Haloalkanes and Haloarenes

Classification and Nomenclature

Alkyl halides are formed when a hydrogen atom in a hydrocarbon is substituted by a

halogen atom.

Alkyl halides have the general formula, R-X.

Haloarenes are formed when a hydrogen atom in a benzene group is replaced by a halogen
atom.

Alkyl halides can be classified by the number of halogen atoms in the molecule.

Halogen substitutions may be vinylic, allylic or benzylic.

Alkyl halides and benzylic halides can be classified as primary, secondary, or tertiary.

Haloalkanes can be named as substituted alkanes in IUPAC nomenclature.

Haloarenes can be named as substituted arenes in IUPAC nomenclature.

Physical Properties

Alkyl halides are colourless and may have a sweet smell.

As the number of carbons increases for a series of alkyl halides, the boiling point
increases.

Boiling point increases as the halogen increases in size (from fluorine to iodine).
Alkyl halides have higher boiling points than hydrocarbons of similar mass.

Haloalkanes have very low solubility in water, but will dissolve in organic solvents.

Alkyl fluorides and alkyl chlorides are less dense than water, but alkyl bromides and alkyl
iodides are denser than water.

Aryl halides are insoluble in water and denser than water.

Para dihalobenzenes have higher melting points than their ortho and meta isomers.

Chemical Reactions of Alkyl Halides: Nucleophilic Substitution

Nucleophiles are species that can act as Lewis bases or electron pair donors.

Substitution reactions can occur when a nucleophile substitutes for a halide substituent on
carbon.

In the SN2 mechanism, the reaction shows second order kinetics and the mechanism occurs
in a single step with inversion of configuration. Only one product can form in an SN2
mechanism.

In the SN1 mechanism, the reaction shows first order kinetics. The mechanism occurs in
two steps.

Tertiary alky halides, allyl halides and benzylic halides show high reactivity towards the
SN1 reaction.
Chemical Reactions of Alkyl Halides: Nucleophilic Substitution -
Strereochemical Aspect – I

When plane polarized light is passed through a solution of certain compounds, they rotate
the plane polarised light in a specific direction, and are called optically active compounds.

The angle of plane polarised light rotated by a compound is measured by an instrument

called a polarimeter.

If a substance rotates plane polarised light to the right or clockwise as seen by the observer
whom the light is approaching, it is called dextrorotatory.

If a substance rotates plane polarised light to the left or counter-clockwise as seen by the
observer whom the light is approaching, it is called laevorotatory.

Isomers of a compound that rotate plane polarised light are called optical isomers, and the
phenomenon is called optical isomerism.

The asymmetry of a molecule is responsible for optical activity.

Non-super-imposable mirror image isomers are known as enantiomers.

If a mixture contains equimolar proportion of enantiomers, it shows zero optical rotation

and the mixture is known as raceimic modification.

The process of the formation of an equimolar proportion of an enantiomeric mixture from

an optically pure compound is known as racemisation.

Retention of configuration is the preservation of integrity of the spatial arrangement of

bonds to an asymmetric centre during a chemical transformation.

Inversion of configuration in a reaction yields a product whose configuration is opposite to

that of the reactant or the substrate.
Chemical Reactions of Alkyl Halides: Nucleophilic Substitution -
Strereochemical Aspect – II

An SN1 reaction is accompanied by racemisation, but an SN2 reaction proceeds with an

inversion of configuration.

The stereochemical aspects of nucleophilic substitution reactions are illustrated by taking

an optically active alkyl halide as a substrate.

The racemisation process in an SN1 reaction is due to the attack of the nucleophile from
both the faces of the planar carbocation intermediate with equal ease.

The inversion of configuration in an SN2 reaction is due to the backside attack of the
nucleophile with respect to the leaving group.

Chemical Reactions of Alkyl Halides: Elimination Reactions

According to Zaitsev’s rule or Sayzeff’s rule, in dehydrohalogenation reactions, the

preferred product is the alkene that has the greater number of alkyl groups attached to the
doubly bonded carbon atoms.

Most organic chlorides, bromides and iodides will react with certain metals to form
compounds containing carbon-metal bonds. Such compounds are called organometallic
compounds.

Grinard reagents are alkyl magnesium halides. They have the general formula RMgX,
where R is an alkyl or aryl group, and X is chloride, bromide or iodide.

Since Grinard reagents readily react with water, it is very important to prevent them from
coming with even traces of moisture.
Polyhalogen Compounds

Dichloromethane is used as a solvent and as an aerosol propellant.

Chloroform was used as an anaesthetic. It is used as a solvent and to make Freon R-22.

Dichloromethane and chloroform are both toxic and harmful to the central nervous system.

Triiodomethane has an unpleasant odour. It was formely used for its antiseptic properties.

Carbon tetrachloride has a variety of uses. Carbon tetrachloride is a likely carcinogen.

Freons, or chlorofluorocarbons, are useful refrigerants.

Freons in the atmosphere are linked to the depletion of the ozone layer.

DDT is a pesticide that has caused serious environmental problems for many species.