Beruflich Dokumente
Kultur Dokumente
2.8 Haloalkanes
Haloalkanes
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 CCl 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 carbonhalogen 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
Learning Objective(s)
Nucleophilic substitution
Elimination
11
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 RX (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
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
12
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 HCCCCCH 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 C+X- bond is polar with + charge on C and a - charge on the halogen because halogens are more electronegative than carbon. The electron deficient carbon, C+ 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
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.
13
2.8 Haloalkanes
Because the C in the CX bond carries a +, it is attacked by nucleophiles. Because CF is the most polar and CI is the least polar, we will expect that CF 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 CI 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 CF [CH] CCl CBr CI Bond Energy KJ mol-1
467
CF bond is strongest
CI bond is weakest
Examples of nucleophiles are shown below. They all carry a - 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.
14
2.8 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 = RX + OH- ROH + XOverall mechanism
HALOALKANES + NITRILE)
CYANIDE ION
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
15
2.8 Haloalkanes
Nitriles RCN (
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.
16
2.8 Haloalkanes
the hydroxide ion forms a co-ordinate bond with a hydrogen atom the bonding pair of electrons from the carbonhydrogen bond forms a second covalent bond between two carbon atoms the carbonbromine 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 carbonhalogen 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:
17
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
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.
Lets 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, CCl or CI? 3. Which bond is more polar, CCl or CI? 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
18
2.8 Haloalkanes
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.
19
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 .
+
+
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
20
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 Cl2
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.
21
2.8 Haloalkanes
H R C
H C O H
H H Alcohol
Nucleo Sub
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
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.
4. Carboxylic 5. acid 6.
Practice Questions