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Nucleophilic Substitution Reactions

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Nucleophilic Substitution Reactions

How do we get from a halogenoalkane to a molecule such as an alcohol, nitrile or amine? These are all examples of nucleophilic substitution reactions.

  • This article is about nucleophilic substitution reactions in organic chemistry.
  • We'll define nucleophilic substitution before looking at the differences between nucleophilic and electrophilic substitution reactions.
  • After that, we'll turn our attention to halogenoalkane nucleophilic substitution reactions, focusing on their mechanism and reactivity.
  • We'll then consider stereochemical aspects of nucleophilic substitution reactions.
  • This will be followed by examples of nucleophilic substitution reactions. These include reactions with the hydroxide ion, the cyanide ion, ammonia, and silver nitrate solution.
  • We'll end by discussing the importance of nucleophilic substitution reactions.

Nucleophilic substitution reaction definition

Nucleophilic substitution reactions are reactions in which a nucleophile attacks a molecule and replaces one of its functional groups.

Let's break the term nucleophilic substitution down a little. First, substitution.

A substitution reaction is a reaction in which one functional group on a molecule is replaced by a different functional group.

Next, let's look at nucleophilic. It refers to nucleophiles.

A nucleophile is an electron pair donor.

Nucleophiles are chemical species that react by donating a lone pair of electrons to an electron-deficient species to form a covalent bond. Nucleophiles are all negatively or partially negatively charged (which we represent using the delta symbol, δ) and feature a lone pair of electrons.

An electron-deficient species is simply a molecule or ion that has an area of positive charge. Any fully or partially positively charged species is electron-deficient.

By looking more closely at the term nucleophile, we can form a picture of what these species actually are. -phile comes from the Greek word philos, which means to love, and nucleo- refers to nuclei, which are the positively charged areas of atoms. Therefore, nucleophiles must ‘love’ positive regions - they are attracted to them.

Examples of nucleophiles include:

  • The cyanide ion, :CN-.
  • The hydroxide ion, :OH-.
  • Ammonia, NH3.

Note how ammonia is not an ion. However, it is still a nucleophile, because it has a lone pair of electrons and an atom with a partial negative charge. In this case, that atom is nitrogen.

Difference between nucleophilic and electrophilic substitution reactions

You'd be forgiven for getting nucleophilic substitution mixed up with a similar term: electrophilic substitution. Whilst the two types of reactions have some features in common, they involve very different species. It is important that you know the difference between them:

  • Nucleophilic substitution reactions involve an attack by a nucleophile, an electron-pair donor.
  • Electrophilic substitution reactions, on the other hand, involve an attack by an electrophile, an electron-pair acceptor.

Examples of electrophiles include:

  • Hydrogen halides, HX.
  • The nitronium ion, NO2+.

However, both nucleophilic substitution and electrophilic substitution are still examples of substitution reactions. This means that they swap one functional group in an organic molecule for a different functional group.

You'll look at an example of an electrophilic substitution reaction in more depth in Reactions of Benzene.

Halogenoalkane nucleophilic substitution reactions

We know that halogenoalkanes are polar molecules (explore Halogenoalkanes to refresh your memory). Because the halogen atom in the C-X bond is a lot more electronegative than the carbon atom, it attracts the shared pair of electrons towards itself. Electrons are negatively charged. This makes the halogen atom partially negatively charged and leaves the carbon partially positively charged.

Nucleophilic substitution reactions C-X bond polarity StudySmarterC-X bond polarity. StudySmarter Originals

Nucleophiles, which we now know ‘love’ positive regions, can attack this partially charged carbon atom, in an example of a nucleophilic substitution reaction.

Halogenoalkane nucleophilic substitution reaction mechanism

Nucleophilic substitution reactions of halogenoalkanes all follow one of two similar mechanisms. The mechanism used depends on the classification of the halogenoalkane.

  • Primary halogenoalkanes react using an SN2 mechanism. The S stands for substitution, the N stands for nucleophilic, and the number 2 lets us know that the initial reaction step involves two species: the halogenoalkane and the nucleophile.
  • Tertiary halogenoalkanes react using an SN1 mechanism. Once again, the S and N stand for substitution and nucleophilic, but this time the number 1 tells us that the initial reaction step involves just one species: the halogenoalkane itself.
  • Secondary halogenoalkanes use a mixture of both the SN1 and the SN2 mechanisms.

As we mentioned, the SN1 and the SN2 reaction mechanisms are similar, but they do have their differences. We explore them both fully in the article Nucleophilic Substitution Mechanism. There, you'll be able to see mechanism diagrams showing electron movement to help you differentiate between the two processes.

You should also note that if your exam board doesn't specifically refer to SN1 or SN2 mechanisms, then when it mentions nucleophilic substitution, it means the SN2 mechanism that is used by primary and secondary halogenoalkanes. And if you don't know the difference between primary, secondary and tertiary halogenoalkanes, check out Halogenoalkanes.

The overall equation for both mechanisms is the same:

RCH2X + Nu- → RCH2Nu + X-

We've shown the equation using a primary halogenoalkane for simplicity, but it is easy enough to adapt it to fit other halogenoalkane classifications. You merely need to swap one or both of the halogenoalkane's hydrogen atoms with an extra one or two R groups.

Reactivity of halogenoalkanes in nucleophilic substitution

The halogen, or halide ion, is known as the leaving group.

A leaving group is a fragment of a molecule that leaves the parent molecule in a chemical reaction. When the chemical bond joining the leaving group and parent molecule together is broken, the bonding pair of electrons moves over to the leaving group.

Some halogens are more capable to act as a leaving group than others. This means that they react much more readily in nucleophilic substitution reactions. Their ability to act in this way increases as you move down the periodic table and is thanks to atomic radius.

For example, fluoroalkanes with C-F bonds do not undergo nucleophilic substitution whereas iodoalkanes with weak C-I bonds react rapidly with nucleophiles. This is because iodine is a much larger atom than fluorine. Its valence electrons are a lot further away from its nucleus and the C-I bond is longer than the C-F bond. This means the bond has a much lower enthalpy and requires less energy to break. The bond is more reactive. Bond lengths increase as you move down the group in the periodic table. Therefore, the reactivity of halogenoalkanes in nucleophilic substitution increases as you move down the group.

Substitution reactions, fluorine iodine atom size nucleophilic substitution, StudySmarterThe relative sizes of fluorine (F) and iodine (I). Image credits: commons.wikimedia.org

For more information on halogenoalkanes and their reactivity, see Halogenoalkanes.

Stereochemical aspects of nucleophilic substitution reactions

Above, we saw how nucleophilic substitution can have an SN1 or SN2 mechanism. These two different mechanisms produce products with different stereochemical aspects:

  • SN2 mechanisms produce just one product. The bonds in this product are inverted compared to the bonds in the original reacting molecule.
  • SN1 mechanisms produce two enantiomers. Enantiomers are stereoisomers with the same structural formulae but different arrangements of atoms around a central carbon. These two enantiomers are produced in a 50:50 mixture known as racemic mixture, or a racemate.

We've shown these stereochemical aspects using a halogenoalkane nucleophilic substitution reaction:

Nucleophilic substitution reactions stereochemical aspects products mechanism sn1 sn2 StudySmarterStereochemical aspects of the products of nucleophilic substitution reactions. StudySmarter Originals

Notice how in the SN2 mechanism above, the bonds in the product are inverted compared to the original reacting molecule. Compare this to the SN1 mechanism, which produces two different enantiomer products. One of the products is inverted, whilst the other keeps the original arrangement of bonds.

Once again, stereochemical aspects of nucleophilic substitution will all become clearer in Nucleophilic Substitution Mechanism. You can also learn more about stereoisomers and racemic mixtures in Optical Isomerism.

Examples of nucleophilic substitution reactions

Let's now move on to examples of nucleophilic substitution. We'll focus on nucleophilic substitution reactions involving halogenoalkanes.

Halogenoalkanes can react with the hydroxide ion, cyanide ion and ammonia molecule in nucleophilic substitution reactions. These reactions all use either the SN2 or SN1 mechanism that we looked at earlier, depending on the classification of the reacting halogenoalkane. Remember:

  • Primary halogenoalkanes use an SN2 mechanism.
  • Tertiary halogenoalkanes use an SN1 mechanism.
  • Secondary halogenoalkanes use both an SN2 and SN1 mechanism.

Nucleophilic substitution reaction with the hydroxide ion

Halogenoalkanes react with aqueous sodium or potassium hydroxide (NaOH or KOH) to form an alcohol (ROH) and a halide ion (X-). Alcohols have the hydroxyl functional group (-OH) and are represented by the general formula CxH2x+1OH. The potassium/sodium ion acts as a spectator ion and is not shown in the mechanism.

A spectator ion is an ion that remains in the same form on both sides of the reaction equation. It keeps the same physical state, charge, and oxidation state.

If we write out all the ions involved in a reaction, we can see which are spectators. For example, in the reaction between hydrochloric acid (HCl) and sodium hydroxide (NaOH) , the sodium ions (Na+) and chloride ions (Cl-) are all spectators - they stay in the same state and aren’t changed in the reaction.

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) Na+(aq) + Cl-(aq) + H2O(l)

Let’s look at the conditions for nucleophilic substitution with hydroxide ions. Halogenoalkanes do not readily mix with water, so ethanol is used as a solvent for the substitution reaction. The mixture is warmed under reflux to increase the rate of reaction:

  • Warming the mixture increases the kinetic energy of the molecules. This means that not only do they move faster and so have more collisions, but on average they also have more energy when they collide. This means that they are more likely to have the activation energy needed for a reaction. There will be a higher proportion of successful collisions and thus a faster reaction.
  • Reflux is a reaction technique that involves heating the mixture in a sealed vessel. When volatile components in the mixture evaporate, they are trapped in a condenser and cannot escape out of the system, and instead condense back into the container. We can reach higher temperatures and carry the reaction out over a longer period. This increases the opportunity for a successful reaction.

For more on rates of reaction, see Collision Theory and Increasing Rates.

For example, bromoethane (CH3CH2Br) reacts with potassium hydroxide to form ethanol (CH3CH2OH) and a bromide ion. The bromide ion then reacts with the potassium ion to form potassium bromide. This can be shown by the following overall equation:

CH3CH2Br + KOH → CH3CH2OH + KBr

Remember to use structural formulae when writing equations to show the molecule’s structure and the position of the new functional group.

Another example is the nucleophilic attack of 2-chloro-2-methylpropane (CH3CCl(CH3)CH3) by sodium hydroxide, forming 2-methylpropan-2-ol (CH3COH(CH3)CH3) and sodium chloride. Here's the equation:

CH3CCl(CH3)CH3 + NaOH → CH3CCl(CH3)CH3 + NaCl

There is another type of reaction involving halogenoalkanes and hydroxide ions. It is called an elimination reaction. In elimination reactions, the hydroxide ion acts as a base instead of a nucleophile. It produces an alkene, water and a halide ion. The conditions are slightly different too - we use hot and concentrated ethanolic potassium (or sodium) hydroxide. Explore this in Elimination Reactions.

Nucleophilic substitution reaction with the cyanide ion

Potassium or sodium cyanide (KCN or NaCN) react with halogenoalkanes in ethanolic solution to form a nitrile (RCN) and a halide ion. Nitriles have the functional group -CN, which contains a C≡N triple bond. Once again, the reaction mixture is heated under reflux. This nucleophilic substitution reaction is important industrially as it increases the length of the carbon chain.

For example, chloromethane (CH3Cl) heated in ethanolic potassium cyanide produces ethanenitrile (CH3CN) and a chloride ion. The chloride ion then reacts with potassium to form potassium chloride. The overall equation is as follows:

CH3Cl + KCN → CH3CN + KCl

For more information on nitriles, see the article specifically dedicated to them: Nitriles.

Nucleophilic substitution reaction with ammonia

The reaction between halogenoalkanes and an excess of ammonia (NH3) produces a primary amine (RNH2), a halide ion and an ammonium ion (NH4+). Amines are ammonia derivatives, where one or more of the hydrogen atoms has been replaced by an alkyl group.

Nucleophilic substitution reactions ammonia primary amine ammonium ion StudySmarterAmmonia, a primary amine and the ammonium ion. StudySmarter Originals

We saw earlier in the article that although ammonia is not a negative ion, it is still a nucleophile. It contains a partially negatively charged atom, Nδ-, with a lone pair of electrons. When the nitrogen atom donates its lone pair of electrons to the carbon atom, the nitrogen atom becomes positively charged. This isn’t great for the molecule - it wants to be neutral, as that’s a lot more stable. To solve this problem, it kicks out a hydrogen atom, but keeps the bonded pair of electrons. The hydrogen atom is now a positive ion, and reacts with a second molecule of ammonia to form a positive ammonium ion. This positive ammonium ion can then react with the bromide ion produced in the substitution reaction, forming an ammonium salt. Overall, the reaction requires two moles of ammonia for each mole of halogenoalkane.

The reaction is carried out heated in ethanolic solution, in a sealed container under pressure.

For example, bromoethane (CH3CH2Br) and ammonia react together to form ethanamine (CH3CH2NH2), a bromide ion, and an ammonium ion. The ammonium ion reacts with the bromide ion to form an ammonium salt, ammonium bromide (NH4Br):

CH3CH2Br + 2NH3 → CH3CH2NH2 + NH4Br

Nucleophilic substitution reaction with silver nitrate solution

Let's now consider the reaction of halogenoalkanes with silver nitrate solution (AgNO3(aq)) mixed with ethanol. We use this process to identify the halogen present in the halogenoalkane. The ethanol acts as a solvent and allows everything to dissolve, whilst the water in the silver nitrate solution acts as the nucleophile, producing an alcohol, a hydrogen ion (H+), and a halide ion (X-). The halide ion then reacts with the silver nitrate to form a coloured precipitate, and the colour of the precipitate gives us the identity of the halogen.

Halogen presentReaction with AgNO3(aq)Further details
FluorineNo observable reactionNo precipitate as AgF is soluble in water
ChlorineWhite precipitate
BromineCream precipitate
IodineYellow precipitate

Because this reaction produces a visible precipitate, it is a great way to compare the relative rates of reaction of different halogenoalkanes:

  • Iodoalkanes produce a precipitate much faster than chloroalkanes. As we explored earlier in the article, this is because the C-X bond enthalpy decreases as you move down the halogen group in the periodic table, making the halogenoalkane more reactive and leading to a faster rate of reaction.
  • Tertiary halogenoalkanes produce a precipitate much faster than primary halogenoalkanes. This is because tertiary halogenoalkanes use the SN1 mechanism, whilst primary halogenoalkanes use the SN2 mechanism. The SN1 mechanism is a lot quicker than the SN2 mechanism, leading to a faster rate of reaction.

Importance of nucleophilic substitution reactions

Finally, we'll discuss the importance of nucleophilic substitution reactions.

  • They allow us to swap one functional group for another in certain organic molecules. This makes them important stepping stones in industrial processes.
  • Particular nucleophilic substitution reactions, specifically the reaction with the cyanide ion (:CN-), increase the length of the carbon chain. This is quite tricky in organic chemistry.

Nucleophilic Substitution Reactions - Key takeaways

  • Nucleophilic substitution reactions are reactions in which a nucleophile attacks an organic molecule and replaces one of its functional groups with a different functional group.
  • A nucleophile is an electron-pair donor with a negative or partially negative charge, and a lone pair of electrons.
  • Common nucleophiles are the hydroxide ion (:OH-), cyanide ion (:CN-), ammonia (NH3), and water (H2O). These nucleophiles can all react with halogenoalkanes in nucleophilic substitution reactions, releasing a halide ion.
  • Nucleophilic substitution reactions are important because they swap one functional group for another and can increase the length of the carbon chain.

Frequently Asked Questions about Nucleophilic Substitution Reactions

A nucleophilic substitution reaction is a reaction in which a functional group on a molecule is replaced by a nucleophile. Nucleophiles are electron pair donors with a negative or partial negative charge and a spare pair of electrons.

Benzene derivatives, such as chlorobenzene, can undergo nucleophilic substitution reactions. However, benzene itself undergoes electrophilic substitution instead. This is because the high charge density of its ring of delocalised electrons is appealing to electrophiles.

There are multiple types of nucleophilic substitution reactions. Examples include the substitution of halogenoalkanes using hydroxide ions or cyanide ions.

Factors affecting nucleophilic substitution reactions include the partial charge of the carbon atom, the strength of the bond between the carbon and the leaving group, and the strength of the nucleophile. 

Final Nucleophilic Substitution Reactions Quiz

Question

What is a nucleophile?

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Answer

An electron pair donor with a negative or δ- charge, and a lone pair of electrons.


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Question

The main product of the reaction between a hydroxide ion and a halogenoalkane is:


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Answer

An alcohol.

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Question

Give the conditions for the nucleophilic substitution reaction between cyanide ions and a halogenoalkane.


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Answer

Warm, reflux, ethanolic.


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Question

Give the conditions for the nucleophilic substitution reaction between hydroxide ions and a halogenoalkane.


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Answer

Aqueous and ethanolic, heat, reflux.

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Question

Why is reflux used in the nucleophilic substitution of halogenoalkanes with sodium hydroxide?


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Answer

It prevents the escape of volatile components before they can react and increases the time available for reaction.

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Question

What is a substitution reaction?

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Answer

A reaction in which one functional group is removed from a molecule and replaced by a different functional group.

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Question

Which type of halogenoalkane reacts the fastest in nucleophilic substitution reactions?

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Answer

Fluoroalkanes

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Question

Which type of halogenoalkane reacts the fastest in nucleophilic substitution reactions?

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Answer

Tertiary halogenoalkanes

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Question

What sort of mechanism is used in the nucleophilic substitution of primary halogenoalkanes?

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Answer

SN2

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Question

What sort of mechanism is used in the nucleophilic substitution of secondary halogenoalkanes?

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Answer

Both SN1 and SN2

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Question

What sort of mechanism is used in the nucleophilic substitution of tertiary halogenoalkanes?

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Answer

SN1

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