The Appel reaction is an

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 ...

that converts an

alcohol Alcohol most commonly refers to: * Alcohol (chemistry), an organic compound in which a hydroxyl group is bound to a carbon atom * Alcohol (drug), an intoxicant found in alcoholic drinks Alcohol may also refer to: Chemicals * Ethanol, one of sev ...

into an alkyl chloride using

triphenylphosphine Triphenylphosphine (IUPAC name: triphenylphosphane) is a common organophosphorus compound with the formula P(C6H5)3 and often abbreviated to P Ph3 or Ph3P. It is widely used in the synthesis of organic and organometallic compounds. PPh3 exists a ...

and

carbon tetrachloride Carbon tetrachloride, also known by many other names (such as tetrachloromethane, also IUPAC nomenclature of inorganic chemistry, recognised by the IUPAC, carbon tet in the cleaning industry, Halon-104 in firefighting, and Refrigerant-10 in HVAC ...

. The use of

carbon tetrabromide Tetrabromomethane, CBr4, also known as carbon tetrabromide, is a carbon bromide. Both names are acceptable under IUPAC nomenclature. Physical properties Tetrabromomethane has two polymorphs: crystalline II or β below 46.9 °C (320.0 ...

bromine Bromine is a chemical element with the symbol Br and atomic number 35. It is the third-lightest element in group 17 of the periodic table (halogens) and is a volatile red-brown liquid at room temperature that evaporates readily to form a simila ...

as a halide source will yield alkyl bromides, whereas using

carbon tetraiodide Carbon tetraiodide is a tetrahalomethane with the molecular formula CI4. Being bright red, it is a relatively rare example of a highly colored methane derivative. It is only 2.3% by weight carbon, although other methane derivatives are known with s ...

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 ...

iodine Iodine is a chemical element with the symbol I and atomic number 53. The heaviest of the stable halogens, it exists as a semi-lustrous, non-metallic solid at standard conditions that melts to form a deep violet liquid at , and boils to a vi ...

gives

alkyl iodide Organoiodine compounds are organic compounds that contain one or more carbon–iodine bonds. They occur widely in organic chemistry, but are relatively rare in nature. The thyroxine hormones are organoiodine compounds that are required for he ...

s. The reaction is credited to and named after

Rolf Appel Rolf Appel (25 February 1921 – 30 January 2012) was an inorganic chemist who worked in the area of organophosphorus chemistry Education Appel received his PhD at age 30. He was appointed in 1962 to both the University of Bonn along with the ...

, it had however been described earlier. The use of this reaction is becoming less common, due to

being restricted under the

Montreal protocol The Montreal Protocol is an international treaty designed to protect the ozone layer by phasing out the production of numerous substances that are responsible for ozone depletion Ozone depletion consists of two related events observed sinc ...

Drawbacks to the reaction are the use of toxic halogenating agents and the coproduction of organophosphorus product that must be separated from the organic product. The phosphorus reagent can be used in

catalytic Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...

quantities. The corresponding alkyl bromide can also be synthesised by addition of

lithium bromide Lithium bromide (LiBr) is a chemical compound of lithium and bromine. Its extreme hygroscopic character makes LiBr useful as a desiccant in certain air conditioning systems.Wietelmann, Ulrich and Bauer, Richard J. (2005) "Lithium and Lithium Compo ...

as a source of bromide ions. A greener, more sustainable catalytic Appel reaction, free from chlorinated solvents, has also been reported. Catalytic Appel Reaction Scheme

Mechanism

The Appel reaction begins with the formation of the

phosphonium In polyatomic cations with the chemical formula (where R is a hydrogen or an alkyl, aryl, or halide group). These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions. Types of phosphonium ...

salt 3, which is thought to exist as a tight ion pair with 4 and therefore is unable to undergo an alpha-elimination to give

dichlorocarbene Dichlorocarbene is the reactive intermediate with chemical formula CCl2. Although this chemical species has not been isolated, it is a common intermediate in organic chemistry, being generated from chloroform. This bent diamagnetic molecule rapidly ...

Deprotonation Deprotonation (or dehydronation) is the removal (transfer) of a proton (or hydron, or hydrogen cation), (H+) from a Brønsted–Lowry acid in an acid–base reaction.Henry Jakubowski, Biochemistry Online Chapter 2A3, https://employees.csbsju.ed ...

of the alcohol, forming

chloroform Chloroform, or trichloromethane, is an organic compound with chemical formula, formula Carbon, CHydrogen, HChlorine, Cl3 and a common organic solvent. It is a colorless, strong-smelling, dense liquid produced on a large scale as a precursor to ...

, yields an alkoxide 5. The

nucleophilic displacement In chemistry, a nucleophilic substitution is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile). The ...

of the chloride by the alkoxide yields intermediate 7. With primary and secondary alcohols, the halide reacts in a S_N2 process forming the alkyl halide 8 and

triphenylphosphine oxide Triphenylphosphine oxide (often abbreviated TPPO) is the organophosphorus compound with the formula OP(C6H5)3, also written as Ph3PO or PPh3O (Ph = C6H5). This colourless crystalline compound is a common but potentially useful waste product in ...

. Tertiary alcohols form the products 6 and 7 via a S_N1 mechanism. The driving force behind this and similar reactions is the formation of the strong PO double bond. The reaction is somewhat similar to the

Mitsunobu reaction The Mitsunobu reaction is an organic reaction that converts an alcohol into a variety of functional groups, such as an ester, using triphenylphosphine and an azodicarboxylate such as diethyl azodicarboxylate (DEAD) or diisopropyl azodicarboxylat ...

, where the combination of an

organophosphine Organophosphines are organophosphorus compounds with the formula PR''n''H3−''n'', where R is an organic substituent. These compounds can be classified according to the value of ''n'': primary phosphines (''n'' = 1), secondary phosphines ...

as an oxide acceptor, an

azo compound Azo compounds are organic compounds bearing the functional group diazenyl (, in which R and R′ can be either aryl or alkyl groups). IUPAC defines azo compounds as: "Derivatives of diazene (diimide), , wherein both hydrogens are substituted ...

as a hydrogen acceptor reagent, and a

nucleophile In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are ...

are used to convert alcohols to esters and other applications like this. Appel-Reaktion_M-v3

Illustrative use of the Appel reaction is the chlorination of

geraniol Geraniol is a monoterpenoid and an alcohol. It is the primary component of citronella oil and is a primary component of rose oil, palmarosa oil. It is a colorless oil, although commercial samples can appear yellow. It has low solubility in w ...

to geranyl chloride.

Modifications

The Appel reaction is also effective on

carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic ...

s; this has been used to convert them to

oxazoline Oxazoline is a five-membered heterocyclic organic compound with the formula . It is the parent of a family of compounds called oxazolines (emphasis on plural), which contain non-hydrogenic substituents on carbon and/or nitrogen. Oxazolines are the ...

oxazine Oxazines are heterocyclic compounds containing one oxygen and one nitrogen atom in a doubly unsaturated six-membered ring. Isomers exist depending on the relative position of the heteroatoms and relative position of the double bonds. By extensi ...

s and

thiazoline Thiazolines (or dihydrothiazoles) are a group of isomeric 5-membered heterocyclic compounds containing both sulfur and nitrogen in the ring. Although unsubstituted thiazolines are rarely encountered themselves, their derivatives are more common a ...

s. ::

References

{{Organic reactions Substitution reactions Name reactions

Mechanism

Modifications

See also

References