Benzidine

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Benzidine
Benzidine 200.svg
Identifiers
CAS number 92-87-5 YesY
PubChem 7111
ChemSpider 6844 YesY
KEGG C16444 YesY
ChEMBL CHEMBL15901 YesY
Jmol-3D images Image 1
Properties
Molecular formula C12H12N2
Molar mass 184.24 g/mol
Appearance Grayish-yellow, reddish-gray, or white crystalline powder[1]
Density 1.25 g/cm3
Melting point 122 to 125 °C (252 to 257 °F; 395 to 398 K)
Boiling point 400 °C (752 °F; 673 K)
Solubility in water 0.94 g/100 mL at 100 °C
Related compounds
Related compounds biphenyl
Hazards
Main hazards carcinogenic
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Benzidine (trivial name), also called 4,4'-diaminobiphenyl (systematic name), is the organic compound with the formula (C6H4NH2)2. it is an aromatic amine. It is a component of a test for cyanide. Related derivatives are used in the production of dyes. Benzidine has been linked to bladder and pancreatic cancer.[2]

Synthesis and properties[edit]

Benzidine is prepared in a two step process from nitrobenzene. First, the nitrobenzene is converted to 1,2-diphenylhydrazine, usually using iron powder as the reducing agent. Treatment of this hydrazine with mineral acids induces a rearrangement reaction to 4,4'-benzidine. Smaller amounts of other isomers are also formed.[3] The benzidine rearrangement, which proceeds intramolecularly, is a classic mechanistic puzzle in organic chemistry.[4]

Benzidine rearrangement.png

The conversion is described as a [5,5]sigmatropic reaction.[5][6]

Benzidine rearrangement mechanism

In terms of its physical properties, 4,4'-benzidine is poorly soluble in cold water but can be recrystallized from hot water, where it crystallises as the monohydrate. It is dibasic, the deprotonated species has Ka values of 9.3 × 10−10 and 5.6 × 10−11. Its solutions react with oxidizing agents to give deeply coloured quinone-related derivatives.

Applications[edit]

As with some other aromatic amines such as 2-Naphthylamine, benzidine has been significantly withdrawn from use in most industries because it is so carcinogenic. In the past, benzidine was used to test for blood. An enzyme in blood causes the oxidation of benzidine to a distinctively blue-coloured derivative. The test for cyanide relies on similar reactivity. Such applications have largely been replaced by methods using phenolphthalein/hydrogen peroxide and luminol.

Related 4,4’-benzidines[edit]

A variety of derivatives of 4,4’-benzidine are commercially produced on the scale of one to a few thousand kilograms per year, mainly as precursors to dyes and pigments.[3] These derivatives include, in order of scale, the following:

Safety[edit]

In August 2010 benzidine dyes were included in the U.S. EPA's List of Chemicals of Concern.[7]

References[edit]

  1. ^ NIOSH Pocket Guide to Chemical Hazards Centers for Disease Control and Prevention. 2011-04-04
  2. ^ "Known and Probable Carcinogens". American Cancer Society. 2011-06-29. 
  3. ^ a b Schwenecke, H.; Mayer, D. (2005). "Benzidine and Benzidine Derivatives". Ullmann’s Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_539. 
  4. ^ March, J. (1992). Advanced Organic Chemistry (5th ed.). New York: J. Wiley and Sons. ISBN 0-471-60180-2. 
  5. ^ Shine, H. J.; Zmuda, H.; Park, K. H.; Kwart, H.; Horgan, A. G.; Collins, C.; Maxwell, B. E. (1981). "Mechanism of the benzidine rearrangement. Kinetic isotope effects and transition states. Evidence for concerted rearrangement". Journal of the American Chemical Society 103 (4): 955–956. doi:10.1021/ja00394a047. .
  6. ^ Shine, H. J.; Zmuda, H.; Park, K. H.; Kwart, H.; Horgan, A. G.; Brechbiel, M. (1982). "Benzidine rearrangements. 16. The use of heavy-atom kinetic isotope effects in solving the mechanism of the acid-catalyzed rearrangement of hydrazobenzene. The concerted pathway to benzidine and the nonconcerted pathway to diphenyline". Journal of the American Chemical Society 104 (9): 2501–2509. doi:10.1021/ja00373a028. 
  7. ^ "Benzidine Dyes Action Plan Summary". U. S. Environmental Protection Agency. 2010-08-18.