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Halogenoalkanes (or alkyl halides)

Halogenoalkanes are compounds in which one or more hydrogen atoms in an alkane have been replaced by halogen atoms (fluorine, chlorine, bromine or iodine). For example:

The different kinds of halogenoalkanes Halogenoalkanes fall into different classes depending on how the halogen atom is positioned on the chain of carbon atoms. There are some chemical differences between the various types. Primary halogenoalkanes In a primary (1) halogenoalkane, the carbon which carries the halogen atom is only attached to one other alkyl group.
Some examples of primary halogenoalkanes include:

Secondary halogenoalkanes In a secondary (2) halogenoalkane, the carbon with the halogen attached is joined directly to two other alkyl groups, which may be the same or different. Examples:

Tertiary halogenoalkanes In a tertiary (3) halogenoalkane, the carbon atom holding the halogen is attached directly to three alkyl groups, which may be any combination of same or different. Examples:

Halogenoarenes (Aryl halides) These compounds have a halogen atom attached directly to an aromatic carbon ring. For example, C6H5Cl is chlorobenzene. C6H5Br is bromobenzene.

Physical Properties

Boiling points of RX (R is an alkyl group; X stands for a halogen atom) are higher than their corresponding alkanes (alkanes with the same number of carbon atoms). Simplest members are colourless gases (e.g. chloromethane, bromomethane and chloroethane) Halogenoalkanes and halogenoarenes are only slightly polar and are insoluble in aqueous medium (e.g. water) but are soluble in organic solvents. Thus, reactions , involving halogenoalkanes are usually carried out in the presence of some alcohol, where alcohol is the polar solvent.

Uses
- solvents; - anesthetics; - refrigerants; - pesticides; - raw material for making plastics such as poly(chloroethane) usually known as PVC - Making of poly(tetrafIuoroethene) - PTFE.

Reactions of halogenoalkanes
Nucleophilic Substitution Reaction of halogenalkane with sodium hydroxide
In a substitution reaction, the halogen atom is replaced by an -OH group to give an alcohol. For example:

In the example, 2-bromopropane is converted into propan-2-ol. The halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide. Heating under reflux means heating with a condenser placed vertically in the flask to prevent loss of volatile substances from the mixture.

Mechanism: Nucleophilic Substitution Bimolecular (SN2) The reaction of bromoethane and sodium hydroxide to form ethanol is an example of a nucleophilic substitution. This reaction is observed to be first order with respect to each reactant and second order overall. Rate = k[bromoethane][OH-] This rate equation suggests that the ratedetermining step is bimolecuIar. The symbol given to this mechanism is SN2, which means Substitution Nucleophilic Bimolecular.

The mechanism takes place in one step: mechanism like this:

The C-X bond in the halogenoalkane is polar due to the differences in electronegativity between the carbon and the halogen atom. The nucleophile attacks the partially positive charged carbon atom from the side opposite the halogen atom. A bond begins to form between the nucleophile and the carbon atom and the C-X bond is weakened and begins to break. An unstable, activated complex is formed where the incoming nucleophile and the leaving halide ion are partially bonded to the same carbon atom. This is referred as the transition state. The nucleophile supplies the pair of electrons that form the new C-Nu bond and the pair of electrons in the C-X bond is gradually acquired completely by the halogen atom to form a halide anion. Bond breaking and bond forming occur simultaneously. As the displacement takes place, the configuration of the carbon atom under attack inverts. This mechanism is favourable for primary halogenoalkanes. Reaction of halogenoalkane with ammonia This page looks at the reaction between halogenoalkanes (haloalkanes or alkyl halides) and ammonia. This is a potentially very complicated series of reactions, so it is important to know exactly what your examiners want. The halogenoalkane is heated with a concentrated solution of ammonia in ethanol. The reaction is carried out in a sealed tube. You couldn't heat this mixture under reflux, because the ammonia would simply escape up the condenser as a gas. We'll talk about the reaction using 1-bromoethane as a typical primary halogenoalkane. There is no difference in the details of the reaction if you chose a secondary or tertiary halogenoalkane instead. You get a series of amines formed together with their salts. The reactions happen one after another. The type of reaction (or reaction mechanism) is still nucleophilic substitution. The nucleophile is ammonia, where the nitrogen atom in ammonia molecule has a lone

pair and attacks the electron deficient carbon of the halogenoalkane. (Remember, delta negative atom attacks delta positive atom [in this case carbon is delta positive in halogenalkane]) Making a primary amine RCH2-X + NH3 (alcohol) RCH2-NH2 + HX amine Reagent : excess ammonia in ethanol Conditions : heat in sealed tube Reaction of halogenoalkane with cyanide ions (CN-) If a halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol, the halogen is replaced by a -CN group and a nitrile is produced. Heating under reflux means heating with a condenser placed vertically in the flask to prevent loss of volatile substances from the mixture. For example, using 1-bromopropane as a typical primary halogenoalkane: You could write the full equation rather than the ionic one, but it slightly obscures what's going on:

The bromine (or other halogen) in the halogenoalkane is simply replaced by a -CN group - hence a substitution reaction. In this example, butanenitrile is formed. Secondary and tertiary halogenoalkanes behave similarly. The type of reaction is still nucleophilic substitution. Why these reactions matter This reaction with cyanide ions is a useful way of lengthening carbon chains. For example, in the equations above, you start with a 3-carbon chain and end up with a 4-carbon chain. There aren't very many simple ways of making new carbon-carbon bonds. It is fairly easy to change the -CN group at the end of the new chain into other groups.

Nucleophilic Substitution of Halogenoarenes


Simple halogenoarenes (C6H5X) like chlorobenzene are very resistant to nucleophilic substitution. It is possible to replace the chlorine with a OH group only under very severe industrial conditions (e.g. 360 C, 150 atm). Thus under normal laboratory conditions, nucleophilic substitution does NOT take place for halogenoarenes. In the lab, C6H5Cl + NaOH(aq) no reaction

Why is that so? Extra strength of the carbonhaIogen bond in halogenoarenes. Overlap of the (electrons of the ) porbital of the halogen atom with piorbital of the benzene ring. Some double bond character is introduced in the C-Cl bond (bond strength stronger than that in a halogenoalkane) thus the CCI bond is not easily broken during nucleophilic substitution. In other words, the C-Cl bond is strong and is not attacked by a nucleophile such as OH- ions.