p-Phenylenediamine
| |||
| |||
| Names | |||
|---|---|---|---|
| Preferred IUPAC name
Benzene-1,4-diamine | |||
| Other names
Paraphenylenediamine
1,4-Diaminobenzene 1,4-Phenylenediamine | |||
| Identifiers | |||
3D model (JSmol)
|
|||
| 749029 | |||
| ChEBI | |||
| ChEMBL | |||
| ChemSpider | |||
| DrugBank | |||
| ECHA InfoCard | 100.003.096 | ||
| EC Number |
| ||
| KEGG | |||
PubChemCID
|
|||
| RTECS number |
| ||
| UNII | |||
| UN number | 1673 | ||
CompTox Dashboard(EPA)
|
|||
| |||
| |||
| Properties | |||
| C6H8N2 | |||
| Molar mass | 108.144g·mol−1 | ||
| Appearance | White crystalline solid, darkens upon exposure to air[1] | ||
| Melting point | 145 to 147 °C (293 to 297 °F; 418 to 420 K)[1] | ||
| Boiling point | 267 °C (513 °F; 540 K)[1] | ||
| 10% at 40°C, 87% at 107 C, 100% at 140 C[2] | |||
| Vapor pressure | <1 mmHg (20°C)[3] | ||
| Acidity(pKa) |
| ||
| -70.28·10−6cm3/mol | |||
| Hazards | |||
| GHSlabelling: | |||
  
| |||
| Danger | |||
| H301,H311,H317,H319,H331,H410 | |||
| P261,P264,P270,P271,P272,P273,P280,P301+P310,P302+P352,P304+P340,P305+P351+P338,P311,P312,P321,P322,P330,P333+P313,P337+P313,P361,P363,P391,P403+P233,P405,P501 | |||
| NFPA 704(fire diamond) | |||
| Flash point | 156 °C; 312 °F; 429 K[3] | ||
| 400 °C (752 °F; 673 K) | |||
| Lethal doseor concentration (LD, LC): | |||
LD50(median dose)
|
80 mg/kg (rat, oral) 98 mg/kg (rat, oral) 145 mg/kg (guinea pig, oral)[5] | ||
LDLo(lowest published)
|
250 mg/kg (rabbit, oral) 100 mg/kg (cat, oral)[5] | ||
| NIOSH(US health exposure limits): | |||
PEL(Permissible)
|
TWA 0.1 mg/m3[skin][3] | ||
REL(Recommended)
|
TWA 0.1 mg/m3[skin][3] | ||
IDLH(Immediate danger)
|
25 mg/m3[3] | ||
Except where otherwise noted, data are given for materials in theirstandard state(at 25 °C [77 °F], 100 kPa).
| |||
p-Phenylenediamine(PPD) is anorganic compoundwith the formula C6H4(NH2)2.This derivative ofanilineis a white solid, but samples can darken due to air oxidation.[1]It is mainly used as a component of engineeringpolymersand composites likekevlar.It is also an ingredient inhair dyesand is occasionally used as a substitute forhenna.
Production
[edit]PPD is produced via three routes. Most commonly,4-nitrochlorobenzeneis treated withammoniaand the resulting4-nitroanilineis then hydrogenated:
In the DuPont route, aniline is converted to diphenyltriazine, which is then converted by acid-catalysis to 4-aminoazobenzene. Hydrogenation of the latter affords PPD.[7]
Uses
[edit]Precursor to polymers
[edit]PPD is a precursor toaramidplastics and fibers such askevlarandtwaron.These applications exploit PPD's difunctionality, i.e. the presence of twoamineswhich allow the molecules to be strung together. This polymer arises from the reaction of PPD andterephthaloyl chloride.The reaction of PPD withphosgenegives the diisocyanate,a precursor tourethanepolymers.[7]
Dyeing
[edit]This compound is a commonhair dye.Its use is being supplanted by otheranilineanalogues and derivatives such as 2,5-diamino(hydroxyethylbenzene and2,5-diaminotoluene). Other popular derivatives include tetraaminopyrimidine and indoanilines andindophenols.Derivatives of diaminopyrazole give both red and violet colours.[8]In these applications, the nearly colourless dye precursor oxidizes to the dye.
Rubber antioxidant
[edit]PPD is easily oxidized, and for this reason, derivatives of PPD are used asantiozonantsin the production ofrubberproducts (e.g.,IPPD). The substituents (naphthyl, isopropyl, etc.) affect the effectiveness of their antioxidant roles as well as their properties as skin irritants.[9]
Other uses
[edit]A substituted form of PPD sold under the name CD-4 is also used as a developing agent in theC-41color photographic film development process, reacting with the silver grains in the film and creating the colored dyes that form the image.
PPD is also used as a henna surrogate for temporarytattoos.Its usage can lead to severecontact dermatitis.
PPD is also used as ahistological stainforlipidssuch asmyelin.
PPD is used bylichenologistsin thePD testto aid identification of lichens.[10] PPD is used extensively as a cross-linking agent in the formation of COFs (covalent organic frameworks), which have a number of applications in dyes and aromatic compounds adsorption.
Safety
[edit]The aquaticLD50of PPD is 0.028 mg/L.[7]The U.S. Environmental Protection Agency reported that in rats and mice chronically exposed to PPD in their diet, it simply depressed body weights, and no other clinical signs of toxicity were observed in several studies.[11]One review of 31 English-language articles published between January 1992 and February 2005 that investigated the association between personal hair dye use and cancer as identified through the PubMed search engine found "at least one well-designed study with detailed exposure assessment" that observed associations between personal hair dye use and non-Hodgkin's lymphoma, multiple myeloma, acute leukemia, and bladder cancer,[12]but those associations were not consistently observed across studies. A formal meta-analysis was not possible due to the heterogeneity of the exposure assessment across the studies.
In 2005–06, it was the tenth-most-prevalentallergeninpatch tests(5.0%).[13]
TheCDClists PPD as being a contactallergen.Exposure routes are through inhalation, skin absorption, ingestion, and skin and/or eye contact. Symptoms of exposure to PPD include throat irritation (pharynxandlarynx), bronchialasthma,and sensitizationdermatitis.[14][15]Sensitization is a lifelong issue, which may lead to active sensitization to products, including but not limited to black clothing, various inks, hair dye, dyed fur, dyed leather, and certain photographic products. It was votedAllergen of the Yearin 2006 by the American Contact Dermatitis Society.
Poisoning by PPD is rare in Western countries.[16]In contrast, poisoning by PPD has occurred in Eastern countries, such as Pakistan, where people have committed suicide by consuming it.[17]
See also
[edit]References
[edit]- ^abcdMerck Index,11th Edition,7256
- ^"P-Phenylenediamine (1,4-Diaminobenzene)".Archived fromthe originalon 2012-03-13.Retrieved2011-07-14.
- ^abcdeNIOSH Pocket Guide to Chemical Hazards."#0495".National Institute for Occupational Safety and Health(NIOSH).
- ^Haynes, William M., ed. (2016).CRC Handbook of Chemistry and Physics(97th ed.).CRC Press.pp. 5–89.ISBN978-1498754286.
- ^ab"p-Phenylene diamine".Immediately Dangerous to Life or Health Concentrations (IDLH).National Institute for Occupational Safety and Health(NIOSH).
- ^"p-Phenylenediamine MSDS".Thermo Fisher Scientific.
- ^abcUllmann's Encyclopedia of Industrial Chemistry(1 ed.). Wiley. 2003-03-11.doi:10.1002/14356007.a19_405.ISBN978-3-527-30385-4.
- ^Thomas Clausen et al. "Hair Preparations" inUllmann's Encyclopedia of Industrial Chemistry,2007, Wiley-VCH, Weinheim.doi:10.1002/14356007.a12_571.pub2
- ^Hans-Wilhelm Engels et al., "Rubber, 4. Chemicals and Additives" inUllmann's Encyclopedia of Industrial Chemistry,2007, Wiley-VCH, Weinheim.doi:10.1002/14356007.a23_365.pub2
- ^"Chemical Tests".The British Lichen Society.Retrieved2019-04-30.
- ^p-Phenylenediamine,U.S. Environmental Protection Agency
- ^Rollison, DE; Helzlsouer, KJ; Pinney, SM (2006). "Personal hair dye use and cancer: a systematic literature review and evaluation of exposure assessment in studies published since 1992".Journal of Toxicology and Environmental Health Part B: Critical Reviews.9(5): 413–39.Bibcode:2006JTEHB...9..413R.doi:10.1080/10937400600681455.PMID17492526.S2CID23749135.
- ^Zug, Kathryn A.; Warshaw, Erin M.; Fowler, Joseph F.; Maibach, Howard I.; Belsito, Donald L.; Pratt, Melanie D.; Sasseville, Denis; Storrs, Frances J.; Taylor, James S.; Mathias, C. G. Toby; Deleo, Vincent A.; Rietschel, Robert L.; Marks, James (2009)."Patch-test results of the North American Contact Dermatitis Group 2005-2006".Dermatitis: Contact, Atopic, Occupational, Drug.20(3): 149–160.doi:10.2310/6620.2009.08097.ISSN2162-5220.PMID19470301.S2CID24088485.
- ^"The NIOSH Pocket Guide to Chemical Hazards".Archived fromthe originalon 2017-10-24.Retrieved2017-09-07.
- ^"NIOSH Registry of Toxic Effects of Chemical Substances (RTECS) entry for p-Phenylenediamine (PPD)".Archived fromthe originalon 2010-03-31.Retrieved2017-09-07.
- ^Ashraf, W.; Dawling, S.; Farrow, L. J. (1994). "Systemic Paraphenylenediamine (PPD) Poisoning: A Case Report and Review".Human & Experimental Toxicology.13(3): 167–70.Bibcode:1994HETox..13..167A.doi:10.1177/096032719401300305.PMID7909678.S2CID31229733.
- ^Omer Sultan, Muhammad; Inam Khan, Muhammad; Ali, Rahmat; Farooque, Umar; Hassan, Syed Adeel; Karimi, Sundas; Cheema, Omer; Pillai, Bharat; Asghar, Fahham; Javed, Rafay (2020-05-29)."Paraphenylenediamine (Kala Pathar) Poisoning at the National Poison Control Center in Karachi: A Prospective Study".Cureus.12(5): e8352.doi:10.7759/cureus.8352.ISSN2168-8184.PMC7325408.PMID32617225.