92-87-5

Basic information

• Product Name: Benzidine
• Synonyms: [1,1'-Biphenyl]-4,4'-diamine;4,4’-bianiline;4,4’-biphenylenediamine;4,4’-diamino-bipheny;4,4’-diaminodiphenyl;4,4’-diphenylenediamine;4,4'-Bianiline;4,4'-Biphenylenediamine
• CAS NO: 92-87-5
• Molecular Formula: C₁₂H₁₂N₂
• Molecular Weight: 184.24
• EINECS: 202-199-1
• Product Categories: Intermediates of Dyes and Pigments;Azo dye;Amines;Aromatics;Method 8270More...Close...;8000 Series Solidwaste Methods;Analytical Standards;AromaticsChemical Class;AromaticsMethod Specific;BenzidinesEPA;Chemical Class;A-BMethod Specific;Aryl Amines MAK III, Category 1Alphabetic;Alpha Sort;B;BA - BHEnvironmental Standards;Benzidines;Oeko-Tex Standard 100;Volatiles/ Semivolatiles
• Mol File: 92-87-5.mol
• Article Data: 78

Chemical Properties

• Melting Point: 127-128 °C
• Boiling Point: 402°C
• Flash Point: 11 °C
• Appearance: off-white solid
• Density: 1.25
• Vapor Pressure: 2.5E-05mmHg at 25°C
• Refractive Index: 1.6266 (estimate)
• Storage Temp.: 2-8°C
• Solubility: Soluble in ethanol (U.S. EPA, 1985) and ether (1 g/50 mL) (Windholz et al., 1983)
• PKA: 4.66(at 30℃)
• Water Solubility: Sparingly soluble.
• Stability: Stable. Combustible. Incompatible with strong oxidizing agents.
• Merck: 13,1077
• BRN: 742770
• CAS DataBase Reference: Benzidine(CAS DataBase Reference)
• NIST Chemistry Reference: Benzidine(92-87-5)
• EPA Substance Registry System: Benzidine(92-87-5)

Safety Data

• Hazard Codes: T,N,F,Xn
• Statements: 45-22-50/53-52/53-39/23/24/25-23/24/25-11-36/37/38-20/21/22-51/53-67
• Safety Statements: 53-45-60-61-36/37-16-7-36-26
• RIDADR: UN 1885 6.1/PG 2
• WGK Germany: 3
• RTECS: DC9625000
• F: 8
• HazardClass: 6.1(a)
• PackingGroup: II
• Hazardous Substances Data: 92-87-5(Hazardous Substances Data)

Usage

Chemical properties

It appears as white or light pink crystalline powder with a melting point of 125 ℃, the boiling point of 400 ℃, (98.7kPa) and the relative density of 1.250 (20/4 ℃). It is soluble in boiling ethanol, acetic acid and diluted hydrochloric acid, slightly soluble in ether, slightly soluble in boiling water and slightly soluble in cold water. Its color is darkened under air and light. Analysis reagents are usually benzodine hydrochloride or acetate, which is more soluble, and sulfate is commonly used in the industry. Benzidine acetate is white or nearly white crystals, being soluble in water, acetic acid and hydrochloric acid, as an indicator. Benzidine sulfate is a white crystalline powder or flaky crystal, being soluble in ether, very slightly soluble in water, dilute acid and alcohol.

Uses

Different sources of media describe the Uses of 92-87-5 differently. You can refer to the following data:
1. Important dye intermediates, benzidine and its derivatives can be used to make direct dyes, acid dyes, vat dyes, ice dyed dyes, sulfur dyes, reactive dyes and organic pigments. More than 250 dyes are made from benzidine, of which the most important is the direct black EW. The benzidine yellow is a widely used organic pigment.
2. Benzidine was used extensively in the manu facture of dyes. Because of its cancer-causingeffects in humans, its application in dyes hasbeen curtailed. Other uses of this compoundare in chemical analysis: as a reagent for thedetermination of hydrogen peroxide in milkand in the analysis of nicotine. Its hydrochlo ride is used as a reagent to analyze metalsand sulfate.
3. Manufacture of dyestuffs; hardener for rubber; laboratory reagent
4. Potentially mutagenic compound.

Toxicity

Benzidine is highly toxic, can be absorbed through the respiratory tract, skin and digestive tract, and is highly toxic, belonging to a carcinogen. Both solid and vapor are quickly absorbed through the skin, causing blood damage and causing bladder cancer. Mistakenly eating it can cause nausea, vomiting, liver and kidney damage. Mice oral LD50: 214mg / kg (body weight), rat oral LD50: 309 mg / kg (body weight). Rabbits and dogs have an oral minimum lethal dose of 200mg / kg (weight). The major toxic effect is hemorrhagic cystitis. The effect on the formation of methemoglobin is weak. It has stimulation effect on the skin and mucous membranes, being capable of causing contact dermatitis. It can cause liver cancer in mice and hamsters, causing rat liver, Zymbal gland, breast and colon cancer and cause bladder cancer in dogs. A variety of short-term mutagenicity test has given positive results. The International Agency for Research on Cancer (IARC) classifies it as a human carcinogen (well-documented) with the targets being bladder. The relative risk of bladder cancer in dyes chemical worker is 19 with the incubation period of about 19 years.

Description

Benzidine is a white, greyish-yellow, or slightly reddish crystalline solid or powder. The major use for benzidine is in the production of dyes, especially azo dyes in the leather, textile, and paper industries and as a synthetic precursor in the preparation and manufacture of dyestuffs. It is also used in the manufacture of rubber, as a reagent, and as a stain in microscopy. It is slightly soluble and slowly changes from a solid to a gas.

Chemical Properties

Different sources of media describe the Chemical Properties of 92-87-5 differently. You can refer to the following data:
1. Off-White Solid
2. Benzidine is a white, grayish-yellow, or slightly reddish crystalline solid or powder. The major use for benzidine is in the production of dyes, especially azo dyes in the leather, textile, and paper industries, as a synthetic precursor in the preparation and manufacture of dyestuffs. It is also used in the manufacture of dyes and rubber, as a reagent, and as a stain in microscopy. It is slightly soluble and slowly changes from a solid to a gas.
3. Benzidine is a white, grayish-yellow crystalline solid or powder. Turns brownish-red on exposure to air and light;

Physical properties

Grayish-yellow to pale reddish powder or crystals. Darkens on exposure to air or light. Odorless.

Definition

ChEBI: A member of the class of biphenyls that is 1,1'-biphenyl in which the hydrogen at the para-position of each phenyl group has been replaced by an amino group.

Preparation

1-Nitrobenzene restore 1,2-Diphenylhydrazine?turn with acid rearrangement.

Production Methods

Benzidine production is now exclusively for captive consumption and must be carried out in closed systems under stringent workplace controls. Benzidine is used in the synthesisofdyesanddyeintermediates,asahardenerforrubber, and as a laboratory reagent. The ?rst successful synthetic direct dye was Congo Red, a diazo derivative prepared from benzidinebyBoettigerin1884.Nearlyalldirectdyesareazo products. Congo Red is used in humans intravenously for the medical diagnosis of amyloidosis. The basis for its use is an unexplained af?nity for amyloid, which rapidly removes the dye from the blood. It is used medically for the management of profuse capillary hemorrhage such as the one occurring in septicemias and in the terminal phases of leukemia.

Synthesis Reference(s)

The Journal of Organic Chemistry, 41, p. 2661, 1976 DOI: 10.1021/jo00877a041Synthesis, p. 40, 1976 DOI: 10.1055/s-1976-23952

General Description

A grayish-yellow to grayish-red, crystalline solid. Toxic by ingestion, inhalation, and skin absorption. Combustion produces toxic oxides of nitrogen. Used to make other chemicals and in chemical and biological analysis.

Air & Water Reactions

Darkens on exposure to air and light. Soluble in hot water.

Reactivity Profile

Benzidine forms insoluble salts with sulfuric acid. Can be diazotized, acetylated and alkylated. Is hypergolic with red fuming nitric acid . Neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides.

Hazard

Highly toxic by ingestion, inhalation, and skin absorption. Confirmed carcinogen.

Health Hazard

Different sources of media describe the Health Hazard of 92-87-5 differently. You can refer to the following data:
1. Benzidine is a known carcinogen, causingbladder cancer in humans. Numerous reportsin the literature document its carcinogenicityin animals and humans. Oral or subcutaneousapplication of this compound in experimentalanimals produced tumors in liver, blood,lungs, and skin. The routes of entry intohuman body are primarily the inhalation of its dusts and absorption through skin. Whilehumans and dogs develop bladder cancerfrom benzidine, rodents primarily developliver cancer.Relatively little information is availableon the noncancer health hazard from ben zidine. The acute oral toxicity in animalswas moderate. Ingestion can produce nausea,vomiting, kidney, and liver damage. The oralLD50 values in test animals were in the range150–300 mg/kg.The mechanism of carcinogenicity of ben zidine is thought to involve its metabolictransformations forming reactive intermedi ates binding to DNA. Such DNA adductshave been identified in rodent liver. It testedpositive in most genotoxic tests. Its car cinogenicity may possibly be related to theslow rate of liver detoxification by acetyla tion allowing activation of benzidine or itsmetabolites in urine (Whysner et al. 1996)..
2. Poisonous if inhaled, swallowed or absorbed through skin. May cause contact dermatitis, irritation or sensitization. Ingestion may cause nausea and vomiting.
3. Exposure to benzidine causes irritation to the eyes. Laboratory animals exposed to benzidine at as low as 0.01% to 0.08% in food showed adverse health effects, such as organ weight decrease in the liver, kidney, and body weight, and an increase in spleen weight, swelling of the liver, and blood in the urine. Exposure may cause an increase in urination, blood in the urine, and urinary tract tumors. Benzidine is considered acutely toxic to humans by ingestion, with an estimated oral lethal dose of between 50 and 500 mg/kg. The symptoms of acute ingestion exposure include cyanosis, headache, mental confusion, nausea, and vertigo. Dermal exposure may cause skin rashes and irritation. Prolonged exposure to benzidine causes bladder injury in humans

Safety Profile

Confirmed human carcinogen producing bladder tumors. Experimental carcinogenic and tumorigenic data. Poison by ingestion and intraperitoneal routes. Human mutation data reported. Can cause damage to blood, including hemolysis and bone marrow depression. On ingestion causes nausea and vomiting, which may be followed by liver and kidney damage. Any exposure is considered extremely hazardous. When heated to decomposition it emits highly toxic fumes of NOx. See also AROMATIC AMINES.

Potential Exposure

Benzidine is used primarily in the manufacture of azo dyestuffs; there are over 250 of these produced. Other uses, including some which may have been discontinued, are in the rubber industry as a hardener; in the manufacture of plastic films; for detection of occult blood in feces, urine, and body fluids; in the detection of H2O2 in milk; in the production of security paper; and as a laboratory reagent in determining HCN, sulfate, nicotine, and certain sugars. No substitute has been found for its use in dyes. Free benzidine is present in the benzidine-derived azo dyes. According to industry, quality control specifications require that the level not exceed 20 ppm and in practice the level is usually below 10 ppm. Regulations in the USA concerning this chemical define strict procedures to avoid worker contact: mixture containing 0.1% or more must be maintained in isolated or closed systems; employees must observe special personal hygiene rules, and certain procedures must be followed in case of emergencies. Some p-phenylenediamine compounds have been used as rubber components, and DFG warns of danger of skin sensitization. Benzidine and dyes metabolized to benzidine: The following three benzidine-based dyes have been tested and found to cause cancer in rodents after oral exposure for 13 weeks (NCI 1978, IARC 1982): C.I. direct black 38 (CAS 1937-37-7) caused liver cancer in rats and mice, mammary-gland cancer in mice, and colon and urinary-bladder cancer in rats. C.I. direct Blue 6 (CAS 2602-46-2) caused liver cancer in rats. C.I. direct brown 95 (CAS 16071-86-6) caused hepatocellular adenoma in the liver and one malignant liver tumor in rats.

Carcinogenicity

Benzidine is known to be a human carcinogen based on sufficient evidence of carcinogenicity from studies in humans.

Source

Benzidine can enter the environment by transport, use, and disposal, or by dyes and pigments containing the compound. A photodegradation product of 3,3′-dichlorobenzidine. Based on laboratory analysis of 7 coal tar samples, benzidine was ND (EPRI, 1990).

Environmental fate

Biological. In activated sludge, <0.1% mineralized to carbon dioxide after 5 d (Freitag et al., 1985). Kincannon and Lin (1985) reported a half-life of 76 d when benzidine in sludge was applied to a sandy loam soil. Soil. Benzidine was added to different soils and incubated in the dark at 23 °C under a carbon dioxide-free atmosphere. After 1 yr, 8.3 to 11.6% of the added benzidine degraded to carbon dioxide primarily by microbial metabolism and partially by hydrolysis (Graveel et al., 1986). Tentatively identified biooxidation compounds using GC/MS include hydroxybenzidine, 3- hydroxybenzidine, 4-amino-4′-nitrobiphenyl, N,N′-dihydroxybenzidine, 3,3′-dihydroxybenzidine and 4,4′-dinitrobiphenyl (Baird et al., 1977). Under aerobic conditions, the half-life was estimated to be 2 to 8 d (Lu et al., 1977).Chemical/Physical. Benzidine is not subject to hydrolysis (Kollig, 1993). Reacts with HCl forming a salt (C12H12N2?2HCl) that is very soluble in water (61.7 mg/L at 25 °C) (Bowman et al., 1976).

storage

Benzidine should be kept stored in a cool, well-ventilated area, in closed, sealed containers and out of sunlight and away from heat.

Shipping

UN1885 Benzidine, Hazard Class: 6.1; Labels: 6.1—Poisonous materials. PGII.

Purification Methods

Its solution in *benzene is decolorized by percolating through two 2-cm columns of activated alumina, then concentrated until benzidine crystallises on cooling. Recrystallise alternately from EtOH and *benzene to constant absorption spectrum [Carlin et al. J Am Chem Soc 73 1002 1951]. It has also been crystallised from hot water (charcoal) and from diethyl ether. Dry it under vacuum in an Abderhalden pistol. Store it in the dark in a stoppered container. CARCINOGENIC. [Beilstein 13 IV 364.]

Properties and Applications

white or pink micro crystalline powder. Melting point 125 ℃, boiling point 400 ℃, relative density 1.250 (20 ℃). Soluble in ethanol, rare hydrochloric acid and acetic acid boiling, slightly soluble in ethyl ether, slightly soluble in water, very slightly soluble in cold water. In the air and light color line darker. This product is the dye and organic pigments intermediate.

Toxicity evaluation

Industries release benzidine into the environment in the form of liquid waste and sludges. Benzidine may also be released into the environment due to spillage during transport. In air, benzidine is found bound to suspended particles or as a vapor, which may be brought back to the earth’s surface by rain or gravity.

Incompatibilities

Dust may form explosive mixture with air. Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. On contact with strong reducing agents, such as hydrides may form flammable gases. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Contact with red fuming nitric acid may cause fire. Oxidizes in air. Neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides.

Waste Disposal

Incineration; oxides of nitrogen are removed from the effluent gas by scrubber, catalytic or thermal device. Package spill residues and sorbent media in 17 hour epoxy-lined drums and move to an EPA-approved disposal site. Treatment may include destruction by potassium permanganate oxidation, hightemperature incineration, or microwave plasma methods. 398 Benzidine Encapsulation by organic polyester resin or silicate fixation. These disposal procedures should be confirmed with responsible environmental engineering and regulatory officials.

Precautions

At high temperatures, benzidine breaks down and releases highly poisonous fumes. During use and handling, workers should wear butyl rubber gloves, goggles, and full body plastic coveralls and ensure that no skin is exposed.

InChI:InChI=1/C12H12N2/c13-11-5-1-9(2-6-11)10-3-7-12(14)8-4-10/h1-8H,13-14H2

Synthetic route

4-(4-bromophenyl)bromobenzene (92-86-4) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With C24H12Cu2F9N4O7; tetrabutylammomium bromide; ammonia; caesium carbonate In water; ethylene glycol at 110 - 140℃; for 16h;	100%
With bis(tri-ortho-tolylphosphine)palladium(0); (R)-(-)-1-[(S)-2-(dicyclohexylphosphino)ferrocenyl]ethyl-di-tert-butylphosphine; ammonia; sodium t-butanolate In 1,4-dioxane at 100℃; for 12h; Inert atmosphere;	79%

p-aminoiodobenzene (540-37-4) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With magnesium In water at 100℃; for 2h; Sealed tube;	96%
With tetrabutylammomium bromide; palladium diacetate; potassium carbonate In water; N,N-dimethyl-formamide Buchwald-Hartwig Coupling;	75%
With tetrabutylammonium tetrafluoroborate In acetonitrile at 20℃; for 8h; Electrochemical reaction;	38%

4,4'-dinitrobiphenyl (1528-74-1) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With hydrazine In methanol at 50℃;	95%
With sodium tetrahydroborate In ethanol at 24.84℃; for 2h;	95%
With hydrazine hydrate In ethanol at 70℃; for 4h; chemoselective reaction;	93%

4-chloro-aniline (106-47-8) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With carbon dioxide; aluminium; 1-butyl-3-methylimidazolium trifluoromethanesulfonimide at 65℃; under 116262 Torr; for 16h; Ullmann reaction;	95%
With 4-(3'-butyl-1'-imidazolio)-1-butanesulfonic acid hydrogen sulfate; aluminium In carbon dioxide at 45℃; under 116262 Torr; for 16h; Ullmann reaction; Supercritical conditions;	94%
With sulphonic acid functionalized porphyrin meso-substituted triazolium anchored ionic liquid at 20℃; for 16h; Catalytic behavior; Time; Ullmann Condensation; Irradiation;	91%

4-bromo-aniline (106-40-1) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With palladium 10% on activated carbon; potassium acetate; bis(pinacol)diborane In ethanol at 60℃; for 8h; Suzuki-Miyaura Coupling; Inert atmosphere;	94.3%
With potassium carbonate In N,N-dimethyl-formamide for 0.75h;	90%
With magnesium In water at 100℃; for 3.5h; Sealed tube;	85%

4,4'-diiodobiphenyl (3001-15-8) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With copper(l) iodide; tetra(n-butyl)ammonium hydroxide; ammonia In water at 25℃; for 24h; Inert atmosphere; Sealed tube; chemoselective reaction;	91%

N4,N4'-bis(diphenylmethylene)biphenyl-4,4'-diamine (1221066-38-1) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With hydrogenchloride In tetrahydrofuran; water at 20℃; for 2h;	82%

para-nitrophenyl bromide (586-78-7) → 4-bromo-aniline (106-40-1) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With hydrazine hydrate In ethanol at 70℃; for 4h; chemoselective reaction;	A 82% B 7%

(4-aminophenyl)boronic acid (89415-43-0) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With dipotassium peroxodisulfate; potassium carbonate In water; acetone for 3h;	80%

diphenyl hydrazine (122-66-7) → 2,4'-diaminobiphenyl (492-17-1) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
In ethanol; water	A 30% B 70%
With hydrogenchloride; lithium chloride In ethanol at 0℃; for 0.5h; Product distribution; kinetic isotope effects; reaction of var. labeled hydrazobenzenes, var. time;	A 91.5 mg B 15.8%
With hydrogenchloride; lithium chloride In ethanol at 0℃; for 0.5h;	A 91.5 mg B 15.8%

para-nitrophenyl bromide (586-78-7) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With L-Cysteine; potassium hydroxide In water; dimethyl sulfoxide at 100℃; for 0.333333h; Green chemistry;	70%
Multi-step reaction with 2 steps 1: copper / N,N-dimethyl-formamide / Heating 2: hydrazine; 3% Pd/C / ethanol / Heating View Scheme
Multi-step reaction with 2 steps 1: copper / N,N-dimethyl-formamide / 12 h / 160 °C 2: hydrazine; 3% Pd/C / ethanol / 12 h / 20 - 100 °C View Scheme

1,2,3,4-tetrahydroisoquinoline (635-46-1) + 4-amino-4'-nitrobiphenyl (1211-40-1) → quinoline (91-22-5) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With nickel-nitrogen-doped carbon framework In water at 145℃; for 18h; Inert atmosphere; Sealed tube; Green chemistry;	A 68% B 70%

diphenyl hydrazine (122-66-7) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With hydrogenchloride In water for 3h; Reflux;	67%
With hydrogenchloride In ethanol at 0℃; for 2.5h; Rearrangement;	51%
Thermodynamic data;

Azobenzene (1227476-15-4) → aniline (62-53-3) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With LiCrH4*2LiCl*2THF In tetrahydrofuran at 25℃; for 12h;	A 64% B 31%
With hydrogenchloride; N-benzylthiazolium bromide; benzaldehyde; triethylamine 1) MeOH, r.t., 20 h, 2) MeOH, HCl; Yield given. Multistep reaction. Yields of byproduct given;

p-nitrobenzene iodide (636-98-6) → p,p'-diaminobiphenyl (92-87-5) + p-aminoiodobenzene (540-37-4)

Conditions	Yield
With hydrazine hydrate In ethanol at 70℃; for 4h; chemoselective reaction;	A 27% B 55%

4-chlorobenzonitrile (100-00-5) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With L-Cysteine; potassium hydroxide In water; dimethyl sulfoxide at 100℃; for 0.666667h; Green chemistry;	55%

4-bromo-aniline (106-40-1) + zinc (7440-66-6) → NH2C6H4ZnBr (301300-48-1) + aniline (62-53-3) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With trifluoroacetic acid; cobalt(II) bromide; zinc dibromide In acetonitrile the mixt. in CH3CN was stirred at room temp., then arylbromide was added, stirred at room temp.; GC analysis;	A 40% B 52% C 0%

nitrobenzene (98-95-3) → aniline (62-53-3) + Azobenzene (1227476-15-4) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With lithium aluminium tetrahydride; titanium tetrachloride In diethyl ether at 20℃; for 15h; Solvent; Inert atmosphere;	A 48% B 25% C 5%

biphenyl (92-52-4) → 1,1'-biphenyl-2,2'-diamine (1454-80-4) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With 9,10-Dicyanoanthracene; ammonia In water; acetonitrile for 20h; Irradiation;	A 13% B 43%

4-bromo-2-fluoroaniline (367-24-8) → 2-fluorobenzidine + 3,3'-difluorobiphenyl-4,4'-diamine (448-97-5) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With sodium hydroxide; sodium formate; cetyltrimethylammonim bromide; palladium on activated charcoal In water for 4h; Heating;	A 15% B 33% C 10%
Stage #1: 4-bromo-2-fluoroaniline With palladium on activated charcoal; sodium formate; cetyltrimethylammonim bromide; sodium hydroxide In water for 4h; Reflux; Stage #2: With sodium acetate for 20h; Reflux;

bromochlorobenzene (106-39-8) + (adamantane-1,3-diyl)dimethanamine (52234-21-6) → 3-(4-chlorophenylaminomethyl)adamantane-1-carbaldehyde (1287287-13-1) + 4-chloro-N-[3-(4-chlorophenylaminomethyl)adamantan-1-ylmethyl]aniline (1287287-09-5) + 4-chloro-aniline (106-47-8) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In 1,4-dioxane for 7h; Inert atmosphere; Reflux;	A 25% B 31% C 18% D 7%

3-methyl-1,5-diphenyl-4,5-dihydro-1H-pyrazole (2515-46-0) → trans-2-styrylindole (29475-88-5) + (E)-benzalacetone (1896-62-4) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With PPA; Polyphosphoric acid (PPA) at 170℃; for 0.666667h;	A 30% B n/a C 0.35 g

3-methyl-1,5-diphenyl-4,5-dihydro-1H-pyrazole (2515-46-0) → trans-2-styrylindole (29475-88-5) + 1-Phenylbut-1-en-3-one (122-57-6) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With PPA at 130℃; Product distribution; Mechanism; studies of the Fischer indole synthesis;	A 25% B 21% C 18%
With PPA at 130℃;	A 25% B 21% C 18%

1.4-dibromobenzene (106-37-6) + 1,3-bis(aminoethyl)adamantane (51545-05-2) → C20H26BrNO + C26H33BrN2 + 4-bromo-N-(2-{3-[2-(4-bromophenylamino)ethyl]adamantan-1-yl}ethyl)aniline (1287287-20-0) + 4-bromo-aniline (106-40-1) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate In 1,4-dioxane for 7h; Inert atmosphere; Reflux;	A n/a B n/a C 11% D 7% E 9%

2-(2-bromophenyl)propanol (7073-69-0) + 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)aniline (214360-73-3) → C15H17NO + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium carbonate Suzuki Coupling; Inert atmosphere;	A 10% B n/a

tetrahydrofuran (109-99-9) + phenylcalcium iodide (24488-76-4) → biphenyl (92-52-4) + n-butyl phenyl ether (1126-79-0) + Azobenzene (1227476-15-4) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With dinitrogen monoxide Ambient temperature; Yield given;	A n/a B n/a C 6% D n/a
With dinitrogen monoxide Product distribution; Ambient temperature;	A n/a B n/a C 6% D n/a

pyridine (110-86-1) + 4,4'-Bis-(N'-phenyl-hydrazino)-biphenyl (855256-72-3) + acetic acid (64-19-7) → 4,4'-Bis-(phenyl-trans-azo)-biphenyl (120623-26-9) + aniline (62-53-3) + 4'-phenylazo-biphenyl-4-ylamine (1797-23-5) + p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
unter Kohlendioxid;

p-nitrobenzene iodide (636-98-6) → p,p'-diaminobiphenyl (92-87-5)

Conditions	Yield
With potassium hydroxide; hydrazine hydrate; palladium

acetic anhydride (108-24-7) + p,p'-diaminobiphenyl (92-87-5) → N,N'-Diacetylbenzidin (613-35-4)

Conditions	Yield
Acetylation;	100%
In acetone for 3h;	100%
for 0.00277778h; Green chemistry;	98%

p,p'-diaminobiphenyl (92-87-5) → benzidine dication

Conditions	Yield
With ammonium vanadate; sulfuric acid	100%
With ammonium cerium(IV) nitrate; sulfuric acid In water

4-chlorobenzaldehyde (104-88-1) + p,p'-diaminobiphenyl (92-87-5) → N4-[1-(4-Chloro-phenyl)-meth-(E)-ylidene]-biphenyl-4,4'-diamine

Conditions	Yield
for 120h; Ambient temperature;	100%

(NCNdipp)3Lu3(μ2-Me)3(μ3-Me)(μ3-CH2) + p,p'-diaminobiphenyl (92-87-5) → {(PhC(NC6H3iPr2-2,6)2)3Lu3(μ-Me)3(μ3-Me)}2{μ-η1:η1:η3:η3:η1:η1-N(C6H4)2N}

Conditions	Yield
In tetrahydrofuran at 20℃; for 48h;	100%

2-(2,4-dichlorophenoxy)acetyl chloride (774-74-3) + p,p'-diaminobiphenyl (92-87-5) → 2-(2,4-dichloro-phenoxy)-N-{4'-[2-(2,4-dichloro-phenoxy)-acetylamino]-biphenyl-4-yl}-acetamide

Conditions	Yield
With sodium hydroxide; PEG-600 In dichloromethane; water at 20℃; for 1h; Acylation;	99%

N-(tert-butoxycarbonyl)-D-proline (37784-17-1) + p,p'-diaminobiphenyl (92-87-5) → (2R,2'R)-di-tert-butyl 2,2'-(([1,1'-biphenyl]-4,4'-diylbis(azanediyl))bis(carbonyl))bis(pyrrolidine-1-carboxylate)

Conditions	Yield
With N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In dichloromethane at 20℃; for 2h;	99%
With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 2h;	99%

3-tert-butyl-2-hydroxybenzaldehyde (24623-65-2) + p,p'-diaminobiphenyl (92-87-5) → C34H36N2O2

Conditions	Yield
With formic acid In methanol at 20℃; for 25h; Reflux;	99%

bis(1H-benzo[d][1,2,3]triazol-1-yl)methanethione (4314-19-6) + p,p'-diaminobiphenyl (92-87-5) → N,N'-bis(benzotriazole-1-thiocarbamoyl)benzidine

Conditions	Yield
In acetonitrile for 0.166667h; Milling; Green chemistry;	99%

C9H11ClOSn + p,p'-diaminobiphenyl (92-87-5) → C30H30Cl2N2Sn2

Conditions	Yield
In melt for 0.333333h;	99%

benzenesulfonyl chloride (98-09-9) + p,p'-diaminobiphenyl (92-87-5) → N,N'-(biphenyl-4,4'-diyl)dibenzenesulfonamide (52945-06-9)

Conditions	Yield
With pyridine In dichloromethane at 20℃; for 4h; pH=Ca. 8;	98%
With pyridine

meta-bromotoluene (591-17-3) + chlorobenzene (108-90-7) + p,p'-diaminobiphenyl (92-87-5) → 4,4'-bis(m-tolylphenylamino)biphenyl (65181-78-4)

Conditions	Yield
With chloro[2-(dicyclohexylphosphino)-3 ,6-dimethoxy-2’,4’, 6’-triisopropyl- 1,1’-biphenyl] [2-(2-aminoethyl)phenyl]palladium(II); sodium t-butanolate; ruphos In 1,4-dioxane at 110℃; for 24h; Inert atmosphere;	98%

9-chloro-1,2,3,4-tetrahydroacridine (5396-30-5) + trifluoroacetic acid (76-05-1) + p,p'-diaminobiphenyl (92-87-5) → N-(4-{4-[(1,2,3,4-tetrahydroacridin-9-yl)amino]phenyl}phenyl)-1,2,3,4-tetrahydroacridin-9-amine tetra(trifluoroacetic acid)

Conditions	Yield
Stage #1: 9-chloro-1,2,3,4-tetrahydroacridine; p,p'-diaminobiphenyl With trichlorophosphate In pentan-1-ol for 40h; Reflux; Stage #2: trifluoroacetic acid In water	98%

2,3-dihydroxybenzaldehyde (24677-78-9) + p,p'-diaminobiphenyl (92-87-5) → bis-(2,3-dihydroxy-benzylidene)-benzidine

Conditions	Yield
In methanol	97%
With ethanol

di-tert-butyl dicarbonate (24424-99-5) + p,p'-diaminobiphenyl (92-87-5) → tert-butyl (4'-amino-[1,1'-biphenyl]-4-yl)carbamate (206182-66-3)

Conditions	Yield
With potassium carbonate In tetrahydrofuran; water; N,N-dimethyl-formamide at 20℃; for 5h;	97%
With sodium carbonate In 1,4-dioxane Ambient temperature;	90%
In 1,4-dioxane at 20℃; for 24h; Inert atmosphere;	85%
In 1,4-dioxane for 24.5h; Inert atmosphere;	85%
In 1,4-dioxane at 20℃; for 25h; Inert atmosphere;	85%

p,p'-diaminobiphenyl (92-87-5) + naphthalen-2-ylmethyl pyridine-2-carbimidothioate hydrobromide → N,N'-([1,1'-biphenyl]-4,4'-diyl)dipicolinimidamide dihydrochloride

Conditions	Yield
Stage #1: p,p'-diaminobiphenyl; naphthalen-2-ylmethyl pyridine-2-carbimidothioate hydrobromide In ethanol; acetonitrile at 20℃; Cooling with ice; Stage #2: With sodium hydroxide In ethanol at 0℃; pH=Ca. 10; Stage #3: With hydrogenchloride In ethanol at 0 - 20℃;	97%

1-(benzyloxy)-3-((2,4-difluorobenzyl)carbamoyl)-2-oxo-1,2-dihydro-1,8-naphthyridin-4-yl 4-methylbenzenesulfonate (1613522-41-0) + p,p'-diaminobiphenyl (92-87-5) → 4-((4'-amino-[1,1'-biphenyl]-4-yl)amino)-1-(benzyloxy)-N-(2,4-difluorobenzyl)-2-oxo-1,2-dihydro-1,8-naphthyridine-3-carboxamide (1613522-45-4)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 50℃; for 1h;	97%

2-(2-chloroacetamido)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile (58125-40-9) + p,p'-diaminobiphenyl (92-87-5) → 2-((4'-amino-[1,1'-biphenyl]-4-yl)amino)-N-(3-cyano-4,5,6,7-tetrahydrobenzo[b]thiophen-2-yl)acetamide

Conditions	Yield
In 1,4-dioxane for 4h; Reflux;	97%

C12H8ClN3OS (188047-59-8) + p,p'-diaminobiphenyl (92-87-5) → C36H28Cl2N8O2S2 (1190107-86-8)

Conditions	Yield
In acetonitrile at 20 - 25℃; for 0.75h; Sonication;	96%

4-methoxy-benzaldehyde (123-11-5) + phosphonic acid diethyl ester (762-04-9) + p,p'-diaminobiphenyl (92-87-5) → tetraethyl (1,4-phenylene bis(azanediyl))bis(p-methoxymethylene)diphosphonate

Conditions	Yield
With 1,10-((ethane-1,2-diylbis(oxy))bis(ethane-2,1-diyl))bis(3-sulfo-1H benzimidazol-3-ium)chloride In neat (no solvent) at 50℃; for 1h; Green chemistry;	96%

p,p'-diaminobiphenyl (92-87-5) → 4,4'-dinitrobiphenyl (1528-74-1)

Conditions	Yield
With tert.-butylhydroperoxide; potassium iodide In water; acetonitrile at 80℃; for 15h;	95%
With tert.-butylhydroperoxide; 3 A molecular sieve; zirconium(IV) tert-butoxide In dichloromethane for 5h; Ambient temperature;	90%
With sulfuric acid Diazotization.Behandlung der Diazoniumsalz-Loesung mit NaNO2 und Kupfer(I)-kupfer(II)-sulfit;

4-hydroxy-benzaldehyde (123-08-0) + p,p'-diaminobiphenyl (92-87-5) → 4-amino-4'-(p-hydroxy)benzylideneimino-1,1'-biphenyl (132556-90-2)

Conditions	Yield
With toluene-4-sulfonic acid In N,N-dimethyl-formamide at 80℃; for 4h;	95%
With piperidine In ethanol Heating;

2-isocyanatobenzoyl chloride (5100-23-2) + p,p'-diaminobiphenyl (92-87-5) → 3,3'-(4,4'-Biphenylene)bis(2,4-dioxo-1,2,3,4-tetrahydroquinazoline) (131526-24-4)

Conditions	Yield
With triethylamine In toluene 1.) 1 h, 0 deg C, 2.) 1 h, room temperature, 3.) 36 h, reflux;	95%

formic acid (64-18-6) + p,p'-diaminobiphenyl (92-87-5) → N-monoformylbenzidine

Conditions	Yield
In di-isopropyl ether Heating;	95%

chlorobenzene (108-90-7) + p,p'-diaminobiphenyl (92-87-5) → N,N'-diphenyl-p-phenylenediamine (531-91-9)

Conditions	Yield
With sodium t-butanolate; Ni(0)*2IPr In 1,4-dioxane at 100℃;	95%
With palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl; sodium hydroxide In tetrahydrofuran; ethanol; water; toluene; tert-butyl alcohol at 100℃; for 16h; Glovebox; Inert atmosphere; Schlenk technique;	116.5 mg

salicylaldehyde (90-02-8) + p,p'-diaminobiphenyl (92-87-5) → 4,4'-bis{5-(1-formyl-2-hydroxyphenyl)azo}diphenyl (70952-41-9)

Conditions	Yield
Stage #1: p,p'-diaminobiphenyl With hydrogenchloride; sodium nitrite In water Cooling with ice; Stage #2: salicylaldehyde With sodium hydroxide In water at 0 - 5℃;	95%
Multistep reaction.;	76%

9-hydroxyxanthene (90-46-0) + p,p'-diaminobiphenyl (92-87-5) → N4,N4'-di(9H-xanthen-9-yl)-[1,1'-biphenyl]-4,4’-diamine (1408244-78-9)

Conditions	Yield
With ferric hydrogen sulphate In ethanol for 0.5h; Reflux; regioselective reaction;	95%

Upstream product

• 110-86-1 pyridine 
• 855256-72-3 4,4'-Bis-(N'-phenyl-hydrazino)-biphenyl 
• 64-19-7 acetic acid 
• 122-66-7 diphenyl hydrazine 
• 98-95-3 nitrobenzene 
• 5435-44-9 (E)-3-Ureido-but-2-enoic acid ethyl ester 
• 1227476-15-4 Azobenzene 
• 6921-34-2 benzylmagnesium chloride 
• 495-48-7 azoxybenzene 
• 949-88-2 1-(4-chlorophenyl)-2-phenylhydrazine 
• 540-37-4 p-aminoiodobenzene 
• 1562-93-2 4-(2-phenyldiazen-1-yl)benzoic acid 
• 92-52-4 biphenyl 
• 106-47-8 4-chloro-aniline 

Downstream Products

• 92-90-0 N,N'-biphenyl-4,4'-diyl-bis-acetoacetamide 
• 2177-26-6 4,4'-bis-(2-pyridinethiocarboxamido)-biphenyl 
• 76257-64-2 1,1'-biphenyl-4,4'-diyl-bis-pyrrolidin-2-one 
• 3278-30-6 1,1'-biphenyl-4,4'-diyl-bis-pyrrole-2,5-dione 
• 80902-25-6 1,1'-biphenyl-4,4'-diyl-bis-pyrrolidine-2,5-dione 
• 349640-92-2 N,N'-(biphenyl-4,4'-diyl)dithiophene-2-carboxamide 
• 856211-59-1 2-(4'-amino-biphenyl-4-ylcarbamoyl)-nicotinic acid 
• 108247-78-5 N,N'-bis-(3-[2]furyl-3-oxo-propionyl)-benzidine 
• 108247-77-4 N,N'-bis-(3-oxo-3-[2]thienyl-propionyl)-benzidine 
• 27327-81-7 2-(4'-amino-biphenyl-4-yl)-benz[de]isoquinoline-1,3-dione 
• 613-35-4 N,N'-Diacetylbenzidin 
• 80396-12-9 N,N'-biphenyl-4,4'-diyl-bis-diacetamide 

Relevant articles and documents

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Surface Silylation of Hybrid Benzidinium Lead Perovskite and its Influence on the Photocatalytic Activity

Surface coating of benzidinium lead iodide perovskite has been successfully accomplished by silanization with three different silylating agents, obtaining samples with average thickness from 2 to 6 nm as revealed by transmission electron microscopy. The obtained (organo)silica-coated hybrid perovskites exhibit enhanced hydrophobic character and, therefore, increased stability against moisture. However, its photocatalytic activity towards the cis-to-trans isomerization of stilbene diminishes as a function of the coating thickness, although a notable activity for this photocatalytic reaction is still observed.

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Ligand and Base Free Synthesis of Biaryls from Aryl Halides in Aqueous Media with Recyclable Ti0.97Pd0.03O1.97 Catalyst

Abstract: Facile protocol for the synthesis of biaryls from aryl halides in presence of magnesium metal without prior formation of organometallic intermediate has been exploited. Irrespective of aqueous medium, Ti0.97Pd0.03O1.97 catalyst supports C–C bond formation reaction in presence of metals rather than dehalogenation without any additives. Homocoupling of 16 different aryl halides furnished corresponding biphenyls in good yield with better functional group tolerance. The recovery of the catalyst was carried out by employing catalyst coated cordierite monolith up to 7th cycle with high yields. A new approach for the cross-coupling reaction is also attempted. Graphic Abstract: [Figure not available: see fulltext.]

Cu/CuxS-Embedded N,S-Doped Porous Carbon Derived in Situ from a MOF Designed for Efficient Catalysis

The reasonable design of the precursor of a carbon-based nanocatalyst is an important pathway to improve catalytic performance. In this study, a simple solvothermal method was used to synthesize [Cu(TPT)(2,5-tdc)] ? 2H2O (Cu-MOF), which contains N and S atoms, in one step. Further in-situ carbonization of the Cu-MOF as the precursor was used to synthesize Cu/CuxS-embedded N,S-doped porous carbon (Cu/CuxS/NSC) composites. The catalytic activities of the prepared Cu/CuxS/NSC were investigated through catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). The results show that the designed Cu/CuxS/NSC has exceptional catalytic activity and recycling stability, with a reaction rate constant of 0.0256 s?1, and the conversion rate still exceeds 90 % after 15 cycles. Meanwhile, the efficient catalytic reduction of dyes (CR, MO, MB and RhB) confirmed its versatility. Finally, the active sites of the Cu/CuxS/NSC catalysts were analyzed, and a possible multicomponent synergistic catalytic mechanism was proposed.

Cobalt-catalyzed cross-coupling reactions of aryl- And alkylaluminum derivatives with (hetero)aryl and alkyl bromides

A simple cobalt complex, such as Co(phen)Cl2, turned out to be a highly efficient and cheap precatalyst for a host of cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl and alkyl bromides. New C(sp2)-C(sp2) and C(sp2)-C(sp3) bonds were formed in good to excellent yields and with high chemoselectivity, under mild reaction conditions.