Chapter17
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Transcript of Chapter17
Chapter 17
Spring 2009
Benzene• Six-membered ring• Is planar• All C-C bond lengths are equal
Kekulé structure
Resonance description of benzeneImplication of
the geometry of the structure above
Shorter isolated double bonds
Longer single bonds Common representation of
benzene
BenzeneBenzene is the parent aromatic molecule.Benzene has the following characteristics that are common among all aromatic compounds•Benzene is cyclic and conjugated•Benzene is unusually stable in comparison to a molecule with three isolated pi bonds•Benzene is planar and has the shape of a regular hexagon. All bond angles are 120º, all carbon atoms are sp2 hybridized, and all carbon-carbon bond lengths are intermediate in length between a single and double bond. •Benzene undergoes substitution reactions rather than electrophilic addition reactions that would destroy its conjugation.
Larger aromatic hydrocarbons
http://www.cem.msu.edu/~reusch/VirtualText/react3.htm
Pictures of Benzene
Electrostatic potential surface
Benzene molecular orbitalIn top picture notice a p
orbital on each C atom.Bottom picture show the overlap of the p orbitals.
Orbital picture of benzene
each carbon atom is sp2 hybridized
The resonance picture indicates why each C-C bond is the same length.
Electrostatic potential surface
Electron-rich portion represents π electron cloud
For a compound to be classified as aromatic, it must fulfill both of the of the following criteria:
• It must have an uninterrupted cyclic cloud of π electrons above and below the plane of the molecule (this is often called the π cloud. Also, the π cloud must be cyclic, uninterrupted, and planar.
• The p cloud must contain an odd number of pairs of π electrons. (4n+2 rule)
Common names for aromatic compounds
IUPAC names
• To name benzene ring with one substituent, name the substituent and add the word benzene.
ethyl benzene
?
If the alkane chain is longer than six carbon atoms name the benzene ring as a phenyl substituent.
Benzyl
Benzyl substituent
Disubstituted benzenes
1,2-dimethylbenzene 1,3-dimethylbenzene 1,4-dimethylbenzene
IUPAC names
Same substituent
meta-dichlorobenzeneor, 1,3-dichlorobenzene
Different substituents
These two have common root names
Different substituents
These two have common root names
toluene
analine
Different substituents
These two have common root names
meta-chlorotoluene
ortho-chloroanaline
Different substituents
These don’t have a common root name so alphabetize the name of the substituents.
Different substituents
These don’t have a common root name so alphabetize the name of the substituents.
ortho-bromochlorobenzene
para-bromonitrobenzene
Heat of hydrogenation dataThe low heat of hydrogenation means that benzene is especially stable – this extra stability is characteristic of all aromatic compounds.
Reaction of aromatic compounds
• Benzene does not undergo addition reactions typical of other unsaturated hydrocarbons.
What makes a compound aromatic?
• A molecule must be cyclic
• Planar
• Completely conjugated (alternating single-double bonds)
• Have a particular number of π electrons
This molecule is non-aromatic
It is cyclic, completely conjugated, non-planar, and contains 8 π electrons
This molecule is anti-aromatic
Cyclic, planar, completely conjugated, and contain four π electrons.
Aromatic, anti-aromatic, or non-aromatic
• Aromatic: A cyclic planar, completely conjugated compound with 4n+2 π electrons
• Anti-aromatic: A cyclic, planar, completely conjugated compound with 4n π electrons
• Non-aromatic: A compound that lack one (or more) of the following requirements for aromaticity.
Aromatic compounds can have more than one ring.
Aromatic rings can contain a single ring with lots of alternating single-double bonds
atomic orbitals
molecular orbitals
Anti-aromatic
The inscribed polygon method
• Draw the polygon in question inside a circle with its vertices touching the circle and one of the vertices pointing down. Mark the points at which the polygon intersects the circle.
• Draw a line horizontally through the center of the circle and label MOs as bonding, nonbonding, or antibonding.
• Add the electrons, beginning with the lowest energy MO.
Label the cation, radical, and anion as aromatic, antiaromatic, or
nonaromatic.
Heterocyclic aromatic compounds
Nucleic acids
Thymine
Aromatic Question
Thiamin, or vitamin B1, contains a five-membered, nitrogen-sulfur heterocycle called a thiazalium ring. Explain why the thiazolium ring is aromatic.
Cycloheptatrienyl cation, radical and
anion problem