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a) Development of the theory of the Benzene Structure:
In 1825 Faraday isolated benzene from coal gas. In 1834 Mitscherlich obtained
it by distilling benzoic acid with lime. These investigators could not know that their
substance was to become recognized as the parent of by far the largest series of organic
chemical compounds. The rapid extension which this branch of chemistry underwent in
later decades was dependent on the success in the first steps taken to develop a theory
of the structure of benzene.
In the early 1860's organic chemistry was emerging from the type theory Through the
efforts of Frankland, Williamson, Kekule, and others, the rules of valency, and of
formulation of structures, had been made clear, largely by reference to compounds of
the aliphatic series. However, there also existed a group of "aromatic" substances, not
yet very numerous, which in composition and behaviour differed from aliphatic
compounds, and seemed to form a notable exception to the rules of structure, and of
valency. In 1865, Kekule showed how this anomaly might be removed, pointing out
that aromatic compounds could be brought within the established rules, if it were
assumed that all contained a common "nucleus" of six carbon atoms. He then proceeded
to develop his hypothesis that the atoms formed a ring of alternate single and double
bonds, leaving each atom with one unit of combining power. He believed, though he
admitted that he could not prove, that the six combining positions were equivalent.

The next few decades were characterized by intense activity in the building of the main
frame of aromatic chemistry.

By 1874 Ladenburg had completed a proof of Kekule's

postulate of six-fold equivalence: The demonstration was improved and simplified in
1878 by Wroblew- sky, and in 1879 by Hubner.
Wroblewky's demonstration still ranks as one of the best examples of the method
and logic of organic-chemical structure-determination, He prepared the five then
conceivable mono bromobenzoic acids in order to see how many of them were different.
The starting point for all preparations was p-toluidine, whose methyl group marked the
position of the final carboxyl group. The principle of the method was to introduce
bromine, either directly or by way of a nitro-group, and then to use the bromine, or the
nitro-group, or a conversion product of the latter, such as an amino-group or iodine, in
order to block the position or positions occupied, while bromine, or a substituent that
could be converted to bromine, was introduced elsewhere in the molecule, all blocking
groups being afterwards replaced by hydrogen. First one position, then this and a
second, then these two and a third, and finally, these three and a fourth, were thus
blocked. The five final products contained two identical pairs. Ladenburg had already
shown that such a demonstration of the presence of two pairs of positions equivalent for
a second substituent, could be used to complete a proof of the equivalence of all six
positions for a first substituent. For the three hydroxyl benzoic acids gave the same
phenol on decarboxylation and the same benzoic acid by reduction, and the phenol

could be converted, by way of bromobenzene, into the benzoic acid. This showed that
four positions were equivalent for a first substituent. And now it was known that two
of the hydroxybenzoic acids had this property namely, that each contained its hydroxyl
group in one of a pair of equivalent positions.

Since equivalence for a second

substituent must be preserved when the first is specialized to hydrogen, so that what
was the second substituent becomes the first, this result showed that the fifth and sixth
positions in benzene were each equivalent to any of the first four. In the same period,
the problem of determining the relative positions of substituents was solved in principle.
At first there was great confusion. Then Kekule proposed that all compounds
whose substituents were considered to be in the same relative positions as those of a
standard "ortho-compound" should be called "ortho-," and similarly for other such
Originally the designations were used without any accepted implication as to the
positional relations to which they corresponded. When later it was found that most
compounds which had been classified as ortho- had their substituents in 1,2-positions,
the prefix "ortho-" was reserved for 1,2-compounds, and similarly for the other prefixes.
The proposed principle of classification was simple.

Fixed standards had first to be

secured; and this could be done in a limited number of favorable cases.
Thus, Graebe in 1869 deduced the formula of naphthalene and therefrom that phthalic
acid is a 1,2-derivative of benzene that those substituted benzenes whose sub-

substituents genetically connected with the carboxyl groups of phthalic acid are 1,2derives compounds.

But though the principle was simple. It worked properly. The

reason was that some of the reactions which were used to establish genetic connection
, notably hydroxylation’s by treatments of sulphonic acids with alkali, and cyanisations
by the reaction of halogeno-nitro-compounds with alkali cyanides, frequently involved
rearrangements: (for reasons which are even now not fully understood): such
disturbances were at the outset difficult to recognize and locate. Then, in 1874, a secure
basis for the orientation of substituents in benzene compounds was offered by Griess,
Salkowsky, and Koyrner

independently. It involved demonstrating relations, not

between one substituted benzene and another, but between di- and-tri substituted

Thus, of the six known diaminobenzoic acids, two on decarboxylation

gave one diaminobenzene, while three gave another, and the remaining acid the third;
and therefore, the first diaminobenzene had to be ortho-, the second meta-, and the third
In studying such relations one was not at the mercy of un recognized rearrangements.
Subsequent work on the orientation of substituents in benzene derivatives has been
based on this method.
Thus the two problems, of symmetry, and of orientation, were solved in the first decade
after the publication of Kekule's fundamental paper. In the same period the attack was
opened on the much greater problem, one which was to occupy chemists for many years

afterwards, namely, that of the actual disposition and function of the six carbon
valencies of benzene, which are not required to maintain the ring or to hold the hydrogen
Kekule's assignment, in 1865, of the six valences to three double bonds was provisional:
for the symmetry question was then unsettled. In 1872, Kekule issued a supplementary
hypothesis to the effect that an oscillation occurred between the two possible
arrangements of double bonds.

His reason was that, as Ladenburg had already pointed out, the original formula
admitted unrealized possibilities of isomerism in benzene derivatives. It soon became
clear that the additional symmetry introduced by the oscillation hypothesis was
demanded by the observed extent of isomerism.
Subsequently to the original theory, but before its emendation, two other attempts were
made to represent the symmetry that seemed to be indicated by the observed isomerism.
One is expressed in the prism formula for benzene (below), first seriously advocated in
1869 BY Ladenburg. This formula requires the correct numbers of all the Different kinds
of substitution products. But the symmetry properties of the combining positions are

3-. .5-dihydroxyterephthalate. while meta.4. and one compound. and -1. One result of this was an exceedingly awkward formula for naphthalene.derivatives. -1. meta-positions (2 trios) at the corners of triangular faces. ethyl succinosuccinate. and para-benzene compounds gave cyclohexane-1. In 1886 Baeyer commenced a series of experimental researches designed to determine the arrangement of the valencies of benzene. and para-positions (3 pairs) at the ends of longitudinal edges.and also para. and to determine the constitutions of the reduction products by the standard methods of aliphatic chemistry. in contrast to the bonding arrangements in the simple ring structure.2-. in which all three pairs of para-positions are labelled. Thus. his method being to reduce benzene derivatives to cyclohexadiene. For ortho-. gave a reduction product. positions are directly bound. meta-. This work disproved the prism structure. in the prism structure. respectively. ortho-positions are not directly bound.such that these positions have to be correlated with those of a simple ring formula as indicated by the numbering: Ortho-positions (6 pairs) are at the ends of face-diagonals. cyclo-hexene. ethyl 2. or cyclohexane compounds.

without much regards for any metrical properties the molecules might possess). in 1882 Claus suggested that the para-bonds should be regarded as radically differ from all other bonds. (The difficulty of arranging for this in Euclidian space was not seriously felt at a time when formulae were considered essentially as symbols of chemical relationships. a difficulty insoluble in terms of already established concepts. by the use of a special symbol.having all substituents where they would be expected if benzene had the simple ring structure.and ortho – bonds to have identical properties. But. Especially the new view was represented more explicitly in the modified symbol known as the centric formula: . thus taking the first step in admitting. first advanced in 1867 by Claus. Originally clause assumed that the para. The other early formula of the requisite symmetry was the diagonal formula. so that each carbon atom was bound to three others in exactly the same way.

Originally. the centric formula expresses by the symmetry of the benzene. and was finally accepted Claus as a suitable expression of his ideas. Quite the most advanced of the early attempts to interpret aromatic . he argued. it is what we should say today. while pyrrole could do so only by making use of all its nitrogen valencies. one could understand why pyridine has the basic properties of the tertiary amines. Since. He attempted to correlate stability in different aromatic types by means of the assumption that the six-fold character of the centric valency group was the essential factor of stability. in 1982 Bamberger used it in a discussion of stability. but was agnostic with respect to all other properties.It was first used by Armstrong. was at once adopted by Baeyer as the best symbolic representation of his results. while pyrrole was practically non-basic: As far as it goes this is completely correct: reading electrons valencies. However. pyridine could form a sextuple valency group without employing the salt forming valencies of its nitrogen atom.

where un-neutralized free affinity was available. while still satisfying the symmetry condition. Through a general study of unsaturation. the possibilities of division could lead to what he called "conjugation" between the double bonds. there can be but little additive reactivity. so that the main opportunities for reaction appeared at the ends of the chain. so that all ring bonds became equivalent: . that is. Then he pointed out that in Kekule's benzene structure the conjugation is cyclic: there being no ends. The symmetry condition was fulfilled by starting with either of Kekule's oscillating structures. a more even spread of affinity over the double bonds and intervening single bonds.saturated systems in the aliphatic series. he had been led to assume the reactive valencies of double bonds to be in principle continuously divisible. and allowing the affinity redistribution to proceed equally to coincidence. and he had shown how in a chain of alternate single and double bonds. was that made in 1898 by Thiele.stability. Thus he interpreted terminal addition to conjugated un. and to exist in most circumstances partly bound and partly in the free state.

Thiele's formula expresses the symmetry. as a possibility. or ortho-quinonoid. At a very early date Dewar had proposed. and interprets the stability. of course. The main general characteristics of aromatic systems with which a structural theory should be concerned are its symmetry. produce either addition products. or para-quinonoid. In 1922 the writer revived it. interpreting the para-bond as qualitatively . the bridged formula of benzene: as a static formula. and all such conversions are more easily understood in terms of Kekule's formula than of the others. indicates appeal to Kekule's formula. Transformations which destroy the aromatic system. its stability. derivatives. it was quite unacceptable. Thus it came about that the last of the pre . and its transformations. The centric formula expresses the symmetry. in association with his dynamic hypothesis in order to satisfy the symmetry requirements. lacking the necessary symmetry. But any consideration of the modes in which benzenoid systems are disrupted. and is not inconsistent with the stability.The outstanding merit of this theory was that it dealt with aromatic stability on the basis of concepts developed outside the aromatic series.electronic attempts to make a theory of benzene structure took the form of an expansion of Kekule's dynamic hypothesis. without opening the ring.

. This was the apparent cul de sac to which classical chemical considerations led: the symmetry condition could be fulfilled in various ways. However. except through the undeveloped idea that the inter conversion of forms might be rapid enough to restrict reaction in any one form. historically. but no one way satisfactorily interpreted both the stability and the transformations. in a more complex dynamical system: The argument focused attention on the transformations of the aromatic system. they ended in different places. According to which of these characteristics was taken as guide. and. A decade after the promulgation of the latter. either of two roads would be followed. showing that the two theories could be considered to represent complementary aspects or appearances of the same interior physical situation. the other in the expanded dynamic hypothesis. the stability problem was not dealt with. the main object of including the two types of structure being to permit parallel interpretations of ortho.comparable to the reactive component of a double bond. and he proposed to incorporate Dewar's formula with Kekule's. the one in Thiele's theory.and para-quinonoid conversions. each with the orientations (two or three) needed to fulfil symmetry condition. the electronic theory of chemical binding brought about the reconciliation that had seemed invisibly distant.

The mesomerism of benzene was first discussed explicitly and in detail by E. Huckel in 1931-32. Fig: Charge Distributing of 𝝅 electron shell in benzene . and for that reason is not very simply correlated with valency concepts. known as the molecular orbital method. had been invented by Lennard-Jones somewhat earlier. but now as mere headings. to the discovery of the electronic theory of valency (1916). of the physical nature of covalency (1927). One of them. and of its interpretation by an extension of that of covalency (1929).b) Mesomerism in the Benzenoid Nucleus: Only for the sake of continuity of narrative do we refer again. He applied to the problem two approximate formalisms. and it has been much developed by Mulliken and others since. of mesomerism as a general phenomenon (1926). This treatment characteristically under-emphasizes the covalent nature of binding in molecules.

Huckel. In setting up the problem. with single σ bonds. It is easily shown that the plane of the atomic nuclei is a nodal plane for all the π electrons. over-emphasizing the covalent character of the binding. The technique of this method was simplified by Pauling and Wheland. is known as the valencybond treatment. The answer depends on the assumptions made about the extra motion permitted to these electrons. It goes to the other extreme. which together must produce a charge-density distribution having total hexagonal symmetry. to form a molecular group of six π electrons. as in a Kekule formula. which Huckel himself invented. having its symmetry axis at right angles to the molecular plane. that is.The second method. The remaining electrons are left to hold. The common object of these techniques is to compute the mesomeric energy or aromatic resonance energy. and likewise Pauling and Wheland assumed that each carbon atom of benzene supplies one electron in an atomic p orbital. the regular hexagonal frame of six CH carbonium-ionic centers. as illustrated in Figure. . it appears particularly easily in the role of an interpretation of valency concepts. Each π electron is then considered as moving in the combined potential field of the framework and the smoothed-out field of the remaining π electrons. for that very reason. and. the extra stability that arises from not confining the electrons to three static double bonds. who applied it to benzene and other aromatic hydrocarbons.

never belonging. One might feel surprised that such a calculation gives a sensible result. Pauli's principle. In considering this comparison. interaction between the π electrons is neglected during the computation of the orbitals available to any one such electrons as it moves among the atoms in the total molecular field: only afterwards is Pauli's principle introduced. the electrons being assigned in pairs to the more stable of the orbitals thus computed: and at no stage is the simplest treatment is π electron interaction allowed for.00 β. 5. If β is given the value 20 kcal. or in Pauling and Wheland's treatment. in Huckel's.32 β. The calculated energies for benzene. But the calculated energies are derived in terms of an unevaluated energy-quantity. These coefficients are approximately in the right ratios. 3. and 5. In the valency-bond method. are 2. anthracene. to fewer than two atoms. called β: in principle. are introduced from the outset. it must be remembered that what are called "observed" mesomeric energies themselves involve interpretative factors of an arbitrary nature.In the molecular orbital treatment. naphthalene. β is a disposable constant. and electron interaction. and phenanthrene.45 β. into which much of the error of method can be absorbed by choosing it to give the best possible fit with empirical data. β represents the energy effect of allowing one atomic p electron to spread its motion into one adjacent p orbital: in practice.68 β./mole. The electrons are assumed to remain as three spin-coupled pairs. the comparison with thermo chemically determined mesomeric energies works out as shown in Table. . respectively.

It was found necessary to include not only the Kekule but also the Dewar structures. but that the latter are not negligible. in defining the limits of mobility of the mobile bonds: no other structures are involved. But they are mobile bonds. anthracene. are 1. always changing among the positions between which they were assumed to move in the earlier dynamical representations of benzene. The calculated energies for benzene. chosen to give the best fit with experimental data. bonds having the internal energies and mutually repulsive interactions of two-electron bonds.1α. 3. in the composition of the mesomeric state. as in the formation of the π component of a static double bond. The mesomeric energy is expressed in terms of an energy quantity called α: in principle. The wave-function M of the normal mesomeric state is therefore constituted from those of Kekule and Dewar structures.They are. as is required by symmetry.625(K1 + K2) + 0.09 α. respectively. Pauling and Wheland's coefficients for them are as indicated in the following equation: M = 0. taken with two and three orientations.04 α. α represents the energy effect of allowing two adjacent atomic p electrons to undergo exchange. in practice α is a disposable constant. K and D. respectively. naphthalene. and 3. The Dewar structures contribute about 20% of the calculated mesomeric energy. indeed. and phenanthrene.15 α. because bonds cannot cross. 2.271 (A + D2 + D3) They show that the Kekule structures are more important than the Dewar structures. the last two values involving a minor .

A with 12 orientations. The coefficients have again approximately the right ratios. not only do the "calculated" values depend heavily on empirical data. but also the "observed" values depend in part on inter pretative assumption. (To calculate α non-empirically would be a heavy task. the more that are included. If α is chosen as 35 kcal./mole.O.algebraic approximation. P with . the better the results should be. method Constant (with β = 20) (with α = 35) Benzene 37 36 40 39 Naphthalene 75 - 74 71 Anthracene 105 - 106 108 Phenanthrene 110 - 109 110 The valency-bond method has since been considerably refined within its own framework. Observed Energy Calculated Hydrogenation M. There are two types of singly dipolar structures with adjacent charges. and B with 12 and three types with non-adjacent charges. we have the position that. method V.) What was inadequate in the earlier applications of the method was the specification of mesomerism exclusively in terms of fully covalent structures: and what is needed is the inclusion of dipolar structures: in general. though it has not yet proved possible to eliminate its dependence on a disposable constant.B. Again however.

and R with 6 orientations.6. to cite them in the probable order of diminishing importance: The work on the inclusion of such polar structures in the valency bond treatment was initiated by Sklar. Q with 24... but it suggests that higher approximations would shift the energy by only a few kcal. as well as doubly and trebly dipolar types. for the present any really close agreement with experiment must remain dependent on making the final result of calculation partly dependent on experiment. who has solved the problem. This shows that quite large un-certainties are involved in the treatment based on non-polar structures only. and has been developed by Craig. with inclusion. .03(B1 + B2+ .17(D1 + D2 + D3) + 0./mole below Pauling and Wheland's normal mesomeric state. B12) The energy is calculated to lie 17 kcal.. His wave-function for the normal mesomeric state is as follows: M = 0. of the twenty-four adjacentcharge structures A and B. besides the five non-polar structures K and D.39(K1 + K2) + 0.07(A1 + Az + . However./mole further.A12) + 0.

involves allowing for the circumstance that the interaction energy of the π electrons will change their motions. and has been of value in classifying some of its spectroscopically known. so that it is not correct to average it over motion assumed undisturbed. in as much as they constitute. excited electronic states. as calculated by simple molecular orbital theory. having assigned the electrons in pairs to the three lowest orbitals. The next step. in principle. The necessary energy terms were nonempirically evaluated by Sklar and Lyddane and Parr and Crawford. carried through by Craig. a technique for the non-empirical evaluation of the energies of π electron states. First. At the moment. and made the wave-functions totally antisymmetric to satisfy Pauli's principle fully. so satisfying Pauli's principle in the atoms. they allowed for the energy of mutual repulsion of the π electrons by averaging it over the orbitals. not entirely within its original framework. in ways which are theoretically interesting. into "antisymmetric" additive combinations.The molecular orbital method has been developed. The original steps were taken by Goeppert-Mayer and Sklar. Indeed. but the treatment of benzene does give a qualitatively satisfactory account of its energy levels. the numerical accuracy of the calculations is insufficient to give quantitative agreement with experimental values. but must be allowed to move . thereby placing the motion of the π electrons under the restriction that not more than two could be together in the same atom. Then. the π electron pairs have nob to be firmly assigned to three antisymmetrical orbitals. they formed the product wave-functions.

to think of those electron pairs as having immediately come from localized positions. namely. in a chemical transformation affecting an aromatic nucleus. we attach the curved-arrow signs to Kekule formulae. the electron pairs are regarded as largely localized. The component processes have to be considered as simultaneous and not successive like the bond-breaking and bond-forming processes in the bimolecular substitutions of . even though such formulae could not by themselves account for the stability of the nucleus. In principle this method. It will easily be understood why. which is described as allowing for "configuration interaction. Such a concept is possible if it is agreed to dissect the total transformation into two superposed processes. until the energy is minimized. gives molecular wave functions as good as any that could be formed by the initial use of only p atomic wavefunctions. why. or in the transition state of such a transformation. valency-bond formulae. changing the total electronic wave-function.among all the orbitals. for instance. and (b) a chemical reaction on ordinary lines involving the valency structure. particularly those of the relatively stable Kekule structures." and was first developed in its molecular applications by Craig. as in every resonance problem. retain their usefulness for the interpretation of the transformations of the aromatic nucleus. If. despite the mesomerism of the aromatic nucleus. (a) an excitation of the normal mesomeric state into a valency structure. then it is convenient. for the purpose of following the reaction mechanism.

26 D in pyridine. breaks up the mesomeric system will be increased by the mesomerism. and their transformations. or those properties. But the activation energy of any process which permanently. the negative sign meaning that. however. or temporarily. -2. Thus does the theory of mesomerism fulfil the three main requirements in the problem of aromatic nuclei. their stability. and of the effects of carbon chain extension. On the basis of our analysis of the dipole moments of simple alkylamines. as one should expect. namely.0D would be expected to arise from the effect of the electronegativity . even if not by the full amount of the mesomeric energy. The theory of benzene provides a basis for modification to give a qualitative pattern for that of pyridine. the electrons have concentrated towards the electronegative nitrogen atom.saturated compounds. which arise primarily from π electron delocalization. The hetero-atom does. and exaltation of diamagnetic susceptibility. chiefly the mesomeric energy. Observation shows that the introduction of the hetero-atom does not much change the size and shape of the molecule. so that the whole of the energy of mesomerism has not to be supplied. created by the hetero-atom. create a dipole moment. for new but unknown energy integrals. before process (b) can commence. a moment of only about —1. But the possibilities of a satisfactory quantitative calculation of the energy states of pyridine are very much reduced by the need. to interpret their symmetry. in order to complete process (a).

which in isoquinoline acts appreciably on the electrons of the more remote ring. We are thus led to assume that a moment of —1.73 D. several times more than the average from the σ electrons.of the nitrogen atom on the σ bond electrons in pyridine. and isoquinoline -2. These moments are also due to the electronegativity of the nitrogen atom.29 D. .04 A. an average displacement of 0. Quinoline has a moment of -2.2 D arises from a displacement of the electrons of the π shell.

there are three Kekule-like formulae for naphthalene. the pi electron problem loses much of its symmetry. and becomes very much more complicated. but. these last (B1. If we do this.and B-type Kekule structures in the mixed wavefunction.c) Condensed Poly Cyclic Benzenoid System: On passing from benzene to naphthalene. and is greater than that of the other bonds. Corresponding to the two Kekule formulae for benzene. one with a center of symmetry (A). it is an insignificant further step to take these weights as equal the interesting conclusion then follows that the multiplicity of the l. and two without. all of which have the multiplicity 4/3: . 2bonds of naphthalene is 5/3. The whole system is so complicated that one is tempted to see whether any useful considerations can be set down after simplification on very drastic lines. B2) being identical but for orientation: There are also 39 non-polar structures with trans-annular bonds. and many more polar structures. in spite of their large numbers. The most drastic approximation that one can make is to neglect the bridged and polar structures completely. there still remains the problem of weighting the A. after what has been done.

just as 1.4-diphenylbutadiene. and the two added hydrogen atoms appear in the 1. These conclusions bring to mind much general chemical experience 2-Naphthol halogenates and diazo-couples in the 1-position. not as easily as an olefm would.From this it appears that the 1.3-position.3-position exactly as in the case of 1. Naphthalene adds chlorine.2-position. Phenanthrene has five Kekule-like structures. and also that the whole 1. in naphthalene.3-diene. Phenanthrene is another example in which these simple considerations lead to chemically reasonable results.4 diphenylbuta-l. Metrical evidence supporting the above distribution of bond multiplicities will be mentioned later.2-bonds of naphthalene should be more like double bonds than any of the bonds of benzene. Naphthalene is reduced by sodium dissolving in alcohol.4-system in naphthalene should be somewhat similar to buta-l.4-positions. leaving an un attacked double bond in the 2.2. rather than one having its double bond located in the 2.4-di-phenylbutadiene is.3-diene.3. as if its phenolic system preferred to resemble an phenolic system with a double bond in the 1. and probably still more similar to 1. which are . but much more readily than benzene.

Anthracene lies on the reverse side of the picture.10-positions.10-bond certainly agrees with its chemistry. If we work out the bond multiplicities from the four Kekule-like structures. which are of two types. though the alternates are less pronounced than those of naphthalene. and therefore should be closely similar to a double bond. The non-angular bonds of the lateral rings show alternating multiplicities.10-positions (to give phenanthraquinone and di-phenic acid). allowing all the structures equal weight. as in naphthalene. The conclusion concerning the 9. it is readily reduced to give a 9.10-bond resembles fairly closely the double bond of stilbene. the following values: . two structures differing only in orientation.of four different types. In all these properties the 9.10 has the multiplicity 9/5. the bond multiplicities work out as follows: The 9. Phenanthrene adds bromine in the 9. and it is easily in the 9. each type having two orientations. we obtain. If we weight all five equally.

and so also are 9. in which the bonds of the CH-groups are as in benzene. but easily interconvertible. Anthracene is reduced by sodium amalgam to 9. bromine. It is desirable thus to test the qualitative reliability of so simple an approach as that of mixing all and only Kekule structures equally. first in the 9.and then in the 10-position. 9-Anthranol and 9-anthrone are separately isolable. The reverse is the case.10-dihydroanthryl-10-acetate. and nitrating agents substitute anthracene. but also . which readily under goes further conversion to 9-nitroanthracene. But having tested it. as in naphthalene but more strongly.10anthrahydroquinone and 9-hydroxy-10-anthrone. viz. that it is not' only unsound in theory.. as we knew.They suggest that the additive reactivity of the lateral rings. but by nitration in acetic acid an intermediate addition compound. should completely overshadow that of the central ring. we should accept the answer. in which the bond multiplicities alternate. can be isolated.10dihydroanthracene. tautomers. 9-nitro-9. Chlorine.

The general relationships between benzene and pyridine are expected to apply as between napthalene and quinoline or isoquinoline. and so on.untrustworthy in practice This approach should not be used. Attempts have been made to calculate electron distributions in polycyclic aromatic systems quantitatively. Such calculations are sometimes qualitatively suggestive. but none commands confidence in its quantitative validity. in as much as the uncertainties introduced by the approximations made are nearly always of the order of magnitude of the quantities being calculated. . as it has on occasion been. as a foundation on which to build an argument. or as between anthracene and acridine.

should be the first pi electron group to show closed shell stability through double-bond de-localization. it can have no direct relevance. Thus. for π electrons arranged on a circle. the benzene group of six electrons. with 4n + 2 electrons. analogous to the electron shells of an atom. with six (benzene). with eight (cyclo-octatetraene). The idea of a Stable bonding group of six electrons. on essentially that basis. with 4n electrons. an objection to the rule that it does not predict the stability of acenaphylene which has twelve π electrons. as it does in its empirical aspect. with all the weight of his incorporation. implying the tendency of a system which starts with somewhat fewer than six to build up six such electrons. Thus he developed the idea of molecular electron shells. going back. but not with 4 π electrons (cyclo butadiene). to which in view of its derivation. a bonding sextet. Filled shells would occur with two π electrons (ethylene). and. It is not.d) Non-benzenoid Closed-Conjugated Systems. the successively occupied molecular π orbitals started with a single one and then went onto higher energies in successive degenerate pairs. in general. Huckel rationalized the idea. the rule is valid up to the eight-membered ring. In the monocyclic series. . In this original application of molecular orbital theory to benzene Huckel observed that. of the five-membered heterocyclic in the aromatic family. for example. is immediately acceptable. Huckel's 4n+2 rule applies only to monocyclic π electron systems though some authors have applied it to polycyclic systems. in general. the aromatic sextet.

The significance of the classification is that. in view of the simple nature of the theory from which it was derived. the π electrons are distributed unevenly among the π centers. which in the next stage of refinement should be made to take account of inter electronic repulsion. Many non-alternant molecules are . in which pi electron systems are classed as "alternant" Inter science of formulae below. they concentrate at alternate atoms in the separate rings. Such concentrations of charge on certain π centers may be expected to limit delocalization. with an increase of charge at one end of bond at the expense of the other. if spin-labels could be attached to the pi electron centers in an unbrokenly alternating way. Coulson and Rushbrooke were led to another useful classification. Cyclobutadiene is too unstable to be kept. according to calculation. in non-alternate hydrocarbons. but for these rings it would seem that the Huckel principle is not the dominating factor in their stability. in azulene. and "non-alternate" otherwise. but also. but the effect is not large. In attempting this. we should probably not expect much more from it. the π electrons not only concentrate. or lack of it.and. rings from ten-membered upwards are incompletely known.octatetraene can be kept. Huckel's classification of pi electron systems was based on elementary molecular orbital theory-. Cyclo. but it is a highly reactive. Monocyclic closed-conjugated non-planar polyolefin. Thus. towards the five membered ring from the seven-membered (as if each ring were striving after a sextet). as dipole moments show.

Thus the valency bond calculation predicts large . and their mesomeric energies are not abnormally low. together with a third. The elementary molecular orbital and valency bond calculations made by Huckel on benzene lead to consistent results in that case. is not closely associated with aromaticity.known. The annexed illustrations show these two classifications. described below. but markedly discrepant results when applied to his open-shell 4n systems. Alternant character in short.

and the number of such inter changes which reverse spin-labels. . The rule can be followed with the aid of any of the above diagrams. Although such calculations are feasible only in the simplest cases. as they have been in the treatment of benzene. as described already with the added condition (fulfilled in the diagrams) that any avoidable break in alternation is set at a single bond in a Kekule. very low mesomeric energies are predicted for Cyclobutadiene and for cyclo octatetraene. the molecule is classed as "pseudo-aromatic”. This criterion is limited to molecules with at least one two-fold rotational axis of symmetry passing through at least two pi electron centers. based on symmetry. which is aimed specifically at the conditions for aromaticity. Such discrepancies must diminish as the methods are refined. If the sum of these two numbers is odd. A two-fold axis through atoms (vertical or horizontal in the diagrams) is then selected. Craig was led by this study to suggest a more general criterion. and has shown that. in calculations made by molecular orbital and valency bond methods which have been free from certain approximations inherent in the simple treatments. The molecule is first spin-labelled.type structure. and the molecule is imagined to be turned over by rotation around it. for recognizing the circumstances in which only small mesomeric energies arise. Craig has investigated the factors underlying the discrepancies.mesomeric energies for cyclobutadiene and cyclo-octatetraene. One now counts the resulting number of interchanges of pi centers. and thus to propose at a classification of pi electron systems.

the truly aromatic molecules the symmetry test is applicable only if the necessary symmetry is present in a molecular model. the molecule is “aromatic" This classification bears no relation to the number of pi electrons or to the number of rings. They all can be concluded so to lack aromatic stability that they can fairly be called "pseudo-aromatic. Many molecules with unsymmetrical ground states can be thought of. which. The test described is really one of whether the poly electronic wave-function of the ground state has or has not a lower symmetry than the nuclear framework. But all monocyclic systems of Huckel's 4n class are pseudo-aromatic. for example. and hence no agreement in calculated energies could be expected. in calculations on pseudo-aromatic molecules are always of a different symmetry class. According to Craig. but all except cyclo-octatetraene are unstable. be applied to Phenanthrene. nor to the stable non-olefinic diphenylene.If the sum is even. less dependent on numerical data obtained empirically from other molecules. the lower symmetry. nor to the typically . It cannot. or unknown.." The elementary molecular orbital and valency bond approaches would then assign to their ground states different lower symmetries. If it has. and so to lead to low mesomeric energies. the main need is to make the calculations less empirical. would be expected to be inimical to general π electron delocalization. viz. that is. generally regarded as typically aromatic. analogously to the introduction of nodes into orbitals. a number having resisted some quite determined attempts to synthesize them.

"strain." a factor which we consider more generally Ring strain can in principle affect all types of rings. in closed-conjugated systems. we assume that the benzene rings are not strongly conjugated with each other through the intervening rings. Its most prevalent component is the stress in beat bonds. and this component too must be at its maximum in fourmembered rings. Diphenylene must involve to an important degree the destabilizing factor of ring. In such cases we can only try to judge which simpler and more symmetrical "parent" will control the stability of the derivative. we assume control by the benzene rings: that is. one which can arise only in much larger rings. The last two of these compounds are formulated below. In the two molecules formulated. for none of these molecules has a two-fold axis through atoms. and. including π electron rings. involves . A third factor.diolefinic dibenzopentalene. this is at its maximum in fourmembered rings. An occasionally important component is trans-annular non-bonding pressure between ring atoms.

Its properties. and later cope and his coworkers. that it is not a di-radical. On attempting to liberate the hydrocarbon one obtains only products of its polymerization or addition reactions.trans-annular non-bonding pressures between atoms which are attached to the rings and find themselves turned inwards in rings of a certain size. Then Rappe obtained the substance by polymerization of acetylene in the presence of nickel cyanide in tetrahydrofuran. those of a highly reactive polyolefin. some derivatives have. These are stereospecific enough to show that Cyclobutadiene has a singlet ground state.e. but it has. called in question.. Cyclobutadiene has not been isolated in a free state. and accordingly Willstatter's work was repeatedly. a method allowing the production of large quantities. and he. i. Rappe confirmed Wilstatter’s findings. been obtained in the form of metal complexes. Cyclo-octatetraene was first prepared by Willstatter. who obtained it from pseudopelletierin by reactions which included removal of the nitrogen bridge in two steps of exhaustive methylation. were a surprise to everyone. though never justifiably. such as (C4H4) Fe(CO)3. as. have greatly extended our knowledge of the physical properties and chemical .

if it should go into a single plane. non-conjugated.40. 1639 cm-1.transformations of cyclo-octatetraene.470 A. for the unsymmetrical π electron ground state of the flat molecule cannot supply a compensating amount of mesomeric energy. Cyclo-octatetraene is a saddle-shaped molecule (above). Such as would be diagnostic of cyclic . composed of four flat and essentially strain less ethylene units. prepared the substance again by Wilstatter's route. are 1. The CC bond lengths alternate. The ring angle is 126. It also shows no exaltation of diamagnetic susceptibility. each ±0. And Cope. double bond. in order to get the record straight.. The C:C stretching frequency. i. is normal for an isolated.322 and 1. and.005 A. and it has nothing to gain in compensation for the loss of strainlessness which it would suffer. like benzene.40± 0. by an X-ray study of the monocarboxylic acid. The molecule shows scarcely any exaltation of refraction. so rotated about the single bonds between that there is only slight π orbital overlap between the units. The molecule thus achieves strainlessness.e.

and adds hydrogen halides. the double bonds move round the ring. normally conjugated. but that. but its visible color arises only because the long vibrational of an absorption band. and Reppe and Cope have carefully elucidated some of these processes.electron delocalization. The underlying phenomenon of intra-annular valency tautomerism is shown by Anet and by Roberts and their coworkers by the method of nuclear magnetic resonance that in cyclo-octatetraene itself. It is reduced by alkali metals. encroaches on the visible region of the spectrum. Heats of formation and reaction allow it only a little mesomeric energy. for instance.and deutero-carbethoxy-derivatives. because nuclear deformations are involved. less than would be expected for an open-chain. It is a yellow liquid. tetra-ene. Willstatter had noticed ring-bridging during additions. and is converted by numerous reagents to benzene derivatives. It is reduced catalytically in the expected stages to cyclo-octane. and in various of its simple substitution products. and halogens. centered well up in the ultraviolet. an activation barrier resists the movement: . by chromic oxide to terephthalic acid. such as the fluoro. Cyclo-octatetraene is isomerized by heat to styrene.

these conformations become unstable. the flat conformations represented below. and retain. [14]annulene and [18]-annulene.For cyclo-octatetraene itself. —60° for [14]-annulene and room temperature for [18]-annulene. are the best known. the lives of the successive stable con formations being of the order of a centisecond at 0°. Several closed-conjugated large rings have been prepared./mole. alkane or alkene αω –di – ynes. and subjecting the formed cyclic poly-ynes to graduated prototropic re arrangements and reductions. They are 4n + 2 hydrocarbons. In some substitution products the barriers are somewhat higher. Their nuclear magnetic resonance spectra show that they attain. by Sondheimer and his coworkers. and the individual conformers may live for several seconds at that temperature. and also the greater stability of the flat conformation of [18]-annulene.7 kcal. C14H14 and C18H18. room temperature for [14]-annulene and + 60° for [18]annulene. as they are called. At higher temperatures. or cyclically polycondensing. the energy of activation of the cyclic bond shift is 13. by the general method of oxidative cyclizing. at sufficiently reduced temperatures. for instance. We can understand this. inasmuch as the interior .

and both are declared as unstable. 1. Azulene is well known and is. but the bridge-bond.48 A. but [30]-anntilene is a 4n+2 hydrocarbon. the parent of a great series of compounds. which is single in both Kekule structures (above). and an X-ray analysis of the crystal has shown that the molecule is flat. though heptalene has been obtained as a colored./mole. Probably Huckel's rule loses some of its force in such attenuated π electron systems as these very large rings present. readily polymerising polyolefin. 1. is considerably longer. Azulene has a dipole moment equal to 1. despite many attempts to synthesize them. though it becomes double in some polar structures. [24]Annulene is of the 4n. having a wide natural distribution in essential oils. unstable. indeed.40 A. Pentalene and benzodipentadiene are so far unknown. series. Azulene is a blue solid. and has the bond lengths given below: The average bond length is as in benzene.hydrogen atoms must be under a mutual compression which is strong in flat [14]annulene. The mesomeric energy by heat of combustion of the latter is 100 kcal. .0 D. and appreciable in flat [18] annulene.

/mole./mole for the strain in the azulene ring would have to be added. in order to reach an estimate of the mesomeric energy in azulene./mole less than that of naphthalene. for the molecule is somewhat sensitive to drastic reagents. and 2-cyano-azulene show that the electron dis placement in the parent hydrocarbon is from the seven-membered to the fivemembered ring. Azulenes undergo most of the typical electrophilic aromatic substitutions. which we know to carry the negative dipole charge of the hydrocarbon. indeed. Friedel-Crafts acylation’s. along with Pauling's figure for the latter molecule. 2-bromo-. they occur where . mesomeric energy. nitrations. sulphonations. It has been estimated as being 30 kcal. a term of the order of 10 kcal. It can probably be said that the uncorrected mesomeric energy of azulene must be approximately one-half that of naphthalene: and to the uncorrected value. though sometimes the conditions have to be carefully regulated.and measurements on 2 chloro-. though not yet closely agreed. would give 45 kcal. Azulene has an exaltation of diamagnetic susceptibility almost equal to that of its isomer naphthalene. Azulene has a large. that is they occur. in the five-membered ring./mole to azulene. This means that cyclic electron delocalization is approximately as good in azulene as it is in naphthalene. and this. The substitutions occur successively in the 1. but an independent measurement by hydrogenation has given the value 31 kcal. and diazo-couplings. as they should.and 3positions.

above 700°. when various acenaphthenesulphonic and disulphonic acids are desulphonated with alkali.bridge in Phenanthrene./mole. rather like the -CH: CH. the electronic spectrum shows that there must be considerable interaction between the benzene rings. as of halogens. and substituted derivatives are formed only after a subsequent elimination./mole) becomes a large fraction of that in biphenyl (about 79 kcal. Strong oxidation leads to naphthalic acid. is mainly a center of additions. The ./mole). Wilson Baker writes that "it is not possible to handle diphenylene without becoming convinced that in nearly all respects it is a typical . Diphenylene was first prepared by Lothrop from 2. CH2.CH: CH. from its dihydro -derivative acenaphthene (with a. is added. formed in numerous high-temperature reactions. including the pyrolytic loss of hydrogen. It is produced. As to its chemical properties. But it is a very stable hydrocarbon. bridge).2'-di-iodobiphenyl and cuprous oxide at 350°. On the other hand. Bridge in acenaphthylene. as deduced from its heat of combustion./mole. the term properly attributable to π electron delocalization (more than 50 kcal.maxima of pi electron densities have been placed by calculation the physical properties of acenaphthylene seem not yet to have been studied. about 22 kcal. It has a considerable mesomeric energy. and it is also formed from the latter by mild oxidizing agents. which cannot be much less than 30 kcal. CH2. and when the strain energy. with an abnormal loss of hydrogen.

This residue is terminally dihydrogenated with sodium. and disulphonated. and the second the 6-position only. and dicarboxylic acid." Nearly all its known reactions are normal electrophilic aromatic substitutions. described by Blood and Linstead. nitrated. and with mixed acid dinitrated. is a compound of a very different type.polynuclear aromatic compound. and with excess of reagents diacetylated. All these reactions leave the benzene rings untouched. 2: 4. amalgam. Its known reactions are all of the central butadiene residue. as far as is known. The first substituent enters the 2-position only. acetylated. and broken up completely on ozonolysis to form benzil-2. tetra hydrogenated with hydrogen and palletized charcoal. 1. . It can be halogenated. 5-Dibenzopentalene. 2’.

as in pyrrole differs qualitatively from that of the six-membered nuclei of the type benzene and pyridine. The principal structures which are required in order to express the mesomerism of a pyrrole are as follows: These structures allow the pi electrons to circulate completely round the ring. Thus the mesomerism of the five-membered heterocyclic nuclei.e) Odd-Membered Aromatic Nuclei: The valency bond structure in odd-membered rings cannot be closed-conjugated. . are quite fundamental to the mesomerism of a nucleus such as that of Pyrrole. Dipolar structures. which have to be included only in second approximation in the treatment of benzene. Thus the clockwise electron movement. but one pair of electrons remains continuously unshared.

and the distinction shows in heterocyclic molecules with other hetero atoms. in the mesomeric state. molecules such as furan and thiophen. and the nitrogen atom is.Shifts the unshared pair one step anticlockwise. Pyrrole has the dipole moment +1. and to the five-membered components of condensed systems. such as those of thiophen. but for furan the exaltation is large though smaller than for benzene or pyridine. For thiophen the exaltation is as large as for benzene and pyridine. The pyrrole moment can be approximately analyzed as below. oxazole. furan. such as those of indole. The exaltation of diamagnetic susceptibility of pyrrole seems not to have been measured. but it is smaller than that of benzene or pyridine. purine.. as of indole with naphthalene or quinoline. so that the carbon atoms are partly anionic.80 D. to a considerable extent. carbazole. cationic.3 D arises from a mesomeric transfer of nitrogen electrons . etc. in the opposite direction to the dipole moment of pyridine. etc. This means that. The analysis shows that a moment of +2. thionaphthen. and the same difference runs through a comparison of analogous polynuclear compounds. The same theory applies to other five-membered aromatic nuclei. the unshared electrons are spread all round the ring. glyoxaline. and the process can be continued as indicated by the arrows in the second formula. Pyrrole has a large mesomeric energy.

The imino-hydrogen atoms pyrrole. like the imino hydrogen atoms of succinimide and phthalimide.8 X 2.3 = . The theory of their mesomerism explains this.8 Although pyridine. and acridine are bases. their odd-ring analogues. indole and carbazole are distinctly acidic. quinoline.3 -0. .to the ring. and carbazole. indole. of the same order of basic strength as aniline. spreading negative charges round the carbon atoms of the ring and leaving the nitrogen atom with a positive charge.3 2. pyrrole. as the above polar valency structures would indicate: ANALYSIS FOR PYRROLE NH Bond1 Electroneg.1. somewhat in the same way as Bam berger's theory did: the unshared nitrogen electrons are fundamentally involved in the aromatic system. are practically non basic. 2 Mesomeric 3 1.

four or five hydrogen atoms are replaced. This shows clearly that carbon unsaturation is not localized in the 2. on ozonolysis. give both glyoxal and methylglyoxal. 2. It has been shown that 2. mesomerism confers a positive charge on the nitrogen atom. The carbon positions in the pyrrole nucleus are enormously more reactive than those of the pyridine nucleus. or even more. To give one example." This is just what should be concluded from the theory that unshared nitrogen electrons are spread all round the ring. .The theory account for this also: in each case. it is usual to work in very dilute solution: even then. the action of halogens on pyrrole is extremely energetic. and in order to secure sufficient control for preparative purposes. or of benzene. but is distributed all-round the ring as the preceding formulae illustrate. of course. 5-dimethylpyrrole and 1.and 4 5-bonds. 5-trimethyl-Pyrrole. 3. This behaviour is. As one standard text-book of organic chemistry remarks "The great reactivity of the methine hydrogen’s in pyrrole quite remarkable. in general. They can be replaced by the most diverse atoms and groups with the same facility as the imine hydrogen. The capacity of cyclopentadiene to yield stable sodium and other alkali metal salts (the property used to separate it from the light fraction from coal tar) is evidently associated with the same type of mesomerism. completely different from that of benzene and much more different from that of pyridine.

somewhat unstable compounds are produced. The valency structures are shown below.The free hydrocarbon is not aromatic—its mesomeric energy is about the same as that of buta-l. the anionic charge being equally divided between the five carbon atoms in the mesomeric state: Indene and fluorine also form alkali metal salts.3-diene. is made alkaline. The colored substance from dimethyl-9-fluorenylsulphonium salts has been investigated in some detail. in the same way as is pyrrole. . highly colored. When an aqueous solution of a. But the anion is aromatic. and shown to be dimethylsulphonium-9-fruorenylide. quaternary 9-fluorenylammonium salt. or of a 9-fluorenyl-sulphonium salt. And thus the anion is much less unstable than hydrocarbon anions usually are.

and Wittig and his coworkers have made the trimethylammonium-. The free cyclopentadienylide ion should have full pentagonal symmetry.and trimethylarsonium-'ylides: In the nitrogen compounds no question of absorption of the 'ylide electrons into the cationic center can arise. Krollpfeiffer and Schneider prepared the corresponding pyridinium-'ylide. trimethylphosphonium-.The reason for its formation is evidently that the anionic center is stabilized by mesomerism of the cyclopentadienide -ion type. even though the latter has unoccupied orbitals. What has been proved convincingly by X-ray analysis is that its . The large dipole moment of the compound shows that the unshared carbon electrons are not absorbed into the sulphur atom to a predominating extent.

it adds Br2. The extent of observed isomerism among derivatives of ferrocene has created the impression that no large barrier exists to rotation of the separate rings around the pentagonal axis. But just how the iron atom absorbs the anionic charges without seriously impairing their delocalization is not completely clear. in part attracts an entering acyl group to the 2and 3-positions of the same ring. and the adduct losses .Crafts acylation’s. as Doering and Knox showed. first prepared by Kealy and Pauson. But an alkyl substituent. sulphonations and Friedel. (C5H6)2Fe. though it is obvious that the 3d orbitals of the iron atom must be involved cycloheptatriene (tropilidene) is a polyolefm of no very special stability.iron derivative. But. the first two substituents enter one in each ring. has the configuration of a pentagonal antiprism. for instance. already in one ring. It is not prone to additions. with the iron atom at the center of symmetry. In these reactions. sensitive to oxidising agents. but can undergo some electrophilic substitutions. All this suggests a considerable degree of aromaticity. and stable to heat. ferrocene. The substance is volatile. but stable towards reducing agents.

The tropylium ion should have full heptagonal symmetry. But the tropylium ion has considerable stability in water. an outstandingly stable carbonium ion. the unbridged set being as shown below. reacting with it reversibly.HBr. Most carbonium ions are destroyed instantly and irreversibly by water. to give the ionic bromide of the cycloheptatrienylium ion. but here only to a small equilibrium extent. and qualitatively in the manner of the cation of a pseudo-base. with a delocalized π sextet. and indeed by any basic substance. neutral or anionic. to form pseudo-basic cycloheptatrienol (tropenol): . to which several sets of seven equivalent valency structures can be assigned.

typified by boratropylene and beryllatropylene. the tropylium ion is the more stable species. and. It is obvious that a whole series of seven-membered hetero-aromatic systems. in view of the strong contrast with the properties of carbonium ions in general.Even in dilute solution. this is a striking illustration of the stabilizing effect of a delocalized six-electron π shell. the electron deficient counterparts of pyrrole and furan. remain undiscovered the present time: .

Structure and Mechanism in Organic Chemistry. Second Edition.References: [1]. C.K.INGOLD .