Haloalkanes and haloarenes are the hydrocarbons in which one or more hydrogen atoms have been replaced with halogen atoms. The primary difference between haloalkanes and haloarenes is that haloalkanes are derived from open-chain hydrocarbons (alkanes) whereas haloarenes are derived from aromatic hydrocarbons.
On the Basis of Number of Halogen Atoms: These may be classified as mono, di, or polyhalogen (tri-,tetra-, etc.) compounds depending on whether they contain one, two or more halogen atoms in their structures.
On the Basis of Compounds Containing sp3 C—X Bond (X= F, Cl, Br, I): This class includes
On the Basis of Compounds Containing sp2 C—X Bond: This class includes:
The common names of alkyl halides are derived by naming the alkyl group followed by the name of halide. In the IUPAC system of nomenclature, alkyl halides are named as halosubstituted hydrocarbons. For mono halogen substituted derivatives of benzene, common and IUPAC names are the same.
Halogen atoms are more electronegative than carbon, therefore, carbon-halogen bond of alkyl halide is polarised; the carbon atom bears a partial positive charge whereas the halogen atom bears a partial negative charge.
From Alcohols: The hydroxyl group of an alcohol is replaced by halogen on reaction with concentrated halogen acids, phosphorus halides or thionyl chloride. Thionyl chloride is preferred because in this reaction alkyl halide is formed along with gases SO2 and HCl. The two gaseous products are escapable, hence, the reaction gives pure alkyl halides. The reactions of primary and secondary alcohols with HCl require the presence of a catalyst, ZnCl2. With tertiary alcohols, the reaction is conducted by simply shaking the alcohol with concentrated HCl at room temperature. Constant boiling with HBr (48%) is used for preparing alkyl bromide.
From Hydrocarbons:
(I) From alkanes by free radical halogenation Free radical chlorination or bromination of alkanes gives a complex mixture of isomeric mono- and polyhaloalkanes, which is difficult to separate as pure compounds. Consequently, the yield of any single compound is low.
(II) From alkenes:
Halogen Exchange: Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with NaI in dry acetone. This reaction is known as Finkelstein reaction.
From hydrocarbons by electrophilic substitution: Aryl chlorides and bromides can be easily prepared by electrophilic substitution of arenes with chlorine and bromine respectively in the presence of Lewis acid catalysts like iron or iron(III) chloride.
From amines by Sandmeyer’s reaction: When a primary aromatic amine, dissolved or suspended in cold aqueous mineral acid, is treated with sodium nitrite, a diazonium salt is formed. Mixing the solution of freshly prepared diazonium salt with cuprous chloride or cuprous bromide results in the replacement of the diazonium group by –Cl or –Br.
Alkyl halides are colourless when pure. However, bromides and iodides develop colour when exposed to light. Many volatile halogen compounds have sweet smell.
Melting and boiling points: Methyl chloride, methyl bromide, ethyl chloride and some chlorofluoromethanes are gases at room temperature. Higher members are liquids or solids. As we have already learnt, molecules of organic halogen compounds are generally polar. Due to greater polarity as well as higher molecular mass as compared to the parent hydrocarbon, the intermolecular forces of attraction (dipole-dipole and van der Waals) are stronger in the halogen derivatives.
Density: Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than water. The density increases with increase in number of carbon atoms, halogen atoms and atomic mass of the halogen atoms.
Solubility: The haloalkanes are very slightly soluble in water. In order to dissolve haloalkane in water, energy is required to overcome the attractions between the haloalkane molecules and break the hydrogen bonds between water molecules.
The reactions of haloalkanes may be divided into the following categories:
Nucleophilic substitution reactions are most common reactions of alkyl halides. The most common nucleophiles are OH- , CN-, NO2-, SH-, NH2-, OR- and RCOO-. Following are some examples:
Nucleophilic substitution may take place in two ways:
A. SN1 Mechanism:
The tertiary alkyl halides react by SN1 mechanism via formation of carbocation as intermediate. The reactivity order for SN1 reaction is
Benzyl > Allyl > 3̊ > 2̊ > 1̊ > CH3X.
B. SN2 Mechanism:In case of SN2 reactions the halide ion leaves from the front side whereas the nucleophiles attacks from the back side; due to this reason SN2 reactions are always accompanied by the inversion of configuration. Thus formation of another enantiomer is lead by SN2 reaction of an optically active halide i.e. optical activity is retained but with opposite configuration.
This reaction involves the loss of two atoms or groups from the substrate as by product with formation of pi-bond. A halogen along with a hydrogen atom is removed from adjacent carbon atoms to form a double bond. This elimination introduces multiple bonds. It can be classified into E1 and E2 reaction.
Most organic chlorides, bromides and iodides react with certain metals to give compounds containing carbon-metal bonds. Such compounds are known as organo-metallic compounds. An important class of organo-metallic compounds discovered by Victor Grignard in 1900 is alkyl magnesium halide, RMgX, referred as Grignard Reagents. These reagents are obtained by the reaction of haloalkanes with magnesium metal in dry ether.
Wurtz reaction: Alkyl halides react with sodium in dry ether to give hydrocarbons containing double the number of carbon atoms present in the halide. This reaction is known as Wurtz reaction.
Nucleophilic substitution: Aryl halides are extremely less reactive towards nucleophilic substitution reactions due to the following reasons:
Carbon compounds containing more than one halogen atom are usually referred to as polyhalogen compounds. Many of these compounds are useful in industry and agriculture. Some polyhalogen compounds are described in this section.
Dichloromethane is widely used as a solvent as a paint remover, as a propellant in aerosols, and as a process solvent in the manufacture of drugs. It is also used as a metal cleaning and finishing solvent. Methylene chloride harms the human central nervous system. Exposure to lower levels of methylene chloride in air can lead to slightly impaired hearing and vision.
Chemically, chloroform is employed as a solvent for fats, alkaloids, iodine and other substances. The major use of chloroform today is in the production of the freon refrigerant R-22. It was once used as a general anaesthetic in surgery but has been replaced by less toxic, safer anaesthetics, such as ether. As might be expected from its use as an anaesthetic, inhaling chloroform vapours depresses the central nervous system.
It was used earlier as an antiseptic but the antiseptic properties are due to the liberation of free iodine and not due to iodoform itself. Due to its objectionable smell, it has been replaced by other formulations containing iodine.
It is produced in large quantities for use in the manufacture of refrigerants and propellants for aerosol cans. It is also used as feedstock in the synthesis of chlorofluorocarbons and other chemicals, pharmaceutical manufacturing, and general solvent use. Until the mid 1960s, it was also widely used as a cleaning fluid, both in industry, as a degreasing agent, and in the home, as a spot remover and as fire extinguisher.
The chlorofluorocarbon compounds of methane and ethane are collectively known as freons. They are extremely stable, unreactive, non-toxic, non-corrosive and easily liquefiable gases. Freon 12 (CCl2F2) is one of the most common freons in industrial use. It is manufactured from tetrachloromethane by Swarts reaction.
DDT, the first chlorinated organic insecticides, was originally prepared in 1873, but it was not until 1939 that Paul Muller of Geigy Pharmaceuticals in Switzerland discovered the effectiveness of DDT as an insecticide. Paul Muller was awarded the Nobel Prize in Medicine and Physiology in 1948 for this discovery.
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