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Its molecular formula has been shown to be C6H6, which implies four degrees of unsaturation in the molecule. Several incorrect structures of benzene have been proposed in the past:
Of these, only Claus benzene has not been synthesized. All of the other structures represent unstable substances which isomerize to benzene in very exothermic reactions. The correct molecular structure of benzene is:
Benzene is relatively inert. Among the reactions it does undergo is the reaction with bromine in the presence of catalytic amounts of FeBr3:
Monosubstituted benzenes are often named by adding a prefix to the word benzene:
For tri- and more highly substituted benzenes, the ring carbons are numbered to give the substituents the lowest set of numbers, as in cyclohexane nomenclature:
The naming of three substituted benzene systems do not follow IUPAC nomenclature in the Chemical Abstracts indexing preferences: phenol, benzaldehyde and benzoic acid. Ring substituted compounds of these substances are named by numbering the ring positions or using the prefixes o-, p- and m-.
The carbon carrying the substituent giving the compound its base name is given the number 1.
The electronic structure of the benzene ring consists of 6 sp2 carbon atoms, with each p-orbital overlapping the p-orbitals of its nearest neighbors.
The heat of hydrogenation of benzene can be experimentally measured using special catalysts and is measured to be 29.6 kcal mol-1 less than the calculated heat for the hypothetical molecule, 1,3,5-cyclohexatriene.
Benzene is much more stable than a molecule containing alternating double and single bonds. The difference in stability is called the resonance energy of benzene, about 30 kcal mol-1.
The cyclic system is stabilized relative to the acyclic one. Two of the orbitals have been lowered in energy in benzene (1 and 3) while one has been raised (2). The drop in energy of 1 and 3 more than offsets the rise in energy of 2.
These concerted aromatic transition states have lower energies than the alternative sequential bond-breaking and bond-making mechanism.
The electronic spectra of aromatic compounds varies with the introduction of substituents (useful in designing dye molecules). Simple substituted benzenes absorb between 250 and 290 nm. 4-Aminobenzoic acid (PABA) has a max of 289 nm and a high extinction coefficient of 18,600. It is used in sunscreen lotions to filter out harmful UV light in this wavelength region.
The specific substitution pattern determines the precise location of the C-H out-of-plane bending absorptions. For the dimethylbenzenes: 1,2-dimethylbenzene (o-) 1,4-dimethylbenzene (p-) 1,3-dimethylbenzene (m-) 738 cm-1 793 cm-1 690 and 765 cm-1
The NMR spectra of benzene derivatives show the effects of an electronic ring current.
The cyclic delocalization of the electrons in the aromatic ring gives rise to unusual deshielding:
Aromatic ring hydrogens: Alkenyl hydrogens: Benzene hydrogens: 6.5-8.5 ppm 4.6-5.7 ppm 7.27 ppm (single peak)
This aromatic deshielding is due to ring currents produced by the electrons moving in the external magnet field, H0.
The magnetic field from the ring current opposes H0 inside the loop but opposes it outside the loop where the hydrogens are located, resulting in deshielding. The effect is strongest closest to the ring and diminishes rapidly with distance.
Benzylic nuclei are deshielded only about 0.4-0.8 ppm more than their allylic counterparts.
Hydrogens farther away from system have chemical shifts similar to those in the alkanes.
The presence of a substituent renders the ortho, meta and para hydrogens non-equivalent and subject to mutual coupling.
4-(N,N-dimethylamino)benzaldehyde shows a large chemical shift difference between the two sets of ring hydrogens and a near first-order pattern of two doublets. The 9 Hz coupling constant is typical of splitting between ortho protons.
All three types of coupling can be seen in the first order spectrum of 1-methoxy-2,4-dinitrobenzene (2,4-dinitroanisole).
Ortho hydrogen (to methoxy)
Doublet, =7.23 ppm, 9 Hz coupling
The 13C NMR spectra of benzene derivatives is not greatly affected by ring current shifts, since the induced ring current flows directly above and below the ring carbons. Benzene carbons exhibit chemical shifts similar to those in alkanes (120-135 ppm when unsubstituted). Benzene exhibits a single line at =128.7 ppm.
Quaternary carbons are numbered using the preceding carbon in the sequence followed by a letter indicating its distance to the preceding carbon.
The UV spectrum of naphthalene indicates an extended, conjugated system with peaks at wavelengths as long as 320 nm.
The electrons in naphthalene are more delocalized than in benzene and several resonance structures can be drawn:
The overlap of the 10 p orbitals results in a fairly even distribution of electron density.
X-ray crystallographic measurements have determined the exact bond distances and angles in naphthalene.
The C-C bond distances deviate slightly from those in benzene, 1.39 , C-C single bonds, 1.54 and C=C double bonds, 1.33 .
The 1H NMR spectrum of naphthalene shows two symmetric multiples at = 7.49 and 786 ppm.
Coupling constants in the naphthalene nucleus are similar to those in substituted benzenes:
Jortho = 7.5 Hz Jmeta = 1.4 Hz Jpara = 0.7 Hz
The 13C NMR spectrum shows three lines with chemical shifts in the range of other benzene derivatives:
Free 1,3-cyclobutadiene can be prepared and observed only at very low temperatures. Cyclobutadiene can act as either a diene or a dienophile in its rapid Diels-Alder reactions:
Substituted cyclobutadienes are less reactive and have been used to study the spectroscopic features of the 4 electron cyclic system. In 1,2,3-tris(1,1-dimethylethyl)cyclobutadiene, the ring hydrogen resonates at = 5.38 ppm, much higher than expected for an aromatic system.
It is a yellow liquid (b.p. 152oC), is stable while cold, but polymerizes when heated. It is oxidized by air, catalytically hydrogenated to cyclooctane, and subject to electrophilic additions and to cycloadditions.
The 1H NMR spectrum shows a sharp singlet at = 5.68 ppm, typical of an alkene. The molecular structure of cyclooctatetraene is non-planar and tub shaped. The double bonds are nearly orthogonal and are not conjugated.
double bonds. It is relatively stable and undergoes electrophilic aromatic substitution. It can be described by a set of 2 resonance forms.
Hckels rule (2n+2) in cyclical conjugated polyenes can be explained by the following: The p orbitals mix to give an equal number of molecular orbitals. All levels are composed of degenerate pairs of orbitals except for the lowest bonding and highest antibonding orbitals.
A closed shell system (aromatic) is possible only if all of the bonding orbitals are fully occupied, 4n+2 electrons. In the case of 4n electrons there will always be a pair of singly occupied orbitals, an unfavorable electronic arrangement.
The cyclopentadienyl cation (four electrons) can only be produced at low temperatures and is highly reactive.
If 1,3,5-cycloheptatriene is treated with bromine, a stable salt is formed containing the cycloheptatrienyl cation, an aromatic, 6 electron system.
The cycloheptatrienyl cation is remarkably unreactive for a carbocation, as expected for an aromatic system. The cycloheptatrienyl anion, on the other hand, is antiaromatic (8 electrons) and has a much lower acidity (pKa = 39) than cyclopentadiene (pKa ~ 16).
[16]Annulene can be either reduced to its dianion or oxidized to its dication; both products are aromatic. On formation of the dication, the configuration of the molecule changes.
Under the conditions of this type of reaction, ordinary non-aromatic conjugated polyenes would polymerize rapidly.
Electrophilic aromatic substitution in benzene proceeds by addition of the electrophile followed by proton loss.
Electrophylic aromatic substitution is a two-step process. The cationic intermediate is resonance-stabilized:
The initial attack of the electrophile is endothermic because the sp3 carbon generated interrupts the cyclic conjugation. The transition state is not aromatic. The loss of the proton regenerates the sp2 carbon atom and aromaticity is restored. This process is more favored than the nucleophilic trapping by the anion accompanying E+.
The overall reaction is exothermic because the bonds formed are stronger than the bonds broken.
This activated bromine complex can attack the benzene molecule, allowing the other bromine atom to depart with the good leaving group FeBr4-
The FeBr4- next abstracts a proton from the cyclohexadienyl cation intermediate, and in the process regenerates the original FeBr3 catalyst.
Bond energy calculations show that the electrophilic bromination of benzene is exothermic:
Phenyl-H Br-Br Phenyl-Br H-Br Reaction +112 kcal mol-1 +46 kcal mol-1 -81 kcal mol-1 -87.5 kcal mol-1 -10.5 kcal mol-1
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Fluorination of benzene is very exothermic (explosive). Chlorination and bromination require an activating catalyst. Iodination is endothermic and does not occur.
Benzene can be attacked by concentrated nitric acid in the presence of concentrated sulfuric acid.
The purpose of the sulfuric acid is to generate the more electrophilic nitronium ion:
Aromatic nitration is the best way to introduce nitrogencontaining substituents into the benzene ring. The aromatic nitro group serves as a directing group in further substitutions and as a masked amino function.
Sulfonation is reversible.
Fuming sulfuric acid (8% SO3 in concentrated H2SO4) reacts with benzene to form benzenesulfonic acid.
Because the reaction of SO3 with water is so exothermic, the sulfonation of benzene can be reversed by heating benzenesulfonic acid in dilute aqueous acid. Because sulfonation is reversible, it can be used as a blocking group to control further aromatic substitution and then later removed.
Sulfonate detergents have now been replaced by more biologically friendly, biodegradable detergents. Sulfonation is often used to impart water solubility to organic compounds, as in the manufacture of certain dyes.
Sulfonyl chlorides can be prepared by reaction of the sodium salt of the acid with PCl5 or SOCl2.
Sulfonyl chlorides are frequently used in synthesis, for example to convert the hydroxy group of an alcohol into a good leaving group.
Sulfonamides are derived from the reaction of a sulfonyl chloride with an amine. An important class of sulfonamides are the sulfa drugs:
Friedel-Crafts Alkylation
Carbon-carbon bonds to benzene can be created using a sufficiently electrophilic carbon based electrophile. To create the necessary electrophilic carbon atom, a Lewis acid such as AlCl3 is employed. A haloalkane reacts with benzene in the presence of an aluminum halide to form an alkylbenzene and a hydrogen halide.
The mechanism of the Friedel-Crafts alkylation with primary haloalkanes involves coordination of the Lewis acid to the halogen atom:
With secondary and tertiary haloalkanes, free carbocations are usually formed, which attack the benzene ring in the same way as the cation NO2+.
A new ring can be fused onto the benzene nucleus by means of an intramolecular Friedel-Crafts alkylation:
Any starting material that functions as a precursor to a carbocation can be used in a Friedel-Crafts alkylation:
Polyalkylation occurs because the alkylbenzene first formed is electron-rich and activates the ring towards further substitution. This is in contrast to bromination, nitration and sulfonation, as they deactivate the ring towards further substitution (electron withdrawing substituents).
Skeletal rearrangement of the carbocation is the second unwanted side-reaction in aromatic alkylation. The desired 1-propylbenzene is not obtained when benzene is alkyated using 1-bromopropane:
In the presence of the Lewis acid, the starting haloalkane rearranges to the secondary carbocation by a hydride shift:
Because of polysubstitution and rearrangement reactions, FriedelCrafts alkylations are rarely used in synthesis.
The alkanoyl substituent is electron withdrawing which deactivates the ring and protects it from further substitution.
Also protecting the ring from further substitution is the formation of a strong complex between the newly formed carbonyl oxygen and the aluminum chloride:
Due to this complex formation, at least one full equivalent of AlCl3 is required for the acylation reaction to go to completion.
An aqueous work-up is required to liberate the final ketone from the aluminum chloride complex:
The ketone product of the Friedel-Crafts Alkanoylation can be converted into an alcohol by hydride reduction. The resulting hydroxyl can be converted into a good leaving group that can be further reduced by hydride leading to the corresponding hydrocarbon.
Important Concepts 3. Benzene Displays Unusual UV, IR, and NMR Spectral Data In NMR spectra, the ring hydrogens
are deshielded by an induced ring current Substitution patterns are revealed by examination of the o, m and p coupling constants
5. Electrons Delocalized over All of the Rings Electronic spectra reveal extended
conjugation. Proton NMR reveals deshielding ringcurrent effects. There is little bond alternation.