AROMATIC COMPOUNDS

Benzene Molecular formula: C6H6 6 Cs at the corners of a regular hexagon C-C bond 1.39 , longer than that of a double bond (1.34 ) but shorter than a single bond (1.53 ). C-H bond 1.09 All H-C-C bonds and C-C-C bond angles are 120o. C atoms are all sp2-hybridized.

Double bonds in benzene are not fixed in position. electrons in benzene are completely delocalized over the entire ring. Reactivity of benzene is different from compounds containing localized double bonds. Other characteristics of benzene: 1. Benzene yields only one monosubstitution product, C6H5Y. 2. Benzene yields 3 isomeric disubstitution products, C6H4Y2. Y Y Y
Y

Y ortho meta Y para

3. 4. 5. 6.

Benzene undergoes substitution rather than addition. All C-C bonds in benzene are equal and are intermediate in length between single and double bonds. Benzene is a flat molecule with every C and every H lying in the same plane. Heats of hydrogenation and combustion of benzene are lower than expected.
+ H2 catalyst H = -28.6 kcal/mol (exptl) H = 3(-28.6) kcal/mol = -85.8 kcal/mol (calc'd) H = -49.8 kcal/mol (exptl)

+ 3 H2 "1,3,5-cyclohexatriene + 3 H2 benzene

catalyst

catalyst

Benzene is more stable by 36 kcal/mol than expected for a compound with 3 double bonds in a 6-membered ring. 36 kcal/mol = empirical resonance energy reflects the degree of stabilization of the aromatic ring that is attributed to the delocalization of the electrons. Resonance stabilization of benzene accounts for the lower reactivity of their bonds compared to the bonds of alkenes and alkynes.

Arenes aromatic hydrocarbons: Examples:

CH3 CH3 CH3 1,2-dimethylbenzene o-xylene

methylbenzene toluene H3C CH3

H3C 1,3-dimethylbenzene m-xylene

CH3

1,4-dimethylbenzene p-xylene

Aromatic Compounds: Compounds that have been classified as aromatic always had a sextet of electrons.
H S N pyridine O N

benzene

thiophene

furan

pyrrole

Huckels Rule: Any conjugated monocyclic polyene that is planar and has (4n+2) electrons, with n = 0, 1, 2, will exhibit the special stability associated with aromaticity.
6 electrons benzene 4n + 2 = 6 n=1

H H

H H

H H

18 electrons

4n + 2 = 18 n=4

[18]annulene

Ions, as well as neutral molecules, can be said to have aromaticity.

H 1,3-cyclopentadienyl anion +

tropylium ion

Benzene . Electron-rich, yet inert toward electrophilic addition Addition reactions will break up aromatic sextet. Will react with electrophilic reagents in reactions in which an incoming group substitutes for one of the H atoms on the ring electrophilic aromatic substitution (EAS).

Electrophilic aromatic substitution: 1. Bromination:

Br + Br2 FeBr3 + HBr Br + Br2 Fe + HBr

Br Br Br + Fe Br Br
+ Br Br

+ Br

Br

Br Fe Br Br

Br Fe Br Br

H +

H Br H +

Br H

+ H Br H

H +

Br H

Br + H+

Essential steps in EAS: 1. 2. 3. The substituting reagent is polarized or ionized in such a way as to create an electronpoor species (electrophile). A cationic intermediate is formed by bonding between the electrons of the aromatic ring and the electrophile. A proton is lost from the carbocation to restore the aromatic ring.

The rate-determining step in EAS is the formation of the carbocation intermediate. When electrophile and the aromatic ring react, the transition state involves not only bond breakage, but also disruption of the aromaticity of the benzene ring. Energy barrier for this reaction is high. Loss of proton from the carbocation intermediate is a fast reaction because the aromatic sextet is regenerated. 2. Nitration:

+ HNO3

H2SO4

NO2 + H2O

3. Friedel-Crafts Alkylation:

R + RCl AlCl3 + HCl

4. Friedel-Crafts Acylation:

O O + R C Cl
5. Sulfonation:
SO3H + H2SO4 + SO3H SO3 H 2O

C AlCl3

+ HCl

Aromatic compounds vary in their susceptibility toward EAS reactions. An aromatic ring which is more electron-rich is more attractive to an electrophile. An electron-donating substituent will make the ring more electron-rich. An electrondonating substituent will make the ring more reactive toward EAS reactions. An electron-donating substituent will activate the ring toward EAS. Electron-donating substituent = ring-activating substituent toward EAS. An aromatic ring which is more electron-poor is less attractive to an electrophile. An electron-withdrawing substituent will make the ring more electron-poor. An electronwithdrawing substituent will make the ring less reactive toward EAS reactions. An electron-withdrawing substituent will deactivate the ring toward EAS. Electron-withdrawing substituent = ring-deactivating substituent toward EAS. Order of reactivity towards EAS: EDG

EWG

>
most reactive
Substituent Effects on EAS:

>
least reactive

Ring-activating or ring-deactivating groups The substituent also affects where a second substituent will be going in the aromatic ring.

OH + Br2 CH3COOH

OH Br +

OH + HBr

ortho

Br para

Only ortho- and para-bromophenol are formed. No meta-bromophenol is produced. Therefore, -OH group is said to be an ortho,para-directing substituent. Ortho, para-directing substituents: Substituents which have a pair of nonbonding electrons on the atom bonded to the aromatic ring will direct substitution to the ortho and para positions. Examples: -N(CH3)2, -NH2, -OH, -OCH3, etc. Alkyl groups are electron-donating and are also o,p-directing. When a strongly electron-withdrawing substituent is on the aromatic ring, substitution occurs at the meta-position, because the intermediate formed is the least destabilized. The nitro group is said to be a meta-directing group. Halogens are ring-deactivating, but they are ortho,para-directing. electrons of a halogen can help stabilize the + charge by resonance. The nonbonding

CH3
58.5 4.4 37.2

CH2 CH3
45.0 6.5 48.5

30.0 7.7 62.3 72.7

15.8 11.5

EAS of Phenols
OH
OH OH Br

+ Br2

CH3CO2H 30oC

+
Br

OH

OH

+ Br2

H2O 30oC

Br

Br

Br

EAS of Multiply Substituted Aromatic Compounds: When there are 2 or more substituents already on the aromatic ring, they will act to direct an incoming nucleophile. When the directing influences of the substituents already on the ring are in conflict, the one that is strongly activating will determine the orientation of the new substituent. Relative effectiveness of substituents in directing an incoming electrophile to the ortho or para position when two groups are in competition

NH2 OH O

>

OCH3

>

OCR O NCR H

>

>

CH3

Reactions of Arenes: Oxidation of alkylbenzenes

1) KMnO4 2) H+ COOH

Cr2O 7 H3C CH3 H

+

-2

HOOC

COOH

K2Cr2O7 H2SO4 K2Cr2O7 H2SO4 K2Cr2O7 H2SO4

COOH

COOH

NO REACTION

There must be a benzylic H for oxidation to take place. Halogenation of Alkylbenzenes:

CH3

Cl atom will attack side chain. Cl+ will attack the aromatic ring

Free radical halogenation of alkylbenzenes: The more stable the radical, the more rapidly it is formed. Order of stability of free radicals: Benzylic, allylic > 3o > 2o > 1o > CH3 > vinylic Free radical halogenation will take place on the benzylic position.

. CH2 .

CH2

CH2

CH2

. .

Nucleophilic Aromatic Substitution: NAS The more electron-poor the aromatic ring, the more reactive it is towards a nucleophile. 2 Steps in Bimolecular Displacement Mechanism for NAS: 1. Addition of the nucleophile to give a carbanion intermediate. 2. Elimination of the leaving group to restore the aromatic ring.

X Y
-

X slow

fast

+ X-

The more electron-withdrawing substituents on the ring, the more reactive towards NAS.
Cl O2N NO2 Cl Cl NO2 O2N NO2

>
NO2 Most reactive

>

Least reactive

The position of the electron-withdrawing substituent also affects the reactivity of the aromatic compound toward NAS. Aromatic compounds with electron-withdrawing groups ortho and para to the leaving group are more reactive toward NAS than those with the EWG at the meta position. Other EWGs, besides the nitro group, could also activate the ring toward NAS. Ex. +N(CH3)3, -CN, -SO3H, -COOH, -CHO, -COR. Electron-donating groups deactivate the ring toward NAS. Degree of deactivation depend upon how strongly these groups release electrons. Examples: -NH2 and OH deactivate strongly, -OR moderately, and R weakly Acidity of Phenols: Phenols are stronger acids than water.

OH Stronger acid

OH Weaker base

H2O Weaker acid

Stronger base

..
O
-

-:

..

Presence of electron-withdrawing groups makes a phenol more acidic. Presence of electron-donating groups makes a phenol less acidic.

OH

OH

OH

>
EWG

>
EDG

 The more the number of electron-withdrawing groups present in a phenol, the more acidic the phenol.

OH NO2

OH NO2

OH

OH

>
O2N NO2 Most acidic NO2

>
NO2

>
Least acidic

The position of the substituent also affects acidity of the phenol. Phenols with electron-withdrawing substituents in the ortho or para positions are more acidic than phenols whose EWGs are on the meta position. Phenols with electron-donating substituents in the meta position are more acidic than phenols whose EDGs are in ortho or para positions.
OH OH EWG OH OH

>
EWG EWG OH OH

>
OH EDG

>
EDG

>
EDG