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DNPH2,4-Dinitrophenylhydrazine can be used to qualitatively detect the carbonyl functionality of a ketone or aldehyde functional group.

A positive test is signaled by a yellow or red precipitate (known as a dinitrophenylhydrazone.) If the carbonyl compound is aromatic, then the precipitate will be red; if aliphatic, then the precipitate will have a yellow colour. The reaction between 2,4Dinitrophenylhydrazine and a ketone is shown below: RR'C=O + C6H3(NO2)2NHNH2 C6H3(NO2)2NHNCRR' + H2O This reaction can be described as a condensation reaction, with two molecules joining together with loss of water. It is also considered an addition-elimination reaction: nucleophilic addition of the NH2 group to the C=O carbonyl group, followed by the removal of a H 2O molecule. Bradys reagent is prepared by dissolving 2,4-dinitrophenylhydrazine in a solution containing methanol and some concentrated sulfuric acid. 2,4-Dinitrophenylhydrazine is commercially available usually as a wet powder. It can be prepared by the reaction of hydrazine sulfate with 2,4-dinitrochlorobenzene

Tollens test Tollens' reagent is a chemical reagent most commonly used to determine whether a known carbonylcontaining compound is an aldehyde or a ketone. It is usually ammoniacal silver nitrate, but can also be other mixtures, as long as aqueousdiamminesilver(I) complex is present. It was named after its discoverer, Bernhard Tollens. A positive test with Tollens' reagent results in elemental silver precipitating out of solution, occasionally onto the inner surface of the reaction vessel, producing a characteristic and memorable "silver mirror" on the inner vessel surface. This reagent is not commercially available due to its short shelf life; it must be prepared freshly in the laboratory. One common preparation involves two steps. First a few drops of dilute sodium hydroxide is added to some aqueous silver nitrate. In this solution, the Ag ions from the aqueous silver nitrate exist in a hydrated form as [Ag(H2O)2] complexes, i.e. diaquasilver(I) ion. The OH ions from the sodium hydroxide deprotonate the water ligands that are attached to the Ag ions, to give [Ag(OH)2] ions. These dihydroxyargentate(I) complexes are not at all stable, and immediately they are dehydrated further to give silver oxide, Ag2O. This is insoluble, and precipitates out of the solution as a brown solid. Aqueous sodium nitrate is also produced in the mixture as a by-product. 2 AgNO3 (aq) + 2 NaOH (aq) Ag2O (s) + 2 NaNO3 (aq) + H2O (l) In the next step, aqueous ammonia is added until all of the brown silver(I) oxide is dissolved. At this point the mixture will be clear, and there are now aqueous silver ions existing as
+ + +

[Ag(NH3)2] complexes in the mixture, which is the main component of Tollens' reagent. Sodium hydroxide is reformed at the end of the preparation. Ag2O (s) + 4 NH3 (aq) + 2 NaNO3 (aq) + H2O (l) 2 Ag(NH3)2NO3 (aq) + 2 NaOH (aq) Alternatively, aqueous ammonia can be added in a continuous fashion directly to silver nitrate solution. At first, silver oxide will be formed and precipitate out, but as more ammonia solution is added the precipitate dissolves and the solution becomes clear as diamminesilver(I) is formed. At this point the addition of the ammonia should be stopped. This may be a preferable method as less reagents are involved. Filtering the reagent before use helps to prevent false-positive results. Once it has been ascertained that there is a carbonyl group on an organic molecule using 2,4dinitrophenylhydrazine (also known as Brady's reagent or 2,4-DNPH), Tollens' reagent can be used to determine whether the compound is a ketone or an aldehyde. Importantly, there is a special case in which Tollens' reagent will give a positive for a ketone; if the ketone is an alpha-hydroxy ketone, then the Tollens' reagent will react. The test rests on the premise that aldehydes are more readily oxidised compared with ketones; this is due to the carbonyl-containing carbon in aldehydes having an attached hydrogen. The diamminesilver(I) complex in the mixture is an oxidizing agent and is the essential reactant in Tollens' reagent. The test is generally carried out in a test tube in a warm water bath. In a positive test, the diamminesilver(I) complex oxidizes the aldehyde to a carboxylate ion and in the process is reduced to elemental silver and aqueous ammonia. The elemental silver precipitates out of solution, occasionally onto the inner surface of the reaction vessel, giving a characteristic "silver mirror". The carboxylate ion on acidification will give its corresponding carboxylic acid. The carboxylic acid is not directly formed in the first place as the reaction takes place under alkaline conditions. The ionic equations for the overall reaction are shown below; R refers to an alkyl group. [Ag(NH3)2] (aq) + e Ag (s) + 2 NH3 (aq) RCHO (aq) + 3 OH RCOO + 2 H2O + 2 e
+ -

The negative result for the test is no precipitate of silver formed when the carbonyl to be tested is added. A ketone will give a negative result because it cannot be oxidized easily. A ketone has no available hydrogen atom attached to the carbonyl carbon, meaning it can't be so easily oxidized - unlike an aldehyde, which has this hydrogen atom. Tollens' reagent is also a test for alkynes with a triple bond in the 1-position. A yellow precipitate of the metal acetylide is formed in this case.

Fehling test Fehling's solution is a chemical test used to differentiate between watersoluble aldehyde and ketone functional groups, and as a test for monosaccharides. The test was developed by German chemist Hermann von Fehling in 1849. Fehling's solution is always prepared fresh in the laboratory. It is made initially as two separate solutions, known as Fehling's A and Fehling's B. Fehling's A is a blue aqueous solution of copper(II) sulfate, while Fehling's B is a clear solution of aqueous potassium sodium tartrate (also known as Rochelle salt) and a strong alkali (commonly sodium hydroxide). Equal volumes of the two mixtures are mixed together to get the final Fehling's solution, which is a deep blue colour. In this final mixture, aqueous tartrate ions from the dissolved Rochelle salt chelateto Cu
2+

(aq) ions from the dissolved copper(II) sulfate, as bidentate ligands giving
4-

the bistartratocuprate(II) complex as shown below. The tartarate ions, by complexing copper prevent the formation of Cu(OH)2 from the reaction of CuSO4.2H2O and NaOH present in the solution. Fehling's can be used to determine whether a carbonyl-containing compound is an aldehyde or a ketone. The bistartratocuprate(II) complex in Fehling's solution is an oxidizing agent and the active reagent in the test. The compound to be tested is added to the Fehling's solution and the mixture is heated. Aldehydes are oxidized, giving a positive result, but ketones do not react, unless they are alpha-hydroxy-ketones. The bistartratocuprate(II) complex oxidizes the aldehyde to a carboxylate anion, and in the process the copper(II) ions of the complex are reduced to copper(I) ions. Red copper(I) oxide then precipitates out of the reaction mixture, which indicates a positive result i.e. that redox has taken place (this is the same positive result as with Benedict's solution. A negative result is the absence of the red precipitate; it is important to note that Fehling's will not work with aromatic aldehydes; in this case Tollens' reagent should be used. Fehling's test can be used as a generic test for monosaccharides. It will give a positive result for aldose monosaccharides (due to the oxidisable aldehyde group) but also for ketose monosaccharides, as they are converted to aldoses by the base in the reagent, and then give a positive result. For this reason, Fehling's reagent is sometimes referred to as a general test for monosaccharides. Fehling's can be used to screen for glucose in urine, thus detecting diabetes. Another use is in conversion / breakdown of starch to glucose syrup and maltodextrins, to measure the amount of reducing sugars and calculating the dextrose equivalent (DE) of the starch sugar.

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