HALOGENOALKANES Production of haloalkanes from alkanes Role of haloalkanes in ozone layer depletion Nucleophilic su stitution Elimination

MANUFACTURE OF CHLOROALKANES FROM ALKANES Chloroalkanes can be made from alkanes in a reaction known as a free radical substitution reaction. Eg CH4 + Cl2 CH3Cl + HCl

A substitution reaction is one in which one ato or !rou" of ato s on the or!anic olecule is directl# re"laced b# another$ In this reaction the H atom on the alkane is replaced by a Cl atom. Since all the carbon atoms in alkanes are attached to fo r other atoms! it is not possible to add another species to an alkane nless another species lea"es. #h s addition reactions are not possible and alkanes can ndergo s bstit tion reactions only. A free radical is a s"ecies which contains an un"aired electron$ $ree radicals are "ery reacti"e species and will bond with almost anything they come into contact with. In this reaction the free radical which starts the reaction is a chlorine atom! formed when a chlorine molec le breaks p in the presence of ltra%"iolet light& Cl2 Cl Cl

$ree radicals are represented by a dot ne't to the atom containing an npaired electron. #hey are ca sed by ho ol#tic fission of co"alent bonds. Ho ol#tic fission is the brea%in! of a co&alent bond in such a wa# that one electron !oes to each ato . Mechanis '( free radical substitution

$ree radical s bstit tion reactions proceed in three stages& initiation! propagation and then termination. i) *nitiatation

Initiation is the prod ction of free radicals by homolytic fission of a co"alent bond. (ost bonds do not ndergo homolytic fission nder normal conditions. )enerally! *+ light is re, ired. *+

Cl2
ii) +ro"a!ation

Cl

Cl

-ropagation is the reaction of a free radical with a molec le to prod ce another free radical. #he reaction in"ol"es two propagation steps&

Cl CH3 . iii)

+ +

H Cl

CH3 Cl

HCl CH3Cl

+ +

CH3 . Cl

Ter ination

#ermination is the combination of two free radicals to form a single molec le. Cl

Cl

Cl2

.ote that the Cl radicals are recycled d ring the propagation steps! so the reaction only re, ires a "ery small n mber of Cl%Cl bonds to ndergo fission for the reaction to proceed. ,#-"roducts in free radical substitution( Chloromethane is not generally the only organic prod ct of this reaction. $ree radical reactions tend to res lt in a "ariety of different prod cts. i/ 0ifferent propagation steps

#he propagation steps can contin e beyond the formation of methane! and can res lt in the formation of dichloromethane! trichloromethane or tetrachloromethane& Cl

CH2Cl Cl Cl

HCl CH2Cl2

CH2Cl . . Cl

. CH Cl 2

#hese f rther propagation steps are likely if e'cess chlorine is sed. If e'cess methane is sed! then chloromethane is likely to be the ma1or prod ct. ii/ 0ifferent termination steps

It also possible to get other prod cts from alternati"e termination steps& . CH
3

. CH

CH 3CH 3

#h s when methane reacts with chlorine! a "ariety of prod cts are formed incl ding chloromethane! dichloromethane and ethane. *n order to ensure that chloro ethane is the use e0cess ethane. a.or "roduct/ it is i "ortant to

ROLE OF CHLOROALKANES *N O1ONE LA2ER 3E+LET*ON Chloroalkanes and chlorofl oroalkanes can be sed as sol"ents. 2ne type in partic lar! known as chlorofl orocarbons 3C$Cs/! are widely sed in aerosols and fridges. Chlorofl orocarbons are haloalkanes containing chlorine and fl orine atoms b t not hydrogen atoms! eg CCl2$2 or CCl$3. #he small chlorofl orocarbons are gases and can escape into the atmosphere. *s ally chlorofl orocarbons are "ery nreacti"e. Howe"er in the pper atmosphere the C%Cl bonds can ndergo homolytic fission if e'posed to ltra%"iolet light& Eg C$2Cl2 C$2Cl. + Cl. 24one 323/ is a nat rally occ rring s bstance fo nd in the pper atmosphere. It plays an important role in absorbing ltra%"iolet radiation from the s n and pre"enting it from getting to the earth5s s rface. Howe"er if C$Cs find their way into the pper atmosphere and the ltra%"iolet light breaks them down into Cl. radicals! these Cl. radicals act as catalysts in the destr ction of the o4one layer as follows& Cl. + 23 Cl2. + 22 Cl2. + 23 222 + Cl. #his process can repeat itself indefinitely! meaning that e"en small , antities of chlorine radicals can significantly destroy the o4one layer. #his process has res lted in the formation of a hole in the o4one layer. 6s a res lt of this! chemists s pported legislation to ban C$Cs completely and they ha"e been replaced in fridges and aerosols by alternati"e chlorine%free compo nds. #he hole in the o4one layer is slowly mending itself.

REACT*ONS OF HALOALKANES #he C%7 bond is polar! and the carbon is +"e. #herefore haloalkanes can react with nucleo"hiles. 6 nucleo"hile is a species with a lone pair of electrons which it can se to bond with an electropositi"e carbon atom on an organic molec le. #he n cleophile generally replaces the halogen atom on the molec le. #h s haloalkanes can ndergo nucleo"hilic substitution reactions. Halogenoalkanes can also ndergo eli ination reactions. 6n eli ination reaction is one in which the organic molec le loses two species from ad1acent carbon atoms witho t replacement! res lting in the formation of a do ble bond between the two carbon atoms. Mechanis 4( Nucleo"hilic Substitution

#he three n cleophiles most commonly sed in n cleophilic s bstit tion of halogenoalkanes are hydro'ide ions! 2H%! cyanide ions! C.% and ammonia! .H3. '$ Reaction with h#dro0ide ions

Halogenoalkanes react with hydro'ide ions when boiled nder refl ' with a, eo s .a2H or a, eo s 82H& 9%7 + 2H% 9%2H + 7% #he n cleophile 3ie the hydro'ide ion/ attacks the +"e carbon atom from behind! forcing the 7 atom to lea"e as the halide ion. It is a one%step mechanism& H CH3 HO: H C X H CH3 H C OH

.ote that the hydro'ide ion is beha"ing as a nucleo"hile in this reaction.

Eg

bromoethane ethanol H CH3 C Br H CH3 H C OH

Br

HO: Eg

H 2%chloropropane propan%2%ol H CH3 C Cl

H CH3 CH3 C OH

Cl

HO: 4$

CH3 Reaction with c#anide ions

Cyanide ions are n cleophiles and react with halogenoalkanes by n cleophilic s bstit tion to gi"e nitriles. #he halogenoalkane sho ld be boiled nder refl ' with 8C. in a, eo s ethanol. 9%7 + C.% 9%C. + 7% #he mechanism is e'actly the same as with the hydro'ide ion. H CH3 NC: H C X H CH3 H C CN

.ote that the C.% ion has the following str ct re& :C N

#h s the lone pair of electrons is on the carbon! not the nitrogen. It is th s the carbon which attaches itself to the organic molec le. Eg bromoethane propanenitrile H CH3 NC: H C Br H CH3 H C CN

Br

Eg 2%chloropropane 2%methylpropanenitrile H CH3 NC: C CH3 Cl H CH3 CH3 C CN -

Cl

#he reaction with cyanide ions is significant beca se it increases the n mber of carbon atoms on the chain! so it "ro&ides a wa# of ascendin! the ho olo!ous series. It is th s "ery sef l in organic synthesis. 5$ Reaction with a onia

If a halogenoalkane is heated with ethanolic ammonia in a sealed t be! a primary amine is formed& 9%7 + 2.H3 9%.H2 + .H47 #he mechanism is again n cleophilic s bstit tion& H H CH3 H :NH3 C X CH3 H C H + N H H

#he initial s bstit tion step forms the intermediate 9%.H3+ ion. #he H is remo"ed by another ammonia molec le to form the amine&
H CH3 H C H + N H H : NH3 CH3 H H C N H :

NH+ 4

Eg
H CH3 H

bromoethane aminoethane
H C Br CH3 H C H + N H H :NH3 CH3 H Br H C N H H

:NH3

+ NH4

Eg
H CH3

2%chloropropane 2%aminopropane
H C CH3 Cl CH3 C CH3 H + N H H :NH3 CH3 H C CH3 N H H

:NH3

Cl

+ NH4

6$ Eli ination of h#dro!en halides If halogenoalkanes are boiled with an ethanolic sol tion of 82H instead of with an a, eo s sol tion! they will ndergo elimination of an H7 molec le to gi"e an alkene& 9:92CH9394C;r + 2H% C2H4 + ;r% + H22 .a2H is not sed since it is only sparingly sol ble in ethanol. #his reaction works best if distillation apparat s is sed since the alkene prod ct is "olatile. #he hydrogen is always lost from a carbon atom ad1acent to the carbon atom attached to the halogen 3all the hydrogen atoms which co ld be remo"ed ha"e been circled/. Sometimes this can res lt in more than one possible prod ct&
H H C H H C H Br H H C C H H

bromoethane
H H C H H C H H C H Cl

ethene
H C CH3 C H

:%chloropropane H H C H H C Cl H C H H

propene H C CH3 propene C H

2%chloropropane

H H C H

H C H

H C H

H C H Br

H C C2H5 b t%:%ene C

H H

:%bromob tane

0 ring the abo"e elimination reactions there is only one possible prod ct. H H C H H C H H C Br H H C H H C2H5 C C H

2%bromob tane

b t%:%ene

In this reaction! losing an H atom on the other side of the ;r atom res lts in two different prod cts&
H H C H H C H H C Br H C H H H C CH3 C CH3 H or H CH3 C C CH3 H

2%bromob tane Mechanis

cis b t%2%ene or 5( eli ination

trans b t%2%ene

#he mechanism of this reaction in"ol"es the hydro'ide ion attacking a hydrogen atom on the haloalkane& HO : H R C R R C R X R R C C R R

+ X +

H2O

.ote that the hydro'ide ion is beha"ing as a base! not a n cleophile

Eg :%chloropropane propene

HO : H CH3 C H H C H X CH3 H C C H H + X + H2O

RATES OF REACT*ON OF HALO7ENOALKANES #he rate of s bstit tion or elimination of halogenoalkanes depends on the ease with which the C%7 bond can be broken. #his depends on the strength of the C%7 bond! which in t rn depends on the length of the bond. Since the C%$ bond is "ery short! it is "ery strong and diffic lt to break. #h s fl oroalkanes react "ery slowly. #he C%Cl bond is longer and weaker than the C%$ bond! and the C%7 bonds become progressi"ely longer and weaker on descending the gro p. #h s the C%I bond is the longest! weakest and easiest to break and th s iodoalkanes react the most , ickly. #h s rates of reactions decrease in the order& Iodoalkanes < bromoalkanes < chloroalkanes < fl oroalkanes 6s the halogen atom becomes larger! the C%7 bond becomes longer! weaker and more diffic lt to break and the corresponding halogenoalkanes react more , ickly.

'$ Su

ar# of reactions of haloal%anes

Haloalkane alcohol 9eagent& .a2H3a,/ or 82H3a,/ Conditions& warm nder refl ' E, ation& 9%7 + 2H% 9%2H + 7% (echanism& n cleophilic s bstit tion 9ole of hydro'ide ion& n cleophile Haloalkane nitrile 9eagent& 8C. in a, eo s ethanol Conditions& boil nder refl ' E, ation& 9%7 + C.% 9%C. + 7% (echanism& n cleophilic s bstit tion Haloalkane 6mine 9eagent& ammonia in ethanol in a sealed t be Conditions& heat E, ation& 9%7 + 2.H3 9%.H2 + .H47 (echanism& n cleophilic s bstit tion Haloalkane alkene 9eagent& 82H in ethanol Conditions& heat E, ation&
H R C R R C R X R R C C R + R X + H2O

(echanism& elimination 9ole of hydro'ide ion& base