Tetramethylphenylenediamine

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Tetramethylphenylenediamine
Tetramethylphenylendiamine.svg
Names
Preferred IUPAC name
N1,N1,N4,N4-Tetramethylbenzene-1,4-diamine
Other names
  • N,N,N′,N′-Tetramethyl-1,4-phenylenediamine
  • TMPD
  • Wurster's reagent
  • TL-85
, , also known as TMPD 1,4-Bis(dimethylamino)benzene
Identifiers
3D model (JSmol)
AbbreviationsTMPD
ChEMBL
ChemSpider
ECHA InfoCard 100.002.574 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 202-831-6
PubChem CID
UNII
  • InChI=1S/C10H16N2/c1-11(2)9-5-7-10(8-6-9)12(3)4/h5-8H,1-4H3 X mark.svgN
    Key: CJAOGUFAAWZWNI-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C10H16N2/c1-11(2)9-5-7-10(8-6-9)12(3)4/h5-8H,1-4H3
    Key: CJAOGUFAAWZWNI-UHFFFAOYAJ
  • CN(C)c1ccc(cc1)N(C)C
Properties
C10H16N2
Molar mass 164.252 g·mol−1
AppearanceColorless solid
Density 1.08 g/cm3
Melting point 51 °C (124 °F; 324 K)
Boiling point 260 °C (500 °F; 533 K)
Slightly in cold water more so in hot water
Solubility in other solventsSoluble in alcohol, chloroform
Acidity (pKa)6.35
Hazards
Flash point 110 °C (230 °F; 383 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tetramethylphenylenediamine (TMPD) is an organic compound with the formula C6H4(N(CH3)2)2. It is most studied of three isomers of this formula. It is a colorless solid. With two dimethylamino substituents, the ring is particularly electron rich.

Redox behavior

One-electron oxidation of TMPD gives the deep blue radical cation called Wurster's blue, C6H4(N(CH3)2)+2. It was one of the first radical cations to be reported. Many properties have been described including its rapid rate of self-exchange: [1]

C6H4(N(CH3)2)2 + [C6H4(N(CH3)2)2]+ ⇌ [C6H4(N(CH3)2)2]+ + C6H4(N(CH3)2)2

X-ray crystallography of the TMPD and its iodide salt reveals that oxidation most strongly contracts the C-N(CH3)2 and the HC---CH bonds, indicating that oxidation gives a quinoid-like species. [2]

Structure of 1,4-Bis(dimethylamino)benzene and Its Iodide Salt
CompoundC(phenyl)-NNC---CHHC---CHCH3---N
TMPD1.4081.401.381.46
[TMPD]+I-1.3441.4221.361.454

The monocation illustrates an early step in the oxidation of p-phenylenediamine derivatives, which are widely used for hair dying. [3] N,N-Dimethylphenylenediamine (H2NC6H4N(CH3)2) also easily oxidizes to a radical cation, called Wurster's Red.

The hydrochloride salt of TMPD has been used as a redox indicator in the oxidase test and is also used in electron transport chain analysis as it is capable of donating electrons to cytochrome c. The midpoint potential for titration of the first electron is given as 0.276 V vs Standard hydrogen electrode, and this transition is useful in potentiometric titrations as both a redox mediator and indicator.

History

TMPD was reported in 1879 by Casmir Wurster (7 August 1854 – 29 November 1913), hence it is known as Wurster's reagent. [4]

Further reading

References

  1. ↑ Nelsen, Stephen F. (1993). "Internal Geometry Relaxation Effects on Electron Transfer Rates of Amino Centered Systems". Advances in Electron Transfer Chemistry. pp. 167–189. doi:10.1016/b978-1-4831-0093-7.50007-3. ISBN   978-1-4831-0093-7.
  2. ↑ Ikemoto, I.; Katagiri, G.; Nishimura, S.; Yakushi, K.; Kuroda, H. (1979). "Structure of N , N , N ', N '-tetramethyl- p -phenylenediamine". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry. 35 (9): 2264–2265. Bibcode:1979AcCrB..35.2264I. doi:10.1107/S0567740879009018.
  3. ↑ Morel, Olivier J. X.; Christie, Robert M. (2011). "Current Trends in the Chemistry of Permanent Hair Dyeing". Chemical Reviews. 111 (4): 2537–2561. doi:10.1021/cr1000145. PMID   21265503.
  4. ↑ Wurster, C.; Schobig, E. (1879). "Ueber die Einwirkung oxydirender Agentien auf Tetramethylparaphenylendiamin". Berichte der Deutschen Chemischen Gesellschaft. 12 (2): 1807–1813. doi:10.1002/cber.187901202156.
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