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Unit 2: Chemistry In action

2.8 Haloalkanes

Haloalkanes

After studying this section, you will be able to:
Synthesis of chloroalkanes

   

 

understand the reaction mechanism of methane with chlorine as a freeradical substitution reaction in terms of initiation, propagation and termination steps know that chloroalkanes and chlorofluoroalkanes can be used as solvents understand that ozone, formed naturally in the upper atmosphere is beneficial be able to use equations such as the following to explain why chlorine atoms catalyse the decomposition of ozone and contribute to the formation of a hole in the ozone layer Cl•+ O3 → ClO• + O2 and ClO• + O3 → 2O2 + Cl• know that chlorine atoms are formed in the upper atmosphere when energy from ultra-violet radiation causes C–Cl bonds in chlorofluorocarbons (CFCs) to break appreciate that legislation to ban the use of CFCs was supported by chemists and that they have now developed alternative chlorine-free compounds understand that haloalkanes contain polar bonds understand that haloalkanes are susceptible to Nucleophilic attack, limited to OH , CN and NH3 understand the mechanism of nucleophilic substitution in primary haloalkanes understand that the carbon–halogen bond enthalpy influences the rate of hydrolysis appreciate the usefulness of these reactions in organic synthesis understand concurrent substitution and elimination (including mechanisms) in the reaction of a haloalkane (e.g. 2-bromopropane with potassium hydroxide) and the role of the reagent as both nucleophile and base appreciate the usefulness of this reaction in organic synthesis

For this topic, review the following definitions: 1. 2. Free radical Elimination 3. 4. Nucleophile Nucleophilic substitution

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Learning Objective(s)

Nucleophilic substitution

     

Elimination

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Unit 2: Chemistry In action

2.8 Haloalkanes

1. Haloalkanes
Haloalkanes are alkanes in which one of the hydrogen atoms has been substituted with a halogen – the halogen atom is the functional group. They have the general formula CnH2n+1X or more simply R—X (where X is a halogen). Haloalkanes are important because they have many uses.
Uses of Haloalkanes  Chlofluorocarbons, CFCs were used as refrigerants, solvents, propellants and dry cleaning agents. CFCs however deplete the ozone layer and are now banned in countries that signed the Montreal Protocol.  PVC and PTFE are polymer (plastic) haloalkanes made from Chloroethene, CH2=CHCl and tetrafluoroethene, F2C=CF2 respectively.  Haloalkanes are used as intermediate compounds in the making many synthetic compounds like pharmaceuticals, anaesthetics (chloroform), Teflon and herbicides.

A primary (1o) haloalkane contains the CH2X group where X is a halogen, e.g. 1-chlorobutane, CH3CH2CH2CH2Cl (X is attached to a terminal C atom). A secondary (2o) haloalkane has two carbon atoms attached to CHX group (i.e. X is not on the terminal C of the alkane backbone), e.g. 2-chlorobutane, CH3CH2CHClCH3. A tertiary (3o) haloalkane has three carbon atoms attached to CHX group, e.g. 2-chloro-2methylpropane, (CH3)3CCl.

Naming haloalkanes Haloalkanes are named according to the format x-haloalkane, where x indicates the position of the halogen atom in the chain. Examples of names of some simple haloalkanes are given below.
2-bromobutane 1-bromo-2-methyl propane 1-iodopropane

Draw structural formula

Draw structural formula

Draw structural formula

Where more than one substituent is present on the chain, they are arranged in alphabetical order with the numbering system chosen to give the lowest possible number for any substituent. Where two or more substituents would have the same numbers when numbering

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Unit 2: Chemistry In action

2.8 Haloalkanes

from either side, the substituent that comes first in the alphabet (ignoring di-, tri-,etc.) is chosen to have the lowest position number. For example H H Br H H I I I I I H—C—C—C—C—C—H I I I I I H Cl H H H This is 3-bromo-2-chloropentane
and not i) 2-chloro-3-bromopentane (why not?) or ii) 3-bromo-4-chloropentane (why not?)

Bond Polarity The Cδ+—Xδ- bond is polar with δ+ charge on C and a δ- charge on the halogen because halogens are more electronegative than carbon. The electron deficient carbon, Cδ+ is important in many of the (Nucleophilic) reactions of haloalkanes. Electronegativity decreases down the group for halogens. But the polarity is only slight, and not enough for haloalkanes to dissolve in polar substances like in water. Instead, haloalkanes mix with hydrocarbons and are often used as dry-cleaning agents to remove oily (hydrocarbon) stains.
Element Fluorine Chlorine Bromine Iodine Carbon Electronegativity 4.0 3.5 2.8 2.6 2.5
Electronegativity decreases down group

C—F bond is most polar

C—I bond is least polar

Physical properties of the Haloalkanes Polarity of these molecules is only slight and the main intermolecular forces are dipole-dipole and van der Waal forces. I. II. As the chain length of the hydrocarbon to which the halogen is attached increases, the mass/size of the molecule and the number of electrons increase. Also for a particular chain length, the molecule is larger as we go down the halogen group.

Boiling point increases with increasing chain length and it increases as we go down the halogen group. Branching reduces boiling point. Halogens have a greater molar mass than the corresponding hydrocarbon and have a higher boiling point.

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Unit 2: Chemistry In action

2.8 Haloalkanes

Reactions of the Haloalkanes
The reactions of haloalkanes depend on I. II. How delocalised the electrons in Cδ+—Xδ- bond are (bond polarity), and How easy it is to break the C—X bond (bond enthalpy)

Because the C in the C—X bond carries a δ+, it is attacked by nucleophiles. Because C—F is the most polar and C—I is the least polar, we will expect that C—F will be the most reactive (with nucleophiles) and that reactivity will decrease as we go down the halogen group. Considering bond enthalpies on the other hand (see table below), F, the smallest halogen is more strongly bonded to C and C—I is the weakest bond. Considering bond energy only, we will expect reactivity to increase as we go down the group. In fact, reactivity does increase as we go down the group so bond enthalpy contributes more to reactivity than bond polarity.
Bond C—F [C—H] C—Cl C—Br C—I Bond Energy KJ mol-1
467

[413] 346 290 228

Bond strength increases up group

C—F bond is strongest

C—I bond is weakest

2. Nucleophilic substitution in haloalkanes (SN2)
We have already seen that a Nucleophile is an ion or group of atoms with a negative charge, or a partially negatively charged area, which takes part in an organic reaction by attacking an electron deficient area in another reactant. The polar Cδ+ atom is often attacked by a nucleophile (a reagent that brings a pair of electrons) and the halogen leaves as the halide ion (X-), taking on the two electrons from the C-X bond. R—CH2—X + :Nu- → R—CH2—Nu + :X(:Nu- represents a nucleophile)

Examples of nucleophiles are shown below. They all carry a δ- or - charge and at least one lone pair.

The mechanism is called SN2 because the reaction is a Substitution, the attacking reagent is a Nucleophile and there are 2 species (haloalkane & nucleophile) involved in the first step.

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Unit 2: Chemistry In action

2.8 Haloalkanes

For primary haloalkanes

Examples of Nucleophilic substitutions are shown by HALOALKANES + AQUEOUS NAOH (OR AQ. KOH) – NUCLEOPHILE = :OH- (PRODUCT = ALCOHOL) The reaction mechanism for Nucleophilic substitution of 1-bromopropane by OH- is shown below. Reaction occurs at room temperature (cold aqueous NaOH or KOH). Haloalkanes do not dissolve in water so ethanol is used as the solvent. The reaction is a hydrolysis and the product is an alcohol. Reaction = R—X + OH- → R—OH + XOverall mechanism

HALOALKANES + NITRILE)

CYANIDE ION

– NUCLEOPHILE = :CN- (PRODUCT =

The cyanide ion, CN–, acts as a nucleophile and reacts with haloalkanes in the same way as the OH- ion shown above. The product is a nitrile and has one extra C-atom than the starting haloalkane. It is therefore a means of making new molecules that are longer. (The cyanide ion is often provided by sodium cyanide, NaCN, or potassium cyanide, KCN.) CH3CH2CH2Br + -:CN → CH3CH2CH2CN + :Br–

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Unit 2: Chemistry In action

2.8 Haloalkanes

Nitriles R—CN (

) have the functional group CN.

The carbon atom in the nitrile group is included when counting the carbon atoms in the main chain. So CH3CN is ethanenitrile not methanenitrile.

HALOALKANES + AMMONIA – NUCLEOPHILE = :NH3 (PRODUCT = AMINE) Ammonia, NH3, also acts as a nucleophile (its nitrogen atom has a lone pair of electrons) and it reacts with haloalkanes to produce amines. Excess ammonia is required for the reaction because two ammonia molecules are needed to react with one haloalkane. One ammonia molecule acts as a nucleophile and the other acts as a base. If ammonia was not in excess, the primary amine formed (has a lone pair as well) will further attack the haloalkane to form a secondary amine, which will react further to form a tertiary amine. Excess ammonia makes sure the primary amine is the main product. For example 1-bromopropane reacts with ammonia to form 1-aminopropane: CH3CH2CH2Br + 2NH3 → CH3CH2CH2NH2 + NH4Br Step 1 Ammonia acting as a nucleophile: CH3CH2CH2Br + NH3 → CH3CH2CH2+NH3 + Br– Step 2 Ammonia acting as a base: CH3CH2CH2+NH3 + NH3 → CH3CH2CH2NH2+ NH4+ Here the ammonia molecule accepts a hydrogen ion from the positively charged intermediate. The ammonium ion from step 2 and the bromide ion from step 1 form ammonium bromide.

3. Elimination reactions in haloalkanes
We have already seen that a substitution reaction happens when a hydroxide ion acts as a nucleophile, its lone pair attacking Cδ+ to produce an alcohol. But hydroxide ion can also act as a base leading to an elimination reaction. This produces an alkene instead of an alcohol. If 2-bromopropane is heated strongly with concentrated sodium or potassium hydroxide in ethanol, (instead of aqueous solution) propene is formed: AQA AS Chemistry (CHEM 2) Mo Idriss, Quick Revision Notes

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Unit 2: Chemistry In action CH3CH2CH2Br + OH– → CH3CH=CH2 + H2O + Br– The mechanism involves

2.8 Haloalkanes

• • •

the hydroxide ion forms a co-ordinate bond with a hydrogen atom the bonding pair of electrons from the carbon–hydrogen bond forms a second covalent bond between two carbon atoms the carbon–bromine bond breaks, releases a bromide ion (leaving group).

All three pairs of electrons move simultaneously and there is no intermediate species. The hydrogen atom that is attacked is joined to a carbon atom next to the carbon atom with the carbon–halogen bond. The hydrogen atom is removed as a hydrogen ion, H+, which is accepted by the hydroxide ion to form water. This is how the hydroxide ion acts as a base (H-acceptor). The hydrogen is always lost from a carbon atom adjacent to the carbon atom attached to the halogen (all the hydrogen atoms which could be removed have been circled in the examples below). For long chain halaoalkanes, this can sometimes result in more than one possible product:
H H C H H C H H C Br H H C H H C2H5 C C H H

2-bromobutane

but-1-ene

In this reaction, losing an H atom on the other side of the Br atom results in two different products:

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2.8 Haloalkanes

H H C H

H C H

H C Br

H H C H H C CH3 C

H or CH3

CH3 C H C

H

CH3

2-bromobutane

cis but-2-ene or

trans but-2-ene

Concurrent substitution and elimination When haloalkanes react with hydroxide ions, both types of reaction can happen together. This is called concurrent substitution and elimination. The reaction conditions can be adjusted to favour one type of reaction over the other.    Substitution is favoured by using warm, dilute aqueous sodium hydroxide or potassium hydroxide. Also primary haloalkanes react mostly by substitution. Elimination is favoured by using hot, concentrated ethanolic sodium hydroxide or potassium hydroxide. Also tertiary haloalkanes react mostly by elimination. Secondary haloalkanes tend to react by a mixture of substitution and elimination.

To some extent the two reactions are always in competition with each other because hydroxide ions can act both as a nucleophile and as a base.

Let’s try these 1. Which of the following is a free radical, a nucleophile and a carbocation (ion with + charge on one C atom) a. NH3 ___________________________ b. CH3+ __________________________ c. CH3• __________________________ 2. Which bond is weaker, C—Cl or C—I? 3. Which bond is more polar, C—Cl or C—I? 4. Give the SN2 reaction mechanism between iodomethane and aqueous hydroxide ions 5. Draw the structure of a chlorofluorocarbon and write an equation to show how it can release chlorine radicals in the presence of ultra-violet light. 6. Give the mechanism for the reaction of a. bromoethane with aqueous sodium hydroxide b. 2-chloropropane with potassium cyanide c. 1-iodobutane with ammonia

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Unit 2: Chemistry In action

2.8 Haloalkanes

4. Haloalkanes and the environment
Chlorofluoroalkanes, CFCs are haloalakanes that contain C, Cl and F only. They were widely used in as dry cleaning agents and in aerosols and fridges as they are quite unreactive under normal conditions at sea level. However in the upper atmosphere the C-Cl bonds can undergo homolytic fission when exposed to ultra-violet light: E.g. CF2Cl2  CF2Cl• + Cl• The free radicals formed are known to damage ozone in the upper atmosphere (stratosphere), where ozone plays an important role in absorbing ultra-violet radiation from the sun and preventing it from getting to the earth’s surface. Free radicals damage ozone by reacting with to form molecular oxygen and more free radicals: Cl• + O3 ClO• + O3 2O3   → ClO• + O2 2O2 + Cl• 3O2 eqn. 1 eqn. 2 (summary = adding eqn. 1 & eqn. 2)

The Cl• is regenerated (not used up, therefore essentially a catalyst) and the process can repeat itself indefinitely, meaning that even small quantities of chlorine radicals can significantly destroy the ozone layer. This process has resulted in the formation of a hole in the ozone layer. As a result of this, chemists supported legislation to ban CFCs completely and they are being replaced b more environmentally friendly alternatives including hydrochlorofluorocarbons (HCFCs). It will however take many years to for the large quantity of CFCs accumulated in the atmosphere to disappear. The hole in the ozone layer is slowly mending itself but will take time.

5. Formation of haloalkanes
Chloroalkanes can be made from alkanes by free radical substitution reactions. E.g. CH4 + Cl2  CH3Cl + HCl

A substitution reaction is one in which one atom or group of atoms on the organic molecule is directly replaced by another. In this reaction the H atom on the alkane is replaced by a Cl atom. A free radical is a species which contains an unpaired electron. Free radicals are very reactive species and will bond with almost anything they come into contact with.

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Unit 2: Chemistry In action

2.8 Haloalkanes

In this reaction the free radical which starts the reaction is a chlorine atom, formed when a chlorine molecule breaks up in the presence of ultra-violet light:

Cl2

Cl

Cl

Free radicals are represented by a dot next to the atom containing an unpaired electron. They are caused by homolytic fission of covalent bonds. Homolytic fission is the breaking of a covalent bond in such a way that one electron goes to each atom. Mechanism: free radical substitution There are three stages: initiation, propagation and then termination. i) Initiation

Production of free radicals by homolytic fission of a covalent bond. Most bonds do not undergo homolytic fission under normal conditions. Generally, UV light is required. UV

Cl2
ii) Propagation stages

Cl

Cl

The free radical with a molecule to produce another free radical. (Chain reaction). The reaction involves two propagation steps:

Cl
CH3 .

+
+

H

CH3
Cl Cl

HCl

+
+

CH3 .
Cl

CH3Cl

iii)

Termination

There are several possible termination reactions (where two free radicals combine): Cl• + Cl• → Cl2 Cl• + •CH3 → CH3Cl H3C• + •CH3 → C2H6

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2.8 Haloalkanes

Note that the Cl radicals are recycled during the propagation steps, so the reaction only requires a very small number of Cl-Cl bonds to undergo fission for the reaction to proceed. By-products in free radical substitution: Formation of multi-substituted products occurs when the chlorine free radical collides with a different molecule in the first propagation step: Cl• •CH2Cl Cl• •CHCl2 Cl• •CCl3 + + + + + + CH3Cl → Cl2 → •CH2Cl + HCl Propagation Propagation Propagation Propagation Propagation Propagation

CH2Cl2 + Cl• dichloromethane •CHCl2 + HCl Cl• HCl

CH2Cl2 → Cl2

→ CHCl3 + trichloromethane •CCl3 +

CHCl3 → Cl2

→ CCl4 + Cl• tetrachloromethane

These further propagation steps are likely if excess chlorine is used. If excess methane is used, then chloromethane is likely to be the major product. It also possible to get other products from alternative termination steps: Cl• Cl• H3C• + + + Cl• •CH3 •CH3 → → → Cl2 CH3Cl C2H6 Termination Termination Termination

In order to ensure that chloromethane is the major product, it is important to use excess methane.

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Unit 2: Chemistry In action

2.8 Haloalkanes

Summary of Reactions of Haloalakanes

H R C

H C O H

H H Alcohol

NaoH (aq) Reflux

Nucleo Sub

H R H C R alkene C H OH- Alocoholic soln reflux H Elimination C

H C

H H H Conc NH3 heat in a sealed tube H Br R C C Nucleo Haloalkane H Sub H amine Nucleo KCN, alocoholic Sub Solution, reflux H H C CN
+

NH2

R H2 / LiAlH4

C H

H

Reduction H R C H C NH2

Hydrolysis

H /H2O, reflux H H

O C R C C H topic (Kinetics), learn the following definitions: H next For the amine H H OH

1. 2. 3.

Activation Energy Collision Energy Collision Frequency

4. Carboxylic 5. acid 6.

Heterogeneous catalyst Homogeneous catalyst Maxwell-Boltzmann distribution

Practice Questions

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