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Arene substitution patterns are part of
organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...
IUPAC nomenclature A chemical nomenclature is a set of rules to generate systematic names for chemical compounds. The nomenclature used most frequently worldwide is the one created and developed by the International Union of Pure and Applied Chemistry (IUPAC). The ...
and pinpoint the position of
substituent A substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (In organic chemistry and biochemistry, the terms ''substituent'' and ''functional group'', as well as ''side ...
s other than
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
in relation to each other on an
aromatic hydrocarbon Aromatic compounds, also known as "mono- and polycyclic aromatic hydrocarbons", are organic compounds containing one or more aromatic rings. The parent member of aromatic compounds is benzene. The word "aromatic" originates from the past grouping ...
.


''Ortho'', ''meta'', and ''para'' substitution

* In ''ortho''-substitution, two substituents occupy positions next to each other, which may be numbered 1 and 2. In the diagram, these positions are marked R and ''ortho''. * In ''meta''-substitution the substituents occupy positions 1 and 3 (corresponding to R and ''meta'' in the diagram). * In ''para''-substitution, the substituents occupy the opposite ends (positions 1 and 4, corresponding to R and ''para'' in the diagram). The
toluidine There are three isomers of toluidine, which are organic compounds. These isomers are ''o''-toluidine, ''m''-toluidine, and ''p''-toluidine, with the prefixed letter abbreviating, respectively, ''ortho''; ''meta''; and ''para''. All three are aryl ...
s serve as an example for these three types of substitution.


Synthesis

Electron donating groups, for example
amino In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent s ...
,
hydroxyl In chemistry, a hydroxy or hydroxyl group is a functional group with the chemical formula and composed of one oxygen atom covalently bonded to one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain one or more hydroxy ...
,
alkyl In organic chemistry, an alkyl group is an alkane missing one hydrogen. The term ''alkyl'' is intentionally unspecific to include many possible substitutions. An acyclic alkyl has the general formula of . A cycloalkyl is derived from a cycloalk ...
, and
phenyl In organic chemistry, the phenyl group, or phenyl ring, is a cyclic group of atoms with the formula C6 H5, and is often represented by the symbol Ph. Phenyl group is closely related to benzene and can be viewed as a benzene ring, minus a hydrogen ...
groups tend to be ''ortho''/''para''-directors, and electron withdrawing groups such as
nitro Nitro may refer to: Chemistry *Nitrogen, a chemical element and a gas except at very low temperatures, with which many compounds are formed: **Nitro compound, an organic compound containing one or more nitro functional groups, -NO2 **Nitroalkene, ...
,
nitrile In organic chemistry, a nitrile is any organic compound that has a functional group. The prefix ''cyano-'' is used interchangeably with the term ''nitrile'' in industrial literature. Nitriles are found in many useful compounds, including met ...
, and
ketone In organic chemistry, a ketone is a functional group with the structure R–C(=O)–R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group –C(=O)– (which contains a carbon-oxygen double bo ...
groups, tend to be ''meta''-directors.


Properties

Although the specifics vary depending on the compound, in simple disubstituted arenes, the three isomers tend to have rather similar boiling points. However, the ''para'' isomer usually has the highest melting point, and the lowest solubility in a given solvent, of the three isomers.


Separation of ''ortho'' and ''para'' isomers

Because electron donating groups are both ''ortho'' and ''para'' directors, separation of these isomers is a common problem in synthetic chemistry. Several methods exist in order to separate these isomers: *
Column chromatography Column chromatography in chemistry is a chromatography method used to isolate a single chemical compound from a mixture. Chromatography is able to separate substances based on differential adsorption of compounds to the adsorbent; compounds move th ...
will often separate these isomers, as the ''ortho'' is more
polar Polar may refer to: Geography Polar may refer to: * Geographical pole, either of two fixed points on the surface of a rotating body or planet, at 90 degrees from the equator, based on the axis around which a body rotates * Polar climate, the c ...
than the ''para'' in general. * Fractional crystallisation can be used to obtain pure ''para'' product, relying on the principle that it is less soluble than the ''ortho'' and thus will crystallise first. Care must be taken to avoid
cocrystal Cocrystals are "solids that are crystalline single phase materials composed of two or more different molecular or ionic compounds generally in a stoichiometric ratio which are neither solvates nor simple salts." A broader definition is that cocryst ...
lisation of the ''ortho'' isomer. *Many
nitro compound In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups (). The nitro group is one of the most common explosophores (functional group that makes a compound explosive) used globally. The nitr ...
s' ''ortho'' and ''para'' isomers have quite different
boiling point The boiling point of a substance is the temperature at which the vapor pressure of a liquid equals the pressure surrounding the liquid and the liquid changes into a vapor. The boiling point of a liquid varies depending upon the surrounding envir ...
s. These isomers can often be separated by distillation. These separated isomers can be converted to
diazonium salt Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halide. General properti ...
s and used to prepare other pure ''ortho'' or ''para'' compounds.


''Ipso'', ''meso'', and ''peri'' substitution

Image:Ipso Substitution V.3.svg, ''ipso''- substitution. Image:Meso Substitution V.1.svg, ''meso''- substitution. Image:Peri Substitution V.1.svg, ''peri''- substitution. * ''Ipso''-substitution describes two substituents sharing the same ring position in an intermediate compound in an
electrophilic aromatic substitution Electrophilic aromatic substitution is an organic reaction in which an atom that is attached to an aromatic system (usually hydrogen) is replaced by an electrophile. Some of the most important electrophilic aromatic substitutions are aromatic ni ...
.
Trimethylsilyl A trimethylsilyl group (abbreviated TMS) is a functional group in organic chemistry. This group consists of three methyl groups bonded to a silicon atom minus;Si(CH3)3 which is in turn bonded to the rest of a molecule. This structural group is ch ...
, ''tert''-butyl, and
isopropyl In organic chemistry, propyl is a three-carbon alkyl substituent with chemical formula for the linear form. This substituent form is obtained by removing one hydrogen atom attached to the terminal carbon of propane. A propyl substituent is ofte ...
groups can form stable
carbocation A carbocation is an ion with a positively charged carbon atom. Among the simplest examples are the methenium , methanium and vinyl cations. Occasionally, carbocations that bear more than one positively charged carbon atom are also encountere ...
s, hence are ''ipso'' directing groups. * ''Meso''-substitution refers to the substituents occupying a
benzyl In organic chemistry, benzyl is the substituent or molecular fragment possessing the structure . Benzyl features a benzene ring () attached to a methylene group () group. Nomenclature In IUPAC nomenclature, the prefix benzyl refers to a substi ...
ic position. It is observed in compounds such as
calixarene A calixarene is a macrocycle or cyclic oligomer based on a methylene-linked phenols. With hydrophobic cavities that can hold smaller molecules or ions, calixarenes belong to the class of cavitands known in host–guest chemistry. Nomenclature Cal ...
s and
acridine Acridine is an organic compound and a nitrogen heterocycle with the formula C13H9N. Acridines are substituted derivatives of the parent ring. It is a planar molecule that is structurally related to anthracene with one of the central CH groups re ...
s. * ''Peri''-substitution occurs in
naphthalene Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08  ppm by mass. As an aromati ...
s for substituents at the 1 and 8 positions.


''Cine'' and ''tele'' substitution

* In ''cine''-substitution, the entering group takes up a position adjacent to that occupied by the
leaving group In chemistry, a leaving group is defined by the IUPAC as an atom or group of atoms that detaches from the main or residual part of a substrate during a reaction or elementary step of a reaction. However, in common usage, the term is often limited t ...
. For example, ''cine''-substitution is observed in
aryne Arynes and benzynes are highly reactive species derived from an aromatic ring by removal of two substituents. Arynes are examples of didehydroarenes (1,2-didehydroarenes in this case), although 1,3- and 1,4-didehydroarenes are also known. Arynes a ...
chemistry. * ''Tele''-substitution occurs when the new position is more than one atom away on the ring.


Origins

The prefixes ''ortho'', ''meta'', and ''para'' are all derived from Greek, meaning ''correct'', ''following'', and ''beside'', respectively. The relationship to the current meaning is perhaps not obvious. The ''ortho'' description was historically used to designate the original compound, and an isomer was often called the ''meta'' compound. For instance, the trivial names
orthophosphoric acid Phosphoric acid (orthophosphoric acid, monophosphoric acid or phosphoric(V) acid) is a colorless, odorless phosphorus-containing solid, and inorganic compound with the chemical formula . It is commonly encountered as an 85% aqueous solution, w ...
and trimetaphosphoric acid have nothing to do with aromatics at all. Likewise, the description ''para'' was reserved for just closely related compounds. Thus
Jöns Jakob Berzelius Jöns is a Swedish given name and a surname. Notable people with the given name include: * Jöns Jacob Berzelius (1779–1848), Swedish chemist * Jöns Budde (1435–1495), Franciscan friar from the Brigittine monastery in NaantaliVallis Gratiae ...
originally called the
racemic In chemistry, a racemic mixture, or racemate (), is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as racemates. ...
form of
tartaric acid Tartaric acid is a white, crystalline organic acid that occurs naturally in many fruits, most notably in grapes, but also in bananas, tamarinds, and citrus. Its salt, potassium bitartrate, commonly known as cream of tartar, develops naturally i ...
"paratartaric acid" (another obsolete term:
racemic acid Racemic acid is an old name for an optically inactive or racemic form of tartaric acid. It is an equal mixture of two mirror-image isomers ( enantiomers), optically active in opposing directions. It occurs naturally in grape juice. Tartaric aci ...
) in 1830. The use of the prefixes ''ortho'', ''meta'' and ''para'' to distinguish isomers of disubstituted aromatic rings starts with
Wilhelm Körner Wilhelm Körner, later a.k.a. Guglielmo Körner (April 20, 1839 in Cassel – March 29, 1925 in Milan), was a German chemist. Life Körner studied chemistry at Giessen, where he graduated in 1860. In 1866, he became assistant to Kekulé at ...
in 1867, although he applied the ''ortho'' prefix to a 1,4-isomer and the ''meta'' prefix to a 1,2-isomer. It was the German chemist Karl Gräbe who, in 1869, first used the prefixes ''ortho''-, ''meta''-, ''para''- to denote specific relative locations of the substituents on a disubstituted aromatic ring (namely
naphthalene Naphthalene is an organic compound with formula . It is the simplest polycyclic aromatic hydrocarbon, and is a white crystalline solid with a characteristic odor that is detectable at concentrations as low as 0.08  ppm by mass. As an aromati ...
). In 1870, the German chemist
Viktor Meyer Viktor Meyer (8 September 18488 August 1897) was a German chemist and significant contributor to both organic and inorganic chemistry. He is best known for inventing an apparatus for determining vapour densities, the Viktor Meyer apparatus, and ...
first applied Gräbe's nomenclature to
benzene Benzene is an organic chemical compound with the molecular formula C6H6. The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom attached to each. Because it contains only carbon and hydrogen atoms, ...
. The current nomenclature was introduced by the
Chemical Society The Chemical Society was a scientific society formed in 1841 (then named the Chemical Society of London) by 77 scientists as a result of increased interest in scientific matters. Chemist Robert Warington was the driving force behind its creation. ...
in 1879.


Examples

Examples of the use of this nomenclature are given for
isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Iso ...
s of
cresol Cresols (also hydroxytoluene or cresylic acid) are a group of aromatic organic compounds. They are widely-occurring phenols (sometimes called ''phenolics'') which may be either natural or manufactured. They are also categorized as methylphenol ...
, C6H4(OH)(CH3): File:Ortho-cresol-2D-skeletal.png, ''o''-cresol File:Meta-cresol-2D-skeletal.png, ''m''-cresol File:Para-cresol-vertical-2D-skeletal.png, ''p''-cresol There are three arene substitution isomers of dihydroxybenzene (C6H4(OH)2) – the ''ortho'' isomer
catechol Catechol ( or ), also known as pyrocatechol or 1,2-dihydroxybenzene, is a toxic organic compound with the molecular formula . It is the ''ortho'' isomer of the three isomeric benzenediols. This colorless compound occurs naturally in trace amoun ...
, the ''meta'' isomer
resorcinol Resorcinol (or resorcin) is an organic compound with the formula C6H4(OH)2. It is one of three isomeric benzenediols, the 1,3-isomer (or '' meta''-isomer). Resorcinol crystallizes from benzene as colorless needles that are readily soluble in w ...
, and the ''para'' isomer
hydroquinone Hydroquinone, also known as benzene-1,4-diol or quinol, is an aromatic organic compound that is a type of phenol, a derivative of benzene, having the chemical formula C6H4(OH)2. It has two hydroxyl groups bonded to a benzene ring in a ''para'' ...
: File:Pyrocatechol.svg,
catechol Catechol ( or ), also known as pyrocatechol or 1,2-dihydroxybenzene, is a toxic organic compound with the molecular formula . It is the ''ortho'' isomer of the three isomeric benzenediols. This colorless compound occurs naturally in trace amoun ...
File:Resorcin.svg,
resorcinol Resorcinol (or resorcin) is an organic compound with the formula C6H4(OH)2. It is one of three isomeric benzenediols, the 1,3-isomer (or '' meta''-isomer). Resorcinol crystallizes from benzene as colorless needles that are readily soluble in w ...
File:Hydrochinon.svg,
hydroquinone Hydroquinone, also known as benzene-1,4-diol or quinol, is an aromatic organic compound that is a type of phenol, a derivative of benzene, having the chemical formula C6H4(OH)2. It has two hydroxyl groups bonded to a benzene ring in a ''para'' ...
There are three arene substitution isomers of
benzenedicarboxylic acid Benzenedicarboxylic acid is a group of chemical compounds which are dicarboxylic derivatives of benzene. Benzenedicarboxylic acid comes in three isomers: *Phthalic acid (1,2-benzenedicarboxylic acid) *Isophthalic acid (1,3-benzenedicarboxylic aci ...
(C6H4(COOH)2) – the ''ortho'' isomer
phthalic acid Phthalic acid is an aromatic dicarboxylic acid, with formula C6H4(CO2H)2. Although phthalic acid is of modest commercial importance, the closely related derivative phthalic anhydride is a commodity chemical produced on a large scale. Phthalic aci ...
, the ''meta'' isomer
isophthalic acid Isophthalic acid is an organic compound with the formula C6H4(CO2H)2. This colorless solid is an isomer of phthalic acid and terephthalic acid. The main industrial uses of purified isophthalic acid (PIA) are for the production of polyethylene t ...
, and the ''para'' isomer
terephthalic acid Terephthalic acid is an organic compound with formula C6H4(CO2H)2. This white solid is a commodity chemical, used principally as a precursor to the polyester PET, used to make clothing and plastic bottles. Several million tonnes are produced annua ...
: File:Phthalsäure.svg,
phthalic acid Phthalic acid is an aromatic dicarboxylic acid, with formula C6H4(CO2H)2. Although phthalic acid is of modest commercial importance, the closely related derivative phthalic anhydride is a commodity chemical produced on a large scale. Phthalic aci ...
File:Isophthalsäure.svg,
isophthalic acid Isophthalic acid is an organic compound with the formula C6H4(CO2H)2. This colorless solid is an isomer of phthalic acid and terephthalic acid. The main industrial uses of purified isophthalic acid (PIA) are for the production of polyethylene t ...
File:Terephthalsäure.svg,
terephthalic acid Terephthalic acid is an organic compound with formula C6H4(CO2H)2. This white solid is a commodity chemical, used principally as a precursor to the polyester PET, used to make clothing and plastic bottles. Several million tonnes are produced annua ...
These terms can also be used in six-membered
heterocyclic 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). Heterocyclic chemistry is the branch of organic chemistry dealing with the synthesis, properties, and ...
aromatic systems such as
pyridine Pyridine is a basic heterocyclic organic compound with the chemical formula . It is structurally related to benzene, with one methine group replaced by a nitrogen atom. It is a highly flammable, weakly alkaline, water-miscible liquid with a d ...
, where the
nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
atom is considered one of the substituents. For example,
nicotinamide Niacinamide or Nicotinamide (NAM) is a form of vitamin B3 found in food and used as a dietary supplement and medication. As a supplement, it is used by mouth to prevent and treat pellagra (niacin deficiency). While nicotinic acid (niacin) may ...
and
niacin Niacin, also known as nicotinic acid, is an organic compound and a form of vitamin B3, an essential human nutrient. It can be manufactured by plants and animals from the amino acid tryptophan. Niacin is obtained in the diet from a variet ...
, shown ''meta'' substitutions on a pyridine ring, while the
cation An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
of
pralidoxime Pralidoxime (2-pyridine aldoxime methyl chloride) or 2-PAM, usually as the chloride or iodide salts, belongs to a family of compounds called oximes that bind to organophosphate-inactivated acetylcholinesterase. It is used to treat organophosphat ...
is an ''ortho'' isomer. File:Niacin structure.svg, niacin File:Nicotinamid.svg,
nicotinamide Niacinamide or Nicotinamide (NAM) is a form of vitamin B3 found in food and used as a dietary supplement and medication. As a supplement, it is used by mouth to prevent and treat pellagra (niacin deficiency). While nicotinic acid (niacin) may ...
File:Pralidoxime-2D-skeletal.png,
pralidoxime Pralidoxime (2-pyridine aldoxime methyl chloride) or 2-PAM, usually as the chloride or iodide salts, belongs to a family of compounds called oximes that bind to organophosphate-inactivated acetylcholinesterase. It is used to treat organophosphat ...


See also

*
Descriptor (chemistry) A descriptor is in chemical nomenclature a prefix placed before the systematic substance name, which describes the configuration or the stereochemistry of the molecule. Some listed descriptors are only of historical interest and should not be us ...
*
Isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Iso ...
*
Structural isomerism In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a compound is another compound whose molecule has the same number of atoms of each element, but with logically distinct bonds between them. The term metam ...


References

{{Navbox stereochemistry Aromatic compounds Chemical nomenclature