Conjugation and Aromaticity

The Chemistry of Dienes

      1. Properties of Dienes
When considering compounds having two or more double bonds in a molecule, it is useful to identify three distinct ways in which these functions may be oriented with respect to each other. First, the double bonds may be separated by one or more sp3-hybridized carbon atoms, as in 1,5-hexadiene. In this circumstance each double bond behaves independently of the other, and we refer to them as isolated. A second relationship has the double bonds connected to each other by a single bond, as in 1,3-hexadiene, and we refer to this arrangement as conjugated. Finally, two double bonds might share a carbon atom, as in 1,2-hexadiene. The central carbon atom in such a system is sp-hybridized, and we call such double bonds cumulated. These three isomers are shown in the following diagram, and three other similar isomers will be displayed on clicking the Change Examples button. In cases where stereoisomers are possible only the E-isomer is shown.
Another stereoisomeric factor associated with conjugated dienes will be demonstrated by clicking the Change Examples button a second time. Rotation about the single bond joining the two double bonds (colored blue) converts a trans-like s-trans conformation to its s-cis form. The energy barrier to this conformational isomerisation is normally low, and the s-trans conformer is often more stable than the s-cis conformer, as shown in the diagram.

These categories are based on more than obvious structural variations. We find significant differences in the chemical properties of dienes depending on their structural type. For example, catalytic hydrogenation converts all the dienes shown here to the alkane hexane, but the heats of reaction (heat of hydrogenation) reflect characteristic differences in their thermodynamic stability. This is illustrated in the diagram on the right. Taking the heat of hydrogenation of 1-hexene (30.1 kcal/mole) as a reference, we find that the isolated diene, 1,5-hexadiene, as expected, generates double this heat of reaction on conversion to hexane. The cumulated diene, 1,2-hexadiene, has a 6 kcal/mole higher heat of reaction, indicating it is less stable than the isolated diene by this magnitude. On the other hand, conjugation of double bonds seems to stabilize a diene by about 5 kcal/mole. The increase in stability of 2,4-hexadiene over 1,3-hexadiene (both are conjugated) is due to the increased double bond substitution of the former, a factor noted earlier for simple alkenes.
The stabilization of dienes by conjugation may be rationalized by resonance and molecular orbital descriptions. A resonance description, such as the one shown here, involves charge separation, implying a relatively small degree of stabilization.

CH2=CH-CH=CH2     (+)CH2-CH=CH-CH2:(–)

A molecular orbital model for 1,3-butadiene is shown below. Note that the lobes of the four p-orbital components in each pi-orbital are colored differently and carry a plus or minus sign. This distinction refers to different phases, defined by the mathematical wave equations for such orbitals. Regions in which adjacent orbital lobes undergo a phase change are called nodes. Orbital electron density is zero in such regions. Thus a single p-orbital has a node at the nucleus, and all the pi-orbitals shown here have a nodal plane that is defined by the atoms of the diene. This is the only nodal surface in the lowest energy pi-orbital, π1. Higher energy pi-orbitals have an increasing number of nodes.

To examine a model of the p-orbital components for the s-cis conformer of a 1,3-diene.   Click Here.
To examine the molecular orbitals of both s-trans and s-cis-1,3-butadiene  Click Here.

      2. Addition Reactions of Dienes
Addition reactions of isolated dienes proceed more or less as expected from the behavior of simple alkenes. Thus, if one molar equivalent of 1,5-hexadiene is treated with one equivalent of bromine a mixture of 5,6-dibromo-1-hexene, 1,2,5,6-tetrabromohexane and unreacted diene is obtained, with the dibromo compound being the major product (about 50%).

CH2=CH(CH2)2CH=CH2 + Br2   BrCH2CHBr(CH2)2CH=CH2 + BrCH2CHBr(CH2)2CHBrCH2Br + CH2=CH(CH2)2CH=CH2

Similar reactions of conjugated dienes, on the other hand, often give unexpected products. The addition of bromine to 1,3-butadiene is an example. As shown below, a roughly 50:50 mixture of 3,4-dibromo-1-butene (the expected product) and 1,4-dibromo-2-butene (chiefly the trans-isomer) is obtained. The latter compound is remarkable in that the remaining double bond is found in a location where there was no double bond in the reactant. This interesting relocation requires an explanation.


The expected addition product from reactions of this kind is the result of 1,2-addition, i.e. bonding to the adjacent carbons of a double bond. The unexpected product comes from 1,4-addition, i.e. bonding at the terminal carbon atoms of a conjugated diene with a shift of the remaining double bond to the 2,3-location. These numbers refer to the four carbons of the conjugated diene and are not IUPAC nomenclature numbers. Product compositions are often temperature dependent, as the addition of HBr to 1,3-butadiene demonstrates.

CH2=CH-CH=CH2 + HBr 
reaction temperature
1,2 addition yield
1,4 addition yield
0 ºC
40 ºC

Bonding of an electrophilic atom or group to one of the end carbon atoms (designated #1) of a conjugated diene generates an allyl cation intermediate. Such cations are stabilized by charge delocalization, and it is this delocalization that accounts for the 1,4-addition product produced in such addition reactions. As shown in the diagram, the positive charge is distributed over carbons #2 and #4 so it is at these sites that the nucleophilic component bonds. Note that resonance stabilization of the allyl cation is greater than the corresponding stabilization of 1,3-butadiene, because charge is delocalized in the former, but created and separated in the latter.

An explanation for the temperature influence is shown in the following energy diagram for the addition of HBr to 1,3-butadiene. The initial step in which a proton bonds to carbon #1 is the rate determining step, as indicated by the large activation energy (light gray arrow). The second faster step is the product determining step, and there are two reaction paths (colored blue for 1,2-addition and magenta for 1,4-addition). The 1,2-addition has a smaller activation energy than 1,4-addition, but the 1,4-product is more stable than the 1,2-product. At low temperatures, the products are formed irreversibly and reflect the relative rates of the two competing reactions. This is termed kinetic control. At higher temperatures, equilibrium is established between the products, and the thermodynamically favored 1,4-product dominates.

      3. Diels-Alder Cycloaddition
The unique character of conjugated dienes manifests itself dramatically in the Diels-Alder Cycloaddition Reaction. A cycloaddition reaction is the concerted bonding together of two independent pi-electron systems to form a new ring of atoms. When this occurs, two pi-bonds are converted to two sigma-bonds, the simplest example being the hypothetical combination of two ethene molecules to give cyclobutane. This does not occur under normal conditions, but the cycloaddition of 1,3-butadiene to cyanoethene (acrylonitrile) does, and this is an example of the Diels-Alder reaction. The following diagram illustrates two cycloadditions, and introduces several terms that are useful in discussing reactions of this kind.

In the hypothetical ethylene dimerization on the left, each reactant molecule has a pi-bond (colored orange) occupied by two electrons. The cycloaddition converts these pi-bonds into new sigma-bonds (colored green), and this then designated a [2+2] cycloaddition, to enumerate the reactant pi-electrons that change their bonding location.
The Diels-Alder reaction is an important and widely used method for making six-membered rings, as shown on the right. The reactants used in such reactions are a conjugated diene, simply referred to as the diene, and a double or triple bond coreactant called the dienophile, because it combines with (has an affinity for) the diene. The Diels-Alder cycloaddition is classified as a [4+2] process because the diene has four pi-electrons that shift position in the reaction and the dienophile has two.
The Diels-Alder reaction is a single step process, so the diene component must adopt a cis-like conformation in order for the end carbon atoms (#1 & #4) to bond simultaneously to the dienophile. Such conformations are called s-cis, the s referring to the single bond connecting the two double bonds. The s-cis and s-trans conformers of 1,3-butadiene are shown in the preceding diagram. For many acyclic dienes the s-trans conformer is more stable than the s-cis conformer (due to steric crowding of the end groups), but the two are generally in rapid equilibrium, permitting the use of all but the most hindered dienes as reactants in Diels-Alder reactions. In its usual form, the diene component is electron rich, and the best dienophiles are electron poor due to electron withdrawing substituents such as CN, C=O & NO2. The initial bonding interaction reflects this electron imbalance, with the two new sigma-bonds being formed simultaneously, but not necessarily at equal rates.

      4. Stereospecificity of the Diels-Alder Cycloaddition
We noted earlier that addition reactions of alkenes often exhibited stereoselectivity, in that the reagent elements in some cases added syn and in other cases anti to the the plane of the double bond. Both reactants in the Diels-Alder reaction may demonstrate stereoisomerism, and when they do it is found that the relative configurations of the reactants are preserved in the product (the adduct). The following drawing illustrates this fact for the reaction of 1,3-butadiene with (E)-dicyanoethene. The trans relationship of the cyano groups in the dienophile is preserved in the six-membered ring of the adduct. Likewise, if the terminal carbons of the diene bear substituents, their relative configuration will be retained in the adduct. Using the earlier terminology, we could say that bonding to both the diene and the dienophile is syn. An alternative description, however, refers to the planar nature of both reactants and terms the bonding in each case to be suprafacial (i.e. to or from the same face of each plane). This stereospecificity also confirms the synchronous nature of the 1,4-bonding that takes place.

The essential characteristics of the Diels-Alder cycloaddition reaction may be summarized as follows:

(i) The reaction always creates a new six-membered ring. When intramolecular, another ring may also be formed.
(ii) The diene component must be able to assume a s-cis conformation.
(iii) Electron withdrawing groups on the dienophile facilitate reaction.
(iv) Electron donating groups on the diene facilitate reaction.
(v) Steric hindrance at the bonding sites may inhibit or prevent reaction.
(vi) The reaction is stereospecific with respect to substituent configuration in both the dienophile and the diene.

These features are illustrated by the following eight examples, one of which does not give a Diels-Alder cycloaddition. Try to predict the course of each reaction before disclosing the answers by pressing the "Show Products" button. The formation of a new six-membered ring should be apparent in every case where reaction occurs.

There is no reaction in example D because this diene cannot adopt a s-cis orientation. In examples B, C, F, G & H at least one of the reactants is cyclic so that the product has more than one ring, but the newly formed ring is always six-membered. In example B the the same cyclic compound acts as both the diene colored blue) and the dienophile (colored red). The adduct has three rings, two of which are the five-membered rings present in the reactant, and the third is the new six-membered ring (shaded light yellow). Example C has an alkyne as a dienophile (colored red). The initial Diels-Alder reaction involvee is not drawn).e triple bond, so the adduct retains a double bond at that location. This double bond could still serve as a dienophile, but in the present case the diene is sufficiently hindered to retard a second cycloaddition. The quinone dienophile in reaction F has two dienophilic double bonds. However, the double bond with two methyl substituents is less reactive than the unsubstituted dienophile due in part to the electron donating properties of the methyl groups and in part to steric hindrance. The stereospecificity of the Diels-Alder reaction is demonstrated by examples A, E & H. In A & H the stereogenic centers lie on the dienophile, whereas in E these centers are on the diene. In all cases the configuration of the reactant is preserved in the adduct.

Cyclic dienes, such as those in examples B, C & G, give bridged bicyclic adducts for which an additional configurational feature must be designated. As shown in the following diagram, there are two possible configurations for compounds of this kind. If a substituent (colored magenta here) is oriented cis to the longest or more unsaturated bridge (colored blue here), it is said to be endo. When directed trans to the bridge it is exo. When the Diels-Alder reaction forms bridged bicyclic adducts and an unsaturated substituent is located on this bicyclic structure (as in B & G), the chief product is normally the endo isomer "Alder's Endo Rule". Example C does not merit such a nomenclature, since stereoisomeric orientations of the substituent are not possible.

Additional information about the Diels-Alder reaction may be reached by Clicking Here.

The chemistry of cumulated dienes, Allenes, is somewhat specialized and will not be described here.
The interested reader may pursue this subject a bit further by Clicking Here.

Practice Problems

The following problems concern reactions of dienes. The first question requires you to draw the products of 1,2- & 1,4-addition to some conjugated dienes. The second and third questions asks you to evaluate potential dienes and dienophile reactants in Diels-Alder reactions. For the fourth question you are asked to draw the products expected from some Diels-Alder reactions. The fifth question is similar, but asks you to draw the reactants that will give a specified Diels-Alder adduct. Finally, the sixth question provides a comprehensive test of Diels-Alder reactions.

Benzene and Other Aromatic Compounds

The adjective "aromatic" is used by organic chemists in a rather different way than it is normally applied. It has its origin in the observation that certain natural substances, such as cinnamon bark, wintergreen leaves, vanilla beans and anise seeds, contained fragrant compounds having common but unexpected properties. Cinnamon bark, for example, yielded a pleasant smelling compound, formula C9H8O, named cinnamaldehyde. Because of the low hydrogen to carbon ratio in this and other aromatic compounds (note that the H:C ratio in an alkane is >2), chemists expected their structural formulas would contain a large number of double or triple bonds. Since double bonds are easily cleaved by oxidative reagents such as potassium permanganate or ozone, and rapidly add bromine and chlorine, these reactions were applied to these aromatic compounds. Surprisingly, products that appeared to retain many of the double bonds were obtained, and these compounds exhibited a high degree of chemical stability compared with known alkenes and cycloalkenes (aliphatic compounds). On treatment with hot permanganate solution, cinnamaldehyde gave a stable, crystalline C7H6O2 compound, now called benzoic acid. The H:C ratio in benzoic acid is <1, again suggesting the presence of several double bonds. Benzoic acid was eventually converted to the stable hydrocarbon benzene, C6H6, which also proved unreacive to common double bond transformations, as shown below. For comparison, reactions of cyclohexene, a typical alkene, with these reagents are also shown (green box). As experimental evidence for a wide assortment of compounds was acquired, those incorporating this exceptionally stable six-carbon core came to be called "aromatic".

If benzene is forced to react by increasing the temperature and/or by addition of a catalyst, It undergoes substitution reactions rather than the addition reactions that are typical of alkenes. This further confirms the previous indication that the six-carbon benzene core is unusually stable to chemical modification. The conceptual contradiction presented by a high degree of unsaturation (low H:C ratio) and high chemical stability for benzene and related compounds remained an unsolved puzzle for many years. Eventually, the presently accepted structure of a regular-hexagonal, planar ring of carbons was adopted, and the exceptional thermodynamic and chemical stability of this system was attributed to resonance stabilization of a conjugated cyclic triene.


Here, two structurally and energetically equivalent electronic structures for a stable compound are written, but no single structure provides an accurate or even an adequate representation of the true molecule. The six-membered ring in benzene is a perfect hexagon (all carbon-carbon bonds have an identical length of 1.40 Å). The cyclohexatriene contributors would be expected to show alternating bond lengths, the double bonds being shorter (1.34 Å) than the single bonds (1.54 Å). An alternative representation for benzene (circle within a hexagon) emphasizes the pi-electron delocalization in this molecule, and has the advantage of being a single diagram. In cases such as these, the electron delocalization described by resonance enhances the stability of the molecules, and compounds composed of such molecules often show exceptional stability and related properties.

      1. Electrophilic Substitution Reactions
Many substitution reactions of benzene have been observed, the five most useful are listed below (chlorination and bromination are the most common halogenation reactions). Since the reagents and conditions employed in these reactions are electrophilic, these reactions are commonly referred to as Electrophilic Aromatic Substitution. The catalysts and co-reagents serve to generate the strong electrophilic species needed to effect the initial step of the substitution. The specific electrophile believed to function in each type of reaction is listed in the right hand column. A full treatment of these important reactions will be offered in a forthcoming chapter.

Reaction TypeTypical EquationElectrophile   E(+)
Halogenation: C6H6+   Cl2 & heat
    FeCl3 catalyst
  ——>  C6H5Cl   +   HCl
Cl(+) or Br(+)
Nitration: C6H6+   HNO3 & heat
    H2SO4 catalyst
  ——>  C6H5NO2   +   H2O
Sulfonation: C6H6+   H2SO4 + SO3
    & heat
  ——>  C6H5SO3H   +   H2O
Benzenesulfonic acid
C6H6+   R-Cl & heat
    AlCl3 catalyst
  ——>  C6H5-R   +   HCl
An Arene
C6H6+   RCOCl & heat
    AlCl3 catalyst
  ——>  C6H5COR   +   HCl
An Aryl Ketone

      2. Thermodynamic Stability of Benzene
Evidence for the enhanced thermodynamic stability of benzene was obtained from measurements of the heat released when double bonds in a six-carbon ring are hydrogenated (hydrogen is added catalytically) to give cyclohexane as a common product. In the following diagram cyclohexane represents a low-energy reference point. Addition of hydrogen to cyclohexene produces cyclohexane and releases heat amounting to 28.6 kcal per mole. If we take this value to represent the energy cost of introducing one double bond into a six-carbon ring, we would expect a cyclohexadiene to release 57.2 kcal per mole on complete hydrogenation, and 1,3,5-cyclohexatriene to release 85.8 kcal per mole. These heats of hydrogenation would reflect the relative thermodynamic stability of the compounds. In practice, 1,3-cyclohexadiene is slightly more stable than expected, by about 2 kcal, presumably due to conjugation of the double bonds. Benzene, however, is an extraordinary 36 kcal/mole more stable than expected. This sort of stability enhancement is now accepted as a characteristic of all aromatic compounds.

      3. Molecular Orbitals
A molecular orbital description of benzene leads to a general treatment of "aromaticity", which has proven more satisfying than the resonance model. We know that benzene has a planar hexagonal structure in which all the carbon atoms are sp2 hybridized, and all the carbon-carbon bonds are equal in length. As shown below, the remaining cyclic array of six p-orbitals ( one on each carbon) overlap to generate six molecular orbitals, three bonding and three antibonding. The plus and minus signs shown in the diagram do not represent electrostatic charge, but refer to phase signs in the equations that describe these orbitals (in the diagram the phases are also color coded). When the phases correspond, the orbitals overlap to generate a common region of like phase, with those orbitals having the greatest overlap (e.g. π1) being lowest in energy. The remaining carbon valence electrons then occupy these molecular orbitals in pairs, resulting in a fully occupied (6 electrons) set of bonding molecular orbitals. It is this completely filled set of bonding orbitals, or closed shell, that gives the benzene ring its thermodynamic and chemical stability, just as a filled valence shell octet confers stability on the inert gases.

The Molecular Orbitals of Benzene
To examine a model of the p-orbital components of these benzene orbitals.   Click Here
To examine the benzene pi-molecular orbitals   Click Here

      4. Nomenclature of Benzene Derivatives
The nomenclature of substituted benzene ring compounds is less systematic than that of the alkanes, alkenes and alkynes. A few mono-substituted compounds are named by using a group name as a prefix to "benzene", as shown by the combined names listed below. A majority of these compounds, however, are referred to by singular names that are unique. There is no simple alternative to memorization in mastering these names.

Two commonly encountered substituent groups that incorporate a benzene ring are phenyl, abbreviated Ph-, and benzyl, abbreviated Bn-. These are shown here with examples of their use. Be careful not to confuse a phenyl (pronounced fenyl) group with the compound phenol (pronounced feenol). A general and useful generic notation that complements the use of R- for an alkyl group is Ar- for an aryl group (any aromatic ring).

When more than one substituent is present on a benzene ring, the relative locations of the substituents must be designated by numbering the ring carbons or by some other notation. In the case of disubstituted benzenes, the prefixes ortho, meta & para are commonly used to indicate a 1,2- or 1,3- or 1,4- relationship respectively. In the following examples, the first row of compounds show this usage in red. Some disubstituted toluenes have singular names (e.g. xylene, cresol & toluidine) and their isomers are normally designated by the ortho, meta or para prefix. A few disubstituted benzenes have singular names given to specific isomers (e.g. salicylic acid & resorcinol). Finally, if there are three or more substituent groups, the ring is numbered in such a way as to assign the substituents the lowest possible numbers, as illustrated by the last row of examples. The substituents are listed alphabetically in the final name. If the substitution is symmetrical (third example from the left) the numbering corresponds to the alphabetical order.

      5. Fused Benzene Ring Compounds
Benzene rings may be joined together (fused) to give larger polycyclic aromatic compounds. A few examples are drawn below, together with the approved numbering scheme for substituted derivatives. The peripheral carbon atoms (numbered in all but the last three examples) are all bonded to hydrogen atoms. The six benzene rings in coronene are fused in a planar ring; whereas the six rings in hexahelicene are not joined in a larger ring, but assume a helical turn, due to the crowding together of the terminal ring atoms. This helical configuration renders the hexihelicene molecule chiral, and it has been resolved into stable enantiomers having very high specific rotations (ca. 3700º). Models of corannulene, coronene and hexahelicene may be examined by clicking on the appropriate structure in the diagram.

As these extended aromatic compounds become larger, the ratio of hydrogen to carbon decreases. For example, the symmetrical hexacyclic compound coronene has a H/C ratio =1/2, compared with 1 for benzene. If we were to imagine fused ring systems of this kind to be further extended in space, the H/C ratio would approach zero, and the resulting compound would be a form of carbon. Such a carbon allotrope exists and is called graphite. Another well-characterised carbon allotrope is diamond. The structures for these two forms of carbon are very different, and are displayed below. Diamond is an extended array of sp3 hybridized carbon atoms; whereas, graphite consists of overlapping sheets of sp2 hybridized carbon atoms arranged in a hexagonal pattern. You may examine models of partial diamond and graphite structures by clicking on the appropriate structure below.

Diamond  Graphite

A comparison of the coronene and corannulene models discloses an interesting difference in their shapes. Coronene is absolutely flat and, aside from the peripheral hydrogens, resembles a layer of graphite. Its very high melting point reflects this resemblance. Corannulene, on the other hand, is slightly curved, resulting in a bowl-like shape.

If we extend the structure of corannulene by adding similar cycles of five benzene rings, the curvature of the resulting molecule should increase, and eventually close into a sphere of carbon atoms. The archtypical compound of this kind (C60) has been named buckminsterfullerene because of its resemblance to the geodesic structures created by Buckminster Fuller. It is a member of a family of similar carbon structures that are called fullerenes. These materials represent a third class of carbon allotropes. Alternating views of the C60 fullerene structure are shown on the right, together with a soccer ball-like representation of the 12 five and 20 six-membered rings composing its surface. By clicking on this graphic, a model of C60 will be displayed.
Although C60 is composed of fused benzene rings its chemical reactivity resembles that of the cycloalkenes more than benzene. Indeed, exposure to light and oxygen slowly degrade fullerenes to cage opened products. Most of the reactions thus far reported for C60 involve addition to, rather than substitution of, the core structure. These reactions include hydrogenation, bromination and hydroxylation. Strain introduced by the curvature of the surface may be responsible for the enhanced reactivity of C60.
. Larger fullerenes, such as C70, C76, C82 & C84have elipsoidal or distorted spherical structures, and fullerene-like assemblies up to C240 have been detected. A fascinating aspect of these structures is that the space within the carbon cage may hold atoms, ions or small molecules. Such species are called endohedral fullerenes. The cavity of C60 is relatively small, but encapsulated helium, lithium and atomic nitrogen compounds have been observed. Larger fullerenes are found to encapsulate lanthanide metal atoms.

Interest in the fullerenes has led to the discovery of a related group of carbon structures referred to as nanotubes. As shown in the following illustration, nanotubes may be viewed as rolled up segments of graphite. The chief structural components are six-membered rings, but changes in tube diameter, branching into side tubes and the capping of tube ends is accomplished by fusion with five and seven-membered rings. Many interesting applications of these unusual structures have been proposed.

      6. Other Aromatic Systems
Many unsaturated cyclic compounds have exceptional properties that we now consider characteristic of "aromatic" systems. The following cases are illustrative:

with Br2
1,3-CyclopentadieneAddition ( 0 ºC )Slight
1,3,5-CycloheptatrieneAddition ( 0 ºC )Slight
1,3,5,7-CyclooctatetraeneAddition ( 0 ºC )Slight
FuranSubstitution ( 0 ºC )Moderate

The first three compounds (cyclic polyenes) have properties associated with alkenes in general. Each reacts readily with bromine to give addition products, as do most alkenes. The thermodynamic change on introducing double bonds into the carbon atom ring is also typical of alkenes (a destabilization of ca. 26 kcal/mol for each double bond). Conjugation offsets this increase in energy by a small amount (4-6 kcal/mol).
The remaining four compounds exhibit very different properties, and are considered aromatic. Benzene and pyridine are relatively unreactive with bromine, requiring heat and/or catalysts to force reaction, the result of which is substitution rather than addition. Furan and pyrrole react more rapidly with bromine, but they also give substitution products. This tendency to favor substitution rather than addition suggests that the parent unsaturated ring system has exceptional stability. Thermodynamic measurements support this conclusion. The enhanced stability, often referred to as aromatic stabilization, ranges (in the above cases) from a low of 16 kcal/mol for furan to 36 kcal/mol for benzene.

      7. Factors Required for Aromaticity

1,3-Cyclopentadiene and 1,3,5-cycloheptatriene both fail to meet the first requirement, since one carbon atom of each ring is sp3 hybridized and has no p-orbital. Cyclooctatetraene fails both requirements, although it has a ring of sp2 hybridized atoms. This molecule is not planar ( a geometry that would have 135º bond angles ). Angle strain is relieved by adopting a tub-shaped conformation; consequently, the p-orbitals can only overlap as isolated pairs, not over the entire ring. Furthermore, cyclooctatetraene has 8 π-electrons, a number not consistent with the Hückel Rule.
Benzene is the archetypical aromatic compound. It is planar, bond angles=120º, all carbon atoms in the ring are sp2 hybridized, and the pi-orbitals are occupied by 6 electrons. The aromatic heterocycle pyridine is similar to benzene, and is often used as a weak base for scavanging protons. Furan and pyrrole have heterocyclic five-membered rings, in which the heteroatom has at least one pair of non-bonding valence shell electrons. By hybridizing this heteroatom to a sp2 state, a p-orbital occupied by a pair of electrons and oriented parallel to the carbon p-orbitals is created. The resulting planar ring meets the first requirement for aromaticity, and the π-system is occupied by 6 electrons, 4 from the two double bonds and 2 from the heteroatom, thus satisfying the Hückel Rule.

Four illustrative examples of aromatic compounds are shown above. The sp2 hybridized ring atoms are connected by brown bonds, the π-electron pairs and bonds that constitute the aromatic ring are colored blue. Electron pairs that are not part of the aromatic π-electron system are black. The first example is azulene, a blue-colored 10 π-electron aromatic hydrocarbon isomeric with naphthalene. The second and third compounds are heterocycles having aromatic properties. Pyridine has a benzene-like six-membered ring incorporating one nitrogen atom. The non-bonding electron pair on the nitrogen is not part of the aromatic π-electron sextet, and may bond to a proton or other electrophile without disrupting the aromatic system. In the case of thiophene, a sulfur analog of furan, one of the sulfur electron pairs (colored blue) participates in the aromatic ring π-electron conjugation. The last compound is imidazole, a heterocycle having two nitrogen atoms. Note that only one of the nitrogen non-bonding electron pairs is used for the aromatic π-electron sextet. The other electron pair (colored black) behaves similarly to the electron pair in pyridine.

      8. Annulenes
Monocyclic compounds made up of alternating conjugated double bonds are called annulenes. Benzene and 1,3,5,7-cyclooctatetraene are examples of annulenes; they are named [6]annulene and [8]annulene respectively, according to a general nomenclature system in which the number of pi-electrons in an annulene is designated by a number in brackets. Some annulenes are aromatic (e.g. benzene), but many are not due to non-planarity or a failure to satisfy the Hückel Rule. Compounds classified as [10]annulenes (a Hückel Rule system) serve to illustrate these factors.
As shown in the following diagram, 1,3,5,7,9-cyclodecapentaene fails to adopt a planar conformation, either in the all cis-configuration (severe angle strain) or in its 1,5-trans-isomeric form. The transannular hydrogen crowding that destabilizes the latter may be eliminated by replacing the interior hydrogens with a bond or a short bridge (colored magenta in the drawing on the right). As expected, the resulting 10 π-electron annulene derivatives exhibit aromatic stability and reactivity when compared to the monocyclic compounds. Thus, naphthalene and azulene are [10]annulene analogs stabilized by a transannular bond. Although the CH2 bridged structure to the right of naphthalene in the diagram is not exactly planar, the conjugated 10 π-electron ring is sufficiently close to planarity to achieve aromatic stabilization.
As the number of π-electrons in a [4n+2]annulene increases, the characteristic stability and reactivity that was found for benzene diminishes. Fortunately, 1Hnmr spectroscopy offers an alternative criterion for judging the aromaticity of such compounds. Planar 4n+2 π-electron annulene-like compounds exhibit a π-electron ring current anisotropy that shifts the location of ring hydrogens in a predictable manner. The bridged [14]annulene compound on the far right is found to be aromatic by this measure.

To learn more about magnetic anisotropy and its application in 1Hnmr as a test for aromaticity Click Here.

A [10]annulene, aromatic by nmr criteria, was prepared recently by chemists at California Institute of Technology.
This hydrocarbon proved to be remarkably unstable, in contrast to most other aromatic hydrocarbons.
To learn more Click Here.


      9. Aromatic Ions
Carbanions and carbocations may also show aromatic stabilization. Some examples are:

The three-membered ring cation has 2 π-electrons and is surprisingly stable, considering its ring strain. Cyclopentadiene is as acidic as ethanol, reflecting the stability of its 6 π-electron conjugate base. Salts of cycloheptatrienyl cation (tropylium ion) are stable in water solution, again reflecting the stability of this 6 π-electron cation.

      10. Antiaromaticity
Conjugated ring systems having 4n π-electrons (e.g. 4, 8, 12 etc. electrons) not only fail to show any aromatic properties, but appear to be less stable and more reactive than expected. As noted above, 1,3,5,7-cyclooctatetraene is non-planar and adopts a tub-shaped conformation. The compound is readily prepared, and undergoes addition reactions typical of alkenes. Catalytic hydrogenation of this tetraene produces cyclooctane. Planar bridged annulenes having 4n π-electrons have proven to be relatively unstable. Examples of 8 and 12-π-electron systems are shown below, together with a similar 10 π-electron aromatic compound.

The simple C8H6 hydrocarbon pentalene does not exist as a stable compound, and its hexaphenyl derivative is air sensitive. The 12-π-electron analog heptalene has been prepared, but is also extremely reactive (more so than cyclooctatetraene). On the other hand, azulene is a stable 10-π-electron hydrocarbon that incorporates structural features of both pentalene and heptalene. Azuleneis a stable blue crystalline solid that undergoes a number of typical aromatic substitution reactions. The unexpected instability of 4n π-electron annulenes has been termed "antiaromaticity".
Other examples may be cited. Thus, all attempts to isolate 1,3-cyclobutadiene have yielded its dimer, or products from reactions with other compounds introduced into the reaction system. Similarly, cyclopentadienyl cation (4 π-electrons) and cycloheptatrienyl anion (8 π-electrons) show very high reactivity when forced to form.

Cyclooctatetraene is a fascinating compound. To see more of its chemistry Click Here.


Practice Problems

Four problems concerning the identification and naming of aromatic compounds are offered.


Return to Table of Contents