Cyclic compound

A cyclic compound (ring compound) is a term for a

compound in the eld of chemistry in which one or more
series of atoms in the compound is connected to form a
ring. Rings may vary in size from three to many atoms,
and include examples where all the atoms are carbon (i.e.,
are carbocycles), none of the atoms are carbon (inorganic
cyclic compounds), or where both carbon and non-carbon
atoms are present (heterocyclic compounds). Depending
on the ring size, the bond order of the individual links
between ring atoms, and their arrangements within the
rings, carbocyclic and heterocyclic compounds may be
aromatic or non-aromatic, in the latter case, they may
vary from being fully saturated to having varying numbers of multiple bonds between the ring atoms. Because
of the tremendous diversity allowed, in combination, by
the valences of common atoms and their ability to form
rings, the number of possible cyclic structures, even of
small size (e.g., <17 total atoms) numbers in the many
billions.

is displayed. Indeed, the development of this important chemical concept arose, historically, in reference
to cyclic compounds. Finally, cyclic compounds, because of the unique shapes, reactivities, properties, and
bioactivities that they engender, are the largest majority
of all molecules involved in the biochemistry, structure,
and function of living organisms, and in the man-made
molecules (e.g., drugs, herbicides, etc.).

1 Structural introduction
A cyclic compound or ring compound is a compound
at least some of whose atoms are connected to form a
ring.[1]:unknown Rings vary in size from 3 to many tens or
even hundreds of atoms. Examples of ring compounds
readily include cases where:
all the atoms are carbon (i.e., are carbocycles),

Cyclic compound examples: All-carbon (carbocyclic) and more complex natural cyclic compounds.

none of the atoms are carbon (inorganic cyclic

compounds),[2] or where

Ingenol, a complex, terpenoid natural product, related to but simpler than the paclitaxel that follows,
which displays a complex ring structure including
3-, 5-, and 7-membered non-aromatic, carbocyclic
rings.

both carbon and non-carbon atoms are present

(heterocyclic compounds).
Common atoms can (as a result of their valences) form
varying numbers of bonds, and many common atoms
readily form rings. In addition, depending on the ring
size, the bond order of the individual links between ring
atoms, and their arrangements within the rings, cyclic
compounds may be aromatic or non-aromatic; in the
case of non-aromatic cyclic compounds, they may vary
from being fully saturated to having varying numbers of
multiple bonds. As a consequence of the constitutional
variability that is thermodynamically possible in cyclic
structures, the number of possible cyclic structures, even
of small size (e.g., <17 atoms) numbers in the many
billions.[3]

Cycloalkanes, the simplest carbocycles, including cyclopropane, cyclobutane, cyclopentane, and

cyclohexane. Note, elsewhere an organic chemistry
shorthand is used where hydrogen atoms are inferred
as present to ll the carbons valence of 4 (rather
than their being shown explicitly).
Paclitaxel,
another complex,
plant-derived
terpenoid, also a natural product, displaying a
complex multi-ring structure including 4-, 6-, and
8-membered rings (carbocyclic and heterocyclic,
aromatic and non-aromatic).

Moreover, the closing of atoms into rings may lock

particular functional groupsubstituted atoms into place,
resulting in stereochemistry and chirality being associated with the compound, including some manifestations
that are unique to rings (e.g., congurational isomers);[4]
As well, depending on ring size, the three-dimensional
shapes of particular cyclic structurestypically rings of
5-atoms and largercan vary and interconvert such that
conformational isomerism is displayed.[4]

Adding to their complexity and number, closing of

atoms into rings may lock particular atoms with
distinct substitution (by functional groups) such that
stereochemistry and chirality of the compound results, including some manifestations that are unique to rings (e.g.,
congurational isomers). As well, depending on ring
size, the three-dimensional shapes of particular cyclic
structurestypically rings of 5-atoms and largercan
vary and interconvert such that conformational isomerism
1

6 AROMATICITY

Nomenclature

to break apart and to react with other substances. Organic compounds that are not aromatic are classied as
IUPAC nomenclature has extensive rules to cover the aliphatic compoundsthey might be cyclic, but only aronaming of cyclic structures, both as core structures, and matic rings have especial stability (low reactivity).
as substituents appended to alicyclic structures. The term Since one of the most commonly encountered aromatic
macrocycle is used when a ring-containing compound has systems of compounds in organic chemistry is based on
a ring of 8 or more atoms.[5][6] The term polycyclic is used derivatives of the prototypical aromatic compound benwhen more than one ring appears in a single molecule. zene (an aromatic hydrocarbon common in petroleum
Naphthalene is formally a polycyclic, but is more specif- and its distillates), the word aromatic is occasionally
ically named as a bicyclic compound. Several examples used to refer informally to benzene derivatives, and this is
of macrocyclic and polycyclic structures are given in the how it was rst dened. Nevertheless, many non-benzene
nal gallery below.
aromatic compounds exist. In living organisms, for example, the most common aromatic rings are the doubleringed bases in RNA and DNA. A functional group or
other substituent that is aromatic is called an aryl group.
3 Carbocycles
The earliest use of the term aromatic was in an article by August Wilhelm Hofmann in 1855.[1] Hofmann used the term for a class of benzene compounds,
many of which do have odors (aromas), unlike pure saturated hydrocarbons. Today, there is no general relationship between aromaticity as a chemical property and
the olfactory properties of such compounds (how they
smell), although in 1855, before the structure of ben4 Inorganic cyclic compounds
zene or organic compounds was understood, chemists like
Hofmann were beginning to understand that odiferous
Inorganic atoms form cyclic compounds as well. Exammolecules from plants, such as terpenes, had chemical
ples include sulfur, silicon (e.g., in silanes), phosphorus
properties we recognize today are similar to unsaturated
(e.g., in phosphanes and phosphoric acid variants),
petroleum hydrocarbons like benzene.
and boron (e.g., in triboric acid).
When carbon in benzene is replaced by other elements, In terms of the electronic nature of the molecule, aroe.g., as in borabenzene, silabenzene, germanabenzene, maticity describes a conjugated system often made of alstannabenzene, and phosphorine, aromaticity is retained, ternating single and double bonds in a ring. This conand so aromatic inorganic cyclic compounds are known guration allows for the electrons in the molecules pi
system to be delocalized around the ring, increasing the
and well-characterized.
molecules stability. The molecule cannot be represented
by one structure, but rather a resonance hybrid of different structures, such as with the two resonance struc5 Heterocyclic compounds
tures of benzene. These molecules cannot be found in
either one of these representations, with the longer single
Cyclic compounds that have both carbon and non-carbon bonds in one location and the shorter double bond in anatoms present are termed (heterocyclic compounds); al- other (See Theory below). Rather, the molecule exhibits
ternatively the name can refer to inorganic cyclic com- bond lengths in between those of single and double bonds.
pounds, such as siloxanes and borazines, that have more This commonly seen model of aromatic rings, namely the
type of atom in their rings. HantzschWidman nomen- idea that benzene was formed from a six-membered carclature is recommended by the IUPAC for naming hete- bon ring with alternating single and double bonds (cyclorocycles, but many common names remain in regular use. hexatriene), was developed by August Kekul (see History section below). The model for benzene consists of
two resonance forms, which corresponds to the double
and single bonds superimposing to produce six one-and6 Aromaticity
a-half bonds. Benzene is a more stable molecule than
Cyclic compounds may or may not exhibit aromaticity; would be expected without accounting for charge delobenzene is an example of an aromatic cyclic compound, calization.
The vast majority of cyclic compounds are organic, and
of these, a signicant proportion (and a conceptually important portion) are composed of rings made only of carbon atoms (i.e., they are carbocycles).

while cyclohexane is non-aromatic.In organic chemistry,

the term aromaticity is used to describe a cyclic (ringshaped), planar (at) molecule that exhibits unusual stability as compared to other geometric or connective arrangements of the same set of atoms. As a result of their
stability, it is very dicult to cause aromatic molecules

Simple, mono-cyclic examples

The following are examples of simple and aromatic carbocycles, inorganic cyclic compounds, and heterocycles:
Simple mono-cyclic compounds: Carbocyclic, inorganic, and heterocyclic (aromatic and non-aromatic)
examples.
Cycloheptane, a simple 7-membered carbocyclic
compound, methylene hydrogens shown (nonaromatic).
Benzene, a 6-membered carbocyclic compound. Dimethylcyclohexane, in chair form, minimising steric
methine hydrogens shown, and 6 electrons shown as interactions between the methyl groups in the directly
delocalized through drawing of circle (aromatic).
opposing 1,4-positions of the cyclohexane ring.
General description. The structures are shown in line
Cyclo-octasulfur, an 8-membered inorganic cyclic angle representation, though in the image at left, the lines
compound (non-aromatic).
projecting from the cyclohexane are not terminal methyl
groups; rather, they indicate possible positions that might
Pentazole, a 5-membered inorganic cyclic com- be occupied by substituents (functional groups) attached
pound (aromatic).
to the ring. In the image at left, those groups projecting
upward and downward are termed axial substituents
Azetidine, a 4-membered nitrogen (aza) hetero- (a), and those groups projecting around the conceptual
cyclic compound, methylene hydrogen atoms im- equator are termed equatorial substituents (e). Note, in
plied, not shown (non-aromatic).
general, the axial substituents are closer in space to one
another (allowing for repulsive interactions); moreover,
Pyridine, a 6 membered heterocyclic compound, in the boat form, axial substituents in directly opposing
methine hydrogen atoms implied, not shown, and positions (12 o'clock and 6 o'clock, termed 1,4-") are
delocalized -electrons shown as discrete bonds very close in space, and therefore give rise to even greater
(aromatic).
repulsion. These and other types of strain are used to
explain the observation that the chair conformation of
cyclohexanes is the favored conformation.[4]

Stereochemistry

The closing of atoms into rings may lock particular atoms

with distinct substitution by functional groups such that
the result is stereochemistry and chirality of the compound, including some manifestations that are unique to
rings (e.g., congurational isomers).[4]

Conformational isomerism

Depending on ring size, the three-dimensional shapes

of particular cyclic structurestypically rings of 5atoms and largercan vary and interconvert such that
conformational isomerism is displayed.[4] Indeed, the development of this important chemical concept arose, historically, in reference to cyclic compounds. For instance,
cyclohexanessix membered carbocycles with no double
bonds, to which various substituents might be attached,
see imagedisplay an equilibrium between two conformations, the chair and the boat, as shown in the image.

The chair conformation is the favored conguration, because in this conformation, the steric strain, eclipsing
strain, and angle strain that are otherwise possible are
minimized.[4] Which of the possible chair conformations
predominate in cyclohexanes bearing one or more substituents depends on the substiuents, and where they are
located on the ring; generally, bulky substituents
those groups with large volumes, or groups that are
Chair
otherwise
repulsive in their interactionsprefer to ocand boat conformers in cyclohexanes. Two conformcupy
an
equatorial
location.[4] An example of interactions
ers of cyclohexane, the chair at left, and the boat at right
(in German, respectively, Sessel and Wanne, the latter within a molecule that would lead to steric strain, leading to a shift in equilibrium from boat to chair, is the
meaning bath).

cis1,4-

12

interaction between the two methyl groups in cis1,4dimethylcyclohexane. In this molecule, the two methyl
groups are in opposing positions of the ring (1,4-), and
their cis stereochemistry projects both of these groups toward the same side of the ring. Hence, if forced into the
higher energy boat form, these methyl groups are in steric
contact, repel one another, and drive the equilibrium toward the chair conformation.

10

COMPLEX AND POLYCYCLIC EXAMPLES

11 Principle uses of cyclic structures

Because of the unique shapes, reactivities, properties, and
bioactivities that they engender, are the largest majority
of all molecules involved in the biochemistry, structure,
and function of living organisms, and in the man-made
molecules (e.g., drugs, herbicides, etc.) through which
man attempts to exert control over nature and biological
systems.

Macrocycles
12 Complex and polycyclic examples
The following are examples of cyclic compounds exhibiting more complex ring systems and stereochemical features:
Complex cyclic compounds: Macrocyclic and polycyclic examples

The term macrocycle is used for compounds having a

rings of 8 or more atoms.[5][6] Macrocycles may be fully
carbocyclic, heterocyclic but having limited heteroatoms
(e.g., in lactones and lactams), or be rich in heteroatoms
and displaying signicant symmetry (e.g., in the case of
chelating macrocycles). Macrocycles can access a number of stable conformations, with preference to reside in
conformations that minimize transannular nonbonded interactions within the ring (e.g., with the chair and chairboat being more stable than the boat-boat conformation
for cyclooctane, because of the interactions depicted by
the arcs shown). Medium rings (8-11 atoms) are the
most strained, with between 9-13 (kcal/mol) strain energy, and analysis of factors important in the conformations of larger macrocycles can be modeled using medium
ring conformations.[7] Conformational analysis of oddmembered rings suggests they tend to reside in less symmetrical forms with smaller energy dierences between
stable conformations.[8]

Naphthalene, technically a polycyclic, more specifically a bicyclic compound, with circles showing
delocalization of -electrons (aromatic).
Decalin (decahydronaphthalene), the fully saturated derivative of naphthalene, showing the two
stereochemistries possible for fusing the two rings
together, and how this impacts the shapes available
to this bicyclic compound (non-aromatic).
Longifolene, a terpene natural product, and an example of a tricyclic molecule (non-aromatic).
Paclitaxel, a polycyclic natural product with a tricyclic core: with a heterocyclic, 4-membered D
ring, fused to further 6- and 8-membered carbocyclic (A/C and B) rings (non-aromatic), and with
three further pendant phenyl-rings on its tail, and
attached to C-2 (abbrev. Ph, C6 H5 ; aromatics).
A representative three-dimensional shape adopted
by paclitaxel, as a result of its unique cyclic
structure.[1]
Cholesterol, another terpene natural product, in particular, a steroid, a class of tetracyclic molecules
(non-aromatic).

Chelating macrocyclic structures of interest in inorganic and

supramolecular chemistry, an example array. A, the crown
ether, 18-crown-6; B, the simple tetra-aza chelator, cyclam; C,
an example porphyrin, the unsubstituted porphine; D, a mixed
amine/imine, the Curtis macrocycle; E, the related enamine/imine
Jger macrocycle, and F, the tetracarboxylate-derivative DOTA
macrocycle.

Benzo[a]pyrene, a pentacyclic compound both natural and man-made, and delocalized -electrons
shown as discrete bonds (aromatic).
Pagodane, a complex, highly symmetric, man-made
polycyclic compound (non-aromatic).
Brevetoxin A, a natural product with ten rings, all
fused, and all heterocyclic, and a toxic component associated with the organisms responsible for

13.3

Ring-opening reactions

red tides. The R group at right refers to one of

several possible four-carbon side chains (see main
Brevetoxin article; non-aromatic).
1. ^ J. Lwe, H. Li, K.H. Downing & E. Nogales,
2001, Rened structure of alpha beta-tubulin at 3.5
A resolution, J. Mol. Biol 313:1045-1057 PMID
11700061

13
13.1

Synthetic
rings

reactions

various radical cyclizations;

ring-closing metathesis reactions, which can be
also be used to accomplish a specic type of
polymerization;
the Ruzicka large ring synthesis; and
the Wenker synthesis of aziridines.

altering 13.3 Ring-opening reactions

A variety of further synthetic procedures are particularly

useful in opening carbocyclic and other rings, generally
Important general reactions for form- which contain a double bound or other functional group
handle to facilitate chemistry; these are termed ringing rings
opening reactions. Examples include:
ring opening metathesis, which can be also be used
to accomplish a specic type of polymerization.

13.4 Ring expansion and ring contraction

reactions
Main article: Ring expansion and ring contraction
Dieckmann ring-closing reaction

There are a variety of specialized reactions whose use

is solely the formation of rings, and these will be discussed below. In addition to those, there are a wide variety of general organic reactions that historically have
been crucial in the development, rst, of understanding
the concepts of ring chemistry, and second, of reliable
procedures for preparing ring structures in high yield, and
with dened orientation of ring substituents (i.e., dened
stereochemistry). These general reactions include:
Acyloin condensation;
Anodic oxidations; and
the Dieckmann condensation as applied to ring formation.

13.2

Ring-closing reactions

In organic chemistry, a variety of synthetic procures are

particularly useful in closing carbocyclic and other rings;
these are termed ring-closing reactions. Examples include:
alkyne trimerisation;
the Bergman cyclization;
the Diels-Alder and other cycloaddition reactions;
the Nazarov cyclization reaction;

14 Further reading
Jrgen-Hinrich Fuhrhop & Gustav Penzlin, 1986,
Organic synthesis: concepts, methods, starting
materials, Weinheim, BW, DEU:VCH, ISBN
0895732467, see , accessed 19 June 2015.
Michael B. Smith & Jerry March, 2007, Marchs
Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 6th Ed., New York, NY,
USA:Wiley & Sons, ISBN 0470084944, see , accessed 19 June 2015.
Francis A. Carey & Richard J. Sundberg, 2006, Title Advanced Organic Chemistry: Part A: Structure and Mechanisms, 4th Edn., New York, NY,
USA:Springer Science & Business Media, ISBN
0306468565, see , accessed 19 June 2015.
Michael B. Smith, 2011, Organic Chemistry: An
AcidBase Approach, Boca Raton, FL, USA:
CRC Press, ISBN 1420079212, see , accessed 19
June 2015. [May not be most necessary material for
this article, but signicant content here is available
online.]
Jonathan Clayden, Nick Greeves & Stuart Warren,
2012, Organic Chemistry, Oxford, Oxon, GBR:
Oxford University Press, ISBN 0199270295, see ,
accessed 19 June 2015.

17
Lszl Krti & Barbara Czak, 2005, Strategic Applications of Named Reactions in Organic
Synthesis: Background and Detailed Mechanisms,
Amsterdam, NH, NLD:Elsevier Academic Press,
2005ISBN 0124297854, see , accessed 19 June
2015.

15

See also

Eective molarity
Heterocyclic compound
Lactone
Macrocycle
Open-chain compound

16

External links

Polycyclic Compounds at the US National Library

of Medicine Medical Subject Headings (MeSH)
Macrocyclic Compounds at the US National Library
of Medicine Medical Subject Headings (MeSH)

17

References

[1] March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York:
Wiley, ISBN 0-471-85472-7.
[2] I. Halduc, 1961, Classication of inorganic cyclic compounds, J. Struct. Chem. 2(3):350-358, see , accessed 8
April 2015.
[3] Jean-Louis Reymond, 2015, The Chemical Space
Project, Acc. Chem. Res., 48(3), 722-730, DOI
10.1021/ar500432k, see , accessed 7 April 2015.
[4] William Reusch, 2010, Stereoisomers Part I, In Virtual
Textbook of Organic Chemistry, Michigan State University, see , accessed 7 April 2015.
[5] Still, W. C.; Galynker, I. Chemical consequences of
conformation in macrocyclic compounds: An eective
approach to remote asymmetric induction, Tetrahedron
1981, 37, 3981-3996, see , accessed 19 June 2015.
[6] J. D. Dunitz. Perspectives in Structural Chemistry (Edited
by J. D. Dunitz and J. A. Ibers), Vol. 2, pp. l-70; Wiley,
New York (1968)
[7] Eliel, E.L., Wilen, S.H. and Mander, L.S. (1994) Stereochemistry of Organic Compounds, John Wiley and Sons,
Inc., New York.

REFERENCES

[8] Anet, F.A.L.; St. Jacques, M.; Henrichs, P.M.; Cheng,

A.K.; Krane, J.; Wong, L. Conformational analysis of medium-ring ketones, Tetrahedron 1974, 30,
1629-1637, see [www.sciencedirect.com/science/article/
pii/S0040402001906854], accessed 19 June 2015.

18
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