2,4-Dinitrophenylhydrazine

2,4-Dinitrophenylhydrazine (DNPH) is the organic compound C6H3(NO2)2NHNH2. Dinitrophenylhydrazine is a red to orange solid. It is a substituted hydrazine. The solid is relatively sensitive to shock and friction. For this reason dinitrophenylhydrazine is usually handled as a wet powder. DNPH is a precursor to the drug Sivifene.

2,4-Dinitrophenylhydrazine
Names
Preferred IUPAC name
(2,4-Dinitrophenyl)hydrazine
Other names
2,4-DNPH
2,4-DNP
Brady's reagent
Borche's reagent
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.918
EC Number
  • 204-309-3
KEGG
UNII
Properties
C6H6N4O4
Molar mass 198.14 g/mol
Appearance Red or orange powder
Melting point 198 to 202 °C (388 to 396 °F; 471 to 475 K) dec.
Slight
Hazards
Main hazards Flammable, possibly carcinogenic
Safety data sheet MSDS
GHS pictograms
GHS Signal word Warning
H228, H302, H319
P210, P240, P241, P264, P270, P280, P301+312, P305+351+338, P330, P337+313, P370+378, P501
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
N verify (what is YN ?)
Infobox references

Synthesis

It can be prepared by the reaction of hydrazine sulfate with 2,4-dinitrochlorobenzene:[1]

DNP test

DNPH is a reagent in instructional laboratories on qualitative organic analysis. Brady's reagent or Borche's reagent, is prepared by dissolving 2,4-dinitrophenylhydrazine in a solution containing methanol and some concentrated sulfuric acid. This solution is used to detect ketones and aldehydes. A positive test is signalled by the formation of a yellow, orange or red precipitate of the dinitrophenylhydrazone. Aromatic carbonyls give red precipitates whereas aliphatic carbonyls give more yellow color.[2] The reaction between 2,4-dinitrophenylhydrazine and a generic ketone to form a hydrazone is shown below:

RR'C=O   +   C6H3(NO2)2NHNH2   →   C6H3(NO2)2NHN=CRR'   +   H2O

This reaction is, overall, a condensation reaction as two molecules joining together with loss of water. Mechanistically, it is an example of addition-elimination reaction: nucleophilic addition of the -NH2 group to the C=O carbonyl group, followed by the elimination of a H2O molecule:[3]

X-ray structure of DNP-derived hydrazone of benzophenone. Selected parameters: C=N, 128 pm; N-N, 1.38 pm, N-N-C(Ar), 119[4]
When 3-heptanone is added to a solution of 2,4-DNPH and heated, an orange-red precipitate forms.

DNP-derived hydrazones have characteristic melting points, facilitating identification of the carbonyl. In particular, the use of 2,4-dinitrophenylhydrazine was developed by Brady and Elsmie.[5] Modern spectroscopic and spectrometric techniques have superseded these techniques.

Dinitrophenylhydrazine does not react with other carbonyl-containing functional groups such as carboxylic acids, amides, and esters, for which there is resonance-associated stability as a lone-pair of electrons interacts with the p orbital of the carbonyl carbon resulting in increased delocalization in the molecule. This stability would be lost by addition of a reagent to the carbonyl group. Hence, these compounds are more resistant to addition reactions. Also, with carboxylic acids, there is the effect of the compound acting as a base, leaving the resulting carboxylate negatively charged and hence no longer vulnerable to nucleophilic attack.

Safety

Explosions have resulted from the use of DNPH.[6]

See also

References
  1. Allen, C. F. H. (1933). "2,4-Dinitrophenylhydrazine". Organic Syntheses. 13: 36. doi:10.15227/orgsyn.013.0036.
  2. http://wiki.colby.edu/download/attachments/110920618/Experiment+%232.pdf?version=1&modificationDate=1265312071267
  3. Adapted from Chemistry in Context, 4th Edition, 2000, Graham Hill and John Holman
  4. Tameem, Abdassalam Abdelhafiz; Salhin, Abdussalam; Saad, Bahruddin; Rahman, Ismail Ab.; Saleh, Muhammad Idiris; Ng, Shea-Lin; Fun, Hoong-Kun (2006). "Benzophenone 2,4-dinitrophenylhydrazone". Acta Crystallographica Section e Structure Reports Online. 62 (12): o5686–o5688. doi:10.1107/S1600536806048112.
  5. Brady, Oscar L.; Elsmie, Gladys V. (1926). "The use of 2:4-dinitrophenylhydrazine as a reagent for aldehydes and ketones". Analyst. 51 (599): 77–78. Bibcode:1926Ana....51...77B. doi:10.1039/AN9265100077.
  6. "Bomb disposal squads detonate chemical stocks in British schools". The Guardian. 2 November 2016. Retrieved 19 March 2018.
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