p-Phenylenediamine

Base Information

• Chemical Name: p-Phenylenediamine
• CAS No.: 106-50-3
• Deprecated CAS: 56481-76-6,82785-55-5
• Molecular Formula: C6H8N2
• Molecular Weight: 108.143
• Hs Code.: 292151
• European Community (EC) Number: 203-404-7
• ICSC Number: 0805
• NSC Number: 4777
• UN Number: 1673
• UNII: U770QIT64J
• DSSTox Substance ID: DTXSID9021138
• Nikkaji Number: J4.035E
• Wikipedia: P-Phenylenediamine
• Wikidata: Q415024
• Metabolomics Workbench ID: 52565
• ChEMBL ID: CHEMBL403741
• Mol file: 106-50-3.mol

Synonyms:1,4-benzenediamine;1,4-phenyldiamine;1,4-phenylenediamine;4-phenylenediamine;4-phenylenediamine bromide, ion(1+);4-phenylenediamine dihydrochloride;4-phenylenediamine diperchlorate;4-phenylenediamine ion (1+);4-phenylenediamine monohydrobromide;4-phenylenediamine monohydrochloride;4-phenylenediamine monohydroiodide;4-phenylenediamine monooxalate;4-phenylenediamine monoperchlorate;4-phenylenediamine monosulfate;4-phenylenediamine sulfate;black henna;p-phenylenediamine;para-phenylenediamine;paraphenylenediamine;Ursol-D

Chemical Property of p-Phenylenediamine

Chemical Property:

• Appearance/Colour: white to light purple solid
• Vapor Pressure: 0.00817mmHg at 25°C
• Melting Point: 139 °C
• Refractive Index: 1.66
• Boiling Point: 267.4 °C at 760 mmHg
• PKA: 4.17(at 25℃)
• Flash Point: 135.9 °C
• PSA: 52.04000
• Density: 1.15 g/cm³
• LogP: 2.01340
• Storage Temp.: 2-8°C
• Solubility.: Soluble in alcohol, chloroform, ether and hot benzene.
• Water Solubility.: 47 g/L (25℃)
• XLogP3: -0.3
• Hydrogen Bond Donor Count: 2
• Hydrogen Bond Acceptor Count: 2
• Rotatable Bond Count: 0
• Exact Mass: 108.068748264
• Heavy Atom Count: 8
• Complexity: 54.9
• Transport DOT Label: Poison

Purity/Quality:

99.00% ^*data from raw suppliers

1,4-Phenylenediamine ^*data from reagent suppliers

Safty Information:

• Pictogram(s): T,N,T+,Xn
• Hazard Codes: T:Toxic;;
• Statements: R23/24/25:; R36:; R43:; R50/53:
• Safety Statements: S28A:; S36/37:; S45:; S60:; S61:

MSDS Files:

SDS file from LookChem

Total 1 MSDS from other Authors

Useful:

• Chemical Classes: Nitrogen Compounds -> Amines, Aromatic
• Canonical SMILES: C1=CC(=CC=C1N)N
• Recent EU Clinical Trials: An open label, intra-subject, controlled multi-centre study to assess the concordance (specificity and sensitivity) between Colourstart? Test 73 mcg Cutaneous Patch and Finn Chamber in the detection of para-Phenylenediamine (PPD) allergy in subjects with known or clinically suspected allergy and those with no known allergy.
• Inhalation Risk: A harmful contamination of the air will not or will only very slowly be reached on evaporation of this substance at 20 °C; on spraying or dispersing, however, much faster.
• Effects of Short Term Exposure: The substance is irritating to the eyes. Inhalation of dust may cause asthmatic reactions. Ingestion could cause swelling of mouth and throat. The substance may cause effects on the blood. This may result in the formation of methaemoglobin. Exposure could cause death.
• Effects of Long Term Exposure: Repeated or prolonged contact may cause skin sensitization. Repeated or prolonged inhalation may cause asthma. The substance may have effects on the kidneys. This may result in kidney impairment.
• Description: P-phenylenediamine is one of the simplest aromatic diamine with the pure product being white to purple red crystals. It turns purple or dark brown color when being exposed to the air. It is slightly soluble in cold water, soluble in alcohol, ether, chloroform and benzene. It can be used for making azo dyes, high-molecule polymers and can also be used for the production of fur dyes, rubber antioxidants and photo developer and is mainly used for Kevlar, azo dyes, sulfur dyes, acid dyes as well as being used for the production of black fur D, black fur DB, brown fur N2 as well as rubber antioxidant DNP, DOP and MB. It can also be used as the raw material of cosmetic hair p-Phenylenediamine series, gasoline polymerization inhibitor and developer. P-phenylenediamine, as a chemical dye, is currently permitted for use in hair dye production, but there is a clear usage limits. According to China "Hygienic Standard for Cosmetics," the content of p-phenylenediamine in hair dyes should not exceed 6%. According to the introduction of experts, although five kinds of "Yixihei" shampoo have their p-phenylenediamine content being within 1.1% to 1.4%. However, the shampoo has high frequency of usage with long-term accumulation being prone to pose a threat to the health and safety of consumers. There is still no literatures regarding to whether phenylenediamine is carcinogenic or not; but there is literature basis regarding to that p-phenylenediamine drug is toxic organic. We can refer to Shanghai Science and technology press (November 1985) "reagent Handbook" (second edition), page 980. Overseas research has shown that for population being subject to frequent hair dying has the incidence of breast cancer, skin cancer and leukemia increased. In addition, p-phenylenediamine is also a common sensitive reagent for testing iron and copper. In the international arena, it is also used for aircraft coatings, bullet-proof clothing intima and walls paint. p-phenylenediamine structure Paraphenylenediamine (PPD) is a colorless compound oxidized by hydrogen peroxide in the presence of ammonia. It is then polymerized by a coupling agent to produce a color.
• Uses: P-phenylenediamine is important dye intermediates and is mainly used in the manufacture of dyes and sulfur dyes; it can also be used for the production of fur black D and rubber antioxidant DNP, 288, DOP, DBP etc. P-phenylenediamine can also be used as the raw material of cosmetic hair dye “WuErsi D”, gasoline polymerization inhibitor and developer. p-Phenylenediamine is used for dyeing hairand fur, in the manufacture of azo dyes, inaccelerating vulcanization of rubber, and inantioxidants. A hair dye component, paraphenylenediamine, as a contact allergen for treatment of inflammatory diseases. 4-Phenylenediamine is an azo-dye intermediate; photographic-developing agent; photo-chemical measurements; intermediate in manufacture of antioxidants and accelerators for rubber; laboratory reagent; dye for hair and fur; lithography; photocopying; oils; greases; gasoline; antioxidant/accelerator in the rubber and plastic industry; the hydrochloride is used as blood reagent.
• Production method: It can be obtained from the reduction of P-nitroaniline via iron in acid medium. Put the iron into hydrochloric acid and heat to 90 °C. Add with stirring of p-nitroaniline. After completion of the adding, have them reacted at 95-100 ℃ for 0.5h, and then add drop wise of concentrated hydrochloric acid so that the reduction reaction is completed. After cooling, use saturated sodium carbonate solution for neutralizing to PH7-8, after boiling and have hot filtration; use host water to wash the filter cake. The filtrate and washings were combined and subject to concentration under reduced pressure; after cooling crystallization or vacuum distillation, we can obtain the p-phenylenediamine with the yield of being 95%.
• Physical properties: White, red, or brown crystals. May darken on exposure to air.

Technology Process of p-Phenylenediamine

There total 287 articles about p-Phenylenediamine which guide to synthetic route it. The literature collected by LookChem mainly comes from the sharing of users and the free literature resources found by Internet computing technology. We keep the original model of the professional version of literature to make it easier and faster for users to retrieve and use. At the same time, we analyze and calculate the most feasible synthesis route with the highest yield for your reference as below:

synthetic route:

Reference yield: 85.0%

para-dinitrobenzene (100-25-4) → 4-nitro-aniline (100-01-6,104810-17-5) + 1,4-phenylenediamine (106-50-3)

Guidance literature:

With tris(triphenylphosphine)ruthenium(II) chloride; formic acid; triethylamine; palladium on activated charcoal; In tetrahydrofuran; at 20 - 25 ℃; for 0.5h; Product distribution; selective reduction with a new hydrogen source;

Reference yield: 65.0%

p-nitrophenyl isocyanide (1984-23-2) → 4-nitro-aniline (100-01-6,104810-17-5) + 1,4-phenylenediamine (106-50-3)

Guidance literature:

With graphitic carbon nitride; hydrazine hydrate; In water; at 70 ℃; for 8h; chemoselective reaction; Irradiation; Sealed tube; Green chemistry;

DOI:10.1002/asia.201800515

Reference yield: 30.0%

4-nitrophenyl azide (1516-60-5) → 4-nitro-aniline (100-01-6,104810-17-5) + 1,4-phenylenediamine (106-50-3)

Guidance literature:

With triethylsilane; indium(III) chloride; In acetonitrile; at 0 ℃; for 0.25h;

DOI:10.1021/ol0606637

upstream raw materials:

1,4-dioxane

pyridine

para-dinitrobenzene

4-nitrophenyl azide

Downstream raw materials:

tetrakis-N-(2-hydroxy-ethyl)-p-phenylenediamine

1,4-di(1H-pyrrol-1-yl)benzene

1,4-bis-(acetoacetylamino)-benzene

N,N'-(1,4-phenylene)dimaleimide

Refernces

• 1、 Andrews,Lowy. "-". . p. 1411. Retrieved 1934.
• 2、 Kobayashi,Wakamatsu. "-". . p. 115. Retrieved 1967.
• 3、 Borah, Harsha N.,Prajapati, Dipak,Boruah, Romesh C.. "Bakers' yeast-catalyzed ring opening of benzofuroxans: An efficient green synthesis of aryl-1,2-diamines". . p. 267 - 272. Retrieved 2009.
• 4、 Green,Wolff. "-". . p. 2576. Retrieved 1911.
• 5、 Opallo, Marcin. "The Solvent Effect on the Electro-oxidation of 1,4-Phenylenediamine. The Influence of the Solvent Reorientation Dynamics on the One-electron Transfer Rate". . p. 339 - 348. Retrieved 1986.
• 6、 Shesterkina,Shuvalova,Kirichenko,Strelkova,Nissenbaum,Kapustin,Kustov. "Application of silica-supported Fe–Cu nanoparticles in the selective hydrogenation of p-dinitrobenzene to p-phenylenediamine". . p. 201 - 204. Retrieved 2017.
• 7、 Ravi Kanth,Venkat Reddy,Rama Rao,Maitraie,Narsaiah,Shanthan Rao. "A simple and convenient method for the reduction of nitroarenes". . p. 2849 - 2853. Retrieved 2002.
• 8、 Qi, Bin,Wu, Chenchen,Li, Xin,Wang, Dan,Sun, Liang,Chen, Bo,Liu, Wenjing,Zhang, Haibo,Zhou, Xiaohai. "Self-Assembled Magnetic Gold Catalysts from Dual-Functional Boron Clusters". . p. 2285 - 2290. Retrieved 2018.
• 9、 Lauer,Sunde. "-". . p. 261. Retrieved 1938.
• 10、 Pielesz,Baranowska,Rybak,Wlochowicz. "Detection and determination of aromatic amines as products of reductive splitting from selected azo dyes". . p. 42 - 47. Retrieved 2002.