Halogenation

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In chemistry, halogenation is a chemical reaction which introduces one or more halogens into a chemical compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. [1] This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens ( F2, Cl2, Br2, I2 ). Halides are also commonly introduced using salts of the halides and halogen acids.[ clarification needed ] Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

Contents

Organic chemistry

Several pathways exist for the halogenation of organic compounds, including free radical halogenation, ketone halogenation, electrophilic halogenation, and halogen addition reaction. The nature of the substrate determines the pathway. The facility of halogenation is influenced by the halogen. Fluorine and chlorine are more electrophilic and are more aggressive halogenating agents. Bromine is a weaker halogenating agent than both fluorine and chlorine, while iodine is the least reactive of them all. The facility of dehydrohalogenation follows the reverse trend: iodine is most easily removed from organic compounds, and organofluorine compounds are highly stable.

Free radical halogenation

Halogenation of saturated hydrocarbons is a substitution reaction. The reaction typically involves free radical pathways. The regiochemistry of the halogenation of alkanes is largely determined by the relative weakness of the C–H bonds. This trend is reflected by the faster reaction at tertiary and secondary positions.

Free radical chlorination is used for the industrial production of some solvents: [2]

CH4 + Cl2 → CH3Cl + HCl

Naturally-occurring organobromine compounds are usually produced by free radical pathway catalyzed by the enzyme bromoperoxidase. The reaction requires bromide in combination with oxygen as an oxidant. The oceans are estimated to release 1–2 million tons of bromoform and 56,000 tons of bromomethane annually. [3] [ clarification needed ]

The iodoform reaction, which involves degradation of methyl ketones, proceeds by the free radical iodination.

Fluorination

Because of its extreme reactivity, fluorine (F2) represents a special category with respect to halogenation. Most organic compounds, saturated or otherwise, burn upon contact with F2, ultimately yielding carbon tetrafluoride. By contrast, the heavier halogens are far less reactive toward saturated hydrocarbons.

Highly specialised conditions and apparatus are required for fluorinations with elemental fluorine. Commonly, fluorination reagents are employed instead of F2. Such reagents include cobalt trifluoride, chlorine trifluoride, and iodine pentafluoride. [4]

The method electrochemical fluorination is used commercially for the production of perfluorinated compounds. It generates small amounts of elemental fluorine in situ from hydrogen fluoride. The method avoids the hazards of handling fluorine gas. Many commercially important organic compounds are fluorinated using this technology.

Addition of halogens to alkenes and alkynes

Double-addition of chlorine gas to ethyne

Unsaturated compounds, especially alkenes and alkynes, add halogens:

R−CH=CH−R' + X2 → R−CHX−CHX−R'

In oxychlorination, the combination of hydrogen chloride and oxygen serves as the equivalent of chlorine, as illustrated by this route to 1,2-dichloroethane:

4 HCl + 2 CH2=CH2 + O2 → 2 Cl−CH2−CH2−Cl + 2 H2O
Structure of a bromonium ion Biadamantylidene-bromonium-ion-from-xtal-1994-2D-skeletal.png
Structure of a bromonium ion

The addition of halogens to alkenes proceeds via intermediate halonium ions. In special cases, such intermediates have been isolated. [5]

Bromination is more selective than chlorination because the reaction is less exothermic. Illustrative of the bromination of an alkene is the route to the anesthetic halothane from trichloroethylene: [6]

Halothane synthesis.png

Iodination and bromination can be effected by the addition of iodine and bromine to alkenes. The reaction, which conveniently proceeds with the discharge of the color of I2 and Br2, is the basis of the analytical method. The iodine number and bromine number are measures of the degree of unsaturation for fats and other organic compounds.

Halogenation of aromatic compounds

Aromatic compounds are subject to electrophilic halogenation:

R−C6H5 + X2 → HX + R−C6H4−X

This kind of reaction typically works well for chlorine and bromine. Often a Lewis acidic catalyst is used, such as ferric chloride. [7] Many detailed procedures are available. [8] [9] Because fluorine is so reactive, other methods, such as the Balz–Schiemann reaction, are used to prepare fluorinated aromatic compounds.

Other halogenation methods

In the Hunsdiecker reaction, carboxylic acids are converted to organic halide, whose carbon chain is shortened by one carbon atom with respect to the carbon chain of the particular carboxylic acid. The carboxylic acid is first converted to its silver salt, which is then oxidized with halogen:

R−COO−Ag+ + Br2 → R−Br + CO2 + Ag+Br−
CH3−COO−Ag+ + Br2 → CH3−Br + CO2 + Ag+Br−

Many organometallic compounds react with halogens to give the organic halide:

RM + X2 → RX + MX
CH3CH2CH2CH2Li + Cl2 → CH3CH2CH2CH2Cl + LiCl

Inorganic chemistry

All elements aside from argon, neon, and helium form fluorides by direct reaction with fluorine. Chlorine is slightly more selective, but still reacts with most metals and heavier nonmetals. Following the usual trend, bromine is less reactive and iodine least of all. Of the many reactions possible, illustrative is the formation of gold(III) chloride by the chlorination of gold. The chlorination of metals is usually not very important industrially since the chlorides are more easily made from the oxides and hydrogen chloride. Where chlorination of inorganic compounds is practiced on a relatively large scale is for the production of phosphorus trichloride and disulfur dichloride. [10]

See also

Related Research Articles

<span class="mw-page-title-main">Bromine</span> Chemical element, symbol Br and atomic number 35

Bromine is a chemical element; it has symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between those of chlorine and iodine. Isolated independently by two chemists, Carl Jacob Löwig and Antoine Jérôme Balard, its name was derived from the Ancient Greek βρῶμος (bromos) meaning "stench", referring to its sharp and pungent smell.

<span class="mw-page-title-main">Chlorine</span> Chemical element, symbol Cl and atomic number 17

Chlorine is a chemical element; it has symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen and fluorine.

<span class="mw-page-title-main">Halogen</span> Group of chemical elements

The halogens are a group in the periodic table consisting of six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and the radioactive elements astatine (At) and tennessine (Ts), though some authors would exclude tennessine as its chemistry is unknown and is theoretically expected to be more like that of gallium. In the modern IUPAC nomenclature, this group is known as group 17.

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

A halogen addition reaction is a simple organic reaction where a halogen molecule is added to the carbon–carbon double bond of an alkene functional group.

In chemistry, an electrophile is a chemical species that forms bonds with nucleophiles by accepting an electron pair. Because electrophiles accept electrons, they are Lewis acids. Most electrophiles are positively charged, have an atom that carries a partial positive charge, or have an atom that does not have an octet of electrons.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. Haloarenes are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

<span class="mw-page-title-main">Halomethane</span> Halogen compounds derived from methane

Halomethane compounds are derivatives of methane with one or more of the hydrogen atoms replaced with halogen atoms. Halomethanes are both naturally occurring, especially in marine environments, and human-made, most notably as refrigerants, solvents, propellants, and fumigants. Many, including the chlorofluorocarbons, have attracted wide attention because they become active when exposed to ultraviolet light found at high altitudes and destroy the Earth's protective ozone layer.

<span class="mw-page-title-main">Hydrogen bromide</span> Chemical compound

Hydrogen bromide is the inorganic compound with the formula HBr. It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room temperature. Aqueous solutions that are 47.6% HBr by mass form a constant-boiling azeotrope mixture that boils at 124.3 °C (255.7 °F). Boiling less concentrated solutions releases H2O until the constant-boiling mixture composition is reached.

In chemistry, an interhalogen compound is a molecule which contains two or more different halogen atoms and no atoms of elements from any other group.

In organic chemistry, free-radical halogenation is a type of halogenation. This chemical reaction is typical of alkanes and alkyl-substituted aromatics under application of UV light. The reaction is used for the industrial synthesis of chloroform (CHCl3), dichloromethane (CH2Cl2), and hexachlorobutadiene. It proceeds by a free-radical chain mechanism.

Organochlorine chemistry is concerned with the properties of organochlorine compounds, or organochlorides, organic compounds containing at least one covalently bonded atom of chlorine. The chloroalkane class includes common examples. The wide structural variety and divergent chemical properties of organochlorides lead to a broad range of names, applications, and properties. Organochlorine compounds have wide use in many applications, though some are of profound environmental concern, with TCDD being one of the most notorious.

In organic chemistry, an electrophilic aromatic halogenation is a type of electrophilic aromatic substitution. This organic reaction is typical of aromatic compounds and a very useful method for adding substituents to an aromatic system.

In organic chemistry a halohydrin is a functional group in which a halogen and a hydroxyl are bonded to adjacent carbon atoms, which otherwise bear only hydrogen or hydrocarbyl groups. The term only applies to saturated motifs, as such compounds like 2-chlorophenol would not normally be considered halohydrins. Megatons of some chlorohydrins, e.g. propylene chlorohydrin, are produced annually as precursors to polymers.

<span class="mw-page-title-main">Halonium ion</span> Any onium ion containing a halogen atom carrying a positive charge

A halonium ion is any onium ion containing a halogen atom carrying a positive charge. This cation has the general structure R−+X−R′ where X is any halogen and no restrictions on R, this structure can be cyclic or an open chain molecular structure. Halonium ions formed from fluorine, chlorine, bromine, and iodine are called fluoronium, chloronium, bromonium, and iodonium, respectively. The 3-membered cyclic variety commonly proposed as intermediates in electrophilic halogenation may be called haliranium ions, using the Hantzsch-Widman nomenclature system.

Bromine compounds are compounds containing the element bromine (Br). These compounds usually form the -1, +1, +3 and +5 oxidation states. Bromine is intermediate in reactivity between chlorine and iodine, and is one of the most reactive elements. Bond energies to bromine tend to be lower than those to chlorine but higher than those to iodine, and bromine is a weaker oxidising agent than chlorine but a stronger one than iodine. This can be seen from the standard electrode potentials of the X2/X− couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V; At, approximately +0.3 V). Bromination often leads to higher oxidation states than iodination but lower or equal oxidation states to chlorination. Bromine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Br bonds.

Iodine compounds are compounds containing the element iodine. Iodine can form compounds using multiple oxidation states. Iodine is quite reactive, but it is much less reactive than the other halogens. For example, while chlorine gas will halogenate carbon monoxide, nitric oxide, and sulfur dioxide, iodine will not do so. Furthermore, iodination of metals tends to result in lower oxidation states than chlorination or bromination; for example, rhenium metal reacts with chlorine to form rhenium hexachloride, but with bromine it forms only rhenium pentabromide and iodine can achieve only rhenium tetraiodide. By the same token, however, since iodine has the lowest ionisation energy among the halogens and is the most easily oxidised of them, it has a more significant cationic chemistry and its higher oxidation states are rather more stable than those of bromine and chlorine, for example in iodine heptafluoride.

A cyanogen halide is a molecule consisting of cyanide and a halogen. Cyanogen halides are chemically classified as pseudohalogens.

<span class="mw-page-title-main">Haloform reaction</span> Chemical reaction involving repeated halogenation of an acetyl group (–COCH3)

In chemistry, the haloform reaction is a chemical reaction in which a haloform is produced by the exhaustive halogenation of an acetyl group, in the presence of a base. The reaction can be used to transform acetyl groups into carboxyl groups or to produce chloroform, bromoform, or iodoform. Note that fluoroform can't be prepared in this way.

Organobromine chemistry is the study of the synthesis and properties of organobromine compounds, also called organobromides, which are organic compounds that contain carbon bonded to bromine. The most pervasive is the naturally produced bromomethane.

References

  1. ↑ Hudlicky, Milos; Hudlicky, Tomas (1983). "Formation of Carbon-Halogen Bonds". In S. Patai; Z. Rappoport (eds.). Halides, Pseudo-Halides and Azides: Part 2 (1983). PATAI's Chemistry of Functional Groups. pp. 1021–1172. doi:10.1002/9780470771723.ch3. ISBN   9780470771723.
  2. ↑ Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a06_233.pub2. ISBN   978-3527306732.
  3. ↑ Gribble, Gordon W. (1999). "The diversity of naturally occurring organobromine compounds". Chemical Society Reviews. 28 (5): 335–346. doi:10.1039/a900201d.
  4. ↑ Aigueperse, Jean; Mollard, Paul; Devilliers, Didier; Chemla, Marius; Faron, Robert; Romano, René; Cuer, Jean Pierre (2000). "Fluorine Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a11_307. ISBN   3-527-30673-0.
  5. ↑ T. Mori; R. Rathore (1998). "X-Ray structure of bridged 2,2′-bi(adamant-2-ylidene) chloronium cation and comparison of its reactivity with a singly bonded chloroarenium cation". Chem. Commun. (8): 927–928. doi:10.1039/a709063c.
  6. ↑ Synthesis of Essential Drugs, Ruben Vardanyan, Victor Hruby; Elsevier 2005 ISBN   0-444-52166-6
  7. ↑ Beck, Uwe; Löser, Eckhard (2011). "Chlorinated Benzenes and Other Nucleus-Chlorinated Aromatic Hydrocarbons". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.o06_o03. ISBN   978-3527306732.
  8. ↑ Organic chemistry by Jonathan Clayden, Nick Grieves, Stuart Warren, Oxford University Press
  9. ↑ Edward R. Atkinson, Donald M. Murphy, and James E. Lufkin (1951). "dl-4,4′,6,6′-Tetrachlorodiphenic Acid". Organic Syntheses . 31: 96. doi:10.15227/orgsyn.031.0096 {{cite journal}}: CS1 maint: multiple names: authors list (link).
  10. ↑ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
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