Geometric isomerism (also known as cis-trans isomerism or E-Z isomerism) is a

form of stereoisomerism.
What are isomers?
Isomers are molecules that have the same molecular formula, but have a different
arrangement of the atoms in space. That excludes any different arrangements
which are simply due to the molecule rotating as a whole, or rotating about
particular bonds.
Where the atoms making up the various isomers are joined up in a different order,
this is known as structural isomerism. Structural isomerism is not a form of
stereoisomerism, and is dealt with on a separate page.
What are stereoisomers?
In stereoisomerism, the atoms making up the isomers are joined up in the same
order, but still manage to have a different spatial arrangement. Geometric
isomerism is one form of stereoisomerism.
Geometric (cis / trans) isomerism
How geometric isomers arise
These isomers occur where you have restricted rotation somewhere in a molecule.
At an introductory level in organic chemistry, examples usually just involve the
carbon-carbon double bond - and that's what this page will concentrate on.
Think about what happens in molecules where there isunrestricted rotation about
carbon bonds - in other words where the carbon-carbon bonds are all single. The
next diagram shows two possible configurations of 1,2-dichloroethane.

These two models represent exactly the same molecule. You can get from one to
the other just by twisting around the carbon-carbon single bond. These molecules
are not isomers.
If you draw a structural formula instead of using models, you have to bear in mind
the possibility of this free rotation about single bonds. You must accept that these
two structures represent the same molecule:

But what happens if you have a carbon-carbon double bond - as in 1,2dichloroethene?

These two molecules aren't the same. The carbon-carbon double bond won't rotate
and so you would have to take the models to pieces in order to convert one
structure into the other one. That is a simple test for isomers. If you have to take a
model to pieces to convert it into another one, then you've got isomers. If you
merely have to twist it a bit, then you haven't!
Drawing structural formulae for the last pair of models gives two possible isomers.
In one, the two chlorine atoms are locked on opposite sides of the double bond. This
is known as the trans isomer. (trans : from latin meaning "across" - as in
transatlantic).
In the other, the two chlorine atoms are locked on the same side of the double
bond. This is know as the cis isomer. (cis : from latin meaning "on this side")

The most likely example of geometric isomerism you will meet at an introductory
level is but-2-ene. In one case, the CH3 groups are on opposite sides of the double
bond, and in the other case they are on the same side.

The importance of drawing geometric isomers properly

It's very easy to miss geometric isomers in exams if you take short-cuts in drawing
the structural formulae. For example, it is very tempting to draw but-2-ene as
CH3CH=CHCH3
If you write it like this, you will almost certainly miss the fact that there are
geometric isomers. If there is even the slightest hint in a question that isomers
might be involved, always draw compounds containing carbon-carbon double bonds
showing the correct bond angles (120) around the carbon atoms at the ends of the
bond. In other words, use the format shown in the last diagrams above.

How to recognise the possibility of geometric isomerism

You obviously need to have restricted rotation somewhere in the molecule.
Compounds containing a carbon-carbon double bond have this restricted rotation.
(Other sorts of compounds may have restricted rotation as well, but we are
concentrating on the case you are most likely to meet when you first come across
geometric isomers.) If you have a carbon-carbon double bond, you need to think
carefully about the possibility of geometric isomers.

Aliphatic compounds can be saturated, joined by single bonds (alkanes), or unsaturated, with
double bonds (alkenes) or triple bonds (alkynes). Besides hydrogen, other elements can be bound to
the carbon chain, the most common being oxygen, nitrogen, sulphur, and chlorine.
The simplest aliphatic compound is methane (CH4). Aliphatics include alkanes, alkenes, and alkynes.

Examples of aliphatic compounds / non-aromatic[edit]

The most important aliphatic compounds are:

n-, iso- and cyclo-alkanes (saturated hydrocarbons)

n-, iso- and cyclo-alkenes and -alkynes (unsaturated hydrocarbons).

Important examples of low-molecular aliphatic compounds can be found in the list below (sorted by
the number of carbon-atoms):
Formul
a

CAS-

Name

Number

Structural Formula

Chemical Classification

CH4

Methane

74-82-8

Alkane

C2 H2

Ethyne

74-86-2

Alkyne

C2 H4

Ethene

74-85-1

Alkene

C2 H6

Ethane

74-84-0

Alkane

C3 H4

Propyne

74-99-7

Alkyne

C3 H6

Propene

Alkene

C3 H8

Propane

Alkane

C4 H6

1,2-Butadiene

590-19-2

Diene

C4 H6

1-Butyne

Alkyne

e.g.
C4 H8

Butene

Alkene

C4H10

Butane

Alkane

C6H10

Cyclohexene

110-83-8

Cycloalkene

C5H12

n-pentane

109-66-0

Alkane

C7H14

Cycloheptane

291-64-5

Cycloalkane

108-87-2

Cyclohexane

277-10-1

Cyclobutane

C7H14

C8 H8

Methylcyclohexan
e

Cubane

C9H20

Nonane

111-84-2

Alkane

C10H12

Dicyclopentadiene

77-73-6

Diene, Cycloalkene

C10H16

Phellandrene

99-83-2

Terpene, Diene Cycloalkene

C10H16

-Terpinene

99-86-5

C10H16

Limonene

5989-27-5

C11H24

Undecane

1120-21-4

Alkane

C30H50

Squalene

111-02-4

Terpene, Polyene

C2nH4n

Polyethylene

9002-88-4

Alkane

Terpene, Cycloalkene,
Diene

Terpene, Diene,
Cycloalkene

A cyclic compound (ring compound) is a term for a compound in the field 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 fullysaturated 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.

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

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.

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 fill the carbon's valence of 4 (rather than their being shown explicitly).

Paclitaxel, another complex, plant-derivedterpenoid, also a natural product, displaying a complex multiring structure including 4-, 6-, and 8-membered rings (carbocyclic andheterocyclic, aromatic and nonaromatic).

Adding to their complexity and number, closing of atoms into rings may lock particular atoms with
distinct substitution (by functional groups) such that stereochemistry andchirality of the compound
results, including some manifestations that are unique to rings (e.g., configurational 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 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, andbioactivities 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.).

A heterocyclic compound or ring structure is a cyclic compound that has atoms of at least two
different elements as members of its ring(s).[1] Heterocyclic chemistry is the branch of chemistry
dealing with the synthesis, properties and applications of these heterocycles. In contrast, the rings
of homocyclic compounds consist entirely of atoms of the same element.
Although heterocyclic compounds may be inorganic, most contain at least one carbon. While atoms
that are neither carbon nor hydrogen are normally referred to in organic chemistry as heteroatoms,
this is usually in comparison to the all-carbon backbone. But this does not prevent a compound such
as borazine (which has no carbon atoms) from being labelled "heterocyclic". IUPACrecommends
the Hantzsch-Widman nomenclature for naming heterocyclic compounds.

Classification based on electronic structure[edit]

Heterocyclic compounds can be usefully classified based on their electronic structure. The saturated
heterocycles behave like the acyclic derivatives. Thus, piperidine and tetrahydrofuran are
conventional amines and ethers, with modified steric profiles. Therefore, the study of heterocyclic
chemistry focuses especially on unsaturated derivatives, and the preponderance of work and
applications involves unstrained 5- and 6-membered rings. Included are pyridine, thiophene, pyrrole,
and furan. Another large class of heterocycles are fused to benzene rings, which for pyridine,
thiophene, pyrrole, and furan are quinoline, benzothiophene, indole, and benzofuran, respectively.
Fusion of two benzene rings gives rise to a third large family of compounds, respectively

the acridine, dibenzothiophene, carbazole, and dibenzofuran. The unsaturated rings can be
classified according to the participation of the heteroatom in the pi system.

3-membered rings[edit]
Heterocycles with three atoms in the ring are more reactive because of ring strain. Those containing
one heteroatom are, in general, stable. Those with two heteroatoms are more likely to occur as
reactive intermediates.
Common 3-membered heterocycles with one heteroatom are:
Heteroatom

Nitrogen

Oxygen

Sulfur

Saturated

Aziridine

Oxirane (ethylene
oxide, epoxides)

Thiirane (episulfides)

Unsaturated

Azirine

Oxirene

Thiirene

Those with two heteroatoms include:

Heteroatom

Saturated

Nitrogen

Diaziridine

Nitrogen/oxygen

Oxaziridine

Oxygen

Dioxirane

4-membered rings[edit]
Compounds with one heteroatom:

Unsaturated

Diazirine

Heteroatom

Saturated

Unsaturated

Nitrogen

Azetidine

Azete

Oxygen

Oxetane

Oxete

Sulfur

Thietane

Thiete

Compounds with two heteroatoms:

Heteroatom

Saturated

Unsaturated

Nitrogen

Diazetidine

Diazete

Oxygen

Dioxetane

Dioxete

Sulfur

Dithietane

Dithiete

5-membered rings[edit]
With heterocycles containing five atoms, the unsaturated compounds are frequently more stable
because of aromaticity.
Five-membered rings with one heteroatom:
Heteroatom

Saturated

Unsaturated

Nitrogen

Pyrrolidine (Azolidine is not used)

Pyrrole (Azole is not used)

Oxygen

Tetrahydrofuran (Oxolane is rare)

Furan (Oxole is not used)

Sulfur

Thiolane

Thiophene (Thiole is not used)

Boron

Borolane

Borole

Phospholane

Phosphole

Arsenic

Arsolane

Arsole

Antimony

Stibolane

Stibole

Bismuth

Bismolane

Bismole

Silolane

Silole

Stannolane

Stannole

Phosphorus

Silicon

Tin

The 5-membered ring compounds containing two heteroatoms, at least one of which is nitrogen, are
collectively called the azoles. Thiazoles and isothiazoles contain a sulfur and a nitrogen atom in the
ring. Dithiolanes have two sulfur atoms.

Unsaturated (and
Heteroatom

Saturated

partially
unsaturated)

Nitrogen/nitroge

Imidazolidine

Imidazole (Imidazolin

Pyrazolidine

e)
Pyrazole (Pyrazoline)

Nitrogen/oxygen Oxazolidine

Oxazole (Oxazoline)

Nitrogen/sulfur

Isoxazolidine

Isoxazole

Thiazolidine

Thiazole (Thiazoline)

Isothiazolidin

Isothiazole

Oxygen/oxygen

Dioxolane

Sulfur/sulfur

Dithiolane

A large group of 5-membered ring compounds with three heteroatoms also exists. One example is
dithiazoles that contain two sulfur and a nitrogen atom.

Heteroatom

Saturated

3 Nitrogen

Unsaturated

Triazoles

2 Nitrogen / 1 oxygen

Furazan
Oxadiazole

2 Nitrogen / 1 sulfur

Thiadiazole

1 Nitrogen / 2 sulfur

Dithiazole

Five-member ring compounds with four heteroatoms:

Heteroatom

4 Nitrogen

Saturated

Unsaturated

Tetrazole

With 5-heteroatoms, the compound may be considered inorganic rather than

heterocyclic. Pentazole is the all nitrogen heteroatom unsaturated compound.

6-membered rings[edit]
Six-membered rings with a single heteroatom:
Heteroatom

Saturated

Unsaturated

Nitrogen

Piperidine (Azinane is not used)

Pyridine (Azine is not used)

Oxygen

Oxane

Pyran (2H-Oxine is not used)

Sulfur

Thiane

Thiopyran (2H-Thiine is not used)

Silicon

Salinane

Siline

Germanium

Germinane

Germine

Tin

Stanninane

Stannine

Boron

Borinane

Borinine

Phosphorus

Phosphinane

Phosphinine

Arsenic

Arsinane

Arsinine

With two heteroatoms:

Heteroatom

Saturated

Unsaturated

Nitrogen / nitrogen

Piperazine

Diazines

Oxygen / nitrogen

Morpholine

Oxazine

Sulfur / nitrogen

Thiomorpholine

Thiazine

Oxygen / oxygen

Dioxane

Dioxine

Sulfur / sulfur

Dithiane

Dithiine

With three heteroatoms:

Heteroatom

Saturated

Nitrogen

Unsaturated

Triazine

Oxygen

Trioxane

Sulfur

Trithiane

With four heteroatoms:

Heteroatom

Saturated

Nitrogen

Unsaturated

Tetrazine

With five heteroatoms:

Heteroatom

Saturated

Unsaturated

Nitrogen

Pentazine

The hypothetical compound with six nitrogen heteroatoms would be hexazine.

7-membered rings[edit]
With 7-membered rings, the heteroatom must be able to provide an empty pi orbital (e.g., boron) for
"normal" aromatic stabilization to be available; otherwise, homoaromaticitymay be possible.
Compounds with one heteroatom include:
Heteroatom

Saturated

Unsaturated

Nitrogen

Azepane

Azepine

Oxygen

Oxepane

Oxepine

Sulfur

Thiepane

Thiepine

Those with two heteroatoms include:

Heteroatom

Nitrogen

Saturated

Homopiperazine

Nitrogen/sulfur

Unsaturated

Diazepine

Thiazepine

8-membered rings[edit]
Heteroatom

Nitrogen

Saturated

Azocane

Unsaturated

Azocine

Oxygen

Oxocane

Oxocine

Sulfur

Thiocane

Thiocine

9-membered rings[edit]
Heteroatom

Saturated

Unsaturated

Nitrogen

Azonane

Azonine

Oxygen

Oxonane

Oxonine

Sulfur

Thionane

Thionine

Names in italics are retained by IUPAC and they do not follow the Hantzsch-Widman
nomenclature
Saturated

Heteroatom

Nitrogen

Aziridine

3-Atom Ring

Oxygen

Oxirane

Unsaturated

Sulfur

Thiirane

Nitrogen

Azirine

Oxygen

Oxirene

Sulfur

Thiirene

Azetidine

Oxetane

Thietane

Azete

Oxete

Thiete

Pyrrolidine

Oxolane

Thiolane

Pyrrole

Furan

Thiophene

Piperidine

Oxane

Thiane

Pyridine

Pyran

Thiopyran

Azepane

Oxepane

Thiepane

Azepine

Oxepine

Thiepine

4-Atom Ring

5-Atom Ring

6-Atom Ring

7-Atom Ring

Fused rings[edit]

Heterocyclic rings systems that are formally derived by fusion with other rings,
either carbocyclic or heterocyclic, have a variety of common and systematic names. For
example, with the benzo-fused unsaturated nitrogen heterocycles, pyrrole
provides indole or isoindole depending on the orientation. The pyridine analog
is quinoline or isoquinoline. For azepine, benzazepine is the preferred name. Likewise, the
compounds with two benzene rings fused to the central heterocycle are carbazole, acridine, and
dibenzoazepine.

History of heterocyclic chemistry[edit]

The history of heterocyclic chemistry began in the 1800s, in step with the development
of organic chemistry. Some noteworthy developments:[2]
1818: Brugnatelli isolates alloxan from uric acid
1832: Dobereiner produces furfural (a furan) by treating starch with sulfuric acid
1834: Runge obtains pyrrole ("fiery oil") by dry distillation of bones
1906: Friedlander synthesizes indigo dye, allowing synthetic chemistry to displace a large
agricultural industry
1936: Treibs isolates chlorophyl derivatives from crude oil, explaining the biological origin of
petroleum.
1951: Chargaff's rules are described, highlighting the role of heterocyclic compounds
(purines and pyrimidines) in the genetic code.