HANDOUT 7a – REACTIONS OF HALOGENOALKANES Objectives: recall the chemistry of halogenoalkanes as exemplified by the follow ing nucleophilic substitution reactions

of bromoethane: hydrolysis, formation of nitriles, formation of primary amines by reaction with ammonia and by the elimi nation of hydrogen bromide from 2-bromopropane describe the mechanism of nucleop hilic substitution (by both SN1 and SN2 mechanisms) in halogenoalkanes BOX 7a-A: REACTIONS OF HALOGENOALKANES Pure NaOH in ethanol Heat under reflux BO X 7a-B contd. SN1 Mechanism NH3(aq) in ethanol Heat Halogenoalkanes alkene Heat under reflux This mechanism involves the substitution of a nucleophile which is first order ( one molecule in rate determining step). This mechanism occurs in two stages: KCN(aq) in ethanol Stage 1: Primary amine Nucleophilic substitution Heat under reflux NaOH(aq) in ethanol or water in etha nol nitrile Nucleophilic substitution CH3 H3 C C CH3 Stage 2: CH3 Br H3C C CH3 Br alcohol Nucleophilic substitution BOX 7a-B: HETEROLYTIC NUCLEOPHILIC SUBSTITUTION This mechanism is associated wit h polar covalent bonds (e.g. carbon-halogen). δ δ CH3 H3 C C CH3 OH H3 C CH3 C CH3 OH C Br The positive charge on the carbon allows attack by nucleophiles such as :OH− or :C N− which have lone pairs to onate. There are two mechanisms for nucleophilic substitution, (1) SN1 an







SN2 Mechanism The mechanism involves secon or er (two molecules in rate he Cδ+ an starts to form a covalent tarts to break heterolytically. This ucleophile bon getting stronger an

the substitution of a nucleophile which is etermining step). The nucleophile attacks t bon with it. At the same time the Cδ+ Halδ− bon s is one continuous process with the carbon n the carbon halogen getting weaker.




(2) SN2.




H3 C HO H C H Br H3 C HO H C Br HO H C CH3 Br H H transition state .

have been use as refrigerant.1 . it oes not pro uce the amaging chlorine free ra icals. Therefore. It was a better anaesthetics than ethoxyethane (ether) which was also use an Anae sthetics Since ether is highly flammable. However. BOX 7b B: THE USES OF HALOGEN COMPOUNDS Due to their inertness an stability. many halogenoalkanes are use in several p urposes. it is sel om in use now. Plastics Poly(chloroethene) or PVC an poly(tetrafluoroethene)/PTFE. for example ichloro ifluoromethane or trichlorofluoro methane. In general the g reater the bon strength the lower the reactivity so that fluorocarbons are less reactive than alkanes an the other haloalkanes increasingly more reactive an less stable from Cl to I.2 tetrafluoroethane (CF3CH2F). thus epleting ozone layer in the atmosphere. it causes liver amage. al so known as Teflon are polymers which are synthesise from halogenoalkanes. T he inertness an the high stability of CFCs are the reasons for choosing these. The presence of hy rogen atom increases its reac tivity so it is broken own more easily in atmosphere. However. Therefore. Flame retar ants Bromochloro ifluoromethane (BCF) is very effective at extinguishing fire. CFCs. The ra icals ecompose ozone into oxyg en. it is not in beneral use because the break own pro ucts are poisonous. The relative strength of C Hal bon is C Cl > C F > C Br > C I.g. was once use as anaesthetics. some governments ha ve eci e to restrict the uses of CFCs an change to alternatives such as 1. ue to the stability. Even if it reaches strato sphere. a naesthetics. aerosol propellants or blowing agents. they un ergo photo issociation by ultraviolet ra iati on which pro uces chlorine free ra icals. flame retar ants.1.             ¡         ¡             ¡       ¡   ¡   ¡           ¡                                       ¡ ¡ ¡     ¡   . an plastics with particular reference to hy roly sis an to the relative strengths of the C Hal bon s) explain the uses of fluoro alkanes an fluorohalogenoalkanes in terms of their relative chemical inertness recognise the concern about the effect of chlorofluoroalkanes on the ozone layer nes BOX 7b A: REACTIVITIES OF HALOGENOALKANES BOX 7b B cont .HANDOUT 7b – RELATIVE STRENGTH OF C HAL BONDS Objectives: Interpret the ifferent reactivities of halogenoalkanes e. CFCs Chlorofluorocarbons. although chloroform is not fl ammable. Anae sthetics Trichloromethane (chloroform). However. CHCl3. these agents accumulate in the atmosphere an whe n they reach stratosphere.

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