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.

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.

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, and those showing the bonds going back into the paper. Notice that the molecule has been inverted during the reaction - rather like an umbrella being blown inside-out.
Note: If you aren't happy about the various ways of drawing bonds, it is important to follow this link to find out exactly what the various symbols mean. It is also important to know which of these ways of drawing the mechanism your particular examiners want you to use. If you haven't already checked your syllabus, recent exam papers and mark schemes, you must do so! At the time of writing, Edexcel, for example, wanted the transition state included, and that isn't obvious from their syllabus. You have to check mark schemes and examiners reports. Use the BACK button on your browser to return to this page.

Nucleophilic substitution in tertiary halogenoalkanes

Warning! Check your syllabus, past papers and any support material published by your examiners to find out whether you need this. If there's no mention of tertiary halogenoalkanes or SN1 reactions, then you probably don't need it.

Remember that a tertiary halogenoalkane has three alkyl groups attached to the carbon with the halogen on it. These alkyl groups can be the same or different, but in this section, we shall just consider a simple one, (CH3)3CBr - 2-bromo-2-methylpropane. The nucleophilic substitution reaction - an SN1 reaction

Once again, we'll talk this mechanism through using an ion as a nucleophile, because it's slightly easier, and again we'll look at the reaction of a general purpose nucleophilic ion which we'll call Nu -. This will have at least one lone pair of electrons. Why is a different mechanism necessary? You will remember that when a nucleophile attacks a primary halogenoalkane, it approaches the + carbon atom from the side away from the halogen atom. With a tertiary halogenoalkane, this is impossible. The back of the molecule is completely cluttered with CH 3 groups.

Since any other approach is prevented by the bromine atom, the reaction has to go by an alternative mechanism. The alternative mechanism
Important! To understand this section, you need to know what a carbocation (carbonium ion) is, and about the relative stabilities of primary, secondary and tertiary carbocations. If you follow this link, use the BACK button on your browser to return to this page.

The reaction happens in two stages. In the first, a small proportion of the halogenoalkane ionises to give a carbocation and a bromide ion.

This reaction is possible because tertiary carbocations are relatively stable compared with secondary or primary ones. Even so, the reaction is slow. Once the carbocation is formed, however, it would react immediately it came into contact with a nucleophile like Nu-. The lone pair on the nucleophile is strongly attracted towards the positive carbon, and moves towards it to

create a new bond.

How fast the reaction happens is going to be governed by how fast the halogenoalkane ionises. Because this initial slow step only involves one species, the mechanism is described as SN1 - substitution, nucleophilic, one species taking part in the initial slow step. Why don't primary halogenoalkanes use the SN1 mechanism? If a primary halogenoalkane did use this mechanism, the first step would be, for example:

A primary carbocation would be formed, and this is much more energetically unstable than the tertiary one formed from tertiary halogenoalkanes - and therefore much more difficult to produce. This instability means that there will be a very high activation energy for the reaction involving a primary halogenoalkane. The activation energy is much less if it undergoes an S N2 reaction - and so that's what it does instead.

Nucleophilic substitution in secondary halogenoalkanes

There isn't anything new in this. Secondary halogenoalkanes will use both mechanisms - 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 SN1 mechanism is possible because the secondary carbocation formed in the slow step is more stable than a primary one. It isn't as stable as a tertiary one though, and so the SN1 route isn't as effective as it is with tertiary halogenoalkanes. THE NUCLEOPHILIC SUBSTITUTION REACTIONS BETWEEN HALOGENOALKANES AND HYDROXIDE IONS

This page gives you the facts and simple, uncluttered mechanisms for the nucleophilic substitution reactions between halogenoalkanes and hydroxide ions (from, for example, sodium hydroxide). If you want the mechanisms explained to you in detail, there is a link at the bottom of the page.

The reaction of primary halogenoalkanes with hydroxide ions

Important! If you aren't sure about the difference between primary, secondary and tertiary halogenoalkanes, 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 facts If a halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide, the halogen is replaced by -OH and an alcohol is produced. Heating under reflux means heating with a condenser placed vertically in the flask to prevent loss of volatile substances from the mixture. The solvent is usually a 50/50 mixture of ethanol and water, because everything will dissolve in that. The halogenoalkane is insoluble in water. If you used water alone as the solvent, the halogenoalkane and the sodium hydroxide solution wouldn't mix and the reaction could only happen where the two layers met. For example, 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 an -OH group - hence a substitution reaction. In this example, propan-1-ol is formed. The mechanism Here is the mechanism for the reaction involving bromoethane:

This is an example ofnucleophilic substitution. Because the mechanism involves collision between two species in the slow step (in this case, the only step) of the reaction, it is known as an SN2 reaction.
Note: Unless your syllabus specifically mentions SN2 by name, you can just call it nucleophilic substitution.

If your examiners want you to show the transition state, 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. If the halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide in a mixture of ethanol and water, the halogen is replaced by -OH, and an alcohol is produced. For example:

Or if you want the full equation rather than the ionic one:

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 - the halogenoalkane. It is known as an SN1 reaction.

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 halogenoalkane is heated under reflux with a solution of sodium or potassium hydroxide in a mixture of ethanol and water. For example:

The mechanism Secondary halogenoalkanes use both SN2 and SN1 mechanisms. For example, the SN2 mechanism is:

Should you need it, the two stages of the SN1 mechanism are:

THE NUCLEOPHILIC SUBSTITUTION REACTIONS BETWEEN HALOGENOALKANES AND WATER

This page gives you the facts and simple, uncluttered mechanisms for the nucleophilic substitution reactions between halogenoalkanes and water. If you want the mechanisms explained to you in detail, there is a link at the bottom of the page.

The reaction of primary halogenoalkanes with water

Important! If you aren't sure about the difference between primary, secondary and tertiary halogenoalkanes, 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 facts There is only a slow reaction between a primary halogenoalkane and water even if they are heated. The halogen atom is replaced by -OH. For example, using 1-bromoethane as a typical primary halogenoalkane:

An alcohol is produced together with hydrobromic acid. Be careful not to call this hydrogen bromide. Hydrogen bromide is a gas. When it is dissolved it in water (as it will be here), it's called hydrobromic acid. The mechanism The mechanism involves two steps. The first is a simple nucleophilic substitution reaction:

Because the mechanism involves collision between two species in this slow step of the reaction, it is known as an SN2 reaction.
Note: Unless your syllabus specifically mentions SN2 by name, you can just call it nucleophilic substitution.

The nucleophilic substitution is very slow because water isn't a very good nucleophile. It lacks the full negative charge of, say, a hydroxide ion. The second step of the reaction simply tidies up the product. 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).

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 of tertiary halogenoalkanes with water

The facts If the halogenoalkane is heated under reflux with water, the halogen is replaced by -OH to give an alcohol. Heating under reflux means heating with a condenser placed vertically in the flask to prevent loss of volatile substances from the mixture. The reaction happens much faster than the corresponding one involving a primary

halogenoalkane. 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. This time the slow step of the reaction only involves one species - the halogenoalkane. It is known as an SN1 reaction. Now there is a final stage in which the product is tidied up. A water molecule removes one of the hydrogens attached to the oxygen to give an alcohol and a hydroxonium ion - exactly as happens with primary halogenoalkanes.

The rate of the overall reaction is governed entirely by how fast the halogenoalkane ionises. The fact that water isn't as good a nucleophile as, say, OH- doesn't make any difference. The water isn't involved in the slow step of the reaction.

The reaction of secondary halogenoalkanes with water

It is very unlikely that any of the current UK-based syllabuses for 16 - 18 year olds will ask you about this. In the extremely unlikely event that you will ever need it, secondary halogenoalkanes use both an SN2 mechanism and an SN1. Make sure you understand what happens with primary and tertiary halogenoalkanes, and then adapt it for secondary ones should ever need to.

Where would you like to go now? Help! Talk me through these mechanisms . . . To menu of nucleophilic substitution reactions. . . To menu of other types of mechanism. . . To Main Menu . . .

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, for example, potassium cyanide). If you want the mechanisms explained to you in detail, there is a link at the bottom of the page.

The reaction of primary halogenoalkanes with cyanide ions

Important! If you aren't sure about the difference between primary, secondary and tertiary halogenoalkanes, 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 facts If a halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol, the halogen is replaced by a -CN group and a nitrile is produced. Heating under reflux means heating with a

condenser placed vertically in the flask to prevent loss of volatile substances from the mixture. The solvent is important. If water is present you tend to get substitution by -OH instead of -CN.
Note: A solution of potassium cyanide in water is quite alkaline, and contains significant amounts of hydroxide ions. These react with the halogenoalkane.

For example, 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 - hence a substitution reaction. In this example, butanenitrile is formed.
Note: When you are naming nitriles, you have to remember to include the carbon in the -CN group when you count the longest chain. In this example, there are 4 carbons in the longest chain - hence butanenitrile.

The mechanism Here is the mechanism for the reaction involving bromoethane:

This is an example ofnucleophilic substitution. Because the mechanism involves collision between two species in the slow step (in this case, the only step) of the reaction, it is known as an SN2 reaction.
Note: Unless your syllabus specifically mentions SN2 by name, you can just call it nucleophilic substitution.

THE NUCLEOPHILIC SUBSTITUTION REACTIONS BETWEEN

HALOGENOALKANES AND AMMONIA

This page gives you the facts and simple, uncluttered mechanisms for the nucleophilic substitution reactions between halogenoalkanes and ammonia to produce primary amines. If you want the mechanisms explained to you in detail, there is a link at the bottom of the page. If you are interested in further substitution reactions, you will also find a link to a separate page dealing with these.

The reaction of primary halogenoalkanes with ammonia

Important! If you aren't sure about the difference between primary, secondary and tertiary halogenoalkanes, 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 facts The halogenoalkane is heated with a concentrated solution of ammonia in ethanol. The reaction is carried out in a sealed tube. You couldn't heat this mixture under reflux, because the ammonia would simply escape up the condenser as a gas. We'll talk about the reaction using 1-bromoethane as a typical primary halogenoalkane. The reaction happens in two stages. In the first stage, a salt is formed - in this case, ethylammonium bromide. This is just like ammonium bromide, except that one of the hydrogens in the ammonium ion is replaced by an ethyl group.

There is then the possibility of a reversible reaction between this salt and excess ammonia in the mixture.

The ammonia removes a hydrogen ion from the ethylammonium ion to leave a primary amine - ethylamine. The more ammonia there is in the mixture, the more the forward reaction is favoured.

Note: You will find considerable disagreement in textbooks and other sources about the exact nature of the products in this reaction. 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.

The mechanism The mechanism involves two steps. The first is a simple nucleophilic substitution reaction:

Because the mechanism involves collision between two species in this slow step of the reaction, it is known as an SN2 reaction.

Note: Unless your syllabus specifically mentions SN2 by name, you can just call it nucleophilic substitution.

In the second step of the reaction an ammonia molecule may remove one of the hydrogens on the -NH3+. An ammonium ion is formed, together with a primary amine - in this case, ethylamine.

This reaction is, however, reversible. Your product will therefore contain a mixture of ethylammonium ions, ammonia, ethylamine and ammonium ions. Your major product will only be ethylamine if the ammonia is present in very large excess. Unfortunately the reaction doesn't stop here. Ethylamine is a good nucleophile, and goes on to attack unused bromoethane. This gets so complicated that it is dealt with on a separate page. You will find a link at the bottom

of this page.

The reaction of tertiary halogenoalkanes with ammonia

The facts The facts of the reactions are exactly the same as with primary halogenoalkanes. The halogenoalkane is heated in a sealed tube with a solution of ammonia in ethanol. 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. This time the slow step of the reaction only involves one species - the halogenoalkane. It is known as an SN1 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, together with an amine.

The reaction of secondary halogenoalkanes with ammonia

It is very unlikely that any of the current UK-based syllabuses for 16 - 18 year olds will ask you about this. In the extremely unlikely event that you will ever need it, secondary halogenoalkanes use both an SN2 mechanism and an SN1. Make sure you understand what happens with primary and tertiary halogenoalkanes, and then adapt it for secondary ones should ever need to.

Where would you like to go now? Help! Talk me through these mechanisms . . . To look at further substitution in these reactions . . . To menu of nucleophilic substitution reactions. . . To menu of other types of mechanism. . . To Main Menu . . .

Jim Clark 2000

THE NUCLEOPHILIC ADDITION OF HYDROGEN CYANIDE TO ALDEHYDES AND KETONES

This page gives you the facts and simple, uncluttered mechanisms for the nucleophilic addition reactions between carbonyl compounds (specifically aldehydes and ketones) and hydrogen cyanide, HCN. If you want the

mechanisms explained to you in detail, there is a link at the bottom of the page. Aldehydes and ketones behave identically in their reaction with hydrogen cyanide, and so will be considered together - although equations and mechanisms will be given for both types of compounds for the sake of completeness.

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. For example, 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, don't forget that the longest carbon chain has to include the carbon in the -CN group. In both of the above examples, the longest carbon chain is 3 carbons - hence the "prop" in both names. The carbon with the nitrogen attached is always counted as the number 1 carbon in the chain.

The reaction isn't normally done using hydrogen cyanide itself, because this is an extremely poisonous gas. Instead, 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. The pH of the solution is adjusted to about 4 - 5, because this gives the fastest reaction. The solution will contain hydrogen cyanide (from the reaction between the sodium or potassium cyanide and the sulphuric acid), but still contains some free cyanide ions. This is important for the mechanism.

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. Again the pH of the solution is adjusted to around pH 5 - in other words, the sodium hydroxide is not added to excess. The rate of the reaction falls if the pH is any higher. Whichever set of reagents you use, the reaction contains the same mixture of hydrogen cyanide and cyanide ions.

The mechanisms These are examples of nucleophilic addition. The carbon-oxygen double bond is highly polar, and the slightly positive carbon atom is attacked by the cyanide ion acting as a nucleophile.

Nucleophile: A species (molecule or ion) which attacks a positive site in something else. 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. When you write mechanisms for reactions involving nucleophiles, you must show that lone pair.

The mechanism for the addition of HCN to propanone In the first stage, there is a nucleophilic attack by the cyanide ion on the slightly positive carbon atom.

The negative ion formed then picks up a hydrogen ion from somewhere - for example, from a hydrogen cyanide molecule.

The hydrogen ion could also come from the water or the H3O+ ions present in the slightly acidic solution. You

don't need to remember all of these. One equation is perfectly adequate.

Note: The product molecule here has been drawn differently from the one in the equation further up this page. It has been rotated through 90. There is no reason why you can't do that if it makes the appearance of the mechanism easier to follow.

The mechanism for the addition of HCN to ethanal As before, the reaction starts with a nucleophilic attack by the cyanide ion on the slightly positive carbon atom.

It is completed by the addition of a hydrogen ion from, for example, a hydrogen cyanide molecule.

Note: Again, the product molecule looks different from the one in the equation further up this page. The central carbon atom still has the same four groups attached, but to make the mechanism easier to follow, they are simply arranged differently. That's not a problem - we're still talking about the same substance.

Optical isomerism in 2-hydroxypropanenitrile When 2-hydroxypropanenitrile is made in this last mechanism, it occurs as a racemic mixture - a 50/50 mixture of two optical isomers. It is possible that you might be exected to explain how this arises.

Note: You almost certainly won't be able to tell whether or not you need to know this from the syllabus. You need to refer to recent exam papers and mark schemes. If you haven't already got these, you can obtain them from your Exam Board via links on the syllabuses page.

Optical isomerism occurs in compounds which have four different groups attached to a single carbon atom. In this case, the product molecule contains a CH3, a CN, an H and an OH all attached to the central carbon atom. The reason for the formation of equal amounts of two isomers lies in the way the ethanal gets attacked. Ethanal is a planar molecule, and attack by a cyanide ion will either be from above the plane of the molecule, or from below. There is an equal chance of either happening.

Attack from one side will lead to one of the two isomers, and attack from the other side will lead to the other.

Note: This is probably as much as you need to know for exam purposes, but a full explanation of this is given on the "talk through" page. Follow the link below.

All aldehydes will form a racemic mixture in this way. Unsymmetrical ketones will as well. (A ketone can be unsymmetrical in the sense that there is a different alkyl group either side of the carbonyl group.) 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

and ketones) using sodium tetrahydridoborate (sodium borohydride) as the reducing agent. Only one UK A level Exam Board (AQA) is likely to ask for these mechanisms, and they are happy with a simplified version of what is quite a complex mechanism. Because of that simplification, these reactions are dealt with entirely on this page - without the "talk through" page that you will find for other mechanisms on this site.

The reduction of aldehydes and ketones by sodium tetrahydridoborate

The facts Sodium tetrahydridoborate (previously known as sodium borohydride) has the formula NaBH 4, and contains the BH4- ion. That ion acts as the reducing agent. There are several quite different ways of carrying out this reaction. 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. The reaction produces an intermediate which is converted into the final product by addition of a dilute acid like sulphuric acid. The reaction is carried out in solution in an alcohol like methanol, ethanol or propan-2-ol. This produces an intermediate which can be converted into the final product by boiling it with water.

In each case, reduction essentially involves the addition of a hydrogen atom to each end of the carbon-oxygen double bond to form an alcohol. Reduction of aldehydes and ketones lead to two different sorts of alcohol. The reduction of an aldehyde For example, with ethanal you get ethanol:

Notice that this is a simplified equation - perfectly acceptable to examiners. The H in square brackets means "hydrogen from a reducing agent". In general terms, reduction of an aldehyde leads to a primary alcohol. A primary alcohol is one which only has one alkyl group attached to the carbon with the -OH group on it. They all contain the grouping -CH2OH.

Note: There is one exception to this. Methanol CH3OH is also a primary alcohol. Think of this as H-CH2OH.

The reduction of a ketone For example, with propanone you get propan-2-ol:

Reduction of a ketone leads to a secondary alcohol. A secondary alcohol is one which has two alkyl groups attached to the carbon with the -OH group on it. They all contain the grouping -CHOH.

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, please don't read any further!

The simplified mechanisms The BH4- ion is essentially a source of hydride ions, H-. The simplification used is to write H- instead of BH4-. Doing this not only makes the initial attack easier to write, but avoids you getting involved with some quite complicated boron compounds that are formed as intermediates. The reduction is an example of nucleophilic addition. The carbon-oxygen double bond is highly polar, and the slightly positive carbon atom is attacked by the hydride ion acting as a nucleophile. A hydride ion is a hydrogen atom with an extra electron - hence the lone pair.

Nucleophile: A species (molecule or ion) which attacks a positive site in something else. 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. When you write mechanisms for reactions involving nucleophiles, you must show that lone pair.

The mechanism for the reduction of ethanal In the first stage, there is a nucleophilic attack by the hydride ion on the slightly positive carbon atom. The lone pair of electrons on the hydride ion forms a bond with the carbon, and the electrons in one of the carbon-oxygen bonds are repelled entirely onto the oxygen, giving it a negative charge.

What happens now depends on whether you add an acid or water to complete the reaction. Adding an acid: When the acid is added, the negative ion formed picks up a hydrogen ion to give an alcohol.

Note: You may find that other sources write the hydrogen ion simply as H . That's not good practice, because it + suggests a free hydrogen ion. The hydrogen ion is actually attached to a water molecule as H 3O . Writing that makes + the equation look more complicated. H (aq) is a happy compromise.

Adding water: This time, the negative ion takes a hydrogen ion from a water molecule.

The mechanism for the reduction of propanone As before, the reaction starts with a nucleophilic attack by the hydride ion on the slightly positive carbon atom.

Again, what happens next depends on whether you add an acid or water to complete the reaction. Adding an acid: The negative ion reacts with a hydrogen ion from the acid added in the second stage of the reaction.

Adding water: This time, the negative ion takes a hydrogen ion from a water molecule.

Important! Remember that the equations and mechanisms given on this page are not the truth - they are merely simplifications to suit the demands of a particular A level syllabus.

ELECTROPHILIC ADDITION

Background
Electrophilic addition happens in many of the reactions of compounds containing carbon-carbon double bonds the alkenes. The structure of ethene We are going to start by looking at ethene, because it is the simplest molecule containing a carbon-carbon double bond. What is true of C=C in ethene will be equally true of C=C in more complicated alkenes. Ethene, C2H4, is often modelled as shown on the right. The double bond between the carbon atoms is, of course, two pairs of shared electrons. What the diagram doesn't show is that the two pairs aren't the same as each other. One of the pairs of electrons is held on the line between the two carbon nuclei as you would expect, but the other is held in a molecular orbital above and below the plane of the molecule. A molecular orbital is a region of space within the molecule where there is a high probability of finding a particular pair of electrons. In this diagram, the line between the two carbon atoms represents a normal bond - the pair of shared electrons lies in a molecular orbital on the line between the two nuclei where you would expect them to be. This sort of bond is called a sigma bond. The other pair of electrons is found somewhere in the shaded part above and below the plane of the molecule. This bond is called a pi bond. 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.

Note: This diagram shows a side view of an ethene molecule. The dotted lines to two of the hydrogens show bonds going back into the screen or paper away from you. The wedge shapes show bonds coming out towards you.

The pi electrons are not as fully under the control of the carbon nuclei as the electrons in the sigma bond and, because they lie exposed above and below the rest of the molecule, they are relatively open to attack by other things.

Note: Check your syllabus to see if you need to know how a pi bond is formed. Haven't got a syllabus? If you are working towards a UK-based exam, find out how to get one by following this link.

If you do need to know about the bonding in ethene in detail, follow this link as well.

Electrophiles An electrophile is something which is attracted to electron-rich regions in other molecules or ions. Because it is attracted to a negative region, an electrophile must be something which carries either a full positive charge, or has a slight positive charge on it somewhere.

Note: The ending ". . phile" means a liking for. For example, a francophile is someone who likes the French; an anglophile is someone who likes the English.

Ethene and the other alkenes are attacked by electrophiles. The electrophile is normally the slightly positive ( +) end of a molecule like hydrogen bromide, HBr.

Note: If you aren't sure about why some bonds are polar, read the page on electronegativity. Use the BACK button on your browser to return to this page.

Electrophiles are strongly attracted to the exposed electrons in the pi bond and reactions happen because of that initial attraction - as you will see shortly. You might wonder why fully positive ions like sodium, Na+, don't react with ethene. Although these ions may well be attracted to the pi bond, there is no possibility of the process going any further to form bonds between sodium and carbon, because sodium forms ionic bonds, whereas carbon normally forms covalent ones. Addition reactions In a sense, the pi bond is an unnecessary bond. The structure would hold together perfectly well with a single bond rather than a double bond. The pi bond often breaks and the electrons in it are used to join other atoms (or

groups of atoms) onto the ethene molecule. In other words, ethene undergoes addition reactions. For example, using a general molecule X-Y . . .

Summary: electrophilic addition reactions

An addition reaction is a reaction in which two molecules join together to make a bigger one. Nothing is lost in the process. All the atoms in the original molecules are found in the bigger one.

An electrophilic addition reaction is an addition reaction which happens because what we think of as the "important" molecule is attacked by an electrophile. The "important" molecule has a region of high electron density which is attacked by something carrying some degree of positive charge.

Note: When we talk about reactions of alkenes like ethene, we think of the ethene as being attacked by other molecules such as hydrogen bromide. Because ethene is the molecule we are focusing on, we quite arbitrarily think of it as the central molecule and hydrogen bromide as its attacker. There's no real justification for this, of course, apart from the fact that it helps to put things in some sort of logical pattern. In reality, the molecules just collide and may react if they have enough energy and if they are lined up correctly.

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 are going to assume that Y is more electronegative than X, so that the pair of electrons is pulled slightly towards the Y end of the bond. That means that the X atom carries a slight positive charge.

Note: Once again, if you aren't sure about electronegativity and bond polarity follow this link before you read on. Use the BACK button on your browser to return to this page.

The slightly positive X atom is an electrophile and is attracted to the exposed pi bond in the ethene. Now imagine what happens as they approach each other.

You are now much more likely to find the electrons in the half of the pi bond nearest the XY. As the process continues, the two electrons in the pi bond move even further towards the X until a covalent bond is made. The electrons in the X-Y bond are pushed entirely onto the Y to give a negative Y- ion.

Help! Why does the carbon atom have a positive charge? The pi bond was originally made using an electron from each carbon atom, but both of these electrons have now been used to make a bond to the X atom. This leaves the right-hand carbon atom an electron short - hence positively charged. Note also that we are only showing one of the pairs of electrons around the Y ion. There will be other lone pairs as well, but we are only actually interested in the one we've drawn.
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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).

In the final stage of the reaction the electrons in the lone pair on the Y- ion are strongly attracted towards the positive carbon atom. They move towards it and form a co-ordinate (dative covalent) bond between the Y and the carbon.

Help! A co-ordinate (dative covalent) bond is simply a covalent bond in which both shared electrons originate from the same atom. The bond formed between the X and the other carbon atom was also a co-ordinate bond. Once a coordinate bond has been formed there is no difference whatsoever between it and any other covalent bond.

How to write this mechanism in an exam The movements of the various electron pairs are shown using curly arrows.

Help! If you aren't sure about the use of curly arrows in mechanisms, you must follow this link before you go on. Use the BACK button on your browser to return to this page.

Don't leave this page until you are sure that you understand how this relates to the electron pair movements

drawn in the previous diagrams.

THE REACTION BETWEEN SYMMETRICAL ALKENES AND THE HYDROGEN HALIDES

This page gives you the facts and a simple, uncluttered mechanism for the electrophilic addition reactions between the hydrogen halides and alkenes like ethene and cyclohexene. Hydrogen halides include hydrogen chloride and hydrogen bromide. If you want the mechanisms explained to you in detail, there is a link at the bottom of the page.

Electrophilic addition reactions involving hydrogen bromide

The facts Alkenes react with hydrogen bromide in the cold. The double bond breaks and a hydrogen atom ends up attached to one of the carbons and a bromine atom to the other. In the case of ethene, bromoethane is formed.

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 structures of the cyclohexene and the bromocyclohexane are often simplified:

Note: Each corner in one of these diagrams represents a carbon atom. Each carbon atom has enough hydrogens attached to make the total number of bonds up to 4. In the case of the bromocyclohexane, it isn't necessary to write the new hydrogen into the diagram, but it is helpful to put it there to emphasise that addition has happened.

Be sure that you understand the relationship between these simplified diagrams and the full structures. The mechanisms The reactions are examples of electrophilic addition. 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, hydrogen chloride adds to ethene to make chloroethane:

The only difference is in how fast the reactions happen with the different hydrogen halides. The rate of reaction increases as you go from HF to HCl to HBr to HI.

HF HCl HBr HI

slowest reaction

fastest reaction

The reason for this is that as the halogen atoms get bigger, the strength of the hydrogen-halogen bond falls. 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 differences are minor and the pattern is always the same.

As you have seen in the HBr case, in the first step of the mechanism the hydrogen-halogen bond gets broken. If the bond is weaker, it will break more readily and so the reaction is more likely to happen. The mechanisms The reactions are still examples of electrophilic addition. With ethene and HCl, for example:

This is exactly the same as the mechanism for the reaction between ethene and HBr, except that we've replaced Br by Cl. All the other mechanisms for symmetrical alkenes and the hydrogen halides would be done in the same way.

Suggestion: Find out if your syllabus mentions a particular hydrogen halide, and learn that mechanism. You can simply swap the halogen atom if a different hydrogen halide comes up in an exam. Haven't got a syllabus? If you are working towards a UK-based exam, follow this link to find out how to get one.

THE REACTION BETWEEN SYMMETRICAL ALKENES AND SULPHURIC ACID

This page gives you the facts and a simple, uncluttered mechanism for the electrophilic addition reactions between sulphuric acid and alkenes like ethene and cyclohexene. If you want the mechanisms explained to you in detail, there is a link at the bottom of the page.

The electrophilic addition reaction between ethene and sulphuric acid

The facts Alkenes react with concentrated sulphuric acid in the cold to produce alkyl hydrogensulphates. Ethene reacts to give ethyl hydrogensulphate.

The structure of the product molecule is sometimes written as CH3CH2HSO4, but the version in the equation is better because it shows how all the atoms are linked up. You may also find it written as CH3CH2OSO3H. Confused by all this? Don't be! All you need to do is to learn the structure of sulphuric acid, and after that the mechanism is exactly the same as the one with hydrogen bromide. As you will find out, the formula of the product follows from the mechanism in an inevitable way.

Important! Learn this structure for sulphuric acid. Sketch it over and over again until you can't possibly get it wrong.

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. In the mechanism, we just focus on one of the hydrogen to oxygen bonds, because the other one is too far from the carbon-carbon double bond to be involved in any way. 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 electrophilic addition reaction between cyclohexene and sulphuric acid

This time we are going straight for the mechanism without producing an initial equation. This is to show that you can work out the structure of obscure products provided you can write the mechanism. The mechanism for the reaction between cyclohexene and sulphuric acid

Having worked out the structure of the product, you could then write a simple equation for the reaction if you wanted to.

If your examiners want you to show the transition state, 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. If the halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol, the halogen is replaced by -CN, and a nitrile is produced. For example:

Or if you want the full equation rather than the ionic one:

The mechanism

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. This time the slow step of the reaction only involves one species - the halogenoalkane. It is known as an SN1 reaction.

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. The halogenoalkane is heated under reflux with a solution of sodium or potassium cyanide in ethanol. For example:

The mechanism Secondary halogenoalkanes use both SN2 and SN1 mechanisms. For example, the SN2 mechanism is:

Should you need it, the two stages of the SN1 mechanism are:

Where would you like to go now? Help! Talk me through these mechanisms . . . To menu of nucleophilic substitution reactions. . . To menu of other types of mechanism. . . To Main Menu . . .

THE REACTION BETWEEN SYMMETRICAL ALKENES AND BROMINE

This page gives you the facts and a simple, 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, there is a link at the bottom of the page.

The electrophilic addition of bromine to ethene The facts Alkenes react in the cold with pure liquid bromine, or with a solution of bromine in an organic solvent like tetrachloromethane. The double bond breaks, and a bromine atom becomes attached to each carbon. The bromine loses its original red-brown colour to give a colourless liquid. In the case of the reaction with ethene, 1,2-dibromoethane is formed.

This decolourisation of bromine is often used as a test for a carbon-carbon double bond. If an aqueous solution of bromine is used ("bromine water"), you get a mixture of products. The presence of the water complicates the mechanism beyond what is required by current UK A level (or equivalent) syllabuses. The other halogens, apart from fluorine, behave similarly. (Fluorine reacts explosively with all hydrocarbons including alkenes - to give carbon and hydrogen fluoride.) If you are interested in the reaction with, say, chlorine, all you have to do is to replace Br by Cl in all the equations on this page. The mechanism for the reaction between ethene and bromine The reaction is an example of electrophilic addition.

Warning! There are two versions of the ethene / bromine mechanism in common use, and you must know which your examiners will accept. One version is simplified to bring it into line with the other alkene electrophilic addition mechanisms. You will probably find that your examiners will accept this one, but you must find out to be sure. You almost certainly won't be able to tell this from your syllabus. You need to refer to recent mark schemes, or to any support material that your examiners provide. If you still aren't sure, contact your examiners direct. If you are working towards a UK-based exam, you can find out how to do this by using the link to your Board's web site on the syllabuses page. The person you need to contact will probably have the title Subject Officer for Chemistry or something similar. Ask whether they want the mechanism for the reaction between bromine and alkenes which proceeds via a carbocation or via a bromonium ion intermediate.

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 you draw this mechanism in an exam, write the words "induced dipole" next to the bromine molecule - to show that you understand what's going on. The simplified version of the mechanism

Note: Use this version unless your examiners insist on the more accurate one.

The more accurate version of the mechanism

Note: Don't learn this unless you have to. There is a real risk of getting confused. If your examiners are happy to accept the simple version, there's no point in making life difficult for yourself.

In the first stage of the reaction, one of the bromine atoms becomes attached to both carbon atoms, with the positive charge being found on the bromine atom. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction.

The electrophilic addition of bromine to cyclohexene

The facts Cyclohexene reacts with bromine in the same way and under the same conditions as any other alkene. 1,2dibromocyclohexane is formed.

The mechanism for the reaction between cyclohexene and bromine The reaction is an example of electrophilic addition.

Warning! Again, there are two versions of this mechanism in common use, and you must know which your examiners will accept.

Bromine as an electrophile Again, the bromine is polarised by the approaching pi bond in the cyclohexene. Don't forget to write the words "induced dipole" next to the bromine molecule. 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

Note: Don't learn this unless you have to. If your examiners are happy to accept the simple version, there's no point in making life difficult for yourself.

In the first stage of the reaction, one of the bromine atoms becomes attached to both carbon atoms, with the positive charge being found on the bromine atom. A bromonium ion is formed.

The bromonium ion is then attacked from the back by a bromide ion formed in a nearby reaction.