armatic

6
3
15.2: Naming aromatic compounds: (arenes) large number on non-systematic names (Table 15.1)
CH3 OH OCH3 NH2
benzene
toluene
phenol
anisole
anilin e
styrene
Ψ1: zero nodes Ψ2 and Ψ3: one node Ψ4 and Ψ5: two nodes Ψ6: three node
Bonding Anti-bonding
16
8
15.5 & 15.8: Aromaticity and the Hückel 4n + 2 Rule Cyclic conjugated molecules: not all cyclic conjugated systems are aromatic (no special stability)
the plane of the six-membered ring
13
Arrows in organic chemistry Reaction arrow Equilibrium arrow Resonance arrow Mechanism arrows Double-headed arrow Single-headed arrow
Chapter 15: Benzene and Aromaticity
H H H H H H H H H H H H
C6H6
1
MO’s of a C=C π-bond
π-antibonding MO
π*
+235 KJ/mol
-235 KJ/mol
π-bonding MO
π4-disubstituted:
Y
Note: ortho, meta, and para are not used in systematic nomenclaure
CH3 Cl CH3 CH3 CO2H
2-chlorotoluene ortho-chlorotoluene o-chlorotoluene
Cl
1,3-dimethylbenzene meta-xylene m-xylene
4-chlorobenzoic acid para-chlorobenzoic acid p-chlorobenzoic acid
9
Benzenes with two or more substituents: Choose numbers to get lowest possible values List substituents alphabetically with hyphenated numbers
12
+
2 H2
+
3 H2
+ 206 KJ/mol
6
Structure of Benzene: Kekule benzene: two forms are in rapid equilibrium
154 pm 134 pm
• All bonds are ~139 pm (intermediate between C-C and C=C) • Electron density is distributed evenly between the six carbons • Structure is planar, hexagonal • C–C–C bond angles are 120° • Each carbon is sp2 and has a p orbital perpendicular to
Generally, mono-substituted benzenes are named in a similar manner as hydrocarbons with -benzene as the parent name
Br CH2CH3 NO2
bromobenzene
ethylbenzene
Parent chain
Phenyl group
2-methyl-7-phenyloctane
(1-methylbutyl)benzene
A phenyl substituent (C6H5-) is often abbreviates as PhA C6H5 -CH2- susbtitutent is often referred to as a benzyl group (Bn-) Parent
cyclobutadiene 4 !-electrons
benzene 6 !-electrons
•
•
•
•
The four π-electrons in ψ1 are delocalized over the four p-orbitals
_ +
+
•
•
•• _
Table 14.2 (p. 528): Bond lengths in pm
H3C CH3 H2C CH2 H2C CH CH3 H2C CH CH CH2 H2C CH CH CH2
(1-methylethyl)benzene (i sopropylbenzene)
nitrobenzene
7
When the benzene ring is a substituent of a parent chain, referred to as a phenyl group. The benzene ring is is regarded as a substituent when the parent chain has greater than six carbons. The benzene ring is the parent when the longest alkyl chain substituent is six carbons or less
154
133
149
148
134
4
2
π-molecular orbitals of hexatriene
!6
five nodes
!5
four nodes
!4
three nodes two nodes
six p-orbitals
!3
!2
one node zero nodes
5
6 AO’s = 6 MO’s
!1
Conjugation: series of overlapping p-orbitals Aromaticity: cyclic conjugated organic compounds such as benzene, that exhibit special stability due to resonance delocalization of π-electrons.
2.
3.
4. 5. 6.
15
15.4: Molecular orbitals of benzenes: (figure 15.3) six AO’s = six MO’s
!6
!4
!5
six p-orbitals
!2
!3
!1
Degenerate orbitals: orbitals that have the same energy
14
7
Drawing and Interpreting Resonance Forms (chapter 2.5 and 2.6)
1. No one resonance forms accurately depicts the structure of the molecule. The real structure is a composite or hybrid of all resonance forms Resonance forms differ only by the placement of π- or non-bonding electrons. Neither the position or hybridization of the atoms changes. Resonance forms are not necessarily equivalent. While all resonance forms contribute to the actual structure (resonance hybrid), some forms may contribute more. All resonance forms must be proper Lewis structures. The actual resonance hybrid is more stable than any single resonance form. In general, the greater the number of resonance forms, the more stable the resonance hybrid.
Br2 Br Br H Cl Cl
N o Reaction
CHO CHO
O3
Benzene’s cyclic conjugated structure gives it special stability 11
Benzene undergoes electrophilic substitution reactions (chapter 16) rather than electrophilic addition
ψ2 is the Highest Occupied Molecular Orbital (HOMO) ψ3 is the Lowest Unoccupied Molecular Orbital (LUMO)
3
ψ1 of Butadiene (no nodes, bonding MO)
Bonding Interaction
2
1
π-molecular orbitals of butadiene
3 Nodes 0 bonding interactions 3 antibonding interactions ANTIBONDING MO 2 Nodes 1 bonding interactions 2 antibonding interactions ANTIBONDING MO 1 Nodes 2 bonding interactions 1 antibonding interactions BONDING MO 0 Nodes 3 bonding interactions 0 antibonding interactions BONDING MO
Common names, such as “toluene” can serve as root name (as in TNT)
10
5
15.3: Structure and Stability of Benzene Formula: C6H6, four degrees of unsaturation (section 6.2) three double bonds + one ring The π-bonds of benzene are resistant to the normal reactions of alkenes and alkynes
Br Br + Br Br Fe catalyst Br + H Br
electrophilic addition
electrophilic substitution
Stability of Benzene: Heats of Hydrogenations
+ H2
+ 118 KJ/mol + 230 KJ/mol calc'd value= 336 KJ/mol 6 K J/ mol added stability calc'd value= 354 KJ/mol 148 K J/ mol added stability
chain
Benzyl group
8
4
Disubstituted benzene: relative position of the substitutents
X Y
1,2-disubstituted: 1,3-disubstituted:
ortho (o-) meta (m-) para (p-)