In
organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...
, a rearrangement reaction is a broad class of
organic reaction
Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, mechanistic organ ...
s where the
carbon skeleton of a
molecule
A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
is rearranged to give a
structural isomer
In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a compound is a compound that contains the same number and type of atoms, but with a different connectivity (i.e. arrangement of bonds) between them. The ...
of the original molecule.
Often a
substituent
In organic chemistry, a substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule.
The suffix ''-yl'' is used when naming organic compounds that contain a single bond r ...
moves from one atom to another atom in the same molecule, hence these reactions are usually intramolecular. In the example below, the substituent R moves from carbon atom 1 to carbon atom 2:
:
Intermolecular rearrangements also take place.
A rearrangement is not well represented by simple and discrete
electron transfer
Electron transfer (ET) occurs when an electron relocates from an atom, ion, or molecule, to another such chemical entity. ET describes the mechanism by which electrons are transferred in redox reactions.
Electrochemical processes are ET reactio ...
s (represented by curved arrows in organic chemistry texts). The actual mechanism of
alkyl group
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 group is derived from a cy ...
s moving, as in
Wagner–Meerwein rearrangement, probably involves transfer of the moving alkyl group fluidly along a bond, not
ionic bond
Ionic bonding is a type of chemical bond
A chemical bond is the association of atoms or ions to form molecules, crystals, and other structures. The bond may result from the electrostatic force between oppositely charged ions as in ionic ...
-breaking and forming. In
pericyclic reactions, explanation by orbital interactions give a better picture than simple discrete electron transfers. It is, nevertheless, possible to draw the curved arrows for a sequence of discrete electron transfers that give the same result as a rearrangement reaction, although these are not necessarily realistic. In
allylic rearrangement An allylic rearrangement or allylic shift is an organic reaction, organic chemical reaction in which reaction at a center Vicinal (chemistry), vicinal to a double bond causes the double bond to shift to an adjacent pair of atoms:
It is encountered ...
, the reaction is indeed ionic.
Three key rearrangement reactions are
1,2-rearrangements, pericyclic reactions, and
olefin metathesis.
1,2-rearrangements
A 1,2-rearrangement is an organic reaction where a substituent moves from one atom to another atom in a chemical compound. In a 1,2 shift the movement involves two adjacent atoms but moves over larger distances are possible. Skeletal isomerization is not normally encountered in the laboratory, but is the basis of large applications in
oil refineries
An oil refinery or petroleum refinery is an industrial process plant where petroleum (crude oil) is transformed and refined into products such as gasoline (petrol), diesel fuel, asphalt base, fuel oils, heating oil, kerosene, liquefied pet ...
. In general, straight-chain alkanes are converted to branched isomers by heating in the presence of a catalyst. Examples include isomerisation of
n-butane to
isobutane and
pentane
Pentane is an organic compound with the chemical formula, formula C5H12—that is, an alkane with five carbon atoms. The term may refer to any of three structural isomerism, structural isomers, or to a mixture of them: in the IUPAC nomenclature, h ...
to
isopentane
Isopentane, also called methylbutane or 2-methylbutane, is a branched-chain saturated hydrocarbon (an alkane) with five carbon atoms, with formula or .
Isopentane is a volatile and flammable liquid. It is one of three structural isomers with t ...
. Highly branched alkanes have favorable combustion characteristics for internal combustion engines.
:

Further examples are the
Wagner–Meerwein rearrangement:
:

and the
Beckmann rearrangement,
which is relevant to the production of certain
nylon
Nylon is a family of synthetic polymers characterised by amide linkages, typically connecting aliphatic or Polyamide#Classification, semi-aromatic groups.
Nylons are generally brownish in color and can possess a soft texture, with some varieti ...
s:
:
Pericyclic reactions
A pericyclic reaction is a type of reaction with multiple carbon–carbon bond making and breaking wherein the
transition state
In chemistry, the transition state of a chemical reaction is a particular configuration along the reaction coordinate. It is defined as the state corresponding to the highest potential energy along this reaction coordinate. It is often marked w ...
of the molecule has a cyclic geometry, and the reaction progresses in a concerted fashion. Examples are
hydride shifts

and the
Claisen rearrangement:
Olefin metathesis
Olefin metathesis is a formal exchange of the alkylidene fragments in two alkenes. It is a catalytic reaction with
carbene, or more accurately,
transition metal carbene complex intermediates.

In this example (
ethenolysis, a pair of
vinyl
Vinyl may refer to:
Chemistry
* Polyvinyl chloride (PVC), a particular vinyl polymer
* Vinyl cation, a type of carbocation
* Vinyl group, a broad class of organic molecules in chemistry
* Vinyl polymer, a group of polymers derived from vinyl ...
compounds form a new symmetrical alkene with expulsion of
ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon bond, carbon–carbon doub ...
.
Other rearragement reactions
1,3-rearrangements
1,3-rearrangements take place over 3 carbon atoms. Examples:
* the
Fries rearrangement
* a 1,3-alkyl shift of
verbenone to
chrysanthenone
See also
*
Amadori rearrangement
*
Beckmann rearrangement
*
Curtius rearrangement
*
Hofmann rearrangement
*
Lossen rearrangement
*
Mumm rearrangement
*
Photochemical rearrangement
*
Schmidt reaction
*
Thermal rearrangement of aromatic hydrocarbons
*
Tiemann rearrangement
*
Wolff rearrangement
References
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