An alternative to Brady’s test?

In one of our practicals at the chemistry teaching labs of Queen Mary University of London our students are provided with a mixture of 2 unknown organic compounds that they have to separate and identify with the use of spectroscopic methods and analytical qualitative tests. One of the most common tests during the practical is the Brady’s test for the identification of aldehydes and ketones. In this test a solution of 2,4-Dinitrophenylhydrazine (2,4-DNP) is reacted with the unknown mixture and if there is an aldehyde or a ketone, a yellow to deep red precipitate is observed as a consequence of the formation of the corresponding 2,4-dinitrophenylhydrazone.

Here is a nice video from FranklyChemistry showing examples of how a positive Brady’s test looks like:

For the practical this year I realised we had run out of 2,4-DNP and we needed to buy some more. I tried to buy 2,4-DNP from usual providers such as Sigma Aldrich, Alfa Aesar and VWR among others just to find that the chemical has been discontinued because is explosive.

I thought of alternative tests like Tollen’s and Fehling’s but unfortunately they are not general for carbonyl compounds and they only work for aldehydes easy to oxidise. My next move was to consult with colleagues in the department and in the internet community. Networks like researchgate and projects like #realtimechem on twitter are incredibly useful to connect and exchange knowledge with chemists around the world.

This time, very interesting suggestions as alternatives to 2,4-DNP came from Researchgate, (credit to: Joe Olechno, Matthew Mcgrath and Americo Lemos):

-4-Hydrazino-7-nitro-benzofurazan has been used to make fluorescent derivatives of aliphatic aldehydes including reducing sugars.

-4-Amino-3-hydrazino-5-mercapto-1,2,4-triazole (also known as purpald): Used for the determination of formaldehyde, gives a purple colour with aldehydes and also reacts with ketones but the product is not coloured.

-2,4-dichlorophenylhydrazine as a non-explosive alternative.

I still have to test this alternatives and if successful I hope I can write a post explaining the experience.

Ironically, I have recently found that a suitable alternative to 2,4-DNP is actually 2,4-DNP but as a solution in phosphoric acid. The 2,4-DNP solution in phosphoric acid can be purchased from Sigma Aldrich and it is advertised as an alternative to the explosive 2,4-DNP.

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2 thoughts on “An alternative to Brady’s test?”

  1. Hi have you been able to evaluate using 2’4.DNP in phosphoric acid against 2’4.DCPH in lab tests . The recent stories of badly stored DNPH having to be disposed of by bomb squads has made H/D depts in education some what jumpy. We will also need to find a replacement and if you have evaluated the substances mentioned above it would be most useful

    Liked by 1 person

    1. Hi Josie,

      We have tried 2,4-DNP in phosphoric acid to prepare a derivative of cyclohexanone. The reagent is a bit annoying to handle because is very viscous but it instantaneously forms a precipitate by direct reaction even without solvent. We are still struggling a bit with the protocol to isolate the solid derivative but I can say that 2,4-DNP in phosphoric acid works well as a qualitative test for carbonyl compounds. So far we have only found the reagent in Sigma-Aldrich. And there must be a lot of demand because it takes ages to be delivered.

      http://www.sigmaaldrich.com/catalog/product/sial/42215?lang=en&region=GB

      Regards
      David

      Like

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