P. 1
Chem 212Ch 16

Chem 212Ch 16

|Views: 27|Likes:
Publicado porsaddamixo

More info:

Published by: saddamixo on Nov 02, 2010
Direitos Autorais:Attribution Non-commercial

Availability:

Read on Scribd mobile: iPhone, iPad and Android.
download as PDF, TXT or read online from Scribd
See more
See less

05/20/2011

pdf

text

original

‫‪Chem 212 Exam‬‬ ‫ﺳﻴﻌﻘﺪ اﻣﺘﺤﺎن اﻷول ﻟﻤﺴﺎق اﻟﻜﻴﻤﻴﺎء اﻟﻌﻀﻮﻳﺔ‬ ‫ﻳﻮم اﻟﺨﻤﻴﺲ اﻟﻤﻮاﻓﻖ 4/11/0102‬ ‫51:4-51:5‬

‫اﻟﻘﺎﻋﺔ‬ ‫201 2‪PH‬‬ ‫301 1‪P‬‬ ‫201 1‪P‬‬
‫.‪© 2011 Pearson Education, Inc‬‬

‫اﻟﺸﻌﺒﺔ‬ ‫1‬ ‫2‬ ‫3‬

Organic Chemistry
6th Edition Paula Yurkanis Bruice

Chapter 16
Reactions of Substituted Benzenes

2
© 2011 Pearson Education, Inc.

Chemical Modification of Substituents of Benzene

Reactions of alkyl substituents:

3
© 2011 Pearson Education, Inc.

The resulting halide product can undergo a nucleophilic substitution reaction:

4
© 2011 Pearson Education, Inc.

Remember that halo-substituted alkyl groups can also undergo E2 and E1 reactions (Section 9.8)

5
© 2011 Pearson Education, Inc.

Substitutions with double and triple bonds can undergo catalytic hydrogenation (Sections 4.11 and 6.9)

6
© 2011 Pearson Education, Inc.

7
© 2011 Pearson Education, Inc.

Oxidation of an alkyl group bonded to a benzene ring…

Provided that a hydrogen is bonded to the benzylic carbon,

8
© 2011 Pearson Education, Inc.

The same reagent that oxidizes alkyl substituents will oxidize benzylic alcohols:

9
© 2011 Pearson Education, Inc.

However, aldehydes or ketones can be generated if a milder oxidizing agent is used:

10
© 2011 Pearson Education, Inc.

Reducing a Nitro Substituent

11
© 2011 Pearson Education, Inc.

It is possible to selectively reduce just one of the two nitro groups:

12
© 2011 Pearson Education, Inc.

Examples of Substituted Benzenes

13
© 2011 Pearson Education, Inc.

Nomenclature of Substituted Benzenes
In disubstituted benzenes, the relative positions of the two substituents are indicated by numbers or by prefixes:

14
© 2011 Pearson Education, Inc.

The two substituents are listed in alphabetical order:

15
© 2011 Pearson Education, Inc.

• Common names are preferred in naming certain substituted benzenes, e.g., toluene, aniline, phenol. • Do not deconstruct the common name; e.g., do not change “toluene” to “methylbenzene.” • The substituent that is part of the common name is position 1, but do not label as such in the chemical name.

16
© 2011 Pearson Education, Inc.

Some disubstituted benzenes have common names that incorporate both substituents:

17
© 2011 Pearson Education, Inc.

Naming Polysubstituted Benzenes
The substituents are numbered in the direction that results in the lowest possible number:

18
© 2011 Pearson Education, Inc.

The substituent incorporated into the common name is the 1-position:

Always give substituents the lowest possible numbers!

19
© 2011 Pearson Education, Inc.

Substituted benzenes undergo the five electrophilic aromatic substitution reactions discussed in Chapter 15:

20
© 2011 Pearson Education, Inc.

The slow step of an electrophilic aromatic substitution reaction is the formation of the carbocation intermediate:
• Electron-donating substituents increase the rate of substitution reactions by stabilizing the carbocation intermediate. • Electron-withdrawing substituents decrease the rate of substitution reactions by destabilizing the carbocation intermediate.

21
© 2011 Pearson Education, Inc.

Inductive Electron Withdrawal

Electron Donation by Hyperconjugation

22
© 2011 Pearson Education, Inc.

Resonance Electron Donation and Withdrawal
Substituents such as NH2, OH, OR, and Cl donate electrons by resonance, but they also withdraw electrons inductively:

23
© 2011 Pearson Education, Inc.

Substituents such as C=O, CΞN, SO3H, and NO2 withdraw electrons by resonance:

24
© 2011 Pearson Education, Inc.

Electron-donating substituents increase the reactivity of the benzene ring toward electrophilic aromatic substitution

Electron-withdrawing substituents decrease the reactivity of the benzene ring toward electrophilic aromatic substitution

25
© 2011 Pearson Education, Inc.

Electron-Donating Substituents
Electron donation into the benzene ring by resonance is more significant than inductive electron withdrawal from the ring:

26
© 2011 Pearson Education, Inc.

Resonance donation into the benzene ring competes with resonance donation into the carbonyl Inductive withdrawal into the benzene ring also occurs Overall, these substituents weakly release electrons
27
© 2011 Pearson Education, Inc.

These substituents are less effective in donating electrons into the ring because…

28
© 2011 Pearson Education, Inc.

Alkyl, aryl, and CH=CHR groups are weakly activating substituents because they are slightly more electron donating than they are electron withdrawing:

29
© 2011 Pearson Education, Inc.

These substituents donate into the ring by resonance and withdraw electrons from the ring inductively:

They withdraw electrons inductively more strongly than they donate electrons by resonance
30
© 2011 Pearson Education, Inc.

These substituents withdraw electrons both inductively and by resonance:

31
© 2011 Pearson Education, Inc.

These substituents are powerful electron-withdrawing groups:

Except for the ammonium ions, these substituents withdraw electrons both inductively and by resonance
32
© 2011 Pearson Education, Inc.

The substituent already attached to the benzene ring determines the location of the new substituent:

33
© 2011 Pearson Education, Inc.

All activating substituents are ortho–para directors:

34
© 2011 Pearson Education, Inc.

The weakly deactivating halogens are ortho–para directors:

35
© 2011 Pearson Education, Inc.

All substituents that are more deactivating than halogens are meta directors:

36
© 2011 Pearson Education, Inc.

An ortho,para-directing substituent:

37
© 2011 Pearson Education, Inc.

An ortho,para-directing substituent:

38
© 2011 Pearson Education, Inc.

An meta-directing substituent:

39
© 2011 Pearson Education, Inc.

The Effect of Substituents on pKa
Electron-withdrawing groups stabilize a base and therefore increase the strength of its conjugate acid Electron-donating groups destabilize a base and thus decrease the strength of its conjugate acid

40
© 2011 Pearson Education, Inc.

The more electronic deficient a substituent on phenol, the stronger the acid:

To understand the relative pKa values, consider the delocalization of the phenolate anion (stars show anion distribution): Unstable

More stable anion = lower pKa

Stable: “through resonance” of anion into nitro
© 2011 Pearson Education, Inc.

41

The more electronic deficient a substituent on benzoic acid, the stronger the acid:

Substituent effect on pKa is minimal in benzoic acids because only inductive electronic effects are present: Why? Because the benzene ring is cross conjugated with the carboxylate anion
42
© 2011 Pearson Education, Inc.

The ortho–para product ratio decreases with an increase in the size of the substituents:

43
© 2011 Pearson Education, Inc.

44
© 2011 Pearson Education, Inc.

Methoxy and hydroxy substituents are so strongly activating that halogenation is carried out without a Lewis acid:

The presence of Lewis acid and excess bromine generates the tribromo derivative:

45
© 2011 Pearson Education, Inc.

A benzene ring with a meta director cannot undergo a Friedel–Crafts reaction:

46
© 2011 Pearson Education, Inc.

Aniline and N-substituted anilines do not undergo Friedel–Crafts reaction:

Phenol and anisole undergo Friedel–Crafts reactions at the ortho and para positions Aniline cannot be nitrated, because it is oxidized by nitric acid
47
© 2011 Pearson Education, Inc.

In designing a disubstituted benzene, consider the order of substitution:

48
© 2011 Pearson Education, Inc.

The Friedel–Crafts acylation must be carried out first, because the nitro group is strongly deactivating:

49
© 2011 Pearson Education, Inc.

In the synthesis of para-chlorobenzoic acid from toluene, the methyl group is oxidized after chlorination:

In the synthesis of meta-chlorobenzoic acid, the methyl group is oxidized before chlorination:

50
© 2011 Pearson Education, Inc.

To synthesize p-propylbenzenesulfonic acid: • Introduce the propyl group by Friedel–Crafts acylation followed by reduction. • Sulfonation of the propylbenzene product affords the para derivative.

How is the meta derivative prepared? • Friedel–Crafts acylation • Sulfonation • Carbonyl reduction
51
© 2011 Pearson Education, Inc.

© 2011 Pearson Education, Inc.

What is the best method for carrying out the following reaction?

© 2011 Pearson Education, Inc.

Provide the major organic product(s) of the reactions below.

© 2011 Pearson Education, Inc.

Synthesis of Trisubstituted Benzenes

55
© 2011 Pearson Education, Inc.

Steric hindrance makes the position between the substituents less accessible
56
© 2011 Pearson Education, Inc.

A strongly activating substituent will win out over a weakly activating substituent or a deactivating substituent
57
© 2011 Pearson Education, Inc.

If the two substituents have similar activating properties, neither will dominate:

58
© 2011 Pearson Education, Inc.

Synthesis of Substituted Benzenes Using Arenediazonium Salts

59
© 2011 Pearson Education, Inc.

Preparation of the Diazonium Salt

Mechanism: Nitrosonium ion formation

60
© 2011 Pearson Education, Inc.

Diazonium ion formation:

Caution: Diazonium salts are explosive!
61
© 2011 Pearson Education, Inc.

The reaction stops because a secondary amine lacks a second proton:

62
© 2011 Pearson Education, Inc.

The bulky dialkyl amino group blocks the approach of the nitrosonium ion to the ortho position:

[unnumbered fig, pg 690]

63
© 2011 Pearson Education, Inc.

64
© 2011 Pearson Education, Inc.

Consider the synthesis of para-chloroethylbenzene:

65
© 2011 Pearson Education, Inc.

Fluorination and Iodination of Benzene

66
© 2011 Pearson Education, Inc.

Hydroxylation of Benzene

67
© 2011 Pearson Education, Inc.

Summary of Diazonium Reactions

68
© 2011 Pearson Education, Inc.

Synthesis Example
Synthetic target:
Propose a synthesis from a monosubstituted benzene

Answer:

69
© 2011 Pearson Education, Inc.

The Arenediazonium Ion as an Electrophile

Only highly activated benzene rings can undergo this reaction Substitution takes place preferentially at the para position 70
© 2011 Pearson Education, Inc.

However, if the para position is blocked …

71
© 2011 Pearson Education, Inc.

Mechanism:

72
© 2011 Pearson Education, Inc.

Diazo Dyes
Diazonium coupling affords synthetic dyes:

Large dipole results in deep color (high extinction coefficient):
Electronic “push-pull” produces a dipole

73
© 2011 Pearson Education, Inc.

Diazo Dyes and Sulfa Drugs
Gerhard Domagk studied the antibiotic properties of diazo dyes. He was awarded the Nobel Prize for medicine in 1939 for his work.
The dye prontosil is reduced to the sulfa drug sulfanilamide

Domagk cured his daughter of strep with sulfanilamide

Sulfanilamide looks like PABA, a bacterial nutrient:

74
© 2011 Pearson Education, Inc.

Nucleophilic Aromatic Substitution Reactions
Nucleophilic aromatic substitution reactions require at least one strongly electron-withdrawing substituent to occur:

75
© 2011 Pearson Education, Inc.

Electron-withdrawing substituents increase the reactivity of the benzene ring toward nucleophilic substitution and decrease the reactivity of the benzene ring toward electrophilic substitution

76
© 2011 Pearson Education, Inc.

77
© 2011 Pearson Education, Inc.

The electron-withdrawing substituents must be ortho or para to the site of nucleophile attack,

so that electrons of the attacking nucleophile can be delocalized into these substituents
78
© 2011 Pearson Education, Inc.

The incoming group has to be a stronger base than the group that is being replaced:

79
© 2011 Pearson Education, Inc.

You're Reading a Free Preview

Descarregar
scribd
/*********** DO NOT ALTER ANYTHING BELOW THIS LINE ! ************/ var s_code=s.t();if(s_code)document.write(s_code)//-->