P-Phenylenediamine

Last updated
p-Phenylenediamine
P-phenylenediamine.svg
Para-phenylenediamine-from-xtal-3D-bs-17.png
Para-phenylenediamine-from-xtal-3D-sf.png
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 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 203-404-7
KEGG
PubChem CID
RTECS number
  • SS8050000
UNII
UN number 1673
  • InChI=1S/C6H8N2/c7-5-1-2-6(8)4-3-5/h1-4H,7-8H2 X mark.svgN
    Key: CBCKQZAAMUWICA-UHFFFAOYSA-N X mark.svgN
  • InChI=1/C6H8N2/c7-5-1-2-6(8)4-3-5/h1-4H,7-8H2
    Key: CBCKQZAAMUWICA-UHFFFAOYAD
  • Nc1ccc(N)cc1
Properties
C6H8N2
Molar mass 108.144 g·mol−1
AppearanceWhite 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)
  • 2.97 (doubly protonated form; 20 °C, H2O)
  • 6.31 (conjugate acid; 20 °C, H2O) [4]
-70.28·10−6 cm3/mol
Hazards
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
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)
[5]
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
3
0
0
Flash point 156 °C; 312 °F; 429 K [3]
400 °C (752 °F; 673 K)
Lethal dose or concentration (LD, LC):
80 mg/kg (rat, oral)
98 mg/kg (rat, oral)
145 mg/kg (guinea pig, oral) [6]
250 mg/kg (rabbit, oral)
100 mg/kg (cat, oral) [6]
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 their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

p-Phenylenediamine (PPD) is an organic compound with the formula C6H4(NH2)2. This derivative of aniline is a white solid, but samples can darken due to air oxidation. [1] It is mainly used as a component of engineering polymers and composites like kevlar. It is also an ingredient in hair dyes and is occasionally used as a substitute for henna.

Contents

Production

PPD is produced via three routes. Most commonly, 4-nitrochlorobenzene is treated with ammonia and the resulting 4-nitroaniline is then hydrogenated:

Synthesis 1,4-Phenylendiamine.svg

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]

Synthesis 1,4-Phenylendiamine (2).svg

Uses

Precursor to polymers

PPD is a precursor to aramid plastics and fibers such as kevlar and twaron. These applications exploit PPD's difunctionality, i.e. the presence of two amines which allow the molecules to be strung together. This polymer arises from the reaction of PPD and terephthaloyl chloride. The reaction of PPD with phosgene gives the diisocyanate, a precursor to urethane polymers. [7]

Molecular structure of Kevlar: the monomer subunit is bolded, dashed lines indicate hydrogen bonds. Kevlar chemical structure H-bonds.svg
Molecular structure of Kevlar: the monomer subunit is bolded, dashed lines indicate hydrogen bonds.

Dyeing

This compound is a common hair dye. Its use is being supplanted by other aniline analogues and derivatives such as 2,5-diamino(hydroxyethylbenzene and 2,5-diaminotoluene). Other popular derivatives include tetraaminopyrimidine and indoanilines and indophenols. Derivatives of diaminopyrazole give both red and violet colours. [8] In these applications, the nearly colourless dye precursor oxidizes to the dye.

Rubber antioxidant

PPD is easily oxidized, and for this reason, derivatives of PPD are used as antiozonants in the production of rubber products (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

A substituted form of PPD sold under the name CD-4 is also used as a developing agent in the C-41 color 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 temporary tattoos. Its usage can lead to severe contact dermatitis.

PPD is also used as a histological stain for lipids such as myelin.

PPD is used by lichenologists in the PD test to 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

The aquatic LD50 of 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.

Patch test Epikutanni-test.jpg
Patch test

In 2005–06, it was the tenth-most-prevalent allergen in patch tests (5.0%). [13]

The CDC lists PPD as being a contact allergen. Exposure routes are through inhalation, skin absorption, ingestion, and skin and/or eye contact. Symptoms of exposure to PPD include throat irritation (pharynx and larynx), bronchial asthma, and sensitization dermatitis. [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 voted Allergen of the Year in 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

Related Research Articles

<span class="mw-page-title-main">Dimethylaniline</span> Chemical compound

N,N-Dimethylaniline (DMA) is an organic chemical compound, a substituted derivative of aniline. It is a tertiary amine, featuring a dimethylamino group attached to a phenyl group. This oily liquid is colourless when pure, but commercial samples are often yellow. It is an important precursor to dyes such as crystal violet.

<span class="mw-page-title-main">Hair coloring</span> Practice of changing the hair color

Hair coloring, or hair dyeing, is the practice of changing the color of the hair on humans' heads. The main reasons for this are cosmetic: to cover gray or white hair, to alter hair to create a specific look, to change a color to suit preference or to restore the original hair color after it has been discolored by hairdressing processes or sun bleaching.

<span class="mw-page-title-main">Methylene diphenyl diisocyanate</span> Aromatic diisocyanate

Methylene diphenyl diisocyanate (MDI) is an aromatic diisocyanate. Three isomers are common, varying by the positions of the isocyanate groups around the rings: 2,2′-MDI, 2,4′-MDI, and 4,4′-MDI. The 4,4′ isomer is most widely used, and is also known as 4,4′-diphenylmethane diisocyanate. This isomer is also known as Pure MDI. MDI reacts with polyols in the manufacture of polyurethane. It is the most produced diisocyanate, accounting for 61.3% of the global market in the year 2000.

<span class="mw-page-title-main">Chlorobenzene</span> Aromatic organochlorine compound

Chlorobenzene (abbreviated PhCl) is an aryl chloride and the simplest of the chlorobenzenes, consisting of a benzene ring substituted with one chlorine atom. Its chemical formula is C6H5Cl. This colorless, flammable liquid is a common solvent and a widely used intermediate in the manufacture of other chemicals.

<span class="mw-page-title-main">Ethylenediamine</span> Chemical compound

Ethylenediamine (abbreviated as en when a ligand) is the organic compound with the formula C2H4(NH2)2. This colorless liquid with an ammonia-like odor is a basic amine. It is a widely used building block in chemical synthesis, with approximately 500,000 tonnes produced in 1998. Ethylenediamine is the first member of the so-called polyethylene amines.

<i>m</i>-Phenylenediamine Chemical compound

m-Phenylenediamine, also called 1,3-diaminobenzene, is an organic compound with the formula C6H4(NH2)2. It is an isomer of o-phenylenediamine and p-phenylenediamine. This aromatic diamine is a colourless solid that appears as needles, but turns red or purple on exposure to air due to formation of oxidation products. Samples often come as colourless flakes and may darken in storage.

2-Chloroethanol (also called ethylene chlorohydrin or glycol chlorohydrin) is an organic chemical compound with the chemical formula HOCH2CH2Cl and the simplest beta-halohydrin (chlorohydrin). This colorless liquid has a pleasant ether-like odor. It is miscible with water. The molecule is bifunctional, consisting of both an alkyl chloride and an alcohol functional group.

<span class="mw-page-title-main">Allergic contact dermatitis</span> Medical condition

Allergic contact dermatitis (ACD) is a form of contact dermatitis that is the manifestation of an allergic response caused by contact with a substance; the other type being irritant contact dermatitis (ICD).

<span class="mw-page-title-main">Diphenylamine</span> Chemical compound

Diphenylamine is an organic compound with the formula (C6H5)2NH. The compound is a derivative of aniline, consisting of an amine bound to two phenyl groups. The compound is a colorless solid, but commercial samples are often yellow due to oxidized impurities. Diphenylamine dissolves well in many common organic solvents, and is moderately soluble in water. It is used mainly for its antioxidant properties. Diphenylamine is widely used as an industrial antioxidant, dye mordant and reagent and is also employed in agriculture as a fungicide and antihelmintic.

<span class="mw-page-title-main">Nitroethane</span> Chemical compound

Nitroethane is an organic compound having the chemical formula C2H5NO2. Similar in many regards to nitromethane, nitroethane is an oily liquid at standard temperature and pressure. Pure nitroethane is colorless and has a fruity odor.

<span class="mw-page-title-main">Just for Men</span> American-based mens care brand

Just for Men is an American-based multi-national men's care brand focusing on hair color, beard care, and hair re-growth designed for and marketed to men and manufactured by Combe Incorporated. Just for Men hair color brands are designed to color gray hair, with the Control Gx and Touch of Gray product lines providing options for gradual hair coloring. Just For Men comes in over 12 shades ranging from Sandy Blond to Jet Black.

<span class="mw-page-title-main">Isophorone</span> Alpha-beta unsaturated cyclic ketone

Isophorone is an α,β-unsaturated cyclic ketone. It is a colorless liquid with a characteristic peppermint-like odor, although commercial samples can appear yellowish. Used as a solvent and as a precursor to polymers, it is produced on a large scale industrially.

1,2,4-Trichlorobenzene is an organochlorine compound, one of three isomers of trichlorobenzene. It is a derivative of benzene with three chloride substituents. It is a colorless liquid used as a solvent for a variety of compounds and materials.

<span class="mw-page-title-main">4-Nitroaniline</span> Chemical compound

4-Nitroaniline, p-nitroaniline or 1-amino-4-nitrobenzene is an organic compound with the formula C6H6N2O2. A yellow solid, it is one of three isomers of nitroaniline. It is an intermediate in the production of dyes, antioxidants, pharmaceuticals, gasoline, gum inhibitors, poultry medicines, and as a corrosion inhibitor.

<i>o</i>-Anisidine Chemical compound

o-Anisidine (2-anisidine) is an organic compound with the formula CH3OC6H4NH2. A colorless liquid, commercial samples can appear yellow owing to air oxidation. It is one of three isomers of the methoxy-containing aniline derivative.

<span class="mw-page-title-main">Methyl cyanoacrylate</span> Chemical compound

Methyl cyanoacrylate is an organic compound that contains several functional groups: a methyl ester, a nitrile, and an alkene. It is a colorless liquid with low viscosity. Its chief use is as the main component of cyanoacrylate glues. It can be encountered under many trade names. Methyl cyanoacrylate is less commonly encountered than ethyl cyanoacrylate.

<span class="mw-page-title-main">Henna</span> Vegetable dye

Henna is a reddish dye prepared from the dried and powdered leaves of the henna tree. It has been used since at least the ancient Egyptian period as a hair and body dye, notably in the temporary body art of mehndi resulting from the staining of the skin using dyes from the henna plant. After henna stains reach their peak colour, they hold for a few days, then gradually wear off by way of exfoliation, typically within one to three weeks.

4,4′-Methylenedianiline (MDA) is an organic compound with the formula CH2(C6H4NH2)2. It is a colorless solid, although commercial samples can appear yellow or brown. It is produced on an industrial scale, mainly as a precursor to polyurethanes.

<span class="mw-page-title-main">2,5-Diaminotoluene</span> Chemical compound

2,5-Diaminotoluene is an organic compound with the formula C6H3(NH2)2CH3. It is one isomer of six with this formula. 2,5-Diaminotoluene is a colorless crystalline solid, although commercial samples are often colored owing to air oxidation. It is commonly used in hair coloring.

Butyl acrylate is an organic compound with the formula C4H9O2CCH=CH2. A colorless liquid, it is the butyl ester of acrylic acid. It is used commercially on a large scale as a precursor to poly(butyl acrylate). Especially as copolymers, such materials are used in paints, sealants, coatings, adhesives, fuel, textiles, plastics, and caulk.

References

  1. 1 2 3 4 Merck Index , 11th Edition, 7256
  2. ↑ "P-Phenylenediamine (1,4-Diaminobenzene)". Archived from the original on 2012-03-13. Retrieved 2011-07-14.
  3. 1 2 3 4 5 NIOSH Pocket Guide to Chemical Hazards. "#0495". National Institute for Occupational Safety and Health (NIOSH).
  4. ↑ Haynes, William M., ed. (2016). CRC Handbook of Chemistry and Physics (97th ed.). CRC Press. pp. 5–89. ISBN   978-1498754286.
  5. ↑ "p-Phenylenediamine MSDS". Thermo Fisher Scientific.
  6. 1 2 "p-Phenylene diamine". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  7. 1 2 3 Ullmann's Encyclopedia of Industrial Chemistry (1 ed.). Wiley. 2003-03-11. doi:10.1002/14356007.a19_405. ISBN   978-3-527-30385-4.
  8. ↑ Thomas Clausen et al. "Hair Preparations" in Ullmann's Encyclopedia of Industrial Chemistry, 2007, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a12_571.pub2
  9. ↑ Hans-Wilhelm Engels et al., "Rubber, 4. Chemicals and Additives" in Ullmann's Encyclopedia of Industrial Chemistry, 2007, Wiley-VCH, Weinheim. doi : 10.1002/14356007.a23_365.pub2
  10. ↑ "Chemical Tests". The British Lichen Society. Retrieved 2019-04-30.
  11. ↑ p-Phenylenediamine, U.S. Environmental Protection Agency
  12. ↑ 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. PMID   17492526. S2CID   23749135.
  13. ↑ 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. ISSN   2162-5220. PMID   19470301. S2CID   24088485.
  14. ↑ "The NIOSH Pocket Guide to Chemical Hazards". Archived from the original on 2017-10-24. Retrieved 2017-09-07.
  15. ↑ "NIOSH Registry of Toxic Effects of Chemical Substances (RTECS) entry for p-Phenylenediamine (PPD)". Archived from the original on 2010-03-31. Retrieved 2017-09-07.
  16. ↑ 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. PMID   7909678. S2CID   31229733.
  17. ↑ 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 . ISSN   2168-8184. PMC   7325408 . PMID   32617225.
This page is based on this Wikipedia article
Text is available under the CC BY-SA 4.0 license; additional terms may apply.
Images, videos and audio are available under their respective licenses.