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Dehydrogenation 11.15 Preparation of Alkenylbenzenes industrial preparation of styrene Almost 12 billion lbs. produced annually in U.S.

dehydrogenation dehydration dehydrohalogenation

CH2CH3

630C ZnO

CH + H2

CH2

Acid-Catalyzed Dehydration of Benzylic Alcohols Cl KHSO4 CHCH3 OH Cl H3C CHCH3 + CH heat CH2 (80-82%) Cl H3C

Dehydrohalogenation

CH2CHCH3 Br

NaOCH2CH3

ethanol, 50C

CH (99%)

CHCH3

Hydrogenation

11.16 Addition Reactions of Alkenylbenzenes hydrogenation halogenation addition of hydrogen halides Br

CH3 C CHCH3 H2 Pt Br

CH3 CHCH2CH3

(92%)

Halogenation

Addition of Hydrogen Halides Cl HCl CH Br (82%) CH2 Br +


(75-84%)

Br2 CH CH2

via benzylic carbocation

Free-Radical Addition of HBr

HBr CH CH2 peroxides CH2CH2Br 11.17 Polymerization of Styrene

CH

CH2Br

via benzylic radical

Polymerization of Styrene H2C CHC6H5

Mechanism RO

H2C CH2 CH C6H5 CH2 CH C6H5 polystyrene CH2 CH C6H5

CHC6H5

Mechanism RO H2C CHC6H5 RO H2C CHC6H5

Mechanism

H2C

CHC6H5

H2C

CHC6H5

Mechanism RO H2C CHC6H5 H2C CHC6H5 RO H2C CHC6H5 H2C CHC6H5

Mechanism

H2C

CHC6H5

H2C

CHC6H5

Mechanism RO H2C CHC6H5 11.18 H2C CHC6H5 H2C CHC6H5 Cyclobutadiene and Cyclooctatetraene

H2C

CHC6H5

Heats of Hydrogenation to give cyclohexane (kJ/mol)

Heats of Hydrogenation to give cyclooctane (kJ/mol)

120

231

208

97

205

303

410

heat of hydrogenation of benzene is 152 kJ/mol less than 3 times heat of hydrogenation of cyclohexene

heat of hydrogenation of cyclooctatetraene is more than 4 times heat of hydrogenation of cyclooctene

Structure of Cyclooctatetraene Structure of Cyclobutadiene cyclooctatetraene is not planar has alternating long (146 pm) and short (133 pm) bonds MO calculations give alternating short and long bonds for cyclobutadiene. H H
135 pm 156 pm

Structure of Cyclobutadiene structure of a stabilized derivative is characterized by alternating short bonds and long bonds (CH3)3C C(CH3)3
138 pm 151 pm

Stability of Cyclobutadiene Cyclobutadiene is observed to be highly reactive, and too unstable to be isolated and stored in the customary way. Not only is cyclobutadiene not aromatic, it is antiaromatic. An antiaromatic substance is one that is destabilized by cyclic conjugation.

(CH3)3C

CO2CH3

Requirements for Aromaticity cyclic conjugation is necessary, but not sufficient

Conclusion

there must be some factor in addition to cyclic conjugation that determines whether a molecule is aromatic or not

not aromatic Antiaromatic when square

aromatic

not aromatic Antiaromatic when planar

Hckel's Rule among planar, monocyclic, completely conjugated polyenes, only those with 4n + 2 electrons possess special stability (are aromatic) n the additional factor that influences aromaticity is the number of electrons 0 1 2 3 4 4n+2 2 6 10 14 18 Benzene!

11.19 Hckel's Rule:

Hckel's Rule

Hckel's Rule Frost's circle is a mnemonic that allows us to draw a diagram showing the relative energies of the orbitals of a cyclic conjugated system. 1) draw a circle 2) inscribe a regular polygon inside the circle so that one of its corners is at the bottom 3) every point where a corner of the polygon touches the circle corresponds to a electron energy level 4) the middle of the circle separates bonding and antibonding orbitals

Hckel restricted his analysis to planar, completely conjugated, monocyclic polyenes he found that the molecular orbitals of these compounds had a distinctive pattern one orbital was lowest in energy, another was highest in energy, and the others were arranged in pairs between the highest and the lowest

Frost's Circle

-MOs of Benzene
Antibonding

Antibonding

Bonding

Benzene Bonding

MOs of Benzene

6 p orbitals give 6 orbitals 3 orbitals are bonding; 3 are antibonding

-MOs of Benzene
Antibonding

-MOs of Cyclobutadiene
(square planar) Antibonding

Benzene Bonding

Cyclobutadiene

Bonding

6 electrons fill all of the bonding orbitals all antibonding orbitals are empty

4 p orbitals give 4 orbitals 1 orbital is bonding, one is antibonding, and 2 are nonbonding

-MOs of Cyclobutadiene
(square planar) Antibonding

-MOs of Cyclooctatetraene
(square planar) Antibonding

Cyclobutadiene

Bonding

Cyclooctatetraene

Bonding

4 electrons; bonding orbital is filled; other 2 electrons singly occupy two nonbonding orbitals

8 p orbitals give 8 orbitals 3 orbitals are bonding, 3 are antibonding, and 2 are nonbonding

-MOs of Cyclooctatetraene
(square planar) Antibonding

-Electron Requirement for Aromaticity


4 electrons 6 electrons 8 electrons

Cyclooctatetraene

Bonding

8 electrons; 3 bonding orbitals are filled; 2 nonbonding orbitals are each half-filled

not aromatic

aromatic

not aromatic

Completely Conjugated Polyenes 6 electrons; not completely conjugated

6 electrons; completely conjugated

11.20 Annulenes

aromatic

H not aromatic

Annulenes [10]Annulene Annulenes are planar, monocyclic, completely conjugated polyenes. That is, they are the kind of hydrocarbons treated by Hckel's rule. predicted to be aromatic by Hckel's rule, but too much angle strain when planar and all double bonds are cis 10-sided regular polygon has angles of 144

[10]Annulene
van der Waals strain between these two hydrogens

[14]Annulene
HH HH

incorporating two trans double bonds into the ring relieves angle strain but introduces van der Waals strain into the structure and causes the ring to be distorted from planarity

14 electrons satisfies Hckel's rule van der Waals strain between hydrogens inside the ring

[16]Annulene

[18]Annulene
H H H H H H

16 electrons does not satisfy Hckel's rule alternating short (134 pm) and long (146 pm) bonds is an antiaromatic 4n -electron system

18 electrons satisfies Hckel's rule resonance energy = 418 kJ/mol bond distances range between 137-143 pm

Cycloheptatrienyl Cation

H 11.21 Aromatic Ions H H H +

H H H

6 electrons delocalized over 7 carbons positive charge dispersed over 7 carbons very stable carbocation also called tropylium cation

Cycloheptatrienyl Cation

Cycloheptatrienyl Cation

H H + H H

H H H H H

+
H H Ionic

Br H Br

+
H

Covalent

Tropylium cation is so stable that tropylium bromide is ionic rather than covalent. mp 203 C; soluble in water; insoluble in diethyl ether

Cyclopentadienide Anion

Cyclopentadienide Anion

6 electrons delocalized over 5 carbons negative charge dispersed over 5 carbons stabilized anion

H H

Acidity of Cyclopentadiene H H H+ + H H Ka = H 10-16 H H

Electron Delocalization in Cyclopentadienide Anion H H H H H H H

H H

H Cyclopentadiene is unusually acidic for a hydrocarbon. Increased acidity is due to stability of cyclopentadienide anion. H

H H H

pKa = 16

H H

H H

H H

Compare Acidities of Cyclopentadiene and Cycloheptatriene H H H H H H H H H pKa = 16 Ka = 10-16 H H H H H H

Compare Acidities of Cyclopentadiene and Cycloheptatriene H H H

H H

H H H H Antiaromatic anion 8 electrons

H Aromatic anion 6 electrons

pKa = 36 Ka = 10-36

Cyclopropenyl Cation

Cyclooctatetraene Dianion H H + H H H H H H

H + H

H also written as

H H also written as 2 H H n=2 4n +2 = 10 electrons

H H H H

H H

n=0 4n +2 = 2 electrons

Examples

11.22 Heterocyclic Aromatic Compounds N

N H

Pyridine

Pyrrole

Furan

Thiophene

Examples

11.23 Heterocyclic Aromatic Compounds N


N

and Hckel's Rule

Quinoline

Isoquinoline

Pyridine

Pyrrole

6 electrons in ring lone pair on nitrogen is in an N

lone pair on nitrogen must be part of ring system if ring is to have N H

sp2 hybridized orbital; not part of system of ring

6 electrons lone pair must be in a p orbital in order to overlap with ring system

Furan

two lone pairs on oxygen one pair is in a p orbital and is part O


of ring system; other is in an sp2 hybridized orbital and is not part of ring system