NUCLEOPHILIC SUBSTITUTION

Bonding in the halogenoalkanes Halogenoalkanes (also known as haloalkanes or alkyl halides) are compounds containing a halogen atom (fluorine, chlorine, bromine or iodine) joined to one or more carbon atoms in a chain. The interesting thing about these compounds is the carbon-halogen bond, and all the nucleophilic substitution reactions of the halogenoalkanes involve breaking that bond. The polarity of the carbon-halogen bonds With the exception of iodine, all of the halogens are more electronegative than carbon. Electronegativity values (Pauling scale) C 2.5 F Cl Br I 4.0 3.0 2.8 2.5

That means that the electron pair in the carbon-halogen bond will be dragged towards the halogen end, leaving the halogen slightly negative ( -) and the carbon slightly positive ( +) - except in the carbon-iodine case. Although the carbon-iodine bond doesn't have a permanent dipole, the bond is very easily polarised by anything approaching it. Imagine a negative ion approaching the bond from the far side of the carbon atom:

The fairly small polarity of the carbon-bromine bond will be increased by the same effect. The strengths of the carbon-halogen bonds
Note: If you haven't done any work on bond strengths, or are a bit rusty, it doesn't matter. Just realise that the bigger the

number, the stronger the bond. And don't worry if you have found slightly different numbers in a different data source - there is a lot of variability in the quoted values, but the overall pattern is still the same.

Look at the strengths of various bonds (all values in kJ mol-1). C-H 413 C-F C-Cl C-Br C-I 467 346 290 228

In all of these nucleophilic substitution reactions, the carbon-halogen bond has to be broken at some point during the reaction. The harder it is to break, the slower the reaction will be. The carbon-fluorine bond is very strong (stronger than C-H) and isn't easily broken. It doesn't matter that the carbon-fluorine bond has the greatest polarity - the strength of the bond is much more important in determining its reactivity. You might therefore expect fluoroalkanes to be very unreactive - and they are! We shall simply ignore them from now on. In the other halogenoalkanes, the bonds get weaker as you go from chlorine to bromine to iodine. That means that chloroalkanes react most slowly, bromoalkanes react faster, and iodoalkanes react faster still. Rates of reaction: RCl < RBr < RI Where "<" is read as "is less than" - or, in this instance, "is slower than", and R represents any alkyl group.

Warning! Before you read on it is essential that you know exactly what your syllabus says about these reactions so that you can extract the right amount of detail from what follows. The problem is that there are two different mechanisms depending on the type of halogenoalkane you are using (whether primary, secondary or tertiary). Some syllabuses try to make things simpler by restricting you to just one of the two mechanisms. Where the syllabus is vague, look at recent exam papers and mark schemes, or any support material published by your examiners. Haven't got a syllabus or recent exam papers? If you are working to one of the UK-based syllabuses for 16 - 18 year olds, follow this link to find out how to get them. You must know what your examiners expect in this topic.

Nucleophilic substitution in primary halogenoalkanes
You will need to know about this if your syllabus talks about "primary halogenoalkanes" or about S N2 reactions. If the syllabus is vague, check recent exam papers and mark schemes, and compare them against what follows.

Nucleophiles A nucleophile is a species (an ion or a molecule) which is strongly attracted to a region of positive charge in something else. Nucleophiles are either fully negative ions, or else have a strongly - charge somewhere on a molecule. Common nucleophiles are hydroxide ions, cyanide ions, water and ammonia.

Notice that each of these contains at least one lone pair of electrons, either on an atom carrying a full negative charge, or on a very electronegative atom carrying a substantial - charge. The nucleophilic substitution reaction - an SN2 reaction We'll talk this mechanism through using an ion as a nucleophile, because it's slightly easier. The water and ammonia mechanisms involve an extra step which you can read about on the pages describing those particular mechanisms. We'll take bromoethane as a typical primary halogenoalkane. The bromoethane has a polar bond between the carbon and the bromine. We'll look at its reaction with a general purpose nucleophilic ion which we'll call Nu -. This will have at least one lone pair of electrons. Nu- could, for example, be OH- or CN-.

The lone pair on the Nu- ion will be strongly attracted to the + carbon, and will move towards it, beginning to make a co-ordinate (dative covalent) bond. In the process the electrons in the C-Br bond will be pushed even closer towards the bromine, making it increasingly negative.
Note: A co-ordinate bond is a covalent bond in which both electrons come from one of the atoms.

The movement goes on until the -Nu is firmly attached to the carbon, and the bromine has been expelled as a Br- ion.

Note: We haven't shown all the lone pairs on the bromine. These other lone pairs aren't involved in the reaction, and including them simply clutters the diagram to no purpose.

Things to notice The Nu- ion approaches the + carbon from the side away from the bromine atom. The large bromine atom hinders attack from its side and, being -, would repel the incoming Nu- anyway. This attack from the back is important if you need to understand why tertiary halogenoalkanes have a different mechanism. We'll discuss this later on this page. There is obviously a point in which the Nu- is half attached to the carbon, and the C-Br bond is half way to being broken. This is called a transition state. It isn't an intermediate. You can't isolate it - even for a very short time. It's just the mid-point of a smooth attack by one group and the departure of another. How to write the mechanism The simplest way is:

Note: In exam you must show the lone pair of electrons on the nucleophile (in this case, the Nu ion). It probably doesn't matter whether you show them on the departing Br ion or not. If you aren't happy about the use of curly arrows in mechanisms, follow this link before you go on. Use the BACK button on your browser to return to this page.

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Technically, this is known as an SN2 reaction. S stands for substitution, N for nucleophilic, and the 2 is because the initial stage of the reaction involves two species - the bromoethane and the Nu- ion. If your syllabus doesn't refer to SN2 reactions by name, you can just call it nucleophilic substitution.

Some examiners like you to show the transition state in the mechanism, in which case you need to write it in a bit more detail - showing how everything is arranged in space.

and those showing the bonds going back into the paper. but in this section. These alkyl groups can be the same or different. If you haven't already checked your syllabus. If there's no mention of tertiary halogenoalkanes or SN1 reactions.Be very careful when you draw the transition state to make a clear difference between the dotted lines showing the half-made and half-broken bonds. wanted the transition state included. Note: If you aren't happy about the various ways of drawing bonds.2-bromo-2-methylpropane. and that isn't obvious from their syllabus. The nucleophilic substitution reaction .rather like an umbrella being blown inside-out. It is also important to know which of these ways of drawing the mechanism your particular examiners want you to use. Remember that a tertiary halogenoalkane has three alkyl groups attached to the carbon with the halogen on it. Use the BACK button on your browser to return to this page. past papers and any support material published by your examiners to find out whether you need this. we shall just consider a simple one. you must do so! At the time of writing.an SN1 reaction . (CH3)3CBr . for example. Edexcel. You have to check mark schemes and examiners reports. then you probably don't need it. Notice that the molecule has been inverted during the reaction . recent exam papers and mark schemes. Nucleophilic substitution in tertiary halogenoalkanes Warning! Check your syllabus. it is important to follow this link to find out exactly what the various symbols mean.

and about the relative stabilities of primary. this is impossible. Since any other approach is prevented by the bromine atom. it approaches the + carbon atom from the side away from the halogen atom. If you follow this link. The lone pair on the nucleophile is strongly attracted towards the positive carbon. The reaction happens in two stages. and again we'll look at the reaction of a general purpose nucleophilic ion which we'll call Nu -. because it's slightly easier. use the BACK button on your browser to return to this page. a small proportion of the halogenoalkane ionises to give a carbocation and a bromide ion. Even so. we'll talk this mechanism through using an ion as a nucleophile. With a tertiary halogenoalkane. In the first. This will have at least one lone pair of electrons. and moves towards it to . the reaction is slow. The alternative mechanism Important! To understand this section. the reaction has to go by an alternative mechanism. The back of the molecule is completely cluttered with CH 3 groups.Once again. it would react immediately it came into contact with a nucleophile like Nu-. you need to know what a carbocation (carbonium ion) is. Once the carbocation is formed. secondary and tertiary carbocations. however. This reaction is possible because tertiary carbocations are relatively stable compared with secondary or primary ones. Why is a different mechanism necessary? You will remember that when a nucleophile attacks a primary halogenoalkane.

Why don't primary halogenoalkanes use the SN1 mechanism? If a primary halogenoalkane did use this mechanism.and so that's what it does instead. THE NUCLEOPHILIC SUBSTITUTION REACTIONS BETWEEN HALOGENOALKANES AND HYDROXIDE IONS . and so the SN1 route isn't as effective as it is with tertiary halogenoalkanes. the mechanism is described as SN1 . the first step would be.and therefore much more difficult to produce. Because this initial slow step only involves one species. Secondary halogenoalkanes will use both mechanisms . This instability means that there will be a very high activation energy for the reaction involving a primary halogenoalkane.some molecules will react using the SN2 mechanism and others the SN1. The SN2 mechanism is possible because the back of the molecule isn't completely cluttered by alkyl groups and so the approaching nucleophile can still get at the + carbon atom. The activation energy is much less if it undergoes an S N2 reaction . How fast the reaction happens is going to be governed by how fast the halogenoalkane ionises. The SN1 mechanism is possible because the secondary carbocation formed in the slow step is more stable than a primary one. nucleophilic.substitution. one species taking part in the initial slow step. and this is much more energetically unstable than the tertiary one formed from tertiary halogenoalkanes . for example: A primary carbocation would be formed. Nucleophilic substitution in secondary halogenoalkanes There isn't anything new in this. It isn't as stable as a tertiary one though.create a new bond.

but it slightly obscures what's going on: The bromine (or other halogen) in the halogenoalkane is simply replaced by an -OH group . the halogen is replaced by -OH and an alcohol is produced. sodium hydroxide). If you want the mechanisms explained to you in detail. uncluttered mechanisms for the nucleophilic substitution reactions between halogenoalkanes and hydroxide ions (from. In this example. for example. The facts If a halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide.hence a substitution reaction. using 1-bromopropane as a typical primary halogenoalkane: You could write the full equation rather than the ionic one. Heating under reflux means heating with a condenser placed vertically in the flask to prevent loss of volatile substances from the mixture.This page gives you the facts and simple. The reaction of primary halogenoalkanes with hydroxide ions Important! If you aren't sure about the difference between primary. it is essential that you follow this link before you go on. Use the BACK button on your browser to return to this page. The solvent is usually a 50/50 mixture of ethanol and water. propan-1-ol is formed. there is a link at the bottom of the page. the halogenoalkane and the sodium hydroxide solution wouldn't mix and the reaction could only happen where the two layers met. For example. The mechanism Here is the mechanism for the reaction involving bromoethane: . If you used water alone as the solvent. because everything will dissolve in that. The halogenoalkane is insoluble in water. secondary and tertiary halogenoalkanes.

Because the mechanism involves collision between two species in the slow step (in this case. the only step) of the reaction. and an alcohol is produced. the halogen is replaced by -OH.This is an example ofnucleophilic substitution. it is known as an SN2 reaction. If your examiners want you to show the transition state. If the halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide in a mixture of ethanol and water. For example: Or if you want the full equation rather than the ionic one: . draw the mechanism like this: The reaction of tertiary halogenoalkanes with hydroxide ions The facts The facts of the reaction are exactly the same as with primary halogenoalkanes. Note: Unless your syllabus specifically mentions SN2 by name. you can just call it nucleophilic substitution.

the SN2 mechanism is: . It is known as an SN1 reaction.the halogenoalkane. The halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide in a mixture of ethanol and water. The reaction of secondary halogenoalkanes with hydroxide ions The facts The facts of the reaction are exactly the same as with primary or tertiary halogenoalkanes.The mechanism This mechanism involves an initial ionisation of the halogenoalkane: followed by a very rapid attack by the hydroxide ion on the carbocation (carbonium ion) formed: This is again an example ofnucleophilic substitution. This time the slow step of the reaction only involves one species . For example. For example: The mechanism Secondary halogenoalkanes use both SN2 and SN1 mechanisms.

Use the BACK button on your browser to return to this page. The facts There is only a slow reaction between a primary halogenoalkane and water even if they are heated. there is a link at the bottom of the page. it is essential that you follow this link before you go on. the two stages of the SN1 mechanism are: THE NUCLEOPHILIC SUBSTITUTION REACTIONS BETWEEN HALOGENOALKANES AND WATER This page gives you the facts and simple. The halogen atom is replaced by -OH. If you want the mechanisms explained to you in detail. using 1-bromoethane as a typical primary halogenoalkane: . uncluttered mechanisms for the nucleophilic substitution reactions between halogenoalkanes and water.Should you need it. The reaction of primary halogenoalkanes with water Important! If you aren't sure about the difference between primary. For example. secondary and tertiary halogenoalkanes.

The mechanism The mechanism involves two steps. the halogen is replaced by -OH to give an alcohol. Be careful not to call this hydrogen bromide. Note: Unless your syllabus specifically mentions SN2 by name. The second step of the reaction simply tidies up the product. The reaction of tertiary halogenoalkanes with water The facts If the halogenoalkane is heated under reflux with water. A water molecule removes one of the hydrogens attached to the oxygen to give an alcohol and a hydroxonium ion (also known as a hydronium ion or an oxonium ion). it's called hydrobromic acid. When it is dissolved it in water (as it will be here). a hydroxide ion. say. it is known as an SN2 reaction.An alcohol is produced together with hydrobromic acid. Hydrogen bromide is a gas. The first is a simple nucleophilic substitution reaction: Because the mechanism involves collision between two species in this slow step of the reaction. Heating under reflux means heating with a condenser placed vertically in the flask to prevent loss of volatile substances from the mixture. It lacks the full negative charge of. you can just call it nucleophilic substitution. The hydroxonium ion and the bromide ion (from the nucleophilic substitution stage of the reaction) make up the hydrobromic acid which is formed as well as the alcohol. The reaction happens much faster than the corresponding one involving a primary . The nucleophilic substitution is very slow because water isn't a very good nucleophile.

say. OH.the halogenoalkane. Now there is a final stage in which the product is tidied up. The water isn't involved in the slow step of the reaction. It is known as an SN1 reaction.exactly as happens with primary halogenoalkanes. For example: The mechanism This mechanism involves an initial ionisation of the halogenoalkane: followed by a very rapid attack by the water on the carbocation (carbonium ion) formed: This is again an example ofnucleophilic substitution. The fact that water isn't as good a nucleophile as.halogenoalkane. This time the slow step of the reaction only involves one species .doesn't make any difference. The reaction of secondary halogenoalkanes with water . A water molecule removes one of the hydrogens attached to the oxygen to give an alcohol and a hydroxonium ion . The rate of the overall reaction is governed entirely by how fast the halogenoalkane ionises.

there is a link at the bottom of the page. . Heating under reflux means heating with a . . Use the BACK button on your browser to return to this page. it is essential that you follow this link before you go on. The reaction of primary halogenoalkanes with cyanide ions Important! If you aren't sure about the difference between primary. . To menu of nucleophilic substitution reactions. . . To menu of other types of mechanism. secondary halogenoalkanes use both an SN2 mechanism and an SN1. THE NUCLEOPHILIC SUBSTITUTION REACTIONS BETWEEN HALOGENOALKANES AND CYANIDE IONS This page gives you the facts and simple. uncluttered mechanisms for the nucleophilic substitution reactions between halogenoalkanes and cyanide ions (from. Make sure you understand what happens with primary and tertiary halogenoalkanes. In the extremely unlikely event that you will ever need it. potassium cyanide).It is very unlikely that any of the current UK-based syllabuses for 16 .18 year olds will ask you about this. The facts If a halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol. for example. and then adapt it for secondary ones should ever need to. the halogen is replaced by a -CN group and a nitrile is produced. . To Main Menu . If you want the mechanisms explained to you in detail. . . Where would you like to go now? Help! Talk me through these mechanisms . secondary and tertiary halogenoalkanes.

you can just call it nucleophilic substitution. Because the mechanism involves collision between two species in the slow step (in this case.hence a substitution reaction. The solvent is important. it is known as an SN2 reaction. The mechanism Here is the mechanism for the reaction involving bromoethane: This is an example ofnucleophilic substitution. Note: When you are naming nitriles. Note: A solution of potassium cyanide in water is quite alkaline. and contains significant amounts of hydroxide ions. the only step) of the reaction.condenser placed vertically in the flask to prevent loss of volatile substances from the mixture. you have to remember to include the carbon in the -CN group when you count the longest chain. THE NUCLEOPHILIC SUBSTITUTION REACTIONS BETWEEN . 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 . For example. Note: Unless your syllabus specifically mentions SN2 by name. butanenitrile is formed. In this example.hence butanenitrile. In this example. If water is present you tend to get substitution by -OH instead of -CN. there are 4 carbons in the longest chain . These react with the halogenoalkane.

a salt is formed . The more ammonia there is in the mixture. The reaction happens in two stages. .ethylamine. If you are interested in further substitution reactions. uncluttered mechanisms for the nucleophilic substitution reactions between halogenoalkanes and ammonia to produce primary amines. except that one of the hydrogens in the ammonium ion is replaced by an ethyl group.HALOGENOALKANES AND AMMONIA This page gives you the facts and simple. The ammonia removes a hydrogen ion from the ethylammonium ion to leave a primary amine . This is just like ammonium bromide. Use the BACK button on your browser to return to this page. The facts The halogenoalkane is heated with a concentrated solution of ammonia in ethanol. secondary and tertiary halogenoalkanes. We'll talk about the reaction using 1-bromoethane as a typical primary halogenoalkane. because the ammonia would simply escape up the condenser as a gas.in this case. If you want the mechanisms explained to you in detail. There is then the possibility of a reversible reaction between this salt and excess ammonia in the mixture. there is a link at the bottom of the page. The reaction of primary halogenoalkanes with ammonia Important! If you aren't sure about the difference between primary. You couldn't heat this mixture under reflux. The reaction is carried out in a sealed tube. it is essential that you follow this link before you go on. the more the forward reaction is favoured. ethylammonium bromide. you will also find a link to a separate page dealing with these. In the first stage.

ethylamine. In the second step of the reaction an ammonia molecule may remove one of the hydrogens on the -NH3+. An ammonium ion is formed. reversible. Note: Unless your syllabus specifically mentions SN2 by name. You will find a link at the bottom . ethylamine and ammonium ions. This reaction is. This gets so complicated that it is dealt with on a separate page. and goes on to attack unused bromoethane. The mechanism The mechanism involves two steps. together with a primary amine . Your major product will only be ethylamine if the ammonia is present in very large excess. you can just call it nucleophilic substitution. The first is a simple nucleophilic substitution reaction: Because the mechanism involves collision between two species in this slow step of the reaction. however. ammonia. Ethylamine is a good nucleophile. Some of the information you'll come across is simply wrong! You can read the arguments about the products of this reaction by following this link. Unfortunately the reaction doesn't stop here.in this case.Note: You will find considerable disagreement in textbooks and other sources about the exact nature of the products in this reaction. Your product will therefore contain a mixture of ethylammonium ions. it is known as an SN2 reaction.

There is a second stage exactly as with primary halogenoalkanes. An ammonia molecule removes a hydrogen ion from the -NH3+ group in a reversible reaction. An ammonium ion is formed. The reaction of tertiary halogenoalkanes with ammonia The facts The facts of the reactions are exactly the same as with primary halogenoalkanes.the halogenoalkane. For example: Followed by: The mechanism This mechanism involves an initial ionisation of the halogenoalkane: followed by a very rapid attack by the ammonia on the carbocation (carbonium ion) formed: This is again an example ofnucleophilic substitution. The halogenoalkane is heated in a sealed tube with a solution of ammonia in ethanol. It is known as an SN1 reaction.of this page. together with an amine. . This time the slow step of the reaction only involves one species .

. secondary halogenoalkanes use both an SN2 mechanism and an SN1. . Where would you like to go now? Help! Talk me through these mechanisms . uncluttered mechanisms for the nucleophilic addition reactions between carbonyl compounds (specifically aldehydes and ketones) and hydrogen cyanide. To menu of nucleophilic substitution reactions. In the extremely unlikely event that you will ever need it. .The reaction of secondary halogenoalkanes with ammonia It is very unlikely that any of the current UK-based syllabuses for 16 . If you want the . © Jim Clark 2000 THE NUCLEOPHILIC ADDITION OF HYDROGEN CYANIDE TO ALDEHYDES AND KETONES This page gives you the facts and simple.18 year olds will ask you about this. Make sure you understand what happens with primary and tertiary halogenoalkanes. To Main Menu . . . To look at further substitution in these reactions . and then adapt it for secondary ones should ever need to. To menu of other types of mechanism. . . . HCN. . .

with ethanal (an aldehyde) you get 2-hydroxypropanenitrile: With propanone (a ketone) you get 2-hydroxy-2-methylpropanenitrile: Note: When you are naming these compounds. and so will be considered together . but still contains some free cyanide ions.hence the "prop" in both names. the longest carbon chain is 3 carbons . the aldehyde or ketone is mixed with a solution of sodium or potassium cyanide in water to which a little sulphuric acid has been added. Aldehydes and ketones behave identically in their reaction with hydrogen cyanide.5. because this gives the fastest reaction. This is important for the mechanism.although equations and mechanisms will be given for both types of compounds for the sake of completeness. .mechanisms explained to you in detail. don't forget that the longest carbon chain has to include the carbon in the -CN group. The reaction of aldehydes and ketones with hydrogen cyanide The facts Hydrogen cyanide adds across the carbon-oxygen double bond in aldehydes and ketones to produce compounds known as hydroxynitriles. In both of the above examples. there is a link at the bottom of the page. because this is an extremely poisonous gas. The carbon with the nitrogen attached is always counted as the number 1 carbon in the chain. The solution will contain hydrogen cyanide (from the reaction between the sodium or potassium cyanide and the sulphuric acid). For example. The reaction isn't normally done using hydrogen cyanide itself. The pH of the solution is adjusted to about 4 . Instead.

The hydrogen ion could also come from the water or the H3O+ ions present in the slightly acidic solution. You .for example. there is a nucleophilic attack by the cyanide ion on the slightly positive carbon atom. Again the pH of the solution is adjusted to around pH 5 . The mechanisms These are examples of nucleophilic addition. from a hydrogen cyanide molecule. When you write mechanisms for reactions involving nucleophiles. you must show that lone pair. The carbon-oxygen double bond is highly polar. the sodium hydroxide is not added to excess. The rate of the reaction falls if the pH is any higher.Note: If the reaction is done using hydrogen cyanide itself. a little sodium hydroxide solution is added to produce some cyanide ions from the weakly acidic HCN. Whichever set of reagents you use. Nucleophile: A species (molecule or ion) which attacks a positive site in something else. and the slightly positive carbon atom is attacked by the cyanide ion acting as a nucleophile. The mechanism for the addition of HCN to propanone In the first stage. the reaction contains the same mixture of hydrogen cyanide and cyanide ions. Nucleophiles are either fully negative ions or contain a fairly negative region somewhere in a molecule. All nucleophiles have at least one active lone pair of electrons. The negative ion formed then picks up a hydrogen ion from somewhere .in other words.

That's not a problem . . It is completed by the addition of a hydrogen ion from. It has been rotated through 90°.we're still talking about the same substance. but to make the mechanism easier to follow. Note: The product molecule here has been drawn differently from the one in the equation further up this page. There is no reason why you can't do that if it makes the appearance of the mechanism easier to follow. the reaction starts with a nucleophilic attack by the cyanide ion on the slightly positive carbon atom. It is possible that you might be exected to explain how this arises. The central carbon atom still has the same four groups attached.don't need to remember all of these. the product molecule looks different from the one in the equation further up this page. One equation is perfectly adequate.a 50/50 mixture of two optical isomers. for example. a hydrogen cyanide molecule. Note: Again. The mechanism for the addition of HCN to ethanal As before. Optical isomerism in 2-hydroxypropanenitrile When 2-hydroxypropanenitrile is made in this last mechanism. they are simply arranged differently. it occurs as a racemic mixture .

You need to refer to recent exam papers and mark schemes. an H and an OH all attached to the central carbon atom. Note: This is probably as much as you need to know for exam purposes. and attack from the other side will lead to the other.) What matters is that the product molecule must have four different groups attached to the carbon which was originally part of the carbon-oxygen double bond THE REDUCTION OF ALDEHYDES AND KETONES This page gives you the facts and mechanisms for the reduction of carbonyl compounds (specifically aldehydes . or from below.Note: You almost certainly won't be able to tell whether or not you need to know this from the syllabus. (A ketone can be unsymmetrical in the sense that there is a different alkyl group either side of the carbonyl group. If you haven't already got these. but a full explanation of this is given on the "talk through" page. Unsymmetrical ketones will as well. Follow the link below. There is an equal chance of either happening. you can obtain them from your Exam Board via links on the syllabuses page. In this case. Attack from one side will lead to one of the two isomers. Optical isomerism occurs in compounds which have four different groups attached to a single carbon atom. the product molecule contains a CH3. and attack by a cyanide ion will either be from above the plane of the molecule. a CN. All aldehydes will form a racemic mixture in this way. The reason for the formation of equal amounts of two isomers lies in the way the ethanal gets attacked. Ethanal is a planar molecule.

Methanol CH3OH is also a primary alcohol. Two possible variants (there are several others!) are:   The reaction is carried out in solution in water to which some sodium hydroxide has been added to make it alkaline.ion. The reaction is carried out in solution in an alcohol like methanol. The H in square brackets means "hydrogen from a reducing agent". In each case. and they are happy with a simplified version of what is quite a complex mechanism.and ketones) using sodium tetrahydridoborate (sodium borohydride) as the reducing agent. The reduction of an aldehyde For example. Note: There is one exception to this. This produces an intermediate which can be converted into the final product by boiling it with water.without the "talk through" page that you will find for other mechanisms on this site. A primary alcohol is one which only has one alkyl group attached to the carbon with the -OH group on it. There are several quite different ways of carrying out this reaction. with ethanal you get ethanol: Notice that this is a simplified equation . . ethanol or propan-2-ol. Reduction of aldehydes and ketones lead to two different sorts of alcohol. That ion acts as the reducing agent. these reactions are dealt with entirely on this page . reduction of an aldehyde leads to a primary alcohol. Because of that simplification. and contains the BH4. They all contain the grouping -CH2OH. The reaction produces an intermediate which is converted into the final product by addition of a dilute acid like sulphuric acid. Only one UK A level Exam Board (AQA) is likely to ask for these mechanisms. In general terms. The reduction of aldehydes and ketones by sodium tetrahydridoborate The facts Sodium tetrahydridoborate (previously known as sodium borohydride) has the formula NaBH 4. Think of this as H-CH2OH.perfectly acceptable to examiners. reduction essentially involves the addition of a hydrogen atom to each end of the carbon-oxygen double bond to form an alcohol.

hence the lone pair. .The reduction of a ketone For example. with propanone you get propan-2-ol: Reduction of a ketone leads to a secondary alcohol. The carbon-oxygen double bond is highly polar. Nucleophiles are either fully negative ions or contain a fairly negative region somewhere in a molecule. A hydride ion is a hydrogen atom with an extra electron .ion is essentially a source of hydride ions. Beware! The following mechanisms are simplified for UK A level purposes to the point that they are wrong! If you are working outside the UK A level system. A secondary alcohol is one which has two alkyl groups attached to the carbon with the -OH group on it.instead of BH4-. The reduction is an example of nucleophilic addition. but avoids you getting involved with some quite complicated boron compounds that are formed as intermediates. All nucleophiles have at least one active lone pair of electrons. Doing this not only makes the initial attack easier to write. The simplification used is to write H. you must show that lone pair. When you write mechanisms for reactions involving nucleophiles. H-. Nucleophile: A species (molecule or ion) which attacks a positive site in something else. and the slightly positive carbon atom is attacked by the hydride ion acting as a nucleophile. They all contain the grouping -CHOH. please don't read any further! The simplified mechanisms The BH4.

. because it + suggests a free hydrogen ion. The hydrogen ion is actually attached to a water molecule as H 3O . + Adding water: This time. and the electrons in one of the carbon-oxygen bonds are repelled entirely onto the oxygen. Note: You may find that other sources write the hydrogen ion simply as H . The lone pair of electrons on the hydride ion forms a bond with the carbon. the negative ion takes a hydrogen ion from a water molecule. giving it a negative charge. H (aq) is a happy compromise.The mechanism for the reduction of ethanal In the first stage. That's not good practice. Adding an acid: When the acid is added. there is a nucleophilic attack by the hydride ion on the slightly positive carbon atom. What happens now depends on whether you add an acid or water to complete the reaction. Writing that makes + the equation look more complicated. the negative ion formed picks up a hydrogen ion to give an alcohol.

Adding an acid: The negative ion reacts with a hydrogen ion from the acid added in the second stage of the reaction. what happens next depends on whether you add an acid or water to complete the reaction.they are merely simplifications to suit the demands of a particular A level syllabus. the negative ion takes a hydrogen ion from a water molecule. the reaction starts with a nucleophilic attack by the hydride ion on the slightly positive carbon atom. Important! Remember that the equations and mechanisms given on this page are not the truth . ELECTROPHILIC ADDITION .The mechanism for the reduction of propanone As before. Adding water: This time. Again.

the line between the two carbon atoms represents a normal bond . C2H4. Ethene. two pairs of shared electrons. A molecular orbital is a region of space within the molecule where there is a high probability of finding a particular pair of electrons. This bond is called a pi bond. The pi electrons are not as fully under the control of the carbon nuclei as the electrons in the sigma bond and. What is true of C=C in ethene will be equally true of C=C in more complicated alkenes. What the diagram doesn't show is that the two pairs aren't the same as each other. The electrons in the pi bond are free to move around anywhere in this shaded region and can move freely from one half to the other. The double bond between the carbon atoms is. One of the pairs of electrons is held on the line between the two carbon nuclei as you would expect. because it is the simplest molecule containing a carbon-carbon double bond. In this diagram. but the other is held in a molecular orbital above and below the plane of the molecule. because they lie exposed above and below the rest of the molecule. Note: Check your syllabus to see if you need to know how a pi bond is formed. This sort of bond is called a sigma bond. The wedge shapes show bonds coming out towards you. The other pair of electrons is found somewhere in the shaded part above and below the plane of the molecule. is often modelled as shown on the right.Background Electrophilic addition happens in many of the reactions of compounds containing carbon-carbon double bonds the alkenes. of course.the pair of shared electrons lies in a molecular orbital on the line between the two nuclei where you would expect them to be. . The structure of ethene We are going to start by looking at ethene. find out how to get one by following this link. Haven't got a syllabus? If you are working towards a UK-based exam. The dotted lines to two of the hydrogens show bonds going back into the screen or paper away from you. they are relatively open to attack by other things. Note: This diagram shows a side view of an ethene molecule.

Note: If you aren't sure about why some bonds are polar. . an electrophile must be something which carries either a full positive charge. whereas carbon normally forms covalent ones. the pi bond is an unnecessary bond. there is no possibility of the process going any further to form bonds between sodium and carbon. Na+. follow this link as well.If you do need to know about the bonding in ethene in detail. phile" means a liking for. Addition reactions In a sense.as you will see shortly. because sodium forms ionic bonds. Use the BACK button on your browser to return to this page. HBr. The structure would hold together perfectly well with a single bond rather than a double bond. or has a slight positive charge on it somewhere. a francophile is someone who likes the French. read the page on electronegativity. You might wonder why fully positive ions like sodium. Because it is attracted to a negative region. For example. Ethene and the other alkenes are attacked by electrophiles. Electrophiles An electrophile is something which is attracted to electron-rich regions in other molecules or ions. an anglophile is someone who likes the English. Note: The ending ". Electrophiles are strongly attracted to the exposed electrons in the pi bond and reactions happen because of that initial attraction . The electrophile is normally the slightly positive ( +) end of a molecule like hydrogen bromide. Although these ions may well be attracted to the pi bond. don't react with ethene. The pi bond often breaks and the electrons in it are used to join other atoms (or .

we quite arbitrarily think of it as the central molecule and hydrogen bromide as its attacker. the molecules just collide and may react if they have enough energy and if they are lined up correctly. if you aren't sure about electronegativity and bond polarity follow this link before you read on. There's no real justification for this. Use the BACK button on your browser to return to this page. Note: Once again. All the atoms in the original molecules are found in the bigger one. ethene undergoes addition reactions. of course. In reality. Summary: electrophilic addition reactions An addition reaction is a reaction in which two molecules join together to make a bigger one.groups of atoms) onto the ethene molecule. In other words. An electrophilic addition reaction is an addition reaction which happens because what we think of as the "important" molecule is attacked by an electrophile. . so that the pair of electrons is pulled slightly towards the Y end of the bond. The "important" molecule has a region of high electron density which is attacked by something carrying some degree of positive charge. using a general molecule X-Y . Nothing is lost in the process. We are going to assume that Y is more electronegative than X. . . That means that the X atom carries a slight positive charge. For example. Note: When we talk about reactions of alkenes like ethene. Understanding the electrophilic addition mechanism The mechanism for the reaction between ethene and a molecule X-Y It is very unlikely that any two different atoms joined together will have the same electronegativity. we think of the ethene as being attacked by other molecules such as hydrogen bromide. apart from the fact that it helps to put things in some sort of logical pattern. Because ethene is the molecule we are focusing on.

the two electrons in the pi bond move even further towards the X until a covalent bond is made. This leaves the right-hand carbon atom an electron short . Note also that we are only showing one of the pairs of electrons around the Y ion.ion. The electrons in the X-Y bond are pushed entirely onto the Y to give a negative Y. You are now much more likely to find the electrons in the half of the pi bond nearest the XY.hence positively charged. but both of these electrons have now been used to make a bond to the X atom. Now imagine what happens as they approach each other. but we are only actually interested in the one we've drawn. As the process continues.The slightly positive X atom is an electrophile and is attracted to the exposed pi bond in the ethene. Help! Why does the carbon atom have a positive charge? The pi bond was originally made using an electron from each carbon atom. - . There will be other lone pairs as well.

The bond formed between the X and the other carbon atom was also a co-ordinate bond.ion are strongly attracted towards the positive carbon atom. Once a coordinate bond has been formed there is no difference whatsoever between it and any other covalent bond. They move towards it and form a co-ordinate (dative covalent) bond between the Y and the carbon. How to write this mechanism in an exam The movements of the various electron pairs are shown using curly arrows.Important term An ion in which the positive charge is carried on a carbon atom is called a carbocation or a carbonium ion (an older term). Don't leave this page until you are sure that you understand how this relates to the electron pair movements . you must follow this link before you go on. Help! If you aren't sure about the use of curly arrows in mechanisms. Help! A co-ordinate (dative covalent) bond is simply a covalent bond in which both shared electrons originate from the same atom. In the final stage of the reaction the electrons in the lone pair on the Y. Use the BACK button on your browser to return to this page.

drawn in the previous diagrams. THE REACTION BETWEEN SYMMETRICAL ALKENES AND THE HYDROGEN HALIDES This page gives you the facts and a simple. If you want the mechanisms explained to you in detail. In the case of ethene. Electrophilic addition reactions involving hydrogen bromide The facts Alkenes react with hydrogen bromide in the cold. Hydrogen halides include hydrogen chloride and hydrogen bromide. The structures of the cyclohexene and the bromocyclohexane are often simplified: . there is a link at the bottom of the page. uncluttered mechanism for the electrophilic addition reactions between the hydrogen halides and alkenes like ethene and cyclohexene. bromoethane is formed. The double bond breaks and a hydrogen atom ends up attached to one of the carbons and a bromine atom to the other. Note: Be careful when you write the names of the addition products that you change the ene ending in the original alkene (showing the C=C) into an ane ending (showing that it has been replaced by C-C). With cyclohexene you get bromocyclohexane.

The mechanisms The reactions are examples of electrophilic addition. Each carbon atom has enough hydrogens attached to make the total number of bonds up to 4. Be sure that you understand the relationship between these simplified diagrams and the full structures. it isn't necessary to write the new hydrogen into the diagram. hydrogen chloride adds to ethene to make chloroethane: The only difference is in how fast the reactions happen with the different hydrogen halides. In the case of the bromocyclohexane. but it is helpful to put it there to emphasise that addition has happened.Note: Each corner in one of these diagrams represents a carbon atom. . With ethene and HBr: and with cyclohexene: Electrophilic addition reactions involving the other hydrogen halides The facts Hydrogen chloride and the other hydrogen halides add on in exactly the same way. For example. The rate of reaction increases as you go from HF to HCl to HBr to HI.

As you have seen in the HBr case. The mechanisms The reactions are still examples of electrophilic addition.the differences are minor and the pattern is always the same. for example: This is exactly the same as the mechanism for the reaction between ethene and HBr. it will break more readily and so the reaction is more likely to happen. Bond strengths (measured in kilojoules per mole) are: H-F H-Cl H-Br H-I 568 432 366 298 Note: You may find slightly different values depending on which data source you use. It doesn't matter . the strength of the hydrogen-halogen bond falls. in the first step of the mechanism the hydrogen-halogen bond gets broken. If the bond is weaker. All the other mechanisms for symmetrical alkenes and the hydrogen halides would be done in the same way.HF HCl HBr HI slowest reaction fastest reaction The reason for this is that as the halogen atoms get bigger. With ethene and HCl. . except that we've replaced Br by Cl.

As you will find out. The structure of the product molecule is sometimes written as CH3CH2HSO4. Confused by all this? Don't be! All you need to do is to learn the structure of sulphuric acid. The electrophilic addition reaction between ethene and sulphuric acid The facts Alkenes react with concentrated sulphuric acid in the cold to produce alkyl hydrogensulphates. You may also find it written as CH3CH2OSO3H. .Suggestion: Find out if your syllabus mentions a particular hydrogen halide. there is a link at the bottom of the page. THE REACTION BETWEEN SYMMETRICAL ALKENES AND SULPHURIC ACID This page gives you the facts and a simple. Sketch it over and over again until you can't possibly get it wrong. follow this link to find out how to get one. If you want the mechanisms explained to you in detail. uncluttered mechanism for the electrophilic addition reactions between sulphuric acid and alkenes like ethene and cyclohexene. and after that the mechanism is exactly the same as the one with hydrogen bromide. the formula of the product follows from the mechanism in an inevitable way. Important! Learn this structure for sulphuric acid. and learn that mechanism. You can simply swap the halogen atom if a different hydrogen halide comes up in an exam. but the version in the equation is better because it shows how all the atoms are linked up. Ethene reacts to give ethyl hydrogensulphate. Haven't got a syllabus? If you are working towards a UK-based exam.

The mechanism Look carefully at the structure of the product so that you can see how it relates to the various formulae given earlier (CH3CH2OSO2OH etc). The mechanism for the reaction between cyclohexene and sulphuric acid . This is to show that you can work out the structure of obscure products provided you can write the mechanism. In the mechanism. The electrophilic addition reaction between cyclohexene and sulphuric acid This time we are going straight for the mechanism without producing an initial equation. because the other one is too far from the carbon-carbon double bond to be involved in any way.The mechanism for the reaction between ethene and sulphuric acid Sulphuric acid as an electrophile The hydrogen atoms are attached to very electronegative oxygen atoms which means that the hydrogens will have a slight positive charge while the oxygens will be slightly negative. we just focus on one of the hydrogen to oxygen bonds.

If the halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol. you could then write a simple equation for the reaction if you wanted to.Having worked out the structure of the product. and a nitrile is produced. If your examiners want you to show the transition state. the halogen is replaced by -CN. draw the mechanism like this: The reaction of tertiary halogenoalkanes with cyanide ions The facts The facts of the reaction are exactly the same as with primary halogenoalkanes. For example: Or if you want the full equation rather than the ionic one: The mechanism .

the SN2 mechanism is: Should you need it. It is known as an SN1 reaction. the two stages of the SN1 mechanism are: . The reaction of secondary halogenoalkanes with cyanide ions The facts The facts of the reaction are exactly the same as with primary or tertiary halogenoalkanes. For example. The halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol.This mechanism involves an initial ionisation of the halogenoalkane: followed by a very rapid attack by the cyanide ion on the carbocation (carbonium ion) formed: This is again an example ofnucleophilic substitution.the halogenoalkane. This time the slow step of the reaction only involves one species . For example: The mechanism Secondary halogenoalkanes use both SN2 and SN1 mechanisms.

The bromine loses its original red-brown colour to give a colourless liquid. The electrophilic addition of bromine to ethene The facts Alkenes react in the cold with pure liquid bromine. . 1. In the case of the reaction with ethene. . THE REACTION BETWEEN SYMMETRICAL ALKENES AND BROMINE This page gives you the facts and a simple.2-dibromoethane is formed. The double bond breaks. . . . and a bromine atom becomes attached to each carbon. . . . To menu of nucleophilic substitution reactions. To Main Menu . there is a link at the bottom of the page. or with a solution of bromine in an organic solvent like tetrachloromethane. uncluttered mechanism for the electrophilic addition reactions between bromine (and the other halogens) and alkenes like ethene and cyclohexene. If you want the mechanisms explained to you in detail. To menu of other types of mechanism. .Where would you like to go now? Help! Talk me through these mechanisms .

If you are working towards a UK-based exam. The person you need to contact will probably have the title Subject Officer for Chemistry or something similar. but you must find out to be sure. say. You will probably find that your examiners will accept this one. If an aqueous solution of bromine is used ("bromine water"). The simplified version of the mechanism . The other halogens. The mechanism for the reaction between ethene and bromine The reaction is an example of electrophilic addition. you can find out how to do this by using the link to your Board's web site on the syllabuses page. The presence of the water complicates the mechanism beyond what is required by current UK A level (or equivalent) syllabuses.to show that you understand what's going on. write the words "induced dipole" next to the bromine molecule . and you must know which your examiners will accept. all you have to do is to replace Br by Cl in all the equations on this page. Warning! There are two versions of the ethene / bromine mechanism in common use. If you still aren't sure. (Fluorine reacts explosively with all hydrocarbons including alkenes . behave similarly. If you draw this mechanism in an exam. You almost certainly won't be able to tell this from your syllabus.) If you are interested in the reaction with.to give carbon and hydrogen fluoride. apart from fluorine. chlorine. you get a mixture of products. or to any support material that your examiners provide. You need to refer to recent mark schemes. One version is simplified to bring it into line with the other alkene electrophilic addition mechanisms.This decolourisation of bromine is often used as a test for a carbon-carbon double bond. Ask whether they want the mechanism for the reaction between bromine and alkenes which proceeds via a carbocation or via a bromonium ion intermediate. contact your examiners direct. Bromine as an electrophile The bromine is a very "polarisable" molecule and the approaching pi bond in the ethene induces a dipole in the bromine molecule.

If your examiners are happy to accept the simple version. there's no point in making life difficult for yourself. with the positive charge being found on the bromine atom.Note: Use this version unless your examiners insist on the more accurate one. The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction. one of the bromine atoms becomes attached to both carbon atoms. The more accurate version of the mechanism Note: Don't learn this unless you have to. There is a real risk of getting confused. In the first stage of the reaction. The electrophilic addition of bromine to cyclohexene . A bromonium ion is formed.

The simplified version of the mechanism Note: Use this version unless your examiners insist on the more accurate one. The alternative version of the mechanism . and you must know which your examiners will accept. Bromine as an electrophile Again.2dibromocyclohexane is formed. Don't forget to write the words "induced dipole" next to the bromine molecule. 1. there are two versions of this mechanism in common use. the bromine is polarised by the approaching pi bond in the cyclohexene.The facts Cyclohexene reacts with bromine in the same way and under the same conditions as any other alkene. Warning! Again. The mechanism for the reaction between cyclohexene and bromine The reaction is an example of electrophilic addition.

A bromonium ion is formed. one of the bromine atoms becomes attached to both carbon atoms. In the first stage of the reaction. . there's no point in making life difficult for yourself. The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction. with the positive charge being found on the bromine atom.Note: Don't learn this unless you have to. If your examiners are happy to accept the simple version.