4-Aminodiphenylamine is a diphenylamine with an additional amine substituent. This dimer of aniline has various industrial uses, including as a hair dye ingredient, but also has raised concerns about toxicity by skin contact.[1] It is also a starting material for the synthesis of 6PPD, an antiozonant for various rubber products.[2] A colorimetric test for the quantitative analysis of nitrite, at levels below 100 nanograms per milliliter, is based on nitrite-catalyzed coupling of 4-aminodiphenylamine with N,N-dimethylaniline.[3]
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| Names | |
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| Preferred IUPAC name
N1-Phenylbenzene-1,4-diamine | |
Other names
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| Identifiers | |
3D model (JSmol)
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| 908935 | |
| ChEBI | |
| ChEMBL | |
| ChemSpider | |
| ECHA InfoCard | 100.002.684 |
| EC Number |
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| 241334 | |
PubChem CID
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| RTECS number |
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| UNII | |
| UN number | 1673 |
CompTox Dashboard (EPA)
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| Properties | |
| C12H12N2 | |
| Molar mass | 184.242 g·mol−1 |
| Appearance | purple–black or dark purple |
| Density | 1.09 g/mL |
| Melting point | 75 °C (167 °F; 348 K) |
| Boiling point | 354 °C (669 °F; 627 K) |
| Hazards | |
| GHS labelling: | |
 
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| Warning | |
| H302, H317, H319, H410 | |
| P261, P264, P270, P272, P273, P280, P301 P312, P302 P352, P305 P351 P338, P321, P330, P333 P313, P337 P313, P363, P391, P501 | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Synthesis
editThe most common route of industrial production is by the metal catalysed reaction of aniline with 4‑nitrochlorobenzene to give 4‑nitrodiphenylamine (Buchwald–Hartwig amination):
Subsequent hydrogenation gives 4-aminodiphenylamine.[4] An alternative is the direct reaction of nitrobenzene with aniline via a nucleophilic aromatic substitution of hydrogen (vicarious nucleophilic substitution).[5][6] This again requires a reduction step but is a good example of industrial green chemistry as it eliminates the need for organochlorine starting materials and metal catalysts.
References
edit- ^ Khanna, S. K.; Tewari, Pushpa; Joshi, Anil; Singh, G. B. (1987). "Studies on the skin uptake and efflux kinetics of N-phenyl-p-phenylenediamine: an aromatic amine intermediate". International Journal of Cosmetic Science. 9 (3): 137–147. doi:10.1111/j.1467-2494.1987.tb00470.x. PMID 19456976. S2CID 205555627.137-147&rft.date=1987&rft_id=https://api.semanticscholar.org/CorpusID:205555627#id-name=S2CID&rft_id=info:pmid/19456976&rft_id=info:doi/10.1111/j.1467-2494.1987.tb00470.x&rft.aulast=Khanna&rft.aufirst=S. K.&rft.au=Tewari, Pushpa&rft.au=Joshi, Anil&rft.au=Singh, G. B.&rfr_id=info:sid/en.wikipedia.org:4-Aminodiphenylamine" class="Z3988">
- ^ Engels, Hans-Wilhelm; Weidenhaupt, Herrmann‐Josef; Pieroth, Manfred; Hofmann, Werner; Menting, Karl‐Hans; Mergenhagen, Thomas; Schmoll, Ralf; Uhrlandt, Stefan (2007). "Rubber, 4. Chemicals and Additives". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a23_365.pub2. ISBN 978-3527306732.
- ^ Kadowaki, Ryoichi; Nakano, Shigenori; Kawashima, Takuji (1999). "Sensitive flow injection colorimetry of nitrite by catalytic coupling of N-phenyl-p-phenylenediamine with N,N-dimethylaniline". Talanta. 48 (1): 103–107. doi:10.1016/s0039-9140(98)00227-6. PMID 18967448.103-107&rft.date=1999&rft_id=info:doi/10.1016/s0039-9140(98)00227-6&rft_id=info:pmid/18967448&rft.aulast=Kadowaki&rft.aufirst=Ryoichi&rft.au=Nakano, Shigenori&rft.au=Kawashima, Takuji&rfr_id=info:sid/en.wikipedia.org:4-Aminodiphenylamine" class="Z3988">
- ^ Bochkarev, V.V.; Soroka, L.S.; Bashkin, J.K. (December 2016). "Resource-efficient technology to produce 4-aminodiphenylamine". Resource-Efficient Technologies. 2 (4): 215–224. doi:10.1016/j.reffit.2016.10.011.215-224&rft.date=2016-12&rft_id=info:doi/10.1016/j.reffit.2016.10.011&rft.aulast=Bochkarev&rft.aufirst=V.V.&rft.au=Soroka, L.S.&rft.au=Bashkin, J.K.&rft_id=https://doi.org/10.1016%2Fj.reffit.2016.10.011&rfr_id=info:sid/en.wikipedia.org:4-Aminodiphenylamine" class="Z3988">
- ^ Stern, Michael K.; Hileman, Fredrick D.; Bashkin, James K. (November 1992). "The direct coupling of aniline and nitrobenzene: a new example of nucleophilic aromatic substitution for hydrogen". Journal of the American Chemical Society. 114 (23): 9237–9238. doi:10.1021/ja00049a095.9237-9238&rft.date=1992-11&rft_id=info:doi/10.1021/ja00049a095&rft.aulast=Stern&rft.aufirst=Michael K.&rft.au=Hileman, Fredrick D.&rft.au=Bashkin, James K.&rfr_id=info:sid/en.wikipedia.org:4-Aminodiphenylamine" class="Z3988">
- ^ Bashkin, James; Rains, Roger; Stern, Michael (1999). "Taking green chemistry from the laboratory to chemical plant". Green Chemistry. 1 (2): G41. doi:10.1039/GC990G41.