Aromaticity 239836 223774841 2008-07-05T19:10:12Z Diderot's dreams 5508432 /* Characteristics of aromatic (Aryl) compounds */ content changes, plus more organizing {{Redirect|Aromatic compound|meanings related to [[odor]]|aroma compound}} [[Image:benzene resonance.png|right|Benzene resonance]] '''Aromaticity''' is a chemical property in which a [[conjugated system|conjugated]] ring of [[unsaturated bond]]s, [[lone pair]]s, or [[empty orbital]]s exhibit a stabilization stronger than would be expected by the stabilization of conjugation alone. It can also be considered a manifestation of cyclic [[delocalization]] and of [[Resonance (chemistry)|resonance]].<ref>P. v. R. Schleyer, "Aromaticity (Editorial)", ''Chemical Reviews'', '''2001''', ''101'', 1115-1118. DOI: [http://dx.doi.org/10.1021/cr0103221 10.1021/cr0103221 Abstract].</ref><ref>A. T. Balaban, P. v. R. Schleyer and H. S. Rzepa, "Crocker, Not Armit and Robinson, Begat the Six Aromatic Electrons", ''Chemical Reviews'', '''2005''', ''105'', 3436-3447. DOI: [http://dx.doi.org/10.1021/cr0300946 10.1021/cr0103221 Abstract].</ref><ref>P. v. R. Schleyer, "Introduction: Delocalization-π and σ (Editorial)", ''Chemical Reviews'', '''2005''', ''105'', 3433-3435. DOI: [http://dx.doi.org/10.1021/cr030095y 10.1021/cr030095y Abstract].</ref> This is usually considered to be because [[electron]]s are free to cycle around circular arrangements of [[atom]]s, which are alternately single- and double-[[covalent bond|bonded]] to one another. These bonds may be seen as a hybrid of a single bond and a double bond, each bond in the ring identical to every other. This commonly-seen model of aromatic rings, namely the idea that benzene was formed from a six-membered carbon ring with alternating single and double bonds (cyclohexatriene), was developed by [[Friedrich August Kekulé von Stradonitz|Kekulé]] (see "History" section below). The model for [[benzene]] consists of two [[Resonance (chemistry)|resonance]] forms, which corresponds to the double and single bonds' switching positions. Benzene is a more stable molecule than would be expected without accounting for charge delocalization. ==Theory== [[Image:Benz4.png|right|100px|Modern depiction of benzene]]As is standard for [[resonance (chemistry)|resonance diagrams]], a double-headed arrow is used to indicate that the two structures are not distinct entities, but merely hypothetical possibilities. Neither is an accurate representation of the ''actual'' compound, which is best represented by a hybrid (average) of these structures, which can be seen at right. A C=C bond is shorter than a C−C bond, but benzene is perfectly hexagonal—all six carbon-carbon bonds have the same [[bond length|length]], intermediate between that of a [[single bond|single]] and that of a [[double bond]]. A better representation is that of the circular π bond (Armstrong's ''inner cycle''), in which the electron density is evenly distributed through a [[pi bond|π bond]] above and below the ring. This model more correctly represents the location of electron density within the aromatic ring. The single bonds are formed with electrons in line between the carbon nuclei—these are called [[sigma bond]]s. Double bonds consist of a sigma bond and a π bond. The π-bonds are formed from overlap of [[Atomic orbital|atomic p-orbitals]] above and below the plane of the ring. The following diagram shows the positions of these p-orbitals: [[Image:Benzene-orbitals.png|330px|Benzene electron orbitals]] Since they are out of the plane of the atoms, these orbitals can interact with each other freely, and become delocalised. This means that instead of being tied to one atom of carbon, each electron is shared by all six in the ring. Thus, there are not enough electrons to form double bonds on all the carbon atoms, but the "extra" electrons strengthen all of the bonds on the ring equally. The resulting [[molecular orbital]] has π symmetry. [[Image:benzene-orbitals2.png|Benzene orbital delocalisation]] ==History== The first known use of the word "aromatic" as a ''chemical'' term—namely, to apply to compounds that contain the [[phenyl]] [[Radical (chemistry)|radical]]—occurs in an article by [[August Wilhelm Hofmann]] in 1855.<ref>A. W. Hofmann, "On Insolinic Acid," ''Proceedings of the Royal Society,'' 8 (1855), 1-3.</ref> If this is indeed the earliest introduction of the term, it is curious that Hofmann says nothing about why he introduced an adjective indicating [[olfactory]] character to apply to a group of chemical substances, only some of which have notable aromas. It is the case, however, that many of the most odoriferous organic substances known are [[terpenes]], which are not aromatic in the chemical sense. But terpenes and benzenoid substances do have a chemical characteristic in common, namely higher unsaturation indexes than many [[aliphatic compound]]s, and Hofmann may not have been making a distinction between the two categories. The cyclohexatriene structure for [[benzene]] was first proposed by [[August Kekulé]] in 1865. Over the next few decades, most chemists readily accepted this structure, since it accounted for most of the known isomeric relationships of aromatic chemistry. However, it was always puzzling that this purportedly highly-unsaturated molecule was so unreactive toward addition reactions. The discoverer of the electron [[J. J. Thomson]], in 1921 placed three equivalent electrons between each carbon atom in benzene. [[Image:benzene circle.png|right|alternative representation]] An explanation for the exceptional stability of benzene is conventionally attributed to [[Robert Robinson (scientist)|Sir Robert Robinson]], who was apparently the first (in 1925)<ref>"CCXI.—Polynuclear heterocyclic aromatic types. Part II. Some anhydronium bases" James Wilson Armit and Robert Robinson ''[[Journal of the Chemical Society]], Transactions'', '''1925''', 127, 1604–1618 [http://dx.doi.org/10.1039/CT9252701604 Abstract].</ref> to coin the term ''aromatic sextet'' as a group of six electrons that resists disruption. In fact, this concept can be traced further back, via Ernest Crocker in 1922,<ref>APPLICATION OF THE OCTET THEORY TO SINGLE-RING AROMATIC COMPOUNDS Ernest C. Crocker [[J. Am. Chem. Soc.]]; '''1922'''; 44(8) pp 1618–1630; [http://dx.doi.org/10.1021/ja01429a002 Abstract]</ref> to [[Henry Edward Armstrong]], who in 1890, in an article entitled ''The structure of cycloid hydrocarbons'', wrote ''the (six) centric affinities act within a cycle...benzene may be represented by a '''double ring''' (''sic'') ... and when an additive compound is formed, the inner cycle of affinity suffers disruption, the contiguous carbon-atoms to which nothing has been attached of necessity acquire the ethylenic condition''.<ref>''The structure of cycloid hydrocarbons'' Henry Edward Armstrong Proceedings of the Chemical Society (London), '''1890''', 6, 95 - 106 [http://dx.doi.org/10.1039/PL8900600095 Abstract]</ref> Here, Armstrong is describing at least four modern concepts. First, his "affinity" is better known nowadays as the [[electron]], which was only to be discovered seven years later by [[J. J. Thomson]]. Second, he is describing [[electrophilic aromatic substitution]], proceeding (third) through a [[Wheland intermediate]], in which (fourth) the [[Conjugated system|conjugation]] of the ring is broken. He introduced the symbol '''C''' centered on the ring as a shorthand for the ''inner cycle'', thus anticipating [[Eric Clar]]'s notation. It is argued that he also anticipated the nature of [[wave mechanics]], since he recognized that his affinities had direction, not merely being point particles, and collectively having a distribution that could be altered by introducing substituents onto the benzene ring (''much as the distribution of the electric charge in a body is altered by bringing it near to another body''). The [[quantum mechanical]] origins of this stability, or aromaticity, were first modelled by [[Erich Huckel|Hückel]] in 1931. He was the first to separate the bonding electrons into sigma and pi electrons. == Characteristics of aromatic (Aryl) compounds == An aromatic compound contains a set of [[covalent bond|covalently-bound]] atoms with specific characteristics: # A [[Delocalized electron|delocalized]] conjugated [[pi electron|π]] system, most commonly an arrangement of alternating single and double [[Covalent bond|bonds]] # [[Coplanar]] structure, with all the contributing atoms in the same plane # Contributing atoms arranged in one or more rings # A number of π delocalized electrons that is [[singly even|even, but not a multiple of 4]]. That is, 4n + 2 number of π electrons, where n=0, 1, 2, 3, and so on. This is known as [[Hückel's rule|Hückel's Rule]]. Whereas benzene is aromatic (6 electrons, from 3 double bonds), [[cyclobutadiene]] is not, since the number of π delocalized electrons is 4, which of course is a multiple of 4. The cyclobutadienide (2−) ion, however, is aromatic (6 electrons). An atom in an aromatic system can have other electrons that are not part of the system, and are therefore ignored for the 4n + 2 rule. In [[furan]], the oxygen atom is sp² hybridized. One lone pair is in the π system and the other in the plane of the ring (analogous to C-H bond on the other positions). There are 6 π electrons, so furan is aromatic. Aromatic molecules typically display enhanced chemical stability, compared to similar non-aromatic molecules. A molecule that can be aromatic will tend to alter its electronic or conformational structure to be in this situation. This extra stability changes the chemistry of the molecule. Aromatic compounds undergo [[electrophilic aromatic substitution]] and [[nucleophilic aromatic substitution]] reactions, but not [[electrophilic addition]] reactions as happens with carbon-carbon double bonds. Many of the earliest-known examples of aromatic compounds, such as benzene and toluene, have distinctive pleasant smells. This property led to the term "aromatic" for this class of compounds, and hence the term "aromaticity" for the eventually-discovered electronic property. The circulating π electrons in an aromatic molecule produce [[Aromatic ring current|ring currents]] that oppose the applied magnetic field in [[NMR]]. The NMR signal of protons in the plane of an aromatic ring are shifted substantially further down-field than those on non-aromatic sp² carbons. This is an important way of detecting aromaticity. By the same mechanism, the signals of protons located near the ring axis are shifted up-field. Aromatic molecules are able to interact with each other in so-called [[Aromatic interaction|π-π stacking]]: the π systems form two parallel rings overlap in a "face-to-face" orientation. Aromatic molecules are also able to interact with each other in an "edge-to-face" orientation: the slight positive charge of the substituents on the ring atoms of one molecule are attracted to the slight negative charge of the aromatic system on another molecule. Planar monocyclic molecules containing 4n π electrons are called [[antiaromatic]] and are, in general, destabilized. Molecules that could be [[antiaromatic]] will tend to alter their electronic or conformational structure to avoid this situation, thereby becoming non-aromatic. For example, [[cyclooctatetraene]] (COT) distorts itself out of planarity, breaking π overlap between adjacent double bonds. == Importance of aromatic compounds == Aromatic compounds are important in industry. Key aromatic hydrocarbons of commercial interest are [[benzene]], [[toluene]], [[xylene|''ortho''-xylene]] and [[xylene|''para''-xylene]]. About 35 million tonnes are produced worldwide every year. They are extracted from complex mixtures obtained by the refining of oil or by distillation of coal tar, and are used to produce a range of important chemicals and polymers, including [[styrene]], [[phenol]], [[aniline]], [[polyester]] and [[nylon]]. Other aromatic compounds play key roles in the biochemistry of all living things. Three aromatic amino acids [[phenylalanine]], [[tryptophan]], and [[tyrosine]], each serve as one the 20 basic building blocks of proteins. Further, all 5 nucleotides that make up the sequence of the genetic code in DNA are aromatic [[purines]] or [[pyrimidines]]. == Types of aromatic compunds == The overwhelming majority of aromatic compounds are compounds of carbon, but they need not be hydrocarbons. === Heterocyclics === In [[heterocyclic ring|heterocyclic]] aromatics ('''heteroaromats'''), one or more of the atoms in the aromatic ring is of an element other than carbon. This can lessen the ring's aromaticity, and thus (as in the case of [[furan]]) increase its reactivity. Other examples include [[pyridine]], [[imidazole]], [[pyrazole]], [[oxazole]], [[thiophene]], and their [[benzannulated]] analogs ([[benzimidazole]], for example). === Polycyclics === [[Polycyclic aromatic hydrocarbon]]s are molecules containing two or more simple aromatic rings fused together by sharing two neighboring carbon atoms (see also [[simple aromatic ring]]s). Examples are [[naphthalene]], [[anthracene]] and [[phenanthrene]]. === Substituted aromatics === Many [[chemical compound]]s are aromatic rings with other things attached. Examples include [[trinitrotoluene]] (TNT), [[aspirin|acetylsalicylic acid]] (aspirin), [[paracetamol]], and the nucleotides of [[DNA]]. === Inorganic aromatic compounds === Aromaticity occurs in compounds not made of carbon as well. Inorganic 6 membered ring compounds anlogous to benzene have been synthesized. Silicazine (Si<sub>6</sub>H<sub>6</sub>) and borazine (B<sub>3</sub>N<sub>3</sub>H<sub>6</sub>) are structurally analogous to benzene, with the carbon atoms replaced by another element or elements. In borazine, the boron and nitrogen atoms alternate around the ring. == Aromaticity in other systems == Aromaticity is found in [[ion]]s as well: the [[cyclopropenyl]] cation (2e system), the [[cyclopentadienyl]] anion (6e system), the [[tropylium]] ion (6e) and the [[cyclooctatetraene]] dianion (10e). Aromatic properties have been attributed to non-benzenoid compounds such as [[tropone]]. Aromatic properties are tested to the limit in a class of compounds called [[cyclophane]]s. A special case of aromaticity is found in [[homoaromaticity]] where conjugation is interrupted by a single ''sp''³ [[orbital hybridisation|hybridized]] carbon atom. When carbon in benzene is replaced by other elements in [[borabenzene]], [[silabenzene]], [[germanabenzene]], [[stannabenzene]], [[phosphorine]] or [[pyrylium salt]]s the aromaticity is still retained. Aromaticity is also not limited to compounds of carbon, oxygen and nitrogen. [[Metal aromaticity]] is believed to exist in certain metal clusters of aluminium. [[Möbius aromaticity]] occurs when a cyclic system of molecular orbitals formed from p<sub>π</sub> [[atomic orbitals]] and populated in a [[closed shell]] by 4n (n is an integer) electrons is given a single half-twist to correspond to a Möbius [[topology]]. Because the twist can be [[left-handed]] or [[right-handed]], the resulting Möbius aromatics are ''dissymmetric'' or [[Chirality (chemistry)|chiral]]. Up to now there is no doubtless proof, that a Möbius aromatic molecule was synthesized.<ref>''Synthesis of a Möbius aromatic hydrocarbon'' D. Ajami, O. Oeckler, A. Simon, R. Herges, Nature; '''2003'''; 426 pp 819.</ref><ref>''Investigation of a Putative Möbius Aromatic Hydrocarbon. The Effect of Benzannelation on Möbius [4 n]Annulene Aromaticity'' Claire Castro, Zhongfang Chen, Chaitanya S. Wannere, Haijun Jiao, William L. Karney, Michael Mauksch, Ralph Puchta, Nico J. R. van Eikema Hommes, [[Paul von Rague Schleyer|Paul von R. Schleyer]] [[J. Am. Chem. Soc.]]; '''2005'''; 127(8) pp 2425-2432 [http://dx.doi.org/10.1021/ja0458165 Abstract]</ref> Aromatics with two half-twists corresponding to the [[paradromic]] topologies first suggested by [[Johann Benedict Listing|Johann Listing]] have been proposed by [[Henry Rzepa|Rzepa]] in 2005.<ref>''A Double-Twist Möbius-Aromatic Conformation of [14]Annulene'' Henry S. Rzepa [[Org. Lett.]]; '''2005'''; 7(21) pp 4637 [http://dx.doi.org/10.1021/ol0518333 Abstract]</ref> In [[carbo-benzene]] the ring bonds are extended with alkyne and allene groups. ==See also== * [[Aromatic hydrocarbons]] * [[Aromatic amines]] * [[Hückel's rule]] * [[Polycyclic aromatic hydrocarbon|PAH]] * [[Simple aromatic ring]] == References == {{Reflist}} {{Chemical bonds}} {{Organic chemistry}} [[Category:Aromatic compounds| ]] [[Category:Physical organic chemistry]] [[ar:عطرية]] [[cs:Aromaticita]] [[da:Aromatisk forbindelse]] [[es:Aromaticidad]] [[fa:پیوند آروماتیک]] [[mk:Ароматично соединение]] [[ja:芳香族化合物]] [[no:Aromater]] [[pt:Aromaticidade]] [[ru:Ароматизация]] [[zh:芳香性]]