

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7
Q

Explain Friedel-Crafts acylation.

A

Replacement of H (on benzene) by RCO.

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8
Q

Give the 2-step mechanism of all electrophile aromatic substitution reactions.

A
  1. Addition of the electrophile to form resonance stabilized carbocation
  2. Followed by deprotonation with base
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9
Q

Is bromination of benzene exothermic or endothermic?

A

Exothermic

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10
Q

What compound is used most often as a catalyst in chlorination?

A

AlCl3 (FeCl3 will also work).

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11
Q

What catalyst is used in nitration? And what does it react with?

A

Sulfuric acid (H2SO4); HNO3

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12
Q

Sulfuric acid is used as a catalyst in nitration for…

A

the reaction to be faster and at lower temperatures.

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13
Q

Toluene reacts ___ times faster than benzene.

A

25

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14
Q

Why are ortho and para attacks preferred in nitration reactions?

A

Because their resonance structures include one tertiary carbocation.

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15
Q

Are nitro groups activators or deactivators?

A

Deactivators.

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16
Q

NO2 is also called a…

A

meta director.

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17
Q

Electrophilic substitution reactions for nitrobenzene are how many times faster/slower than what?

A

100,000 times slower than benzene.

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18
Q

Most electron-withdrawing groups are __________ (activators/deactivators) and ____-director.

A

deactivators; meta-

19
Q

What are the worst activators?

A

Alkyls and phenyls

20
Q

Para and ortho-directors are what? (deactivators/activators)

A

Activators.

21
Q

Is CH3 an activator or deactivator?

A

Activator…para/ortho-director.

22
Q

Is nitro an activator or deactivator?

A

Deactivator… meta-director.

23
Q

Are halogens activators or deactivators? And what kind of director?

A

Deactivators; Ortho/para-director

24
Q

Is methoxy an activator or deactivator?

A

Activator…para/ortho-director.

25
Q

Why are halogens deactivators?

A

Because they react slower than benzene.

26
Q

Why are halogens ortho-/para-directors?

A

Because the halogens can stabilize the sigma complex.

27
Q

What can the lone pairs on halogens be used as?

A

To stabilize the sigma complex by resonance.

28
Q

List the order of potential energy used for halogens from least to greatest. (Benzene, ortho, meta, para)

A

Benzene, ortho/para, meta

29
Q

Compounds with lone pairs are most likely to be _________ (activators/deactivators).

A

activators

30
Q

What is a sigma complex?

A

A resonance-stabilized carbocation.
The loss of a p+ gives us the sigma complex.

31
Q

The synthesis of alkyl benzenes from alkyl halides and a Lewis acid, usually AlCl3, is what reaction?

A

Friedel Crafts Alkylation

32
Q

Reactions of alkyl halide with Lewis acid in Friedel Crafts Alkylation produces what?

A

A carbocation, which is an electrophile.

33
Q

Why is HF, a weak acid, preferred in the protonation of alkenes?

A

Because the fluoride ion is a weak nucleophile and will not attack the carbocation.

34
Q

What can alcohols be treated with to form a carbocation?

A

BF3

35
Q

What are 3 limitations of Friedel Crafts?

A

Reaction fails if benzene has a substituent that is more deactivating than halogens.
Rearrangements are possible.
The alkylbenzene product is more reactive than benzene, so polyalkylation occurs.

36
Q

Do Friedel Crafts reactions occur with NH2 groups?

A

No, because NH2 is a strong deactivator.

37
Q

Give the general reactants, catalyst and products for Friedel Crafts Alkylation.

A

Benzene + alkyl halide; lewis acid (AlCl3); aryl halide + acid (HX)

38
Q

3 differences of Friedel Crafts acylation from Alkylation.

A

Acyl chloride used instead of alkyl chloride.
Phenyl ketone is the product (less reactive than benzene).
No poly-acylations.

39
Q

What is nucleophilic aromatic substitution?

A

The substitution of a halogen on a benzene ring by a nucleophile.

40
Q

What are the 2 different nucleophilic aromatic substitutions?

A

Addition-elimination and elimination-addition.

41
Q

Explain the addition-elimination mechanism.

A

Nucleophile adds to halogen substituted carbon and forms resonance stabilized carbanion.
Halogen is removed from the resonance of the electrons.

42
Q

Reactivity Trend of Nu Aromatic Substitution: Electron-withdrawing groups _________ the intermediate
carbanion.

A

stabilize

43
Q

Reactivity Trend of Nu Aromatic Substitution: Increasing the electronegativity of the halogen does what?

A

Increases the reactivity of the aryl halide.

44
Q

Reactivity Trend of Nu Aromatic Substitution: A more electronegative halogen does what?

A

Stabilizes the intermediate carbanion by an inductive effect.