p-Phenylenediamine

Iupac Name：benzene-1,4-diamine

Molecular Weight：108.14112

Modify Date.: 2022-11-12 07:20

Introduction: 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. View more+

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1. Names and Identifiers

1.1 Name: p-Phenylenediamine
1.2 Synonyms: 1,4-BENZENEDIAMINE 1,4-DIAMINOBENZENE 1,4-phenyldiamine 1,4-PHENYLENEDIAMINE 4-AMINOANILINE BENZENE-1,4-DIAMINE C.I. 76060 EINECS 203-404-7 fur black 41866 JAROCOL PPD MFCD00007901 paraphenylenediamine para-phenylenediamine para-Phenylenediamine (PPD) p-Benzenediamine p-diaminobenzene Phenylenediamine

1.3 CAS No.: 106-50-3

1.4 CID: 7814

1.5 EINECS(EC#): 203-404-7

1.6 Molecular Formula: C6H8N2 (isomer)

1.7 Inchi: InChI=1S/C6H8N2/c7-5-1-2-6(8)4-3-5/h1-4H,7-8H2

1.8 InChkey: CBCKQZAAMUWICA-UHFFFAOYSA-N

1.9 Canonical Smiles: C1=CC(=CC=C1N)N

1.10 Isomers Smiles: C1=CC(=CC=C1N)N

2. Properties

2.1 Density: 1.15

2.1 Melting point: 138-143℃

2.1 Boiling point: 267℃

2.1 Refractive index: 1.661

2.1 Flash Point: 156℃

2.2 Precise Quality: 108.06900

2.2 PSA: 52.04000

2.2 logP: 2.01340

2.2 Solubility: Soluble in alcohol, chloroform, ether and hot benzene.

2.3 VaporDensity: 3.7 (vs air)

2.4 Appearance: white to light purple solid

2.5 Storage: Ambient temperatures.

2.6 Autoignition Temperature: 400 °C

2.7 Carcinogenicity: A number of dermal carcinogenesis bioassays have beenreported using p-PDA alone in an organic solvent or incombination with hydrogen peroxide. An 85-week studyin which female Swiss mice were treated with 5% or 10%p-PDAin acetone, 0.02 mL/animal applied topically, showedno evidence of carcinogenicity.p-PDA was not found to be carcinogenic when administeredby diet to male and female F344 rats and B6C3F1 miceat the dietary doses of 625 or 1250 ppm; the high doseapproximated the maximum tolerated dose. AnIARC Working Group concluded that on the basis of lackof human data, and inadequate animal data, p-PDA was notclassifiable as to its carcinogenicity to humans. Arecent meta-analysis of 11 case-control studies and onecohort study of the relationship between p-PDA exposurethrough use of personal hair dye and bladder cancer did notindicate any causal association.

2.8 Chemical Properties: It is white to purple red crystal. It will turn purple red or dark brown when exposure to the air. It can be dissolved in water, alcohol, ether, chloroform and benzene.

2.9 Physical Properties: White, red, or brown crystals. May darken on exposure to air.

2.10 Color/Form: WHITE TO SLIGHTLY RED CRYSTALS
WHITE PLATES FROM BENZENE, ETHER

2.11 Contact Allergens: PPD is a colorless compound oxidized by hydrogenperoxide in the presence of ammonia. It is then polymerizedto a color by a coupling agent. Although a wellknownallergen in hair dyes, PPD can be found as acause of contact dermatitis in chin rest stains or in milktesters. It is also a marker of group sensitivity to paraamino compounds such as benzocaine, some azo dyes,and some previous antibacterial sulphonamides.

2.12 Decomposition: Toxic gases and vapors (such as oxides of nitrogen and carbon monoxide) may be released in a fire involving p-phenylenediamine.

2.13 Ionization Potential: 6.89 eV

2.14 PH: 9 (50g/l, H2O, 20℃)

2.15 pKa: 4.17(at 25℃)

2.16 Water Solubility: 47 g/L (25 oC)

2.17 Spectral Properties: MAX ABSORPTION (CYCLOHEXANE): 246 NM (LOG E= 3.93), 315 NM (LOG E= 3.30); SADTLER REFERENCE NUMBER: 4111 (IR, PRISM); 1187 (UV)
IR: 8322 (Sadtler Research Laboratories IR Grating Collection)
UV: 6-80 (Organic Electronic Spectral Data, Phillips et al, John Wiley & Sons, New York)
MASS: 45 (Aldermaston, Eight Peak Index of Mass Spectra, UK)

2.18 Stability: Stable, but oxidizes when exposed to air. Incompatible with oxidizing agents. Store under inert atmosphere.

2.19 StorageTemp: Store below +30°C.

3. Use and Manufacturing

3.1 Definition: ChEBI: A phenylenediamine in which the amino functions are at positions 1 and 4 of the benzene nucleus.

3.2 General Description: A white to purple crystalline solid (melting point 234 F) that turns purple to black in air. Flash point 309 F. Toxic by skin absorption, inhalation or ingestion. Used for production of aramid fiber, antioxidants, as a laboratory reagent, in photographic developing, and as a dye for hair and furs.

3.3 Potential Exposure: p-Phenylenediamine has been used in dyestuff manufacture, in hair dyes; in photographic developers; in synthetic fibers; polyurethanes, and as a monomer and in the manufacture of improved tire cords. Also used as a gasoline additive and in making antioxidants.

3.4 Purification Methods: Crystallise the diamine from EtOH or *benzene, and sublime it in vacuo; protect it from light. The acetate has m 304o. [Beilstein 13 IV 104.]

3.5 Shipping: UN1673 Phenylenediamines (o-, m-, p-), Hazard Class: 6.1; Labels: 6.1-Poisonous materials.

3.6 Usage: 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.

3.7 Waste Disposal: Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device. p-Phenylenediamine Preparation Products And Raw materials Raw materials

4. Safety and Handling

4.1 Symbol: GHS06, GHS08, GHS09

4.1 Hazard Codes: T

4.1 Signal Word: Danger

4.1 Risk Statements: R23/24/25;R36;R43;R50/53

4.1 Safety Statements: S28;S36/37;S45;S60;S61

4.1 Packing Group: III

4.1 Octanol/Water Partition Coefficient: log Kow= -0.25

4.2 Fire Hazard: Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.

4.3 Other Preventative Measures: SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.
The worker should immediately wash the skin when it becomes contaminated.
The worker should wash daily at the end of each work shift.
Work clothing that becomes wet or significantly contaminated should be removed and replaced.
Workers whose clothing may have become contaminated should change into uncontaminated clothing before leaving the work premises.
SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.

4.4 Hazard Class: 6.1

4.4 Hazard Declaration: H301 + H311 + H331-H317-H319-H370-H410

4.4 DisposalMethods: The following wastewater treatment technologies have been investigated for p-phenylenediamine: biological treatment.
SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

4.5 DOT Emergency Guidelines: /GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Health: TOXIC; inhalation, ingestion, or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution. /Phenylenediamines/
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Fire or Explosion: Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors, and sewers explosion hazards. Those substances designated with a "P" may polymerize explosively when heated or involved in a fire. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form. /Phenylenediamines/
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Public Safety: CALL Emergency Response Telephone Number ... . As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas. /Phenylenediamines/
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Protective Clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible. /Phenylenediamines/
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Evacuation: ... Fire: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. /Phenylenediamines/
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Fire: Small fires: Dry chemical, CO2 or water spray. Large fires: Dry chemical, CO2, alcohol-resistant foam or water spray. Move containers from fire area if you can do it without risk. Dike fire control water for later disposal; do not scatter the material. Fire involving tanks or car/trailer loads: Fight fire from maximum distance or use unmanned hose holders or monitor nozzles. Do not get water inside containers. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks engulfed in fire. /Phenylenediamines/
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Spill or Leak: ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area). Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. Prevent entry into waterways, sewers, basements or confined areas. Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers. DO NOT GET WATER INSIDE CONTAINERS. /Phenylenediamines/
/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ First Aid: Move victim to fresh air. Call 911 or emergency medical service. Give artificial respiration if victim is not breathing. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. Administer oxygen if breathing is difficult. Remove and isolate contaminated clothing and shoes. In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. For minor skin contact, avoid spreading material on unaffected skin. Keep victim warm and quiet. Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed. Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves. /Phenylenediamines/

4.6 RIDADR: UN 1673

4.6 Fire Fighting Procedures: WATER, CARBON DIOXIDE, DRY CHEM ... .

4.7 FirePotential: COMBUSTIBLE WHEN EXPOSED TO HEAT OR FLAME.

4.8 Safety Profile: Suspected carcinogen with experimental tumorigenic data. Poison by ingestion, subcutaneous, intravenous, and intraperitoneal routes. Mildly toxic by skin contact. A human skin irritant. Mutation data reported. Implicated in aplastic anemia, Can cause fatal liver damage. The p-form is more toxic and a stronger irritant than the 0and misomers. Wen used as a hair dye it caused vertigo, anemia, gastritis, exfoliative dermatitis, and death. Has caused asthma and other respiratory symptoms in the fur-dyeing industry. Combustible when exposed to heat or flame; can react vigorously with oxidizing materials. To fight fire, use water, Con, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes. See also other phenylenediamine entries and AMINES

4.9 Caution Statement: P260-P273-P280-P301 + P310-P305 + P351 + P338-P311

4.9 Formulations/Preparations: ONE TECHNICAL GRADE OF PARA-PHENYLENEDIAMINE AVAILABLE IN THE USA HAS THE FOLLOWING SPECIFICATIONS: PURITY, 99.2% MINIMUM; MOISTURE CONTENT, 0.1% MAXIMUM; ORTHO-PHENYLENEDIAMINE (1,2-DIAMINOBENZENE) CONTENT, 0.1% MAXIMUM; AND IRON CONTENT, 50 MG/KG MAXIMUM.

4.10 Incompatibilities: Dust may form explosive mixture with air. A strong reducing agent. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides, acid chlorides; acid anhydrides; chloroformates, and strong bases. Incompatible with organic anhydrides; isocyanates, aldehydes. Heat and light contribute to instability. Keep away from metals.

4.11 WGK Germany: 3

4.11 RTECS: SS8050000

4.11 Protective Equipment and Clothing: Employees should be provided with and required to use impervious clothing, gloves, face shields (eight-inch minimum), and other protective clothing necessary to prevent skin contact ... .
Wear appropriate personal protective clothing to prevent skin contact.
Wear appropriate eye protection to prevent eye contact.
Recommendations for respirator selection. Max concn for use: 2.5 mg/cu m. Respirator Class(es): Any supplied-air respirator operated in a continuous flow mode. Eye protection needed.
Recommendations for respirator selection. Max concn for use: 5 mg/cu m. Respirator Class(es): Any self-contained breathing apparatus with a full facepiece. Any supplied-air respirator with a full facepiece.
Recommendations for respirator selection. Max concn for use: 25 mg/cu m. Respirator Class(es): Any supplied-air respirator that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode.
Recommendations for respirator selection. Condition: Emergency or planned entry into unknown concn or IDLH conditions: Respirator Class(es): Any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode. Any supplied-air respirator that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained breathing apparatus operated in pressure-demand or other positive-pressure mode.
Recommendations for respirator selection. Condition: Escape from suddenly occurring respiratory hazards: Respirator Class(es): Any air-purifying, full-facepiece respirator (gas mask) with a chin-style, front- or back-mounted canister providing protection against the compound of concern and having a high-efficiency particulate filter. Any appropriate escape-type, self-contained breathing apparatus.

4.12 Reactivities and Incompatibilities: Contact with strong oxidizers may cause fires and explosions.
Strong oxidizers.

4.13 Skin, Eye, and Respiratory Irritations: ... Is a skin and respiratory system sensitizer ...
Eye irritation.

4.14 Safety: When tested by the United States Environmental Protection Agency, the EPA reported that in rats and mice chronically exposed to PPD in their diet, it simply depressed body weights, but there were no other clinical signs of toxicity, as were observed in several studies.?From?1992 to 2005 years, thirty-one published articles had been investigating a causal association between PPD and cancer . Associations between personal hair dye use and non-Hodgkin's lymphoma, multiple myeloma, acute leukemia, and bladder cancer ?were observed in at least one well-designed study with detailed exposure assessment, but were not consistently observed across studies.?
Hazard Codes:?T,N,T+,Xn
Risk Statements: 23/24/25-36-43-50/53-63-36/37/38-45-40?
R23/24/25:Toxic by inhalation, in contact with skin and if swallowed.?
R36:Irritating to eyes.?
R43:May cause sensitization by skin contact.?
R50/53:Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.?
R63:Possible risk of harm to the unborn child.?
R36/37/38:Irritating to eyes, respiratory system and skin.?
R45:May cause cancer.?
R40:Limited evidence of a carcinogenic effect.
Safety Statements: 28-36/37-45-60-61-28A-24/25-23-53?
S28:After contact with skin, wash immediately with plenty of soap-suds.?
S36/37:Wear suitable protective clothing and gloves.?
S45:In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.)?
S60:This material and its container must be disposed of as hazardous waste.?
S61:Avoid release to the environment. Refer to special instructions / safety data sheets.?
S24/25:Avoid contact with skin and eyes.?
S23:Do not breathe vapour.?
S53:Avoid exposure - obtain special instructions before use.
RIDADR: UN 1673 6.1/PG 3
WGK Germany: 3
RTECS: SS8050000
F: 8-10-23
HazardClass: 6.1
PackingGroup: III
HS Code: 29215119

4.15 Specification: ?p-Phenylenediamine , its cas register number is 106-50-3. It also can be called 1,4-Benzenediamine ; 1,4-Phenylenediamine ; 4-Phenylenediamine ; CI 76060 ; p-Phenylenediamine ; 1,4-Diaminobenzene ; 4-Aminoaniline ; 6PPD ; AI3-00710 ; BASF ursol D ; Benzofur D ; C.I. 76060 ; C.I. Developer 13 ; C.I. Oxidation Base 10 ; CCRIS 509 ; Fenylenodwuamina ; Fouramine D ; Paraphenylenediamine ; Pelagol D ; p-Aminoaniline ; p-Benzenediamine ; p-Diaminobenzene ; p-Fenylendiamin ; p-Phenyldiamine ; p-Phenylenediamine ; 1,4-Benzenediamine ; Phenylenediamine, para- ; p-Phenylenediamine .It is a white to light purple solid.

4.16 Toxicity

Organism	Test Type	Route	Reported Dose (Normalized Dose)	Effect	Source
bird - wild	LD50	oral	100mg/kg (100mg/kg)	?	Archives of Environmental Contamination and Toxicology. Vol. 12, Pg. 355, 1983.
cat	LDLo	oral	100mg/kg (100mg/kg)	CARDIAC: PULSE RATE INCREASE WITHOUT FALL IN BP LUNGS, THORAX, OR RESPIRATION: RESPIRATORY STIMULATION	Journal of Industrial Hygiene. Vol. 4, Pg. 386, 1923.
dog	LDLo	intravenous	17mg/kg (17mg/kg)	?	Journal of Industrial Hygiene. Vol. 4, Pg. 386, 1923.
dog	LDLo	subcutaneous	100mg/kg (100mg/kg)	BEHAVIORAL: COMA GASTROINTESTINAL: CHANGES IN STRUCTURE OR FUNCTION OF SALIVARY GLANDS GASTROINTESTINAL: NAUSEA OR VOMITING	U.S. Public Health Service, Public Health Bulletin. Vol. 271, Pg. 40, 1941.
guinea pig	LD50	oral	145mg/kg (145mg/kg)	?	Gigiena i Sanitariya. For English translation, see HYSAAV. Vol. 53(7), Pg. 62, 1988.
guinea pig	LD50	unreported	145mg/kg (145mg/kg)	?	Gigiena Truda i Professional'nye Zabolevaniya. Labor Hygiene and Occupational Diseases. Vol. 31(8), Pg. 46, 1987.
man	TDLo	oral	71mg/kg (71mg/kg)	BEHAVIORAL: MUSCLE WEAKNESS LUNGS, THORAX, OR RESPIRATION: ACUTE PULMONARY EDEMA LUNGS, THORAX, OR RESPIRATION: DYSPNEA	Human Toxicology. Vol. 8, Pg. 345, 1989.
mouse	LD50	intraperitoneal	50mg/kg (50mg/kg)	?	National Technical Information Service. Vol. AD277-689,
mouse	LD50	unreported	331mg/kg (331mg/kg)	BRAIN AND COVERINGS: OTHER DEGENERATIVE CHANGES	Gigiena i Sanitariya. For English translation, see HYSAAV. Vol. 50(6), Pg. 78, 1985.
mouse	LDLo	oral	100mg/kg (100mg/kg)	?	Gigiena i Sanitariya. For English translation, see HYSAAV. Vol. 23(5), Pg. 14, 1958.
mouse	LDLo	subcutaneous	140mg/kg (140mg/kg)	?	Journal of the Society of Cosmetic Chemists. Vol. 12, Pg. 500, 1961.
quail	LD50	oral	100mg/kg (100mg/kg)	?	Archives of Environmental Contamination and Toxicology. Vol. 12, Pg. 355, 1983.
rabbit	LDLo	intraperitoneal	150mg/kg (150mg/kg)	LUNGS, THORAX, OR RESPIRATION: OTHER CHANGES	Journal of Infectious Diseases. Vol. 42, Pg. 473, 1928.
rabbit	LDLo	intravenous	300mg/kg (300mg/kg)	LUNGS, THORAX, OR RESPIRATION: DYSPNEA GASTROINTESTINAL: CHANGES IN STRUCTURE OR FUNCTION OF SALIVARY GLANDS	Archives of Internal Medicine. Vol. 36, Pg. 724, 1925.
rabbit	LDLo	oral	250mg/kg (250mg/kg)	CARDIAC: PULSE RATE INCREASE WITHOUT FALL IN BP LUNGS, THORAX, OR RESPIRATION: RESPIRATORY STIMULATION	Journal of Industrial Hygiene. Vol. 4, Pg. 386, 1923.
rabbit	LDLo	skin	5gm/kg (5000mg/kg)	?	Journal of Toxicology and Environmental Health. Vol. 2, Pg. 657, 1977.
rabbit	LDLo	subcutaneous	200mg/kg (200mg/kg)	CARDIAC: PULSE RATE INCREASE WITHOUT FALL IN BP LUNGS, THORAX, OR RESPIRATION: RESPIRATORY STIMULATION	Journal of Industrial Hygiene. Vol. 4, Pg. 386, 1923.
rat	LC50	inhalation	920mg/m3/4H (920mg/m3)	BEHAVIORAL: GENERAL ANESTHETIC KIDNEY, URETER, AND BLADDER: HEMATURIA GASTROINTESTINAL: NAUSEA OR VOMITING	National Technical Information Service. Vol. OTS0530403,
rat	LD50	intraperitoneal	37mg/kg (37mg/kg)	?	Journal of Toxicology and Environmental Health. Vol. 2, Pg. 657, 1977.
rat	LD50	oral	80mg/kg (80mg/kg)	?	Journal of Toxicology and Environmental Health. Vol. 2, Pg. 657, 1977.
rat	LD50	unreported	133mg/kg (133mg/kg)	?	Gigiena Truda i Professional'nye Zabolevaniya. Labor Hygiene and Occupational Diseases. Vol. 31(8), Pg. 46, 1987.
rat	LDLo	intravenous	50mg/kg (50mg/kg)	?	Bulletin de la Societe Royale des Sciences de Liege. Vol. 41, Pg. 302, 1972.
rat	LDLo	subcutaneous	170mg/kg (170mg/kg)	CARDIAC: PULSE RATE INCREASE WITHOUT FALL IN BP LUNGS, THORAX, OR RESPIRATION: DYSPNEA LUNGS, THORAX, OR RESPIRATION: RESPIRATORY STIMULATION	Journal of Industrial Hygiene. Vol. 4, Pg. 386, 1923.

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5. MSDS

2.Hazard identification

2.1 Classification of the substance or mixture

Acute toxicity - Oral, Category 3

Acute toxicity - Dermal, Category 3

Eye irritation, Category 2

Skin sensitization, Category 1

Acute toxicity - Inhalation, Category 3

Hazardous to the aquatic environment, short-term (Acute) - Category Acute 1

Hazardous to the aquatic environment, long-term (Chronic) - Category Chronic 1

2.2 GHS label elements, including precautionary statements

Pictogram(s)
Signal word	Danger
Hazard statement(s)	H301 Toxic if swallowed H311 Toxic in contact with skin H319 Causes serious eye irritation H317 May cause an allergic skin reaction H331 Toxic if inhaled H410 Very toxic to aquatic life with long lasting effects
Precautionary statement(s)
Prevention	P264 Wash ... thoroughly after handling. P270 Do not eat, drink or smoke when using this product. P280 Wear protective gloves/protective clothing/eye protection/face protection. P261 Avoid breathing dust/fume/gas/mist/vapours/spray. P272 Contaminated work clothing should not be allowed out of the workplace. P271 Use only outdoors or in a well-ventilated area. P273 Avoid release to the environment.
Response	P301+P310 IF SWALLOWED: Immediately call a POISON CENTER/doctor/\u2026 P321 Specific treatment (see ... on this label). P330 Rinse mouth. P302+P352 IF ON SKIN: Wash with plenty of water/... P312 Call a POISON CENTER/doctor/\u2026if you feel unwell. P361+P364 Take off immediately all contaminated clothing and wash it before reuse. P305+P351+P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. P337+P313 If eye irritation persists: Get medical advice/attention. P333+P313 If skin irritation or rash occurs: Get medical advice/attention. P362+P364 Take off contaminated clothing and wash it before reuse. P304+P340 IF INHALED: Remove person to fresh air and keep comfortable for breathing. P311 Call a POISON CENTER/doctor/\u2026 P391 Collect spillage.
Storage	P405 Store locked up. P403+P233 Store in a well-ventilated place. Keep container tightly closed.
Disposal	P501 Dispose of contents/container to ...

2.3 Other hazards which do not result in classification

none

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6. NMR Spectrum

ESR : CATION RADICAL, ELECTROXID., PH=4.8

13C NMR : in CDCl3

1H NMR : 90 MHz in CDCl3

IR : KBr disc

IR : nujol mull

Mass

Mass spectrum (electron ionization)

UV/Visible spectrum

7. Synthesis Route

106-50-3Total: 16 Synthesis Route

730-40-5 47 Suppliers

100-01-6 152 Suppliers

106-50-3 252 Suppliers

Literatures:
Journal of Molecular Catalysis A: Chemical, , vol. 318, # 1-2 p. 75 - 84
Yield: ~91%

100-25-4 8 Suppliers

100-01-6 152 Suppliers

106-50-3 252 Suppliers

Literatures:
Journal of Organometallic Chemistry, , vol. 309, p. C63 - C66
Yield: ~86%

100-01-6 152 Suppliers

61594-51-2

106-50-3 252 Suppliers

538-41-0 15 Suppliers

Literatures:
Journal of Chemical Research, Miniprint, , # 10 p. 2774 - 2788
Yield: ~2%

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8. Other Information

8.0 Merck: 14,7285

8.1 BRN: 742029

8.2 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

8.3 Chemical Properties: It is white to purple red crystal. It will turn purple red or dark brown when exposure to the air. It can be dissolved in water, alcohol, ether, chloroform and benzene.

8.4 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.

8.5 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%.

8.6 Acute toxicity: Oral-rat LD50: 80 mg/kg; oral-mouse LDL0: 100 mg/kg.

8.7 Irritation data: Skin-rabbit 250 mg/24 hours, moderate.

8.8 Hazardous characteristics of explosive: It is explosive when mixed with air.

8.9 Flammability and hazard characteristics: It is combustible upon fire, heat and oxidants with combustion releasing toxic fumes of nitrogen oxides.

8.10 Storage characteristics: Treasury: ventilation, low-temperature and dry; store it separately from oxidants and food additives.

8.11 Description: 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.

8.12 Chemical Properties: p-Phenylenediamines are white to slightly red crystalline solids. They have been described as gray “light brown” which may result from exposure to air.

8.13 Physical properties: White, red, or brown crystals. May darken on exposure to air.

8.14 Uses: p-Phenylenediamine is used for dyeing hairand fur, in the manufacture of azo dyes, inaccelerating vulcanization of rubber, and inantioxidants.

8.15 Uses: A hair dye component, paraphenylenediamine, as a contact allergen for treatment of inflammatory diseases.

8.16 Uses: 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.

8.17 Definition: ChEBI: A phenylenediamine in which the amino functions are at positions 1 and 4 of the benzene nucleus.

8.18 General Description: A white to purple crystalline solid (melting point 234 F) that turns purple to black in air. Flash point 309 F. Toxic by skin absorption, inhalation or ingestion. Used for production of aramid fiber, antioxidants, as a laboratory reagent, in photographic developing, and as a dye for hair and furs.

8.19 Air & Water Reactions: Oxidizes on exposure to air. The finely powdered base if suspended in air poses a significant dust explosion hazard. Soluble in water. Even as a solid will spot downwind areas purple/black (Roger Patrick, DuPont Engineer).

8.20 Reactivity Profile: p-Phenylenediamine is the stongest of the weak aromatic bases. p-Phenylenediamine neutralizes acids in weak exothermic reactions to form salts. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Reacts readily with oxidizing agents .

8.21 Health Hazard: p-Phenylenediamine is a moderate to highlytoxic compound; the acute, subacute andchronic toxicity of this amine is greater thanthat of its ortho- and meta-isomers. The acutepoisoning effects in animals were manifestedby lacrimation, salivation, ataxia, tremor,lowering of body temperature, increasedpulse rate, and respiratory depression. Anintraperitoneal dose of 10.8 mg/kg (sus pended in propylene glycol) in male ratscaused the formation of methemoglobin tothe extent of 12.9% after 5 hours (Watan abe et al. 1976). The hydrochloride of thisamine has been reported to cause edemaof the head and neck in animals dosedwith 120–350 mg/kg. p-Phenylenediamine in hair dye formulations produced skinirritation and mild conjunctivial inflamma tion in a variety of test animals (Lloydet al. 1977). In guinea pigs, contact pro duced skin sensitization. Hair dyes con taining p-phenylenediamine damaged visionwhen applied into eyes. In addition, allergicasthma and inflammation of the respiratorytract resulted from exposure to higher con centrations. Reports in early literature citeseveral cases of human poisoning resultingfrom the use of hair dyes containingp-phenylenediamine. The toxic symptomsreported were liver and spleen enlargement,vertigo, gastritis, jaundice, atrophy of liver,allergic asthma, dermatitis, cornea ulcer,burning and redness in eyes, and presbyopia(the latter effects arising from using hair dyeson the eyebrows and eye lashes).
Tests for mutagenicity in Salmonellamicrosome assays (in vitro) were negative.With metabolic activation, upon oxidationwith hydrogen peroxide, most mutagenictests showed positive results. Tests forcarcinogenicity were negative, although itslightly increased the overall tumor ratein experimental animals. After oxidationwith hydrogen peroxide, the amine producedtumors in the mammary glands of female rats(Rojanapo et al. 1986).

8.22 Fire Hazard: Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form.

8.23 Contact allergens: PPD is a colorless compound oxidized by hydrogen peroxide in the presence of ammonia. It is then polymerized to a color by a coupling agent. Although a wellknown allergen in hair dyes, PPD can be found as a cause of contact dermatitis in chin rest stains or in milk testers. It is also a marker of group sensitivity to para amino compounds such as benzocaine, some azo dyes, and some previous antibacterial sulphonamides.

8.24 Biochem/physiol Actions: p-Phenylenediamine causes allergic reactions with skin. It is widely used in hair dyes. It eventually forms Bandrowski′s base, which is found to be the primary cause for allergy. p-Phenylenediamine exposure results in dermatitis, urticaria and anaphylaxis. It acts as an electron donor and is known to reduce cytochrome c.

8.25 Safety Profile: Suspected carcinogen with experimental tumorigenic data. Poison by ingestion, subcutaneous, intravenous, and intraperitoneal routes. Mildly toxic by skin contact. A human skin irritant. Mutation data reported. Implicated in aplastic anemia, Can cause fatal liver damage. The p-form is more toxic and a stronger irritant than the 0and misomers. Wen used as a hair dye it caused vertigo, anemia, gastritis, exfoliative dermatitis, and death. Has caused asthma and other respiratory symptoms in the fur-dyeing industry. Combustible when exposed to heat or flame; can react vigorously with oxidizing materials. To fight fire, use water, Con, dry chemical. When heated to decomposition it emits acrid smoke and irritating fumes. See also other phenylenediamine entries and AMINES

8.26 Potential Exposure: p-Phenylenediamine has been used in dyestuff manufacture, in hair dyes; in photographic developers; in synthetic fibers; polyurethanes, and as a monomer and in the manufacture of improved tire cords. Also used as a gasoline additive and in making antioxidants.

8.27 Carcinogenicity: A number of dermal carcinogenesis bioassays have been reported using p-PDA alone in an organic solvent or in combination with hydrogen peroxide. An 85-week study in which female Swiss mice were treated with 5% or 10% p-PDAin acetone, 0.02 mL/animal applied topically, showed no evidence of carcinogenicity.
p-PDA was not found to be carcinogenic when administered by diet to male and female F344 rats and B6C3F1 mice at the dietary doses of 625 or 1250 ppm; the high dose approximated the maximum tolerated dose. An IARC Working Group concluded that on the basis of lack of human data, and inadequate animal data, p-PDA was not classifiable as to its carcinogenicity to humans. A recent meta-analysis of 11 case-control studies and one cohort study of the relationship between p-PDA exposure through use of personal hair dye and bladder cancer did not indicate any causal association.

8.28 Source: Bulk quantitities may contain m- and o-phenylenediamine and aniline as impurities.

8.29 Environmental fate: Biological. In activated sludge, 3.8% mineralized to carbon dioxide after 5 d (Freitag et al., 1985). In activated sludge inoculum, following a 20-d adaptation period, 80.0% COD removal was achieved (Pitter, 1976).
Photolytic. A carbon dioxide yield of 53.7% was achieved when phenylenediamine (presumably an isomeric mixture) adsorbed on silica gel was irradiated with light (λ >290 nm) for 17 h (Freitag et al., 1985).
Chemical/Physical. p-Phenylenediamine will not hydrolyze because it does not contain a hydrolyzable functional group (Kollig, 1993).

8.30 Shipping: UN1673 Phenylenediamines (o-, m-, p-), Hazard Class: 6.1; Labels: 6.1-Poisonous materials.

8.31 Purification Methods: Crystallise the diamine from EtOH or *benzene, and sublime it in vacuo; protect it from light. The acetate has m 304o. [Beilstein 13 IV 104.]

8.32 Incompatibilities: Dust may form explosive mixture with air. A strong reducing agent. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides, acid chlorides; acid anhydrides; chloroformates, and strong bases. Incompatible with organic anhydrides; isocyanates, aldehydes. Heat and light contribute to instability. Keep away from metals.

8.33 Waste Disposal: Controlled incineration whereby oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device.

8.34 Usage: p-Phenylenediamine is used as a precursor to aramid plastics, Kevlar fibers and to urethane polymers. It serves as a developing agent in photography, antioxidants in rubber products and as a vulcanization accelerator. It is used as a henna surrogate for temporary tattoos and as a histological stain for lipids such as myelin. It is an anti-fade reagent used in fluorescence microscopy to retard photobleaching of fluorescein and other fluorescent dyes. Furthermore, it is also an ingredient in hair dyes.

9. Computational chemical data

Molecular Weight: 108.14112g/mol
Molecular Formula: C₆H₈N₂
Compound Is Canonicalized: True
XLogP3-AA: null
Exact Mass: 108.068748264
Monoisotopic Mass: 108.068748264
Complexity: 54.9
Rotatable Bond Count: 0
Hydrogen Bond Donor Count: 2
Hydrogen Bond Acceptor Count: 2
Topological Polar Surface Area: 52
Heavy Atom Count: 8
Defined Atom Stereocenter Count: 0
Undefined Atom Stereocenter Count: 0
Defined Bond Stereocenter Count: 0
Undefined Bond Stereocenter Count: 0
Isotope Atom Count: 0
Covalently-Bonded Unit Count: 1
CACTVS Substructure Key Fingerprint: AAADccBjAAAAAAAAAAAAAAAAAAAAAAAAAAAwAAAAAAAAAAABAAAAHAAQAAAACAiBEAAwwIBAAACAACRCQACCAAAgAgAIiAAAZIgIICKAkZGAIABgkAAIyAcQAAAAAACAAAAAAAAAAQAAAAAAAAAAAAAAAA==

10. Question & Answer

Theoretical p-Phenylenediamine synthesis Aug 08 2021
I am thinking on an alternative synthesis of pPDA, in which I need counsel. I was thinking about these easy reactions, and I want to ask if it can be done, or maybe you can hint me some reference. I am trough the reading of nitration and reduction of aniline, or from 4-nitrochlorobenzene or the DuP...
P-phenylenediamine Production Process Jul 17 2021
How p-phenylenediamine (PPD) is produced? PPD is used as raw material for Kevlar (Para amid Fiber).

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