1. Aryl Halides - Bonding, Physical Properties and Reactions
Nucleophilic Aromatic Substitution of Chlorobenzene
Nucleophilic Aromatic Substitution: Addition-Elimination 6

2. What’s the Difference Between Ar- and Ph-?6

3. Bonding in Aryl Halides1

4. Aryl Halides
Aryl halides are halides in which the halogen is attached directly to an aromatic ring.
Carbon-halogen bonds in aryl halides are shorter and stronger than carbon-halogen bonds in alkyl halides. 6

5. Dissociation Energies of Selected Compounds
Bond Energy: kJ/mol (kcal/mol)
X = H
X = Cl
sp3
410 (98)
339 (81)
H2C
CHX
sp2
452 (108)
368 (88) X
sp2
469 (112)
406 (97)

6. Resonance Picture
C-X bonds in aryl halides have more double bond character than C-X bonds in alkyl halides

7. Sources of Aryl Halides1

8. Preparation of Aryl Halides
Halogenation of arenes (Section 12.5)
electrophilic aromatic substitution 6

9. Physical Properties of Aryl Halides1

10. Physical Properties of Aryl Halides
resemble alkyl halides
are essentially insoluble in water
less polar than alkyl halides Cl Cl
 1.7 D
 2.2 D

11. Reactions of Aryl Halides: A Review and a Preview1

12. Reactions Involving Aryl Halides
Electrophilic aromatic substitution (Section 12.14)
halide substituents are ortho-para directing & deactivating 6

13. Substitution Reactions Involving Aryl Halides
Nucleophilic substitution on chlorobenzene occurs so slowly that forcing conditions are required. 6

14. Nucleophilic Substitution of Chlorobenzene
This reaction does not proceed via SN2……..

15. Why is Chlorobenzene Unreactive?
the SN2 is not reasonable because the aromatic ring blocks back-side approach of the nucleophile. Inversion is not possible.

16. Aryl Cations are Highly Unstable
SN1 Also Unlikely:
Aryl Cations are Highly Unstable
SN1 not reasonable because:
C—Cl bond is strong; therefore, ionization to a carbocation is a high-energy process
aryl cations are highly unstable

17. SN1 Reaction is Possible with Very
Powerful Leaving Groups such as Dinitrogen
This is a unique case: halides are not good enough leaving groups for this process to occur.

18. What is the Mechanism of This Reaction?

19. Nucleophilic Substitution in Nitro-Substituted Aryl Halides1

20. Nucleophilic Aromatic Substitution (SNAr)?
Reaction 1 - electrophile interacts with the filled HOMO orbital of the aromatic ring
Reaction 2 - nucleophile interacts with the empty LUMO orbital of the aromatic ring. 2

21. The More Electron-Deficient the Haloarene, the Faster the Substitution
1.0
7 x 1010
2.4 x 1015
too fast to measure 7

22. Direct Displacement Doesn’t Occur!7

23. Kinetics of Nucleophilic Aromatic Substitution
follows second-order rate law:
rate = k [aryl halide] [nucleophile]
inference:
both the aryl halide and the nucleophile are involved in rate-determining step 9

24. Effect of Leaving Group Upon Rate of SN2
During SN2 reactions, the C-X bond breaks during the rate-determining step
Reaction Rate Depends on X: I > Br > Cl > F
C-F (485 kJ/mol), C-Cl (327 kJ/mol)
C-Br (285 kJ/ml, C-I (213 kJ/mol) 8