INTRODUCING ACYL CHLORIDES (acid chlorides)

This page explains what acyl chlorides are and looks at their simple physical properties such as boiling points. It introduces their chemical reactivity in a general way, but details of specific reactions are given on separate pages - see the acyl chlorides menu (link at the bottom of the page).

What are acyl chlorides?

Acyl chlorides as "acid derivatives" A carboxylic acid such as ethanoic acid has the structure:

There are a number of related compounds in which the -OH group in the acid is replaced by something else. Compounds like this are described as acid derivatives. Acyl chlorides (also known as acid chlorides) are one example of an acid derivative. In this case, the -OH group has been replaced by a chlorine atom.

The acyl group The acyl group is a hydrocarbon group attached to a carbon-oxygen double bond:

For UK A level purposes, the "R" group is normally restricted to an alkyl group. It could, however, equally well be a group based on a benzene ring.

Naming acyl chlorides The easiest way of thinking about the names is to see the relationship with the corresponding carboxylic acid:

carboxylic acid name acyl chloride name ethanoic acid propanoic acid butanoic acid ethanoyl chloride propanoyl chloride butanoyl chloride

acyl chloride formula CH3COCl CH3CH2COCl CH3CH2CH2COCl

If you have something substituted into the hydrocarbon chain, the carbon in the -COCl group counts as the number 1 carbon. For example, 2-methylbutanoyl chloride is:

Note: Hardly anyone ever mentions methanoyl chloride, HCOCl - derived from methanoic acid. That is because methanoyl chloride is very unstable, decomposing to give carbon monoxide and HCl.

Physical properties of acyl chlorides

Appearance An acyl chloride like ethanoyl chloride is a colourless fuming liquid. The strong smell of ethanoyl chloride is a mixture of the smell of vinegar (ethanoic acid) and the acrid smell of hydrogen chloride gas.

The smell and the fumes are because ethanoyl chloride reacts with water vapour in the air. The reaction with water is given in detail on another page. (Find it from the acyl chlorides menu - link at the bottom of this page.)

Solubility in water Acyl chlorides can't be said to dissolve in water because they react (often violently) with it. The strong reaction means that it is impossible to get a simple aqueous solution of an acyl chloride.

Boiling points Taking ethanoyl chloride as typical: Ethanoyl chloride boils at 51C. It is a polar molecule, and so has dipole-dipole attractions between its molecules as well as van der Waals dispersion forces. However, it doesn't form hydrogen bonds. Its boiling point is therefore higher than, say, an alkane of similar size (which has no permanent dipoles), but not as high as a similarly sized alcohol (which forms hydrogen bonds in addition to everything else.)
Note: If you aren't happy about intermolecular forces (including van der Waals dispersion forces and hydrogen bonds) then you really ought to follow this link before you go on.

Reactivity of acyl chlorides

Substitution of the chlorine atom by other groups Acyl chlorides are extremely reactive, and in their reactions the chlorine atom is replaced by other things. In each case, in the first instance, hydrogen chloride gas is produced as steamy acidic fumes. However, in some cases the hydrogen chloride goes on to react with one of the substances in the reaction mixture. Taking ethanoyl chloride as typical, the initial reaction is of this kind:

The reactions involve things like water, alcohols and phenols, or ammonia and amines. All of these particular cases contain a very electronegative element with an active lone pair of electrons - either oxygen or nitrogen.

MAKING ACYL CHLORIDES (ACID CHLORIDES)

This page looks at ways of swapping the -OH group in the -COOH group of a carboxylic acid for a chlorine atom to make acyl chlorides (acid chlorides), and is a very slightly modified version of a page in the section on reactions of carboxylic acids. It covers the use of phosphorus(V) chloride, phosphorus(III) chloride and sulphur dichloride oxide (thionyl chloride).

Replacing the -OH in a carboxylic acid by -Cl

We'll take the conversion of ethanoic acid to ethanoyl chloride as typical.
Note: If you haven't already done so, it would probably pay you to have a quick look at the beginning of the introduction to acyl chlorides before you go on

Replacing the -OH group using phosphorus(V) chloride, PCl5 Phosphorus(V) chloride is a solid which reacts with carboxylic acids in the cold to give steamy acidic fumes of hydrogen chloride. It leaves a liquid mixture of the acyl chloride and a phosphorus compound, phosphorus trichloride oxide (phosphorus oxychloride) POCl3. The acyl chloride can be separated by fractional distillation. For example:

Replacing the -OH group using phosphorus(III) chloride, PCl3

Phosphorus(III) chloride is a liquid at room temperature. Its reaction with a carboxylic acid is less dramatic than that of phosphorus(V) chloride because there is no hydrogen chloride produced. You end up with a mixture of the acyl chloride and phosphoric(III) acid (old names: phosphorous acid or orthophosphorous acid), H3PO3. For example:

Again, the ethanoyl chloride can be separated by fractional distillation.

Replacing the -OH group using sulphur dichloride oxide (thionyl chloride) Sulphur dichloride oxide (thionyl chloride) is a liquid at room temperature and has the formula SOCl2. Traditionally, the formula is written as shown, despite the fact that the modern name writes the chlorine before the oxygen (alphabetical order). The sulphur dichloride oxide reacts with carboxylic acids to produce an acyl chloride, and sulphur dioxide and hydrogen chloride gases are given off. For example:

The separation is simplified to an extent because the by-products are both gases. You would obviously still have to fractionally distil the mixture to separate the acyl chloride from any excess acid or sulphur dichloride oxide.

THE REACTION OF ACYL CHLORIDES WITH WATER, ALCOHOLS AND PHENOL

This page looks at the reactions of acyl chlorides (acid chlorides) with water, alcohols and phenol. These reactions are all considered together because their chemistry is so similar.

Similarities between the reactions

Comparing the structures of water, ethanol and phenol Each substance contains an -OH group. In water, this is attached to a hydrogen atom. In an alcohol, it is attached to an alkyl group - shown in the diagrams below as "R". In phenol, it is attached to a benzene ring. Phenol is C6H5OH.

Note: If you aren't sure about using this symbol for a benzene ring, you could follow this link to find out all about it. It is likely to take you some time, though, and you may have to visit several other pages as well. It isn't particularly important in the context of the current page. All you need to know is that at each corner of the hexagon there is a carbon atom, together with a hydrogen atom apart from where the -OH group is attached.

What happens when these react with an acyl chloride? We'll take ethanoyl chloride as typical of the acyl chlorides. For UK A level purposes, it is the one you are most likely to be asked about anyway. Taking a general case of a reaction between ethanoyl chloride and a compound X-O-H (where X is hydrogen, or an alkyl group or a benzene ring):

So . . . in each case, hydrogen chloride gas is produced - the hydrogen coming from the -OH group, and the chlorine from the ethanoyl chloride. Everything left over just gets joined together.
Note: If you are interested in exploring the general mechanism for these reactions, you will find it by following this link to another part of the site dealing with nucleophilic addition-elimination reactions.

The individual reactions

The reaction with water Modifying the general equation we've just looked at, you will see that you will get ethanoic acid produced together with hydrogen chloride gas.

This is more usually (and more easily!) written as:

Adding an acyl chloride to water produces the corresponding carboxylic acid together with steamy acidic fumes of hydrogen chloride. The reaction is usually extremely vigorous at room temperature.
Note: If you are want the mechanism for this reaction, you will find it by following this link to another part of the site dealing with nucleophilic addition-elimination reactions.

The reaction with alcohols We'll start by taking the general case of any alcohol reacting with ethanoyl chloride. The equation would be:

The organic product this time is an ester. For example, with ethanol you would get the ester ethyl ethanoate:

. . . or, more commonly:

Note: There is no "right" way of writing these equations. I am using the colour-coded structural versions to try to show the link between the various reactions. You can choose whichever version you want to use. If you are want the mechanism for this reaction, you will find it by following this link to another part of the site dealing with nucleophilic addition-elimination reactions.

This is an easy way of producing an ester from an alcohol because it happens at room temperature, and is irreversible. Making an ester from an alcohol and a carboxylic acid (the usual alternative method) needs heat, a catalyst and is reversible - so that it is difficult to get a 100% conversion.

The reaction with phenols The reaction with phenol itself Phenols have an -OH group attached directly to a benzene ring. In the substance normally called "phenol", there isn't anything else attached to the ring as well. We'll look at that first. The reaction between phenol and ethanoyl chloride isn't quite as vigorous as that between alcohols and ethanoyl chloride. The reactivity of the -OH group is modified by the benzene ring. That apart, the reaction is just the same as with an alcohol.

Or, more simply:

Especially if you write the equation in this second way, it is obvious that you have just produced another ester - in this case, called phenyl ethanoate. But beware! You may come across the structure drawn in a variety of other ways which make it look much more as if it was a derivative of phenol (which of course it is!). For example:

This would tend to happen if you were concentrating on the reactions of the phenol rather than the acyl chloride. Looking at it this way, notice that the hydrogen of the phenol -OH group has been replaced by an acyl group - an alkyl group attached to a carbon-oxygen double bond. You can say that the phenol has been acylated or has undergone acylation. Because of the nature of this particular acyl group, it is also described as ethanoylation. The hydrogen is being replaced by an ethanoyl group, CH3CO-.

Using a similar reaction to make aspirin The reaction with phenol itself isn't very important, but you can make aspirin by a very similar reaction. Here is 2-hydroxybenzoic acid (also known as 2-hydroxybenzenecarboxylic acid). The old name for this is salicylic acid. You might find it written in either of these two ways. They are the same structure with the molecule just flipped over in space.

You might also find it with the -OH group at the top and the -COOH group next door and either to the left or right of it. Life can get very confusing! When this reacts with ethanoyl chloride, it is ethanoylated (or acylated, if you want to use the more general term) to give:

You might find all sorts of other variants on drawing this as well. This molecule is aspirin.

THE REACTION OF ACYL CHLORIDES WITH AMMONIA AND PRIMARY AMINES

This page looks at the reactions of acyl chlorides (acid chlorides) with ammonia and with primary amines. These reactions are considered together because their chemistry is so similar.

Similarities between the reactions

Comparing the structures of ammonia and primary amines Each substance contains an -NH2 group. In ammonia, this is attached to a hydrogen atom. In a primary amine, it is attached to an alkyl group (shown by "R" in the diagram below) or a benzene ring.

Note: If you aren't sure about using this symbol for a benzene ring, you could follow this link to find out all about it. It is likely to take you some time, though, and you may have to visit several other pages as well. It isn't particularly important in the context of the current page. All you need to know is that at each corner of the hexagon there is a carbon atom, together with a hydrogen atom apart from where the -NH2 group is attached. If you want to know more about what primary amines are, you could follow this link to a page introducing amines, and just read the beginning of it. If you choose to follow either of these links, use the BACK button (or the HISTORY file or GO menu) on your browser to return to this page.

What happens when these react with an acyl chloride? We'll take ethanoyl chloride as typical of the acyl chlorides. For UK A level purposes, it is the one you are most likely to be asked about anyway. Taking a general case of a reaction between ethanoyl chloride and a compound XNH2 (where X is hydrogen, or an alkyl group, or a benzene ring). The reaction happens in two stages: First:

So . . . in each case, you initially get hydrogen chloride gas - the hydrogen coming from the -NH2 group, and the chlorine from the ethanoyl chloride. Everything left over just gets joined together. But ammonia and amines are basic, and react with the hydrogen chloride to produce a salt. So the second stage of the reaction is:

This is easier to understand with real compounds - as you will see below.
Note: If you are interested in exploring the general mechanism for these reactions, you will find it by following this link to another part of the site dealing with nucleophilic addition-elimination reactions. Use the BACK button on your browser to return to this page.

The individual reactions

The reaction with ammonia In this case, the "X" in the equations above is a hydrogen atom. So in the first instance you get hydrogen chloride gas and an organic compound called an amide. Amides contain the group -CONH2. In the reaction between ethanoyl chloride and ammonia, the amide formed is called ethanamide.

This is more usually (and more easily!) written as:

The hydrogen chloride produced reacts with excess ammonia to give ammonium chloride.

. . . and you can combine all this together to give one overall equation:

You normally add the ethanoyl chloride to a concentrated solution of ammonia in water. There is a very violent reaction producing lots of white smoke - a mixture of solid

ammonium chloride and ethanamide. Some of the mixture remains dissolved in water as a colourless solution.
Note: If you are want the mechanism for this reaction, you will find it by following this link to another part of the site dealing with nucleophilic addition-elimination reactions. Use the BACK button on your browser to return to this page.

The reaction with primary amines The reaction with methylamine We'll take methylamine as typical of primary amines where the -NH2 is attached to an alkyl group. The initial equation would be:

The organic product this time is called an N-substituted amide. If you compare the structure with the amide produced in the reaction with ammonia, the only difference is that one of the hydrogens on the nitrogen has been substituted for a methyl group. This particular compound is N-methylethanamide. The "N" simply shows that the substitution is on the nitrogen atom, and not elsewhere in the molecule. The equation would normally be written:

You can think of primary amines as just being modified ammonia. If ammonia is basic and forms a salt with the hydrogen chloride, excess methylamine will do exactly the same thing.

The salt is called methylammonium chloride. It is just like ammonium chloride, except that one of the hydrogens has been replaced by a methyl group. You would usually combine these equations into one overall equation for the reaction:

Note: If you are want the mechanism for this reaction (although using ethylamine rather than methylamine as the example), you will find it by following this link to another part of the site dealing with nucleophilic addition-elimination reactions. Use the BACK button on your browser to return to this page.

The reaction looks exactly the same as the one with ammonia. The methylamine is again used as a concentrated solution in water. There is a violent reaction producing a white solid mixture of N-methylethanamide and methylammonium chloride.

The reaction with phenylamine (aniline) Phenylamine is the simplest primary amine where the -NH2 group is attached directly to a benzene ring. Its old name is aniline. In phenylamine, there isn't anything else attached to the ring as well. You can write the formula of phenylamine as C6H5NH2. There is no essential difference between this reaction and the reaction with methylamine, except that the phenylamine is a brownish liquid, and the solid products tend to be stained brownish. The overall equation for the reaction is:

The products are N-phenylethanamide and phenylammonium chloride.

This reaction can sometimes look confusing if the phenylamine is drawn showing the benzene ring, and especially if the reaction is looked at from the point of view of the phenylamine. For example, the product molecule might be drawn looking like this:

If you stop and think about it, this is obviously the same molecule as in the equation above, but it stresses the phenylamine part of it much more. Looking at it this way, notice that one of the hydrogens of the -NH2 group has been replaced by an acyl group - an alkyl group attached to a carbon-oxygen double bond. You can say that the phenylamine has been acylated or has undergone acylation. Because of the nature of this particular acyl group, it is also described as ethanoylation. The hydrogen is being replaced by an ethanoyl group, CH3CO-.

THE REACTION OF ACYL CHLORIDES WITH BENZENE

This page looks at the reaction of acyl chlorides (acid chlorides) with benzene in the presence of an aluminium chloride catalyst. This is known as a Friedel-Crafts acylation.

Friedel-Crafts acylation of benzene

Background and equations Acylation is the term given to substituting an acyl group such as CH3CO- into another molecule. An acyl group is a hydrocarbon group attached to a carbon-oxygen double bond. For UK A level purposes, the most commonly used example of an acyl group is the ethanoyl group, CH3CO-, and so that's the one we will stick with throughout. So, if you react benzene with ethanoyl chloride in the presence of an aluminium chloride catalyst, the equation for the reaction is:

Or, simplifying it without drawing the benzene ring:

In the simplified formula for the product, the phenyl group is usually written on the lefthand side and the alkyl group to the right of the carbon-oxygen double bond - but I doubt if it really matters! The aluminium chloride isn't written into these equations because it is acting as a catalyst. If you wanted to include it, you could write AlCl3 over the top of the arrow. The product is called phenylethanone (old name, acetophenone).
Note: If you are want the mechanism for this reaction, you will find it by following this link to another part of the site dealing with electrophilic substitution reactions. Use the BACK button on your browser to return to this page.

Doing the reaction Ethanoyl chloride is added carefully to a mixture of benzene and solid aluminium chloride in the cold. Hydrogen chloride gas is given off. When all the ethanoyl chloride has been added, the mixture is heated under reflux at a temperature of 60C for about 30 minutes to complete the reaction.
Heating under reflux: Heating the flask with a condenser placed vertically in it to prevent loss of volatile liquids. Separating the product from the reaction mixture is fairly long-winded and beyond the scope of this site. You may find slight variations on the temperature and time for this reaction.

Why the reaction is important Friedel-Crafts acylation is a very effective way of attaching a hydrocarbon-based group to a benzene ring. Although the product is a ketone (a compound containing a carbonoxygen double bond with a hydrocarbon group either side), it is easily converted into other things. For example: The carbon-oxygen double bond can be reduced to give a secondary alcohol, which in turn can undergo a whole lot of other reactions.
Note: This reduction is explored on a page about reduction of aldehydes and ketones. That page doesn't deal specifically with this particular ketone, but the same principles apply. Use the BACK button on your browser to return to this page.

Phenylethanone can also be reduced to produce ethylbenzene. This is known as the Clemmensen reduction and involves heating the ketone with amalgamated zinc (a mixture of zinc and mercury) and concentrated hydrochloric acid for a long time.

This indirect route is the best way of getting an alkyl group attached to a benzene ring. It is possible to attach an alkyl group directly to the ring, but it is impossible to stop at substituting just one. An alkyl group attached to the ring makes the ring more reactive than the original benzene. That means that something like ethylbenzene reacts faster than benzene itself. The result is that you get several ethyl groups substituted around the ring rather than just one. Attaching an acyl group to the ring makes the ring so unreactive that it won't substitute a second one.