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{{chembox {{chembox
| Verifiedfields = changed | Verifiedfields = changed
| Watchedfields = changed | Watchedfields = changed
| verifiedrevid = 477191825 | verifiedrevid = 477191825
| ImageFile = 2,4-Dinitrophenylhydrazin.svg | ImageFile = 2,4-Dinitrophenylhydrazin.svg
| ImageSize = 110px | ImageSize = 110px
| ImageFileL1 = 2,4-dinitrophenylhydrazine-from-xtal-3D-balls.png | ImageFileL1 = 2,4-dinitrophenylhydrazine-from-xtal-3D-balls.png
| ImageFileR1 = 24dnp3d.png | ImageFileR1 = 24dnp3d.png
| PIN = (2,4-Dinitrophenyl)hydrazine | PIN = (2,4-Dinitrophenyl)hydrazine
| OtherNames = 2,4-DNPH<br />2,4-DNP<br />Brady's reagent<br />Borche's reagent | OtherNames = 2,4-DNPH<br />2,4-DNP<br />DNPH<br />Brady's reagent<br />Borche's reagent
|Section1={{Chembox Identifiers | Section1 = {{Chembox Identifiers
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 3001507 | ChemSpiderID = 3001507
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| InChI = 1/C6H6N4O4/c7-8-5-2-1-4(9(11)12)3-6(5)10(13)14/h1-3,8H,7H2 | InChI = 1/C6H6N4O4/c7-8-5-2-1-4(9(11)12)3-6(5)10(13)14/h1-3,8H,7H2
| InChIKey = HORQAOAYAYGIBM-UHFFFAOYAM | InChIKey = HORQAOAYAYGIBM-UHFFFAOYAM
| ChEBI_Ref = {{ebicite|changed|EBI}} | ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 66932 | ChEBI = 66932
| ChEMBL_Ref = {{ebicite|correct|EBI}} | ChEMBL_Ref = {{ebicite|correct|EBI}}
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| CASNo_Ref = {{cascite|correct|CAS}} | CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 119-26-6 | CASNo = 119-26-6
| PubChem = | PubChem = 3772977
| EC_number = 204-309-3
| UNII = 1N39KD7QPJ
| SMILES = c1cc(c(cc1(=O))(=O))NN | SMILES = c1cc(c(cc1(=O))(=O))NN
}} }}
|Section2={{Chembox Properties | Section2 = {{Chembox Properties
| Formula = C<sub>6</sub>H<sub>6</sub>N<sub>4</sub>O<sub>4</sub> | Formula = C<sub>6</sub>H<sub>6</sub>N<sub>4</sub>O<sub>4</sub>
| MolarMass = 198.14 g/mol | MolarMass = 198.14 g/mol
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| Solubility = Slight | Solubility = Slight
}} }}
|Section7={{Chembox Hazards | Section7 = {{Chembox Hazards
| ExternalSDS = | ExternalSDS =
| MainHazards = Flammable, possibly carcinogenic | MainHazards = Flammable, possibly carcinogenic
| FlashPt = | FlashPt =
| AutoignitionPt = | AutoignitionPt =
| GHSPictograms = {{GHS02}}{{GHS07}}
| GHSSignalWord = Warning
| HPhrases = {{H-phrases|228|302|319}}
| PPhrases = {{P-phrases|210|240|241|264|270|280|301+312|305+351+338|330|337+313|370+378|501}}
}} }}
}} }}


'''2,4-Dinitrophenylhydrazine''' ('''DNPH''', '''Brady's reagent''', '''Borche's reagent''') is the ] C<sub>6</sub>H<sub>3</sub>(NO<sub>2</sub>)<sub>2</sub>NHNH<sub>2</sub>. Dinitrophenylhydrazine is a red to orange solid. It is a substituted ], and is often used to qualitatively test for ]s associated with ]s and ]s. The hydrazone ] can also be used as evidence toward the identity of the original compound. The melting point of the derivative is often used, with reference to a database of values, to determine the identity of a specific carbonyl compound. It is relatively sensitive to ] and ]; it is a shock explosive so care must be taken with its use.<ref>{{cite news |url=https://www.theguardian.com/education/2016/nov/02/bomb-disposal-squads-detonate-chemical-stocks-english-schools-a-level-chemistry-24-dnp |newspaper=The Guardian |title=Bomb disposal squads detonate chemical stocks in British schools |date=2 November 2016 |accessdate=19 March 2018 }}</ref> To reduce its explosive hazard, it is usually supplied wet. '''2,4-Dinitrophenylhydrazine''' ('''2,4-DNPH''' or '''DNPH''') is the ] C<sub>6</sub>H<sub>3</sub>(NO<sub>2</sub>)<sub>2</sub>NHNH<sub>2</sub>. DNPH is a red to orange solid. It is a substituted ]. The solid is relatively sensitive to ] and ]. For this reason DNPH is usually handled as a wet powder. DNPH is a precursor to the drug ].


==Synthesis== ==Synthesis==
2,4-Dinitrophenylhydrazine is commercially available usually as a wet powder. It can be prepared by the reaction of ] with ]:<ref>{{OrgSynth | author = Allen, C. F. H. | prep = cv2p0228 | title = 2,4-Dinitrophenylhydrazine | collvol = 2 | collvolpages = 228 | year = 1933 | volume = 13 | pages = 36 | doi = 10.15227/orgsyn.013.0036}}</ref> It can be prepared by the reaction of ] with ]:<ref>{{OrgSynth | author = Allen, C. F. H. | prep = cv2p0228 | title = 2,4-Dinitrophenylhydrazine |year = 1933 | volume = 13 | pages = 36 | doi = 10.15227/orgsyn.013.0036}}</ref>


:] :]


⚫ ==DNP test==
Brady's reagent is prepared by dissolving 2,4-dinitrophenylhydrazine in a solution containing ] and some concentrated ].
DNPH is a reagent in instructional laboratories on ]. '''Brady's reagent''' or '''Borche's reagent''', is prepared by dissolving DNPH in a solution containing ] and some concentrated ]. This solution is used to ] ]s and ]s. A positive test is signalled by the formation of a yellow, orange or red ] of the dinitrophenylhydrazone. Aromatic carbonyls give red precipitates whereas ] carbonyls give more yellow color.<ref>{{cite book |last1=Mohrig |first1=Jerry R. |last2=Hammond |first2=Christina Noring |last3=Morrill |first3=Terence C. |last4=Neckers |first4=Douglas C. |title=Experimental Organic Chemistry: A Balanced Approach, Macroscale and Microscale |date=1998 |publisher=W.H. Freeman and Company |location=New York |isbn=0-7167-2818-4 |url=https://archive.org/details/experimentalorga00mohr/page/n5/mode/2up |page=530 |url-access=registration}}</ref> The reaction between DNPH and a generic ketone to form a ] is shown below:

⚫ ==Brady's test==
2,4-Dinitrophenylhydrazine can be used to qualitatively ] the carbonyl functionality of a ] or ] functional group. A positive test is signalled by the formation of a yellow, orange or red ] (known as a ]). If the carbonyl compound is aromatic, then the precipitate will be red; if aliphatic, then the precipitate will have a more yellow color.<ref>http://wiki.colby.edu/download/attachments/110920618/Experiment+%232.pdf?version=1&modificationDate=1265312071267</ref> The reaction between 2,4-dinitrophenylhydrazine and a generic ketone to form a ] is shown below:


:RR'C=O &nbsp; + &nbsp; C<sub>6</sub>H<sub>3</sub>(NO<sub>2</sub>)<sub>2</sub>NHNH<sub>2</sub> &nbsp; → &nbsp; C<sub>6</sub>H<sub>3</sub>(NO<sub>2</sub>)<sub>2</sub>NHN=CRR' &nbsp; + &nbsp; H<sub>2</sub>O :RR'C=O &nbsp; + &nbsp; C<sub>6</sub>H<sub>3</sub>(NO<sub>2</sub>)<sub>2</sub>NHNH<sub>2</sub> &nbsp; → &nbsp; C<sub>6</sub>H<sub>3</sub>(NO<sub>2</sub>)<sub>2</sub>NHN=CRR' &nbsp; + &nbsp; H<sub>2</sub>O


This reaction is, overall, a ] as two molecules joining together with loss of water. Mechanistically, it is an example of ]: nucleophilic addition of the -NH<sub>2</sub> group to the C=O carbonyl group, followed by the elimination of a H<sub>2</sub>O molecule:<ref>Adapted from ''Chemistry in Context'', 4th Edition, 2000, Graham Hill and John Holman</ref> This reaction is, overall, a ] as two molecules joining together with loss of water. Mechanistically, it is an example of ]: nucleophilic addition of the -NH<sub>2</sub> group to the C=O carbonyl group, followed by the elimination of a H<sub>2</sub>O molecule:<ref>Adapted from ''Chemistry in Context'', 4th Edition, 2000, Graham Hill and John Holman</ref>


:]. Selected parameters: C=N, 128 pm; N-N, 1.38 pm, N-N-C(Ar), 119<ref>{{cite journal |doi=10.1107/S1600536806048112|title=Benzophenone 2,4-dinitrophenylhydrazone|year=2006|last1=Tameem|first1=Abdassalam Abdelhafiz|last2=Salhin|first2=Abdussalam|last3=Saad|first3=Bahruddin|last4=Rahman|first4=Ismail Ab.|last5=Saleh|first5=Muhammad Idiris|last6=Ng|first6=Shea-Lin|last7=Fun|first7=Hoong-Kun|journal=Acta Crystallographica Section E|volume=62|issue=12|pages=o5686–o5688}}</ref>]]
:]
⚫ ] 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 DNPH was developed by Brady and Elsmie.<ref>{{cite journal | author1 = Brady, Oscar L. | author2 = Elsmie, Gladys V. | title = The use of 2:4-dinitrophenylhydrazine as a reagent for aldehydes and ketones | journal = ] | volume = 51 | pages = 77–78 | year = 1926 | doi = 10.1039/AN9265100077 | issue = 599 | bibcode = 1926Ana....51...77B}}</ref> Modern spectroscopic and spectrometric techniques have superseded these techniques.


⚫ DNPH does not react with other carbonyl-containing functional groups such as ], ]s, and ], for which there is resonance-associated stability as a lone-pair of electrons interacts with the ] 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.
⚫ ] is added to a solution of 2,4-DNPH and heated, an orange-red precipitate forms.]]
⚫ Crystals of different hydrazones have characteristic melting and boiling points, allowing the identity of a substance to be determined in a method known as ]. In particular, the use of 2,4-dinitrophenylhydrazine was developed by Brady and Elsmie.<ref>{{cite journal | author1 = Brady, Oscar L. | author2 = Elsmie, Gladys V. | title = The use of 2:4-dinitrophenylhydrazine as a reagent for aldehydes and ketones | journal = ] | volume = 51 | pages = 77–78 | year = 1926 | doi = 10.1039/AN9265100077 | issue = 599 | bibcode = 1926Ana....51...77B}}</ref> Modern spectroscopic and spectrometric techniques have superseded these techniques.


==Safety==
⚫ Dinitrophenylhydrazine does not react with other carbonyl-containing functional groups such as ], ]s, and ], for which there is resonance-associated stability as a lone-pair of electrons interacts with the ] 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.
Dry DNPH is friction and shock sensitive. For this reason, it’s supplied damp or ‘wetted’ when a school purchases it from a chemical supplier.<ref>{{cite web |title=What is 2,4-DNPH and Why Are Schools Carrying Out Controlled Explosions? |url=https://www.compoundchem.com/2016/11/07/24-dnp/ |accessdate=26 October 2022 |website=Compound Interest|date=7 November 2016 }}</ref> If DNPH is stored improperly and left to dry out, it can become explosive.
It is an artificial uncoupler of the electron transport chain (ETC).<ref>{{cite news |url=https://www.theguardian.com/education/2016/nov/02/bomb-disposal-squads-detonate-chemical-stocks-english-schools-a-level-chemistry-24-dnp |newspaper=The Guardian |title=Bomb disposal squads detonate chemical stocks in British schools |date=2 November 2016 |accessdate=19 March 2018 }}</ref>


==See also== ==See also==
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{{Hydrazines}} {{Hydrazines}}


{{DEFAULTSORT:Dinitrophenylhydrazine, 2,4-}} {{DEFAULTSORT:Dinitrophenylhydrazine, 2, 4-}}
] ]
] ]
] ]

Latest revision as of 09:16, 24 January 2024

2,4-Dinitrophenylhydrazine
Names
Preferred IUPAC name (2,4-Dinitrophenyl)hydrazine
Other names 2,4-DNPH
2,4-DNP
DNPH
Brady's reagent
Borche's reagent
Identifiers
CAS Number
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.003.918 Edit this at Wikidata
EC Number
  • 204-309-3
KEGG
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C6H6N4O4/c7-8-5-2-1-4(9(11)12)3-6(5)10(13)14/h1-3,8H,7H2Key: HORQAOAYAYGIBM-UHFFFAOYSA-N
  • InChI=1/C6H6N4O4/c7-8-5-2-1-4(9(11)12)3-6(5)10(13)14/h1-3,8H,7H2Key: HORQAOAYAYGIBM-UHFFFAOYAM
SMILES
  • c1cc(c(cc1(=O))(=O))NN
Properties
Chemical formula 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.
Solubility in water Slight
Hazards
Occupational safety and health (OHS/OSH):
Main hazards Flammable, possibly carcinogenic
GHS labelling:
Pictograms GHS02: FlammableGHS07: Exclamation mark
Signal word Warning
Hazard statements H228, H302, H319
Precautionary statements P210, P240, P241, P264, P270, P280, P301+P312, P305+P351+P338, P330, P337+P313, P370+P378, P501
Safety data sheet (SDS) MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). ☒N verify (what is  ?) Infobox references
Chemical compound

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

Synthesis

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

DNP test

DNPH is a reagent in instructional laboratories on qualitative organic analysis. Brady's reagent or Borche's reagent, is prepared by dissolving DNPH 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. The reaction between DNPH 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:

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
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 DNPH was developed by Brady and Elsmie. Modern spectroscopic and spectrometric techniques have superseded these techniques.

DNPH 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

Dry DNPH is friction and shock sensitive. For this reason, it’s supplied damp or ‘wetted’ when a school purchases it from a chemical supplier. If DNPH is stored improperly and left to dry out, it can become explosive. It is an artificial uncoupler of the electron transport chain (ETC).

See also

References

  1. Allen, C. F. H. (1933). "2,4-Dinitrophenylhydrazine". Organic Syntheses. 13: 36. doi:10.15227/orgsyn.013.0036.
  2. Mohrig, Jerry R.; Hammond, Christina Noring; Morrill, Terence C.; Neckers, Douglas C. (1998). Experimental Organic Chemistry: A Balanced Approach, Macroscale and Microscale. New York: W.H. Freeman and Company. p. 530. ISBN 0-7167-2818-4.
  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. 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. "What is 2,4-DNPH and Why Are Schools Carrying Out Controlled Explosions?". Compound Interest. 7 November 2016. Retrieved 26 October 2022.
  7. "Bomb disposal squads detonate chemical stocks in British schools". The Guardian. 2 November 2016. Retrieved 19 March 2018.
Hydrazines
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