2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (2024)

What is 2,4-Dinitrophenylhydrazine (2,4 DNP Test)?

Brady’s reagent (2,4-dinitrophenylhydrazine) is a red-orange solid, usually supplied wet to reduce the risk of explosion.

Table of Contents

  • 2,4-Dinitrophenylhydrazine Structure
  • Synthesis of 2,4-Dinitrophenylhydrazine
  • Brady’s Reagent
  • Identifying a Carbonyl Compound
  • 2,4-Dinitrophenylhydrazine Laboratory Test
  • Reaction with Ethanal
  • Frequently Asked Questions – FAQs

2,4-Dinitrophenylhydrazine Structure

The structure of 2,4-Dinitrophenylhydrazine is given below.

2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (1)

2,4-DNP derivatives offer a convenient way of separating the components of a mixture of aldehydes and ketones. Rather than attempting to do this directly by fractional distillation, a chemist might take advantage first of the easy separation of 2,4-DNP derivatives by column chromatography. Since their formation from aldehydes and ketones is reversible, hydrolysis of the separated derivatives will then regenerate the original carbonyl compounds.

Synthesis of 2,4-Dinitrophenylhydrazine

Although it’s not a familiarly substituted hydrazine, we can make a reasonable inference that hydrazine H2N-NH2 is a good nucleophile. So the synthesis of 2,4-Dinitrophenylhydrazine can be done from the product, it is prepared by reacting hydrazine with 2,4-dinitrochlorobenzene. The electron-accepting effect of the two nitro groups makes this chloride easy to displace.

2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (2)

Since chlorine is ortho, para directing and deactivating, so we should nitrate chlorobenzene. Chlorobenzene is readily prepared from benzene itself, so the synthesis is complete and the reaction is given below.

2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (3)

Brady’s Reagent

An aqueous solution of 2,4-dinitrophenyl hydrazine (DNP) is known as Brady’s reagent. It reacts with carbonyl compounds (aldehydes and ketone) to give a coloured precipitate. These precipitates have a sharp melting point. The melting points of the precipitates confirm the carbonyl compounds.

Benzoic acid is used as an antiseptic in medicines meant for urinary disorders and in vapour form for disinfecting bronchial tubes.

  • Acetic anhydride reacts with N2O5 to give acetyl nitrate.

(CH3CO)2O + N2O5 → 2CH3COONO2 (Acetyl nitrate)

  • The reaction of the acid chloride with water decreases with the increase of C-atoms in alkyl groups.

CH3COCl > CH3-CH2-COCl > CH3-CH2-CH2COCl > ………

Identifying a Carbonyl Compound

The carbonyl compound is simply mixed with an acid solution of Brady’s reagent in methanol. The derivatives are orange coloured crystalline solids called 2,4-dinitrophenylhydrazones. These crystals are filtered off and purified by re-crystallisation.

Their melting temperatures are measured. The original carbonyl compound is then identified by comparing to the tables of melting points of 2,4-dinitrophenylhydrazine derivatives.

2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (4)

Brady’s reagent can also be used as a test for the presence of a carbonyl compound because orange crystals appear when it is added to either an aldehyde or a ketone.

2,4-Dinitrophenylhydrazine Laboratory Test

2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (5)

  • Place 5ml of the 2,4-dinitrophenylhydrazine reagent in a test tube.
  • Add 10 drops of the unknown compound; sharply tap the test tube with your finger to mix. If crystals do not form immediately, gently heat in a water bath (60oC) for 5min.
  • Cool in an ice bath until crystals form. Collect the crystals by vacuum filtration using Hirsch funnel.
  • Allow the crystals to dry on the Hirsch funnel by drawing air through the crystals. Take a melting point and record on the Report sheet.
  • The crystals are usually pure enough to give a good melting point. However, if the melting point range is too large, recrystallize from a minimum volume of ethanol.

2,4-DinitrophenylhydrazineReaction with Ethanal

2,4-Dinitrophenylhydrazine reacts with both aldehydes and ketones to form a 2,4-dinitrophenylhydrazone. For example with ethanal;

2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (6)

  • The reaction is a condensation reaction (water is eliminated). The product is named using the name of the aldehyde or ketone followed by 2,4-dinitrophenylhydrazone, for example, ethanal 2,4-dinitrophenylhydrazone.
  • 2,4-dinitrophenylhydrazine can be used as a method for identifying aldehydes and ketones – the 2,4-dinitrophenylhydrazone formed is a solid that can be purified and its melting point determined. Comparison of the melting point with a table of known values could identify the aldehyde or ketone.
  • The 2,4-dinitrophenylhydrazone derivatives are all orange/yellow solids.
  • The solution of 2,4-dinitrophenylhydrazine is often called Brady’s reagent.

Frequently Asked Questions – FAQs

Q1

What does a positive 2,4 DNP test indicate?

2,4-Dinitrophenylhydrazine can be used for the qualitative identification of ketone or aldehyde functional group carbonyl functionality. A positive test is indicated by the formation of a precipitate known as dinitrophenylhydrazone, yellow, orange, or red.

Q2

How can you tell the difference between aldehydes and ketones?

The distinction between the aldehyde and ketone is the presence in the aldehyde of a hydrogen atom bound to the double carbon-oxygen bond. Ketones aren’t hydrogen. The presence of the hydrogen atom makes it very simple to oxidize aldehydes, they are fast reduction agents.

Q3

Why are 2,4 Dinitrophenylhydrazones better derivatives than Phenylhydrazones?

2,4-Dinitrophenylhydrazones are, for different reasons, safer derivatives than phenylhydrazones. First, there are higher molecular masses in these derivatives, increasing the volume of substance to be checked. Heavier-mass derivatives also have a greater chance of becoming a solid.

Q4

What will a DNP test determine and how?

2,4-Dinitrophenylhydrazine can be used for the qualitative identification of ketone or aldehyde functional group carbonyl functionality. A successful test is indicated by the formation of a precipitate yellow, orange, or red known as dinitrophenylhydrazone.

Q5

What is Brady’s reagent?

The chemical compound C6H3(NO2)2NHNH2 is 2,4-Dinitrophenylhydrazine (DNPH, Brady’s reactive, Borche’s reagent). Dinitrophenylhydrazine is a solid whose colours can range from red to white. It is a synthetic hydrazine-derivative, which is mostly used for the qualitative research of aldehyde which is a ketone related carbonyl group.

Q6

Does alcohol react with Brady’s reagent?

Aldehydes and ketones react to yellow, orange, or reddish-orange precipitates with the 2,4-dinitrophenylhydrazine reagent, whereas alcohols do not react. This is a successful technique for checking for the existence of a drug or demonstrating its absence.

Q7

Why does glucose not give a 2,4 DNP test?

That’s because glucose doesn’t react with Schiff’s reagent & 2,4DNP reagent despite having an aldehydrated group. It forms either α-anomer after the internal cycling. There is no free aldehyde group present in these forms. Thus, it does not give an aldehyde group reaction.

Q8

Does esters result in a positive 2,4-DNP test?

No, 2,4 DNP is negative for functional groups containing carbonyls, such as amides, carboxylic acids, and esters.

Q9

What color is Brady’s reagent?

2,4-DNP abbreviation for 2,4-Dinitrophenylhydrazine is a compound with a benzene ring, a functional hydrazine group and two nitro groups.It is a red-orange solid. This solution is used to detect the presence of carbonyl group(-CO) in the organic compound.

Q10

When benzoic acid reacts with 2,4-DNP, does any precipitate form?

No, benzoic acids contain the -COOH group and exhibit the stability due to resonance which occurs when a lone pair of electrons on the O-atom interacts with the p orbital of the carbonyl carbon, resulting in increased molecule delocalisation. As a result, they do not react and provide any precipitation with it in order to protect the stability.

2,4 DNP Test (2,4-Dinitrophenylhydrazine)[C6H3(NO2)2NHNH2] - Brady’s Reagent, Synthesis, Structure with Examples (2024)

FAQs

What is the reagent for the 2,4-DNP test? ›

A Brady's reagent can be described as an aqueous solution of 2,4-dinitrophenyl hydrazine (DNP). It reacts with carbonyl compounds (aldehydes & ketone) to produce a coloured precipitate. These resultant precipitates have a sharp melting point. The melting points of these precipitates confirm the carbonyl compounds.

What is the use of 2,4-dinitrophenylhydrazine 2,4-DNPH reagent to detect the presence of carbonyl compounds? ›

An aqueous solution of 2,4-dinitrophenyl hydrazine (DNP) is known as Brady's reagent. It reacts with carbonyl compounds (aldehydes and ketone) to give a coloured precipitate. These precipitates have a sharp melting point. The melting points of the precipitates confirm the carbonyl compounds.

How the 2,4-dinitrophenylhydrazine test can be used to identify aldehydes and ketones? ›

When an aldehyde or a ketone is placed in a 2,4-DNP solution, a bright yellow-orange or red solid results, which constitutes a positive test. If no aldehyde or ketone is present, no bright colored solid is observed, and the solution remains colorless.

What is the chemical equation for the 2,4-DNP test? ›

+ C6H3(NO2)2NHNH2 → C6H3(NO2)2NHN=CRR' + H2O. This reaction is, overall, a condensation reaction as two molecules joining together with loss of water.

What is a positive Brady's test result? ›

2,4-DNPH (Brady's) Test

Most aldehydes or ketones will react with the orange reagent to give a red, orange, or yellow precipitate. Esters and other carbonyl compounds are generally not reactive enough to give a positive result for this test.

What is a positive result of dinitrophenylhydrazine test? ›

2,4-Dinitrophenylhydrazine used for separating and identifying the carbonyl functional group of ketone or aldehyde from a mixture of unknown organic compounds. The positive test result includes the formation of orange, or red precipitate which is called dinitrophenylhydrazone.

What is the Brady's reagent reaction? ›

Brady's reagent is a red to orange solid of DNPH, methanol, and sulfuric acid that reacts with carbonyl compounds such as aldehydes and ketones and produces coloured precipitate. It is very sensitive to friction and shock, so it is usually supplied wet to avoid the risk of explosion.

What does a positive Tollens test indicate? ›

What color is a positive tollens test? The formation of a dark grey precipitate or silver mirror on the bottom and sides of the test tube indicates a positive result, which means that the given sample contains reducing sugars/ aldoses.

What forms a yellow precipitate with 2,4-dinitrophenylhydrazine? ›

The answer is (c) ketone. If a compound gave a yellow precipitate with -dinitrophenyl hydrazine but did not react with Tollens reagent or turn chromic acid green would the compound be a ketone. The compound gave a yellow precipitate with 2,4-dinitrophenyl hydrazine, which indicates that it is a carbonyl compound.

What is the mechanism of the 2,4-DNPH reaction? ›

In terms of mechanisms, this is a nucleophilic addition-elimination 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).

Why does glucose not give a 2,4-DNP test? ›

Glucose does not have an open chain structure and hence it does not have a free − C H O group. Actually − C H O group combines with C 5 − O H to form a hemiacetal ring which is a six-membered oxide ring. Thus glucose largely (99%) exists in the cyclic hemiacetal form and so it does not give 2 , 4 − D N P test.

Does glucose give a DNP test? ›

Glucose does not gives 2,4-DNP test.

What color is a negative 2,4-DNP test? ›

A positive 2,4-DNP test appears as a yellowish precipitate. A negative 2,4-DNP test appears as an orange solution.

What does not react with 2,4-DNP? ›

Glucose does not react with 2,4-DNP, Schiff's reagent or NaHSO3. This is because the aldehyde group in glucose is involved in hemiacetal formation and thus is not free.

What is 2,4-DNP in chemistry A level? ›

2,4-dinitrophenylhydrazine is often abbreviated to 2,4-DNP or 2,4-DNPH. CIE use the 2,4-DNPH version. When an aldehyde or ketone is tested with a solution of 2,4-DNPH, you get a yellow or orange precipitate. This is used as firm evidence of the presence of the carbon-oxygen double bond in these compounds.

How do you make a 2,4-DNP reagent? ›

To a clean, dry 125-mL Erlenmeyer flask and magnetic stir bar, add 3 grams of 2,4-dintrophenylhydrazine, 20 mL of water and 70 mL of 95% ethanol. Place the flask in an ice bath in a beaker. Stir and allow the mixture to cool.

What is the Schiff's reagent? ›

Answer: Schiff's reagent is a type of reagent that is used to make The reagent consists of a solution of fuchsin dye that has been decolorized by sulfur dioxide and is used to test for aldehydes and ketones. Aromatic ketones have no effect on the reagent, however aliphatic aldehydes restore the pink instantly.

What is the Fehling's reagent? ›

Fehling's A is a solution containing copper(II) sulphate, which is blue. Fehling's B is a clear liquid consisting of potassium sodium tartrate (Rochelle salt) and a strong alkali, usually sodium hydroxide. During the test solutions A and B are prepared individually and stored.

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