Name: using frost circles to test aromaticity
Uploaded: 2025-05-22T09:05:43.000Z
Duration: 1 min 18 s
Channel: JoVE

Nach der Hückelschen Regel ist Benzol stabil und aromatisch, während Cyclobutadien und Cyclooctatetraen instabil und nicht aromatisch sind.
Die Aromatizität dieser Verbindungen kann aus ihren Frostkreisdiagrammen verstanden werden.
Der Frost-Kreis für Benzol besteht aus sechs π Molekülorbitalen. Alle niederenergetischen Bindungsorbitale sind vollständig mit sechs π Elektronen belegt, während die hochenergetischen Antibindungsorbitale leer sind. Daher ist Benzol stabil und aromatisch.
Die Frostkreise für Cyclobutadien und Cyclooctatetraen haben vier bzw. acht π Molekülorbitale.
Die Bindungsorbitale sind für beide Verbindungen vollständig belegt, während die nichtbindenden Orbitale einzeln belegt sind. Die Antibonding-Orbitale sind leer.
Es ist offensichtlich, dass das Vorhandensein von π Elektronen in hochenergetischen nichtbindenden Orbitalen die beiden Verbindungen instabil und nicht aromatisch macht.
Insgesamt gilt ein bestimmtes Molekül als aromatisch, wenn alle π Elektronen in bindenden Molekülorbitalen gepaart sind. Verbindungen mit Elektronen in Orbitalen, die nicht gebunden sind, sind nicht aromatisch.

frostkreise für verschiedene konjugierte systeme

Frost Circles for Different Conjugated Systems

Die Methode der eingeschriebenen Polygone steht im Einklang mit der 4n + 2-Regel von Hückel und hilft herauszufinden, ob die gegebene zyklische Verbindung aromatisch ist oder nicht. Die Verbindung ist stabil und aromatisch, wenn jedes bindende Molekülorbital (MO) vollständig mit einem Elektronenpaar gefüllt ist. Wenn jedoch die nichtbindenden oder antibindenden Orbitale mit Elektronen gefüllt sind, ist die Verbindung instabil und nicht aromatisch. Betrachten Sie die Frostkreisdiagramme für Cycloalkene mit 4 bis 8 Kohlenstoffatomen.

<img alt="Figure1" src="/files/ftp_upload/12866/12866_Figure_1.svg" style="text-align: center; height: 75px;">

Wenn man sich die Frostkreise ansieht, erkennt man, dass die Anzahl der Bindungs-MO immer ungerade ist und die erforderliche Anzahl von π-Elektronen im Bindungs-MO entweder 2 oder 6 beträgt. Die Anzahl der Elektronen erfüllt perfekt die 4n + 2-Regel der Aromatizität . Daher sind die Verbindungen mit vollständig ausgefülltem Bindungs-MO aromatisch.

Im Fall von viergliedrigem Cyclobutadien mit 4π-Elektronen und achtgliedrigem Cyclooctatetraen mit 8π-Elektronen sind die bindenden MO vollständig gefüllt und die nichtbindenden MO jeweils einzeln besetzt. Das Vorhandensein von Elektronen in hochenergetischen, nichtbindenden MO macht sie instabil und nicht aromatisch. Das fünfgliedrige Cyclopentadienylanion, das sechsgliedrige Benzol und das siebengliedrige Cycloheptatrienylkation haben jedoch 6π-Elektronen und die entsprechenden bindenden MO sind vollständig besetzt und stabil, sodass sie aromatisch sind.

Insgesamt gelten Moleküle mit vollständig gefüllten bindenden Molekülorbitalen als aromatisch, wohingegen Verbindungen mit Elektronen in anderen Orbitalen als bindenden Molekülen nicht aromatisch sind.

Frostkreise für verschiedene konjugierte Systeme

Die Methode des eingeschriebenen Polygons ist konsistent mit der Hückelschen 4n + 2-Regel und hilft zu lernen, ob die gegebene zyklische Verbindung aromatisch ist oder nicht.

frost-circles-for-different-conjugated-systems

Education

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JoVE Core

Organic Chemistry

Organische Chemie

Unit 1

Einheit 1

Aromatic Compounds

Aromatische Verbindungen

KEY TERMS AND CONCEPTS

KERNBEGRIFFE UND KONZEPTE

using frost circles to test aromaticity

Frost circles help test whether a cyclic compound is aromatic by using the inscribed polygon method and Hückel’s 4n + 2 rule. A compound is stable and aromatic when every bonding molecular orbital (MO) is completely filled with a pair of electrons. If electrons occupy non-bonding or antibonding orbitals, the compound is unstable and not aromatic.

Frost circle diagrams for cycloalkenes with 4 to 8 carbons show a clear pattern. The number of bonding MOs is always odd. The electrons needed to fill only the bonding MOs are usually 2 or 6, and that matches the 4n + 2 rule for aromaticity. When those bonding orbitals are completely filled, the compound is aromatic.

Some examples do not fit this stable pattern. Cyclobutadiene has 4π electrons, and cyclooctatetraene has 8π electrons. In both cases, the bonding MOs are filled, but each non-bonding MO is singly occupied. Electrons in these higher-energy non-bonding orbitals make the compounds unstable and not aromatic.

Other examples do satisfy the aromatic pattern. The cyclopentadienyl anion, benzene, and the cycloheptatrienyl cation each have 6π electrons. Their bonding MOs are fully occupied, so they are stable and aromatic. In general, molecules with completely filled bonding molecular orbitals are aromatic, while molecules with electrons in orbitals other than bonding are not.

Using Frost Circles to Test Aromaticity

aromatic compounds: overview

Aromatic Compounds in Plants and Fuels

Aromatic compounds are linked to both pleasant smells and important chemical structures. The word aromatic first came from fragrant natural sources such as fresh flowers and spices. Early organic chemists isolated benzene derivatives from oils of plants, including vanillin from vanilla, methyl salicylate from wintergreen, and cinnamaldehyde from cinnamon. The history of benzene also helped shape the idea of aromatic compounds. In 1825, Faraday isolated benzene from compressed illuminating gas,...

nomenclature of aromatic compounds with a single substituent

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Naming Benzene Derivatives with One Group

Benzene derivatives with one substituent are named by attaching the substituent name to benzene. Benzene is the simplest aromatic hydrocarbon, also called an arene. For simple monosubstituted benzene compounds, IUPAC naming uses the group name as a prefix. Halogen-substituted benzene compounds follow this pattern. The halogen prefix can be fluoro, chloro, bromo, or iodo. When an alkyl group is attached to the benzene ring, the name depends on the chain length of that group. If the alkyl chain...

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Naming Benzene Rings with Multiple Groups

Naming benzene rings with multiple groups depends on how many substituents are attached. For benzene derivatives with two groups, three constitutional isomers are possible. The position of each group is described with IUPAC naming rules. For disubstituted benzene compounds, the relative positions can be shown with ortho, meta, and para. These terms are also written as o, m, and p. They can also be written with numbers, such as 1,2- for ortho, 1,3- for meta, and 1,4- for para. Dimethyl benzene,...

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Kekule’s Benzene Model and Its Limits

Kekule’s benzene model describes benzene as a six-carbon ring with alternating pi bonds. August Kekule proposed this structure in 1865 from the formula C6H6, the idea that all benzene hydrogens are equivalent, and the rule that each carbon has four bonds because of tetravalency. In this model, each carbon is attached to one hydrogen atom. It also predicts two isomers for 1,2-disubstituted benzene derivatives. In one form, the substituted carbons are linked by a double bond, and in the other...

structure of benzene: molecular orbital model

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Benzene π Orbitals and Electron Delocalization

Benzene has a planar ring structure with delocalized π electrons. Its six carbon atoms form a regular hexagon, and each carbon is sp2 hybridized. The C–C–C and H–C–C bond angles are 120°, which matches the flat shape of the ring. Each carbon is bonded to three other atoms. The C–H bond length is 109 pm, and the C–C bond length is 139 pm. That C–C distance is midway between the single bond length of sp3 hybridized carbons, 154 pm, and the sp2 value, 133 pm. Beneath and above the ring plane,...

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H&uuml;ckel Rule and Aromatic Ring Criteria

Aromatic rings follow H&amp;uuml;ckel’s rule, also called the 4n + 2 rule. This rule helps identify which unsaturated cyclic compounds are aromatic and why some ring systems are unstable instead. Benzene is the classic example, while cyclobutadiene and cyclooctatetraene show different behavior and are not aromatic. Eric H&amp;uuml;ckel, a German chemical physicist, first described the structural features needed for aromaticity. An aromatic compound must be cyclic, planar, and continuously...

h&uuml;ckel's rule diagram of &pi; mos: frost circle

Frost Circle for Pi Orbital Energies

The Frost circle is a graphical method for showing the relative energies of pi molecular orbitals in planar, fully conjugated, monocyclic compounds. It is also called the inscribed polygon method. A. A. Frost and Boris Musulin first described this method in 1953. To build a Frost circle, draw a polygon with the same number of edges as the number of carbons in the cyclic system. Place one vertex pointing downward. Then draw a circle around the polygon so that every vertex touches the circle.

frost circles for different conjugated systems

Frost circles help test whether a cyclic compound is aromatic by using the inscribed polygon method and Hückel’s 4n + 2 rule. A compound is stable and aromatic when every bonding molecular orbital (MO) is completely filled with a pair of electrons. If electrons occupy non-bonding or antibonding orbitals, the compound is unstable and not aromatic. Frost circle diagrams for cycloalkenes with 4 to 8 carbons show a clear pattern. The number of bonding MOs is always odd. The electrons needed to...

aromatic hydrocarbon anions: structural overview

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Cyclopentadienyl Anion and Aromaticity

Cyclopentadiene is a neutral hydrocarbon that is not aromatic. It contains an odd number of carbon atoms and one CH2 group in the ring. With only 4 pi electrons, it does not follow the 4n + 2 pi electron rule. The CH2 carbon is sp3 hybridized, so it has no vacant p orbital to keep p orbitals overlapped around the ring. That break in overlap stops pi electrons from spreading across the entire ring. As a result, cyclopentadiene does not meet the usual aromaticity criteria. If one hydrogen is...

aromatic hydrocarbon cations: structural overview

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Cycloheptatrienyl Cation and Aromaticity

Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon with seven carbon atoms. One carbon in the ring is sp3 hybridized, which breaks the continuous overlap of p orbitals. Even though the ring has three double bonds and 6 π electrons, cycloheptatriene is not aromatic because the p orbitals do not form one uninterrupted loop. Removing one hydrogen from the CH2 group changes the ring. If that hydrogen is removed with both, one, or no electrons, the products are the cycloheptatrienyl...

five-membered heterocyclic aromatic compounds: overview

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Five-Membered Aromatic Rings with Heteroatoms

Five-membered aromatic rings with heteroatoms are cyclic compounds that contain one or more atoms other than carbon in the ring. They are aromatic and can have either five or six atoms in the ring. Common examples include pyrrole, furan, thiophene, and imidazole. These rings differ by the heteroatom present. Pyrrole has one nitrogen atom with one lone pair of electrons. Furan has one oxygen atom, and thiophene has one sulfur atom. Both furan and thiophene have two lone pairs of electrons.

nmr spectroscopy of aromatic compounds

Aromatic Ring Shifts in NMR Spectra

Aromatic ring shifts in NMR spectra help identify aromatic compounds using proton NMR and carbon-13 NMR. Aromatic hydrogens are often strongly deshielded by the aromatic ring current, so they usually appear in the 6.5–8.0 ppm range in proton NMR. In benzene, the hydrogens directly bonded to the ring absorb at 7.3 ppm. Larger aromatic rings can place hydrogens outside the usual range. In [18]annulene, the 12 outer hydrogens are highly deshielded by the ring current and absorb downfield at 9.3...

key terms and concepts

Learn how Frost circles and the inscribed polygon method use Hückel’s 4n + 2 rule to identify aromatic cyclic compounds and unstable non-aromatic cases.

Using Frost Circles to Test Aromaticity | JoVE K12

organic chemistry

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Using Frost Circles to Test Aromaticity

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