Hofmann elimination is an

elimination reaction An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one- or two-step mechanism. The one-step mechanism is known as the E2 reaction, and the two-step mechanism is known as the E1 r ...

of an

amine 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 Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent suc ...

to form

alkene In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic, a ...

s. The least stable alkene (the one with the least number of substituents on the carbons of the double bond), called the Hofmann product, is formed. This tendency, known as the Hofmann alkene synthesis rule, is in contrast to usual elimination reactions, where

Zaitsev's rule In organic chemistry, Zaitsev's rule (or Saytzeff's rule, Saytzev's rule) is an empirical rule for predicting the favored alkene product(s) in elimination reactions. While at the University of Kazan, Russian chemist Alexander Zaitsev studied a va ...

predicts the formation of the most stable alkene. It is named after its discoverer,

August Wilhelm von Hofmann August Wilhelm von Hofmann (8 April 18185 May 1892) was a German chemist who made considerable contributions to organic chemistry. His research on aniline helped lay the basis of the aniline-dye industry, and his research on coal tar laid the ...

. The reaction starts with the formation of a

quaternary ammonium In chemistry, quaternary ammonium cations, also known as quats, are positively charged polyatomic ions of the structure , R being an alkyl group or an aryl group. Unlike the ammonium ion () and the primary, secondary, or tertiary ammonium catio ...

iodide salt by treatment of the amine with excess

methyl iodide Iodomethane, also called methyl iodide, and commonly abbreviated "MeI", is the chemical compound with the formula CH3I. It is a dense, colorless, volatile liquid. In terms of chemical structure, it is related to methane by replacement of one h ...

(exhaustive methylation), followed by treatment with

silver oxide Silver oxide is the chemical compound with the formula Ag2O. It is a fine black or dark brown powder that is used to prepare other silver compounds. Preparation Silver oxide can be prepared by combining aqueous solutions of silver nitrate and a ...

and

water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...

to form a quaternary ammonium hydroxide. When this salt is decomposed by heat, the Hofmann product is preferentially formed due to the steric bulk of 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 ...

causing the hydroxide to abstract the more easily accessible hydrogen. : Example of the Hofmann Elimination Reaction

In the Hofmann elimination, the least substituted alkene is typically favored due to intramolecular steric interactions. The quaternary ammonium group is large, and interactions with alkyl groups on the rest of the molecule are undesirable. As a result, the conformation necessary for the formation of the Zaitsev product is less energetically favorable than the conformation required for the formation of the Hofmann product. As a result, the Hofmann product is formed preferentially. The

Cope elimination The Cope reaction or Cope elimination, developed by Arthur C. Cope, is an elimination reaction of the N-oxide to form an alkene and a hydroxylamine. Mechanism and applications The reaction mechanism involves an intramolecular 5-membered cyclic tr ...

is very similar to the Hofmann elimination in principle, but occurs under milder conditions. It also favors the formation of the Hofmann product, and for the same reasons. An example of a Hofmann elimination (not involving a contrast between a Zaitsev product and a Hofmann product) is the synthesis of

trans-cyclooctene ''trans''-Cyclooctene is a cyclic hydrocarbon with the formula ��(CH2)6CH=CH– where the two C–C single bonds adjacent to the double bond are on opposite sides of the latter's plane. It is a colorless liquid with a disagreeable odor. Cyc ...

. The ''trans'' isomer is selectively trapped as a

complex Complex commonly refers to: * Complexity, the behaviour of a system whose components interact in multiple ways so possible interactions are difficult to describe ** Complex system, a system composed of many components which may interact with each ...

with

silver nitrate Silver nitrate is an inorganic compound with chemical formula . It is a versatile precursor to many other silver compounds, such as those used in photography. It is far less sensitive to light than the halides. It was once called ''lunar caustic ...

(in this diagram the ''trans'' form looks like a ''cis'' form, but see the

article for better images): : In a related

chemical test In chemistry, a chemical test is a qualitative or quantitative procedure designed to identify, quantify, or characterise a chemical compound or chemical group. Purposes Chemical testing might have a variety of purposes, such as to: * Determin ...

, known as the Herzig–Meyer alkimide group determination, a tertiary amine with at least one methyl group and lacking a beta-proton is allowed to react with

hydrogen iodide Hydrogen iodide () is a diatomic molecule and hydrogen halide. Aqueous solutions of HI are known as hydroiodic acid or hydriodic acid, a strong acid. Hydrogen iodide and hydroiodic acid are, however, different in that the former is a gas under sta ...

to the quaternary ammonium salt which when heated degrades to methyl iodide and the secondary amine.

References

External links

An animation of the mechanism of the Hofmann elimination
{{DEFAULTSORT:Hofmann Elimination Elimination reactions Olefination reactions Name reactions

See also

References

External links