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THE TRIIODOMETHANE (IODOFORM) REACTION WITH ALDEHYDES AND KETONES

This page looks at how the triiodomethane (iodoform) reaction can be used to identify the presence of a CH3CO group in aldehydes and ketones.
Note: This reaction can also be used in testing for the CH3CH(OH) group in alcohols. You will find a link to this at the bottom of the page.

Doing the triiodomethane (iodoform) reaction


There are two apparently quite different mixtures of reagents that can be used to do this reaction. They are, in fact, chemically equivalent.
Note: It would be silly to learn both of these methods. Use whichever one your examiners want - find out by looking at past papers and mark schemes. If you haven't got these, go to the syllabuses page to find out how to get hold of them. Use the BACK button on your browser to return to this page.

Using iodine and sodium hydroxide solution This is chemically the more obvious method. Iodine solution is added to a small amount of aldehyde or ketone, followed by just enough sodium hydroxide solution to remove the colour of the iodine. If nothing happens in the cold, it may be necessary to warm the mixture very gently. A positive result is the appearance of a very pale yellow precipitate of triiodomethane (previously known as iodoform) -

CHI3. Apart from its colour, this can be recognised by its faintly "medical" smell. It is used as an antiseptic on the sort of sticky plasters you put on minor cuts, for example. Using potassium iodide and sodium chlorate(I) solutions Sodium chlorate(I) is also known as sodium hypochlorite. Potassium iodide solution is added to a small amount of aldehyde or ketone, followed by sodium chlorate(I) solution. Again, if no precipitate is formed in the cold, it may be necessary to warm the mixture very gently. The positive result is the same pale yellow precipitate as before.
Why the two reactions are equivalent: The reaction happens in two stages: first the aldehyde or ketone reacts with iodine, and the product of that reaction reacts with hydroxide ions. That is obviously the mixture you are adding in the first method above. In the second method, the sodium chlorate(I) solution is an oxidising agent, and oxidises the iodide ions in the potassium iodide to iodine. As well as any possible precipitate, you will also see the typical reddish-brown colour of iodine solution being formed during the reaction. So although you didn't put any iodine into the mixture, it is made in situ. What about the hydroxide ions? Sodium chlorate(I) solution is alkaline and contains enough hydroxide ions to carry out the second half of the reaction. The reason that sodium chlorate(I) is alkaline is that it reacts reversibly with water to form the weak acid chloric(I) acid together with hydroxide ions.

The chemistry of the triiodomethane (iodoform) reaction


What the triiodomethane (iodoform) reaction shows A positive result - the pale yellow precipitate of triiodomethane

(iodoform) - is given by an aldehyde or ketone containing the grouping:

"R" can be a hydrogen atom or a hydrocarbon group (for example, an alkyl group). If "R" is hydrogen, then you have the aldehyde ethanal, CH3CHO.

Ethanal is the only aldehyde to give the triiodomethane (iodoform) reaction. If "R"is a hydrocarbon group, then you have a ketone. Lots of ketones give this reaction, but those that do all have a methyl group on one side of the carbon-oxygen double bond. These are known as methyl ketones.

Equations for the triiodomethane (iodoform) reaction We will take the reagents as being iodine and sodium hydroxide solution. The first stage involves substitution of all three hydrogens in the methyl group by iodine atoms. The presence of hydroxide ions is important for the reaction to happen - they take part in the mechanism for the reaction (not required for UK A level).

In the second stage, the bond between the C I3 and the rest of the molecule is broken to produce triiodomethane (iodoform) and the salt of an acid.

Putting all this together gives the overall equation for the reaction:

Ritter Reaction

The acid-induced nucleophilic addition of a nitrile to a carbenium ion, followed by hydrolysis to the corresponding amide.

Mechanism of the Ritter Reaction


Any substrate capable of generating a stable carbenium ion is a suitable starting material; primary alcohols do not react under these conditions, with exception of benzylic alcohols:

The carbenium ion adds to the nitrile nitrogen to give a nitrilium ion intermediate, which undergoes hydrolysis to the corresponding amide upon aqueous work-up.

Recent Literature

An efficient method for the conversion of aromatic and aliphatic nitriles to the corresponding Ntert-butyl amides: a modified Ritter reaction K. L. Reddy, Tetrahedron Lett., 2003, 44, 1453-1455

Synthesis of N-Benzhydrylamides from Nitriles by Ritter Reactions in Formic Acid G. C. Gullickson, D. E. Lewis, Synthesis, 2003, 681-684.

One-Pot Synthesis of Isocyanides from Alcohols I. Okada, Y. Kitano, Synthesis, 2011, 3997-4002.

A CAN-Induced Cyclodimerization-Ritter Trapping Strategy for the One-Pot Synthesis of 1Amino-4-aryltetralins from Styrenes V. Nair, R. Rajan, N. P. Rath, Org. Lett., 2002, 4, 1575-1577.

ADDITION-ELIMINATION REACTIONS OF ALDEHYDES AND KETONES


This page looks at the reaction of aldehydes and ketones with 2,4-dinitrophenylhydrazine (Brady's reagent) as a test for the carbon-oxygen double bond. It also looks briefly at some other similar reactions which are all known as addition-elimination (or condensation) reactions.

The reaction with 2,4-dinitrophenylhydrazine


2,4-dinitrophenylhydrazine is often abbreviated to 2,4-DNP or 2,4-DNPH. A solution of 2,4-dinitrophenylhydrazine in a mixture of methanol and sulphuric acid is known as Brady's reagent. What is 2,4-dinitrophenylhydrazine? Although the name sounds complicated, and the structure looks quite complicated, it is actually very easy to work out. Start with the formula of hydrazine. That's almost all you need to

remember! Hydrazine is:

In phenylhydrazine, one of the hydrogens is replaced by a phenyl group, C6H5. This is based on a benzene ring.

Note: I'm using the common symbol for a benzene ring. If you aren't familiar with this, there is a carbon atom at each corner of the hexagon, together with a hydrogen atom if there isn't anything else attached. The circle in the middle of the hexagon suggests the delocalised electrons. If you want to read more about the structure of benzene, you could follow this link to another part of the site. It isn't important for the purposes of the present page, and you might have to explore quite a lot of other pages to help you to understand that one. If you do choose to follow this link, use the BACK button (or HISTORY file or GO menu if you get seriously waylaid) on your browser to return to this page.

In 2,4-dinitrophenylhydrazine, there are two nitro groups, NO2, attached to the phenyl group in the 2- and 4- positions. The corner with the nitrogen attached is counted as the number 1 position, and you just number clockwise around the ring.

Doing the reaction Details vary slightly depending on the nature of the aldehyde or ketone, and the solvent that the 2,4-dinitrophenylhydrazine is dissolved in. Assuming you are using Brady's reagent (a solution of the 2,4-dinitrophenylhydrazine in methanol and sulphuric acid): Add either a few drops of the aldehyde or ketone, or possibly a solution of the aldehyde or ketone in methanol, to the Brady's reagent. A bright orange or yellow precipitate shows the presence of the carbon-oxygen double bond in an aldehyde or ketone. This is the simplest test for an aldehyde or ketone.

The chemistry of the reaction The overall reaction is given by the equation:

R and R' can be any combination of hydrogen or hydrocarbon groups (such as alkyl groups). If at least one of them is a hydrogen, then the original compound is an aldehyde. If both are hydrocarbon groups, then it is a ketone. Look carefully at what has happened.

Provided you take care to draw the two starting molecules lined up right, working out the structure of the product is easy. The product is known as a "2,4-dinitrophenylhydrazone". Notice that all that has changed is the ending from "-ine" to "-one". That's possibly confusing! The product from the reaction with ethanal would be called ethanal 2,4-dinitrophenylhydrazone; from propanone, you would get propanone 2,4-dinitrophenylhydrazone - and so on. That's not too difficult! The reaction is known as a condensation reaction. A condensation reaction is one in which two molecules join together with the loss of a small molecule in the process. In this case, that small molecule is water. In terms of mechanisms, this is a nucleophilic additionelimination reaction. The 2,4-dinitrophenylhydrazine first adds across the carbon-oxygen double bond (the addition stage) to give an intermediate compound which then loses a molecule of water (the elimination stage).
Note: This mechanism isn't required by any of the UK A level syllabuses, and so you won't find it anywhere on this site. Sorry!

Using the reaction The reaction has two uses in testing for aldehydes and ketones.

First, you can just use it to test for the presence of the carbon-oxygen double bond. You only get an orange or yellow precipitate from a carbon-oxygen double bond in an aldehyde or ketone.

Secondly, you can use it to help to identify the specific aldehyde or ketone. The precipitate is filtered and washed with, for example, methanol and then recrystallised from a suitable solvent which will vary depending on the nature of the aldehyde or ketone. For example, you can recrystallise the products from the small aldehydes and ketones from a mixture of ethanol and water. The crystals are dissolved in the minimum quantity of hot solvent. When the solution cools, the crystals are reprecipitated and can be filtered, washed with a small amount of solvent and dried. They should then be pure. If you then find the melting point of the crystals, you can compare it with tables of the melting points of 2,4dinitrophenylhydrazones of all the common aldehydes and ketones to find out which one you are likely to have got.

Some other similar reactions


If you go back and look at the equations, nothing in the 2,4dinitrophenylhydrazine changes during the reaction apart from the -NH2 group. You can get a similar reaction if the -NH2 group is attached to other things. In each case, the reaction would look like this:

In what follows, all that changes is the nature of the "X".

with hydrazine

The product is a "hydrazone". If you started from propanone, it would be propanone hydrazone.

with phenylhydrazine

The product is a "phenylhydrazone".

with hydroxylamine

The product is an "oxime" - for example, ethanal oxime.

ADDITION-ELIMINATION REACTIONS OF ALDEHYDES AND KETONES

This page looks at the reaction of aldehydes and ketones with 2,4-dinitrophenylhydrazine (Brady's reagent) as a test for the carbon-oxygen double bond. It also looks briefly at some other similar reactions which are all known as addition-elimination (or condensation) reactions.

The reaction with 2,4-dinitrophenylhydrazine


2,4-dinitrophenylhydrazine is often abbreviated to 2,4-DNP or 2,4-DNPH. A solution of 2,4-dinitrophenylhydrazine in a mixture of methanol and sulphuric acid is known as Brady's reagent. What is 2,4-dinitrophenylhydrazine? Although the name sounds complicated, and the structure looks quite complicated, it is actually very easy to work out. Start with the formula of hydrazine. That's almost all you need to remember! Hydrazine is:

In phenylhydrazine, one of the hydrogens is replaced by a phenyl group, C6H5. This is based on a benzene ring.

Note: I'm using the common symbol for a benzene ring. If you aren't familiar with this, there is a carbon atom at each corner of the hexagon, together with a hydrogen atom if there isn't anything else attached. The circle in the middle of the hexagon suggests the delocalised electrons. If you want to read more about the structure of benzene, you could

follow this link to another part of the site. It isn't important for the purposes of the present page, and you might have to explore quite a lot of other pages to help you to understand that one. If you do choose to follow this link, use the BACK button (or HISTORY file or GO menu if you get seriously waylaid) on your browser to return to this page.

In 2,4-dinitrophenylhydrazine, there are two nitro groups, NO2, attached to the phenyl group in the 2- and 4- positions. The corner with the nitrogen attached is counted as the number 1 position, and you just number clockwise around the ring.

Doing the reaction Details vary slightly depending on the nature of the aldehyde or ketone, and the solvent that the 2,4-dinitrophenylhydrazine is dissolved in. Assuming you are using Brady's reagent (a solution of the 2,4-dinitrophenylhydrazine in methanol and sulphuric acid): Add either a few drops of the aldehyde or ketone, or possibly a solution of the aldehyde or ketone in methanol, to the Brady's reagent. A bright orange or yellow precipitate shows the presence of the carbon-oxygen double bond in an aldehyde or ketone. This is the simplest test for an aldehyde or ketone.

The chemistry of the reaction The overall reaction is given by the equation:

R and R' can be any combination of hydrogen or hydrocarbon groups (such as alkyl groups). If at least one of them is a hydrogen, then the original compound is an aldehyde. If both are hydrocarbon groups, then it is a ketone. Look carefully at what has happened.

Provided you take care to draw the two starting molecules lined up right, working out the structure of the product is easy. The product is known as a "2,4-dinitrophenylhydrazone". Notice that all that has changed is the ending from "-ine" to "-one". That's possibly confusing! The product from the reaction with ethanal would be called ethanal 2,4-dinitrophenylhydrazone; from propanone, you would get propanone 2,4-dinitrophenylhydrazone - and so on. That's not too difficult! The reaction is known as a condensation reaction. A condensation reaction is one in which two molecules join together with the loss of a small molecule in the process. In this

case, that small molecule is water. In terms of mechanisms, this is a nucleophilic additionelimination reaction. The 2,4-dinitrophenylhydrazine first adds across the carbon-oxygen double bond (the addition stage) to give an intermediate compound which then loses a molecule of water (the elimination stage).
Note: This mechanism isn't required by any of the UK A level syllabuses, and so you won't find it anywhere on this site. Sorry!

Using the reaction The reaction has two uses in testing for aldehydes and ketones.

First, you can just use it to test for the presence of the carbon-oxygen double bond. You only get an orange or yellow precipitate from a carbon-oxygen double bond in an aldehyde or ketone. Secondly, you can use it to help to identify the specific aldehyde or ketone. The precipitate is filtered and washed with, for example, methanol and then recrystallised from a suitable solvent which will vary depending on the nature of the aldehyde or ketone. For example, you can recrystallise the products from the small aldehydes and ketones from a mixture of ethanol and water. The crystals are dissolved in the minimum quantity of hot solvent. When the solution cools, the crystals are reprecipitated and can be filtered, washed with a small amount of solvent and dried. They should then be pure. If you then find the melting point of the crystals, you can compare it with tables of the melting points of 2,4dinitrophenylhydrazones of all the common aldehydes and ketones to find out which one you are likely to have got.

Some other similar reactions


If you go back and look at the equations, nothing in the 2,4dinitrophenylhydrazine changes during the reaction apart from the -NH2 group. You can get a similar reaction if the -NH2 group is attached to other things. In each case, the reaction would look like this:

In what follows, all that changes is the nature of the "X".

with hydrazine

The product is a "hydrazone". If you started from propanone, it would be propanone hydrazone.

with phenylhydrazine

The product is a "phenylhydrazone".

with hydroxylamine

The product is an "oxime" - for example, ethanal oxime.