106-50-3

Basic information

• Product Name: p-Phenylenediamine
• Synonyms: 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
• CAS NO: 106-50-3
• Molecular Formula: C₆H₈N₂
• Molecular Weight: 108.1411
• EINECS: 203-404-7
• Product Categories: Chemistry;Fluorenes, etc. (reagent for high-performance polymer research);Functional Materials;Reagent for High-Performance Polymer Research;VARIOUSAMINE;Intermediates of Dyes and Pigments;1,4-Benzenediamine;Fluorescent;Fine Chemicals;Amines;Aromatics;Intermediates & Fine Chemicals;Pharmaceuticals;Environmental;amine series
• Mol File: 106-50-3.mol
• Article Data: 378

Chemical Properties

• Melting Point: 138-143℃
• Boiling Point: 267.4 °C at 760 mmHg
• Flash Point: 135.9 °C
• Appearance: white to light purple solid
• Density: 1.15 g/cm³
• Vapor Density: 3.7 (vs air)
• Vapor Pressure: 0.00817mmHg at 25°C
• Refractive Index: 1.66
• Storage Temp.: 2-8°C
• Solubility: Soluble in alcohol, chloroform, ether and hot benzene.
• PKA: 4.17(at 25℃)
• Water Solubility: 47 g/L (25℃)
• Stability: Stable, but oxidizes when exposed to air. Incompatible with oxidizing agents. Store under inert atmosphere.
• Merck: 14,7285
• BRN: 742029
• CAS DataBase Reference: p-Phenylenediamine(CAS DataBase Reference)
• NIST Chemistry Reference: p-Phenylenediamine(106-50-3)
• EPA Substance Registry System: p-Phenylenediamine(106-50-3)

Safety Data

• Hazard Codes: T:Toxic;;
• Statements: R23/24/25:; R36:; R43:; R50/53:
• Safety Statements: S28A:; S36/37:; S45:; S60:; S61:
• RIDADR: UN 1673 6.1/PG 3
• WGK Germany: 3
• RTECS: SS8050000
• F: 8-10-23
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 106-50-3(Hazardous Substances Data)

Usage

Description

Different sources of media describe the Description of 106-50-3 differently. You can refer to the following data:
1. 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
2. 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.

Chemical Properties

Different sources of media describe the Chemical Properties of 106-50-3 differently. You can refer to the following data:
1. 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. p-Phenylenediamines are white to slightly red crystalline solids. They have been described as gray “light brown” which may result from exposure to air.

Uses

Different sources of media describe the Uses of 106-50-3 differently. You can refer to the following data:
1. 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.
2. p-Phenylenediamine is used for dyeing hairand fur, in the manufacture of azo dyes, inaccelerating vulcanization of rubber, and inantioxidants.
3. A hair dye component, paraphenylenediamine, as a contact allergen for treatment of inflammatory diseases.
4. 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%.

Acute toxicity

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

Irritation data

Skin-rabbit 250 mg/24 hours, moderate.

Hazardous characteristics of explosive

It is explosive when mixed with air.

Flammability and hazard characteristics

It is combustible upon fire, heat and oxidants with combustion releasing toxic fumes of nitrogen oxides.

Storage characteristics

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

Physical properties

White, red, or brown crystals. May darken on exposure to air.

Definition

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

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.

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).

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 .

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).

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.

Flammability and Explosibility

Nonflammable

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.

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.

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

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.

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.

Source

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

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).

Shipping

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

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.]

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.

Waste Disposal

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

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

Synthetic route

para-dinitrobenzene (100-25-4) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With sodium tetrahydroborate In water at 50℃; for 0.0833333h; Green chemistry;	100%
With hydrogen In tetrahydrofuran at 20℃; under 760.051 Torr; for 3h; chemoselective reaction;	100%
With sodium hypophosphite monohydrate; 5%-palladium/activated carbon; hypophosphorous acid In 2-methyltetrahydrofuran; water for 3h; Sonication; chemoselective reaction;	99%

4-nitrophenyl azide (1516-60-5) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
Stage #1: 4-nitrophenyl azide With hydrazine hydrate at 135℃; for 3h; Stage #2: With potassium hydroxide at 135℃; for 24h;	100%
With hydrogen In ethanol at 20℃; under 760.051 Torr; for 5h;	94%
With hydrogenchloride; tin

4-nitro-aniline (100-01-6) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With palladium diacetate; carbon monoxide; triphenylphosphine In water; acetic acid at 56℃; under 532 Torr; for 11h;	100%
With triethylsilane; palladium dichloride In ethanol at 20℃; for 1h; Inert atmosphere;	100%
With 10% palladium on activated charcoal; hydrogen for 2h;	100%

p-nitrophenyl isocyanide (1984-23-2) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With graphitic carbon nitride; hydrazine hydrate In water at 70℃; for 24h; Irradiation; Sealed tube; Green chemistry; chemoselective reaction;	100%

nitrobenzene (98-95-3) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
Stage #1: nitrobenzene With Oxalamide; tetramethyl ammoniumhydroxide; ammonia In dimethyl sulfoxide at 100℃; under 18751.9 Torr; for 7h; Autoclave; Stage #2: With 5%-palladium/activated carbon; hydrogen In methanol at 55℃; under 9000.9 Torr; for 4h; Reagent/catalyst; Autoclave;	99.1%
Multi-step reaction with 2 steps 1: urea, monosodium salt; urea / dimethyl sulfoxide / 2 h / 90 °C 2: 5%-palladium/activated carbon; hydrogen / ethanol / 80 °C / 15001.5 - 22502.3 Torr View Scheme

N-acetyl-p-phenylenediamine (122-80-5) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With ammonium bromide; ethylenediamine at 70℃; for 5h; Microwave irradiation; Inert atmosphere; neat (no solvent);	99%
With ammonium iodide; hydrazine at 50℃; for 12h;	99%
With ammonium iodide; hydrazine hydrate at 50℃; for 12h; Inert atmosphere; Sealed tube;	99%

4-azidoaniline (14860-64-1) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With iron(III) oxide; hydrazine hydrate In water at 120℃; for 2h; Concentration; Temperature; Time; Inert atmosphere;	99%
With zinc In methanol at 20℃; for 5h;	95%
With hydrazine hydrate In ethanol at 20℃; chemoselective reaction;	90%

1.4-dibromobenzene (106-37-6) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With C24H12Cu2F9N4O7; tetrabutylammomium bromide; ammonia; caesium carbonate In water at 110 - 140℃; for 16h;	99%
With ammonia; C16H16N2O2*0.8Ni*0.2Cu at 85℃; under 1500.15 Torr; for 8.5h; Autoclave; Inert atmosphere;	92%
Multi-step reaction with 2 steps 1: copper(ll) sulfate pentahydrate; sodium L-ascorbate; potassium carbonate; ammonium hydroxide / dimethyl sulfoxide; glycerol / 8 h / 100 °C 2: copper(ll) sulfate pentahydrate; sodium L-ascorbate; potassium carbonate; ammonium hydroxide / dimethyl sulfoxide; glycerol / 8 h / 100 °C View Scheme

para-diiodobenzene (624-38-4) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With C24H12Cu2F9N4O7; tetrabutylammomium bromide; ammonia; caesium carbonate In water at 110 - 140℃; for 16h;	99%
With ammonia at 20℃; Reagent/catalyst; Temperature;	97%
With [10%-Pd/Al2O3]; ammonia at 250℃; Catalytic behavior; Temperature; Reagent/catalyst; Inert atmosphere;

para-dinitrobenzene (100-25-4) + 12percent nickel/Al-SBA-15 fiber → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With hydrogen In ethanol at 109.84℃; under 18751.9 Torr; for 7.5h; Autoclave; Green chemistry; chemoselective reaction;	99%

1,4-bromoiodobenzene (589-87-7) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With [Cu2(2,7-bis(pyridin-2-yl)-l,8-naphthyridine)(OH)(CF3COO)3]; tetrabutylammomium bromide; ammonia; caesium carbonate In water at 120℃; for 16h; Sealed tube; chemoselective reaction;	98%
Multi-step reaction with 2 steps 1: chlorotris(triphenylphosphine)cobalt(I); bis[2-(diphenylphosphino)phenyl] ether / toluene / 12 h / 100 °C 2: hydrogenchloride; water / methanol / 1 h / 20 °C View Scheme

p-aminoiodobenzene (540-37-4) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With copper(l) iodide; tetra(n-butyl)ammonium hydroxide; ammonia In water at 25℃; for 24h; Inert atmosphere; Sealed tube; chemoselective reaction;	97%
With acetamidine hydrochloride; caesium carbonate; L-proline; copper(l) iodide In N,N-dimethyl-formamide at 120℃; for 10h;	94%
With copper(l) iodide; ammonia; potassium carbonate In water; dimethyl sulfoxide at 100℃; for 12h;	93%

N-(tert-butoxycarbonyl)-1,4-phenylenediamine (71026-66-9) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
In various solvent(s) at 150℃; for 0.5h; microwave irradiation;	97%
With 1,1,1,3',3',3'-hexafluoro-propanol at 150℃; for 0.5h; Product distribution / selectivity; Microwave irradiation;	97%
With 1,1,1,3',3',3'-hexafluoro-propanol at 150℃; for 0.5h; Product distribution / selectivity; Microwave irradiation;	97%
With 2,2,2-trifluoroethanol at 150℃; for 3h; Product distribution / selectivity; Microwave irradiation;	93%

1,4-diazidobenzene (2294-47-5) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With chloro-trimethyl-silane; sodium iodide In acetonitrile for 0.166667h; Ambient temperature;	96%
With water for 5h; Inert atmosphere; UV-irradiation; Sealed tube; chemoselective reaction;	92%

1,4-Benzochinondioxim (105-11-3, 6133-83-1, 6421-98-3) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With sodium tetrahydroborate at 20℃; for 0.0333333h; neat (no solvent, solid phase);	96%
With iron oxide; zirconium(IV) chloride; sodium cyanoborohydride In neat (no solvent) at 20℃; for 0.0833333h;	94%

p-benzoquinone dioxime (105-11-3, 6133-83-1, 6421-98-3) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With (pyridine)(tetrahydroborato)zinc In tetrahydrofuran for 1h; Heating;	95%
With fermenting. yeast
With hydrogenchloride; tin(ll) chloride

aniline yellow (60-09-3) → aniline (62-53-3) + 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With formic acid; zinc In methanol at 20℃; for 0.0833333h;	A 95% B 93%
With hydrazine hydrate; aluminium In ethanol Heating;	A 94% B 93%
With ammonium acetate; zinc In methanol at 20℃; for 0.05h;	A n/a B 93%

C12H8Cl6N2O6 → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With acetic acid; zinc In water at 0℃; for 0.5h;	95%

N-(4-Nitrophenyl)acetamide (104-04-1) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With [Zn(BH4)2(py)] In tetrahydrofuran for 3.1h; Heating;	94%
With mineral acid durch elektrolytische Reduktion;
With hydrogenchloride; tin

N,N,N',N'-tetrakis(trimethylsilyl)-1,4-phenylenediamine (25811-68-1) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With hydrogenchloride; water In methanol at 20℃; for 1h;	94%
With hydrogenchloride In diethyl ether

aniline yellow (60-09-3) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With ammonium formate; nickel In methanol at 20℃; for 0.0833333h;	93%
With hydrazine hydrate In ethanol Heating;	93%
With water; zinc

4-Aminoazobenzene (60-09-3) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With nickel; hydrazinium monoformate In methanol for 0.0833333h; Heating;	93%

4-bromo-aniline (106-40-1) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With ammonium hydroxide; trans-bis(triphenylphosphine)palladium dichloride; sodium carbonate In neat (no solvent) at 80℃; for 7h;	93%
With ammonium hydroxide; (2-methylacetatobenzyl)triphenylphosphonium hexabromodipalladate(II) at 60℃; for 5h;	92%
With ammonium hydroxide; bis[(2-methylacetatobenzyl)tri(p-tolyl)phosphonium] hexabromodipalladate(II) In neat (no solvent) at 60℃; for 5h;	90%

terephthalamide (3010-82-0) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With water; chlorine; sodium hydroxide at 5 - 80℃; for 4.5h; Reagent/catalyst; Hofmann Rearrangement;	93%

N,N-dibenzyl-4-nitroaniline (65052-89-3) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With formic acid; potassium hydroxide In ethanol at 70℃; for 1h;	93%

benzyl 4-(nitro)phenylcarbamate (53821-12-8) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With hydrogen In ethanol at 20℃; under 760.051 Torr; for 5h;	92%
With methanol; sodium tetrahydroborate; nickel(II) chloride hexahydrate at 20℃; for 0.25h; chemoselective reaction;	86%

para-dichlorobenzene (106-46-7) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With ammonium hydroxide; copper(II) ferrite at 150℃; under 31503.2 - 36003.6 Torr; for 10h; Catalytic behavior; Pressure; Temperature; Autoclave;	91.7%
With copper(l) iodide; 2,2-[μ-(N,N'-piperazindiyl)dimethyl]-bis(4,6-di-tert-butyl-phenol); ammonia at 150℃; under 31503.2 Torr; for 10h; Reagent/catalyst; Temperature; Pressure; Autoclave;	90.6%
With ammonium hydroxide; 1,10-Phenanthroline; copper(I) bromide at 150℃; under 45004.5 Torr; for 0.00555556h; Reagent/catalyst; Temperature; Pressure;	90.6%

4-Azidoaniline hydrochloride → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With tris-(trimethylsilyl)silane; 2-hydroxyethanethiol In water at 100℃; for 4h;	90%

p-dinitrosobenzene (105-12-4) → 1,4-phenylenediamine (106-50-3)

Conditions	Yield
With Saccharomyces cerevisiae BY In methanol at 20℃; pH=7.0; aq. buffer; Enzymatic reaction;	90%

benzaldehyde (100-52-7) + 1,4-phenylenediamine (106-50-3) → N,N'-dibenzylidene-benzene-1,4-diamine (797-20-6)

Conditions	Yield
With aluminum oxide for 5h; Milling;	100%
In chloroform at 20℃; Inert atmosphere;	82%
With sodium hydrogen sulfate; silica gel for 0.0666667h; microwave irradiation;	78%

salicylaldehyde (90-02-8) + 1,4-phenylenediamine (106-50-3) → 2,2'-{(1E,1'E)-[1,4-phenylenebis(azanylylidene)]bis(methanylylidene)}diphenol (119643-02-6)

Conditions	Yield
In methanol for 0.5h; Reflux;	100%
In ethanol for 2h; Heating;	88%
With tin(II) chloride dihdyrate In dichloromethane at 20℃; for 6h;	87.7%

p-toluenesulfonyl chloride (98-59-9) + 1,4-phenylenediamine (106-50-3) → N,N'-ditosyl-p-phenylenediamine (41595-29-3)

Conditions	Yield
With pyridine for 2h; Reflux;	100%
With triethylamine In dichloromethane at 4℃;	100%
With sodium hydroxide In diethyl ether at 0 - 20℃;	90%
With pyridine In tetrahydrofuran at 40℃; for 2h;	74%

di-tert-butyl dicarbonate (24424-99-5) + 1,4-phenylenediamine (106-50-3) → N-(tert-butoxycarbonyl)-1,4-phenylenediamine (71026-66-9)

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 20℃;	100%
With glycerol at 20℃; for 0.333333h; Green chemistry; chemoselective reaction;	97%
In dichloromethane at 20℃; for 18h; Cooling with ice;	97%

5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride + 2,4-diamino-(n-hexadecyloxy)benzene (137819-03-5) + 1,4-phenylenediamine (106-50-3) → soluble polyimide, inherent viscosity: 0.78 dl/g; monomer(s): 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; p-phenylenediamine; 2,4-diamino-(n-hexadecyloxy)benzene

Conditions	Yield
With isoquinoline In various solvent(s) at 70 - 200℃;	100%

5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride + 2,4-diamino-(n-hexadecyloxy)benzene (137819-03-5) + 1,4-phenylenediamine (106-50-3) → soluble polyimide, inherent viscosity: 0.67 dl/g; monomer(s): 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; p-phenylenediamine; 2,4-diamino-(n-hexadecyloxy)benzene

Conditions	Yield
With isoquinoline In various solvent(s) at 70 - 200℃;	100%

5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride + 2,4-diamino-(n-hexadecyloxy)benzene (137819-03-5) + 1,4-phenylenediamine (106-50-3) → soluble polyimide, inherent viscosity: 0.69 dl/g; monomer(s): 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; p-phenylenediamine; 2,4-diamino-(n-hexadecyloxy)benzene

Conditions	Yield
With isoquinoline In various solvent(s) at 70 - 200℃;	100%

5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride + 2,4-diamino-(n-hexadecyloxy)benzene (137819-03-5) + 1,4-phenylenediamine (106-50-3) → soluble polyimide, inherent viscosity: 0.65 dl/g; monomer(s): 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; p-phenylenediamine; 2,4-diamino-(n-hexadecyloxy)benzene

Conditions	Yield
With isoquinoline In various solvent(s) at 70 - 200℃;	100%

5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride + 2,4-diamino-(n-hexadecyloxy)benzene (137819-03-5) + 1,4-phenylenediamine (106-50-3) → soluble polyimide, inherent viscosity: 0.44 dl/g; monomer(s): 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; p-phenylenediamine; 2,4-diamino-(n-hexadecyloxy)benzene

Conditions	Yield
With isoquinoline In various solvent(s) at 70 - 200℃;	100%

5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride + 2,4-diamino-(n-hexadecyloxy)benzene (137819-03-5) + 1,4-phenylenediamine (106-50-3) → soluble polyimide, inherent viscosity: 0.27 dl/g; monomer(s): 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; p-phenylenediamine; 2,4-diamino-(n-hexadecyloxy)benzene

Conditions	Yield
With isoquinoline In various solvent(s) at 70 - 200℃;	100%

5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride + 1,4-phenylenediamine (106-50-3) → soluble polyimide, inherent viscosity: 1.42 dl/g; monomer(s): 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; p-phenylenediamine

Conditions	Yield
With isoquinoline In various solvent(s) at 70 - 200℃;	100%

4-hexylbenzoyl chloride (50606-95-6) + 1,4-phenylenediamine (106-50-3) → N-(4-aminophenyl)-4-hexylbenzamide (1055298-70-8)

Conditions	Yield
In dichloromethane at 20℃; for 17h;	100%

di-tert-butyl dicarbonate (24424-99-5) + 1,4-phenylenediamine (106-50-3) → di(tert‐butyl) 1,4‐phenylenedicarbamate (121680-23-7)

Conditions	Yield
With 1,4-disulfopiperazine-1,4-diium chloride In neat (no solvent) at 20℃; for 0.0833333h; Green chemistry; chemoselective reaction;	100%
With guanidine hydrochloride In ethanol at 35 - 40℃; for 0.333333h;	98%
Stage #1: 1,4-phenylenediamine With caesium carbonate In tetrahydrofuran at 20℃; for 0.5h; Schlenk technique; Stage #2: di-tert-butyl dicarbonate In tetrahydrofuran at 70℃; Schlenk technique;	90%
With triethylamine In dichloromethane at 20℃;	51%
With guanidine hydrochloride In ethanol at 40℃; for 8h;

C50H30N4NiO4 (1443978-57-1) + 1,4-phenylenediamine (106-50-3) → C56H34N6NiO2 (1443978-66-2)

Conditions	Yield
Stage #1: C50H30N4NiO4 With 1,2,4-Trichlorobenzene for 1h; Molecular sieve; Reflux; Stage #2: 1,4-phenylenediamine In pyridine at 220℃; for 16h;	100%

4-tert-butoxycarbonylamino-1-methyl-1H-pyrrole-2-carboxylic acid benzotriazol-1yl ester (77716-16-6) + 1,4-phenylenediamine (106-50-3) → C17H22N4O3

Conditions	Yield
In N,N-dimethyl-formamide at 60℃; for 2h;	100%

C44H47N3O5 + 1,4-phenylenediamine (106-50-3) → C50H53N5O4

Conditions	Yield
With 1H-imidazole In N,N-dimethyl-formamide; toluene at 150℃; Inert atmosphere;	100%

Pyromellitic dianhydride (89-32-7) + 1,4-phenylenediamine (106-50-3) → C10H6O8*C6H8N2

Conditions	Yield
Stage #1: Pyromellitic dianhydride In water at 80℃; for 1h; Inert atmosphere; Stage #2: 1,4-phenylenediamine In water at 80℃; for 4h; Inert atmosphere;	100%

1,4-phenylenediamine (106-50-3) → benzene-1,4-diamine hydrochloride (624-18-0)

Conditions	Yield
With hydrogenchloride In 1,4-dioxane; methanol for 0.166667h;	100%

1,4-phenylenediamine (106-50-3) → C6H8N2*(x)ClH

Conditions	Yield
With hydrogenchloride; tetrabutylammomium bromide In N,N-dimethyl-formamide at 10℃; for 2.5h; Temperature; Reagent/catalyst;	99.5%

1,4-phenylenediamine (106-50-3) + benzyl alcohol (100-51-6) → N1,N4-dibenzylbenzene-1,4-diamine (10368-25-9)

Conditions	Yield
With [((5-Me)PyNPPh2)IrACHTUNGTRENUNG(cod)]; potassium tert-butylate In diethylene glycol dimethyl ether at 70℃; for 48h; Inert atmosphere;	99%
With C41H36AsClN3OPRuS; potassium hydroxide In toluene at 100℃; for 12h;	91%
at 120℃; for 48h; Molecular sieve; Green chemistry;	78%

dodecyl isocyanate (4202-38-4) + 1,4-phenylenediamine (106-50-3) → 1-amino-4-(3-dodecylureido)benzene

Conditions	Yield
In dichloromethane for 1h;	99%

1,4-phenylenediamine (106-50-3) + diisopropyl-carbodiimide (693-13-0) → 2',2'-(1,4-phenylene)bis(1,3-diisopropylguanidine)

Conditions	Yield
With C80H124Cl2N8Nd2O2 In tetrahydrofuran at 60℃; for 0.5h; Reagent/catalyst; Temperature; Time; Schlenk technique; Inert atmosphere; Glovebox;	99%
With [Li(THF)(DME)]3La[μ-η2η1(iPrN)2C(NC6H4p-Cl)]3 at 25℃; for 2h; Inert atmosphere;	98%
[(Me3Si)2N]3Yb(μ-Cl)Li(THF)3 In tetrahydrofuran at 60℃; for 4h;	97%

phthalic anhydride (85-44-9) + 1,4-phenylenediamine (106-50-3) + cis-1,2,3,6-tetrahydrophthalic anhydride (935-79-5) → N-{4-[((1S,6R)-6-Carboxy-cyclohex-3-enecarbonyl)-amino]-phenyl}-phthalamic acid

Conditions	Yield
In acetone at 20℃; for 12h;	99%

Upstream product

• 123-91-1 1,4-dioxane 
• 110-86-1 pyridine 
• 100-25-4 para-dinitrobenzene 
• 108-86-1 bromobenzene 
• 64-17-5 ethanol 
• 659-49-4 4-nitrosoaniline 
• 59-88-1 phenylhydrazine hydrochloride 
• 61594-51-2 4,4'-diaminoazoxybenzene 
• 15257-27-9 bis-(4-dimethylamino-benzylidene)-p-phenylenediamine 
• 64-19-7 acetic acid 
• 100-01-6 4-nitro-aniline 
• 67-64-1 acetone 
• 142-04-1 aniline hydrochloride 
• 60-09-3 aniline yellow 

Downstream Products

• 25538-96-9 tetrakis-N-(2-hydroxy-ethyl)-p-phenylenediamine 
• 24731-73-5 1,4-bis-(acetoacetylamino)-benzene 
• 58442-15-2 N,N'-bis-(4-amino-phenyl)-formamidine 
• 94067-12-6 1,4-bis-(2,4-dimethyl-pyrrol-1-yl)-benzene 
• 3278-31-7 N,N'-(1,4-phenylene)dimaleimide 
• 85933-15-9 N,N'-p-phenylene-bis-succinamic acid 
• 5415-22-5 4-((4-aminophenyl)amino)-4-oxobutanoic acid 
• 100135-37-3 4-(4-amino-phenylcarbamoyl)-3-methyl-cis-crotonic acid 
• 7084-12-0 N,N'-p-phenylene-bis-phthalamic acid 
• 657367-83-4 N-(4-aminophenyl)-6-methoxy-2-methylquinolin-4-amine 
• 101279-00-9 N,N'-(1,4-phenylene)bis(5-nitrofuran-2-carboxamide) 
• 102007-52-3 N,N'-bis-(3-[2]furyl-3-oxo-propionyl)-p-phenylenediamine 
• 100965-39-7 6-(4-amino-anilino)-7-chloro-quinoline-5,8-dione 
• 5466-93-3 diethyl 1,4-phenylenediamine-N,N'-dicarboxylate 

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Relevant articles and documents

Efficiency of Radical-Cation Amination of Aromatic Compounds in Sulfuric Acid Solutions [5]

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Silver nanoparticles supported on P, Se-codoped g-C3N4 nanosheet as a novel heterogeneous catalyst for reduction of nitroaromatics to their corresponding amines

P, Se-codoped g-C3N4 (PSeCN) nanosheet was in situ prepared by facile thermal polymerization of melamine, phosphonitrilic chloride trimer, and selenium black powder as the precursors. It was found as a suitable support for the immobilization of silver nanoparticles (Ag NPs). The prepared nanocatalyst was fully characterized via standard analysis methods including EDX, ICP-OES, XRD, FT-IR, SEM, TEM, and BET. This PSeCN/Ag nanocatalyst with a higher specific surface area compared with CN, showed excellent catalytic activity towards the reduction of several nitroaromatic compounds using sodium borohydride (NaBH4) in short reaction times with high efficiency and good selectivity in water as a green solvent. Significantly, the above-mentioned nanocomposite could be reused six times without appreciable loss of its catalytic activity.

Radical reactions in aqueous medium using (Me3Si)3SiH

(Chemical Equation Presented) (Me3Si)3SiH was used as a successful reagent in a variety of radical-based transformations in water. The system comprising substrate, silane, and initiator (ACCN) mixed in aqueous medium at 100°C worked well for both hydrophilic and hydrophobic substrates, with the only variation that an amphiphilic thiol was also needed in case of the water-soluble compounds.

Efficient hydrogenation catalyst designing via preferential adsorption sites construction towards active copper

Based on the experimental and DFT calculation results, here for the first time we built preferential adsorption sites for nitroarenes by modification of the supported Cu catalysts surface with 1,10-phenathroline (1,10-phen), by which the yield of aniline via reduction of nitroarene is enhanced three times. Moreover, a macromolecular layer was in-situ generated on supported Cu catalysts to form a stable macromolecule modified supported Cu catalyst, i.e., CuAlOx-M. By applying the CuAlOx-M, a wide variety of nitroarene substrates react smoothly to afford the desired products in up to > 99% yield with > 99% selectivity. The method tolerates a variety of functional groups, including halides, ketone, amide, and C = C bond moieties. The excellent catalytic performance of the CuAlOx-M can be attributed to that the 1,10-phen modification benefits the preferential adsorption of nitrobenzene and slightly weakens adsorption of aniline on the supported nano-Cu surface.

Visible-light-induced photocatalytic hydrogenation of 4-nitroaniline over In2S3 photocatalyst in water

Photocatalytic hydrogenation of 4-nitroaniline over the In 2S3 photocatalyst was investigated in water under visible light irradiation (λ ≥ 420 nm). After 90 min of visible light irradiation, 100% of 4-nitroaniline could be reduced t

Preparation and characterization of Ni/mZSM-5 zeolite with a hierarchical pore structure by using KIT-6 as silica template: An efficient bi-functional catalyst for the reduction of nitro aromatic compounds

Ni/mZSM-5 and Ni/H-mZSM-5 were synthesized as hierarchical (micro/meso porous) ZSM-5 zeolites by an indirect template method for the first time. The resulting zeolite materials exhibited significantly enhanced diffusional properties in comparison to purely microporous zeolite materials. The structural and morphological characterization of the prepared catalysts was investigated using XRD, BET, atomic absorption spectroscopy, FT-IR, 27Al-MAS NMR, SEM, TEM, XPS and DRS-UV techniques. These hierarchical zeolites were used as acid-metal bi-functional heterogeneous catalysts for hydride transfer in the reduction of nitro aromatic compounds. In these reactions, NaBH4 was used as a reducing agent. Excellent yields at room temperature and very short reaction times in aqueous media conditions were obtained. Reusability experiments showed the excellent stability of Ni/mZSM-5 and Ni/H-mMZSM-5 and the catalysts could be reused 7 times without much loss of activity in reduction of nitro aromatic compounds. Surprisingly, the acid form of Ni/H-mZSM-5 showed much higher activity than that of Ni/mZSM-5. High yield, short reaction time, green solvent (water), room temperature, no by-product, the easy reusability of catalysts and the low amounts of catalyst required are some of the advantages of these catalysts.

Supported polymer magnets with high catalytic performance in the green reduction of nitroaromatic compounds

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Starch functionalized creatine for stabilization of gold nanoparticles: Efficient heterogeneous catalyst for the reduction of nitroarenes

Selective reduction of nitroaromatic pollutants into amines with recoverable and reusable heterogeneous catalysts is highly desirable. Herein, we prepared and characterized an efficient novel catalyst comprising 4 nm size Au nanoparticles supported on creatine modified starch. Using this catalyst, efficient reduction of nitroarenes into amines at room temperature in aqueous media was achieved. The presence of creatine in the structure of the catalyst plays important role in amount of Au loading, efficiency of the catalyst, recycling times, and leaching of Au compared to starch supported Au without creatine.

Hexafluoro-2-propanol Promotes para-Selective C–H Amination of Free Anilines with Azodicarboxylates

An effective, mild, and clean method for the C–H amination of free anilines with azodicarboxylates in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) without the need for any additional catalysts or reagents was developed. The reaction was found to be highly regioselective and provided a series of p-aminophenylhydrazine derivatives in excellent yields. Moreover, compatibility with a free amino group makes this protocol an attractive strategy in synthetic chemistry.

Comparison between Heterogeneous and Homogeneous Electron Transfer in p-Phenylenediamine Systems

The one-electron oxidation of selected p-phenylendiamines to form the corresponding radical cations has been studied at a Pt electrode in dimethylformamide and acetonitrile solutions containing 0.1 mol dm-3 NaClO4.The standard redox potentials, the diffusion coefficients and the standard rate constants have been evaluated in the range between room temperature and the melting point of the respective solvent using cyclic valtammetry.It has been shown that the dynamics of solvent reorientation affects the heterogeneous electron-transfer rate, as opposed to the homogeneous process.The free energies of activation are much greater in the heterogeneous than in the homogeneous case.Both results are explained by the different shape of the activated complexes, consisting of one or two ellipsoidal molecules.

REDUCTION OF NITRO COMPOUNDS BY CARBON MONOXIDE ON PALLADIUM COMPEXES

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Peculiarities of azobenzene catalytic hydrogenation in 2-propanol aqueous solutions with acid or base additives

It is shown experimentally that the hydrogenation of azobenzenes over a nickel skeleton catalyst in 2-propanol aqueous solutions proceeds selectively with the formation of aniline. It is pointed out that during the reaction, considerable participation of hydrogen bonded with active centers of a catalyst surface was observed. The competitive character of adsorption between the initial azo compound and aniline formed as a result of reaction is established. It is concluded that purposeful change of the azo group hydrogenation rate is possible by introducing acid or base additives into 2-propanol aqueous solution.

Bio-waste chitosan-derived N-doped CNT-supported Ni nanoparticles for selective hydrogenation of nitroarenes

In this study, a facile method for the synthesis of leach proof and earth-abundant non-noble Ni nanoparticles on N-doped carbon nanotubes is reported. The catalyst was synthesized by an impregnation-carbonization method, wherein a Ni-chitosan complex upon carbonization in a 5% H2/N2 atmosphere at 800 °C yielded Ni-containing N-doped CNTs. Chitosan served as a single source of carbon and nitrogen, and the nanotube growth was facilitated by the in situ formed Ni nanoparticles. The nanocatalyst was thoroughly characterized by several techniques; elemental mapping by SEM and TEM analysis confirmed the uniform distribution of Ni nanoparticles on the surface of N-doped CNTs with an average size in the range of 10-15 nm. The catalyst efficiently reduced a variety of nitroarenes (>99%) into their corresponding amines at a moderate pressure (5 bar) and a comparatively lower temperature (80 °C). Furthermore, the easy recovery of the catalyst using an external magnetic field along with high activity and easy recyclability makes the protocol eco-friendly.

Facile reduction of aromatic nitro compounds to aromatic amines catalysed by support-free nanoporous silver

Nanoporous silver was used as the catalyst for the reduction of aromatic nitro compounds even in the presence of some sensitive functional groups under mild conditions with excellent yields. A reduced amount of NaBH4 was used. The reaction kine

Kinetics of the hydrogenation of 2-chloro-4-nitroaniline over skeletal nickel and supported palladium catalysts in an aqueous solution of 2-propanol

The kinetics of the liquid-phase hydrogenation of 2-chloro-4-nitroaniline in an aqueous solution of 2-propanol over skeletal nickel and supported palladium catalysts is studied. The selectivity of the reaction with respect to 2-chloro-1,4-phenylenediamine is determined. It is found that samples of supported palladium catalysts differ with respect to the amount of the active component and the nature of the support. Some of their structural characteristics are provided.

Sustainable and recyclable palladium nanoparticles–catalyzed reduction of nitroaromatics in water/glycerol at room temperature

Palladium nanoparticles with unique catalytic activity and high stability are synthesized. These nanoparticles exhibit excellent catalytic reduction activity for nitroaromatics in green solvents in the presence of H2 at ambient pressure and temperature. The prominent advantages of this nanotechnology include low consumption of catalyst, excellent chemoselectivity, high reusability of the catalyst, and environmentally green solvents.

Immobilized iron oxide nanoparticles as stable and reusable catalysts for hydrazine-mediated nitro reductions in continuous flow

An experimentally easy to perform method for the generation of alumina-supported Fe3O4 nanoparticles [(6±1)nm size, 0.67 wt%]and the use of this material in hydrazine-mediated heterogeneously catalyzed reductions of nitroarenes to anilines under batch and continuous-flow conditions is presented. The bench-stable, reusable nano-Fe3O4@Al2O3 catalyst can selectively reduce functionalized nitroarenes at 1 mol% catalyst loading by using a 20 mol% excess of hydrazine hydrate in an elevated temperature regime (150°C, reaction time 2-6 min in batch). For continuous-flow processing, the catalyst material is packed into dedicated cartridges and used in a commercially available high-temperature/-pressure flow device. In continuous mode, reaction times can be reduced to less than 1 min at 150°C (30 bar back pressure) in a highly intensified process. The nano-Fe3O4@Al2O3 catalyst demonstrated stable reduction of nitrobenzene (0.5 m in MeOH) for more than 10 h on stream at a productivity of 30mmolh-1 (0.72 mol per day). Importantly, virtually no leaching of the catalytically active material could be observed by inductively coupled plasma MS monitoring.

The Anodic Oxidation of 1,4-Diaminobenzene: an Electron Spin Resonance and Electrochemical Study

The electrochemical e.s.r. of 1,4-diaminobenzene, 1,4-diamino-2-chlorobenzene, and 1,4-diamino-2-methylbenzene has been studied in aqueous methanol using an apparatus in which a tube electrode is linked to the e.s.r. cavity.Laminar flow transports species from the electrode into the cavity.The distribution of species in the cavity can be described theoretically and from the variation of e.s.r. signal with current, flow rate, concentration, and pH the protonation and kinetic stability of the 1,4-diaminobenzene cation radical is established.From the electrochemistry, the protonation of the unstable benzoquinone di-imide is deduced.The kinetics and the mechanism of its substitution reaction with water leading to benzoquinone are deduced from the behaviour of the e.s.r. signal from the radical cation with which the benzoquinone di-imide is in equilibrium.

Unprotected and interconnected Ru0 nano-chain networks: Advantages of unprotected surfaces in catalysis and electrocatalysis

Seedless, surfactantless and support-free unprotected, metallic, interconnected nano-chain networks of ruthenium nanoparticles (NPs) were successfully synthesized via the reduction of ruthenium(iii) chloride (RuCl3) with sodium borohydride (NaBH4) at three different temperatures, viz. 30 °C, 45 °C and 60 °C. The molar ratio of RuCl3 solution and borohydride was optimized to be 1:1.5 to produce stable colloids with the optimum final solution pH of 9.7 ± 0.2. Average diameters of the interconnected nano-chain networks prepared at 30 °C (Ru-30), 45 °C (Ru-45) and 60 °C (Ru-60) were 3.5 ± 0.5 nm, 3.0 ± 0.2 nm and 2.6 ± 0.2 nm respectively. The morphology and composition dependent catalytic and electrocatalytic activities of these unprotected Ru nano-chain networks (Ru-30, Ru-45 and Ru-60) were studied in detail. The catalysis study was performed by investigating the transfer hydrogenation of several substituted aromatic nitro compounds. It was observed that Ru-60 was relatively more active compared to Ru-30 and Ru-45, which was reflected in their rate constant values. The electrocatalytic activities of Ru-30, Ru-45 and Ru-60 were screened for anodic water splitting in alkaline medium (0.1 M NaOH) and it was found that all of them showed almost the same activity which required an over-voltage of 308 ± 2 mV to obtain an anodic current density of 10 mA cm-2. The catalytic and electrocatalytic performances of these unprotected Ru0 networks were compared with Ru0 nanomaterials prepared under similar conditions with three different surfactants, viz. CTAB, SDS and TX-100, which revealed that unprotected Ru0 networks are better catalysts than those stabilized with surfactants. The superior catalytic and electrocatalytic performance is due to the availability of unprotected Ru0 surfaces. The present route may provide a new possibility of synthesizing other surfactant-free, unprotected metal colloids for enhanced catalytic and electrocatalytic applications.

Binuclear half-sandwich ruthenium(II) Schiff base complexes: Synthesis, characterization, DFT study and catalytic activity for the reduction of nitroarenes

The binuclear ruthenium(II) p-cymene complexes containing Schiff base ligands of general composition [(Ru(p-cymene)Cl)2L1-6] (1-6) have been synthesized. The complexes were characterized by analytical and spectral (FT?IR, UV–Vis & 1H NMR) methods. The molecular structure of the representative complex [(Ru(p-cymene)Cl)2(L6)] (6) was determined by single-crystal X-ray diffraction and density functional theory (DFT) calculations. Further, these half-sandwich ruthenium complexes are active catalysts for the mild hydrogenation of nitroarenes to aromatic anilines in the presence of NaBH4 in ethanol. The most efficient catalyst 6, was found be compatible with nitroarenes of various functional groups.

Hydrogenation of Substituted Benzenes Containing Nitro and Azo Groups over Skeletal Nickel in Aqueous Solutions of 2-Propanol

Abstract: An analysis is made of the kinetic characteristics of the hydrogenation of 4-nitro- and 2-nitro-2'-hydroxy-5'-methylazobenzenes, 4-nitroaniline and 4-aminoazobenzene over skeletal nickel in neutral azeotropic 2-propanol–water mixture and in the same solvent in the presence of acetic acid or sodium hydroxide. It is found that the selectivity of the hydrogenation of these isomers to the intermediate products depends on the composition and nature of the solvent, and is determined by the rate of reactive group conversion. Compared to the process in the presence of sodium hydroxide, which suppresses the route leading to the predominant hydrogenation of the nitro group, the contribution from the transformation of azo group is considerably greater in the hydrogenation of 4-nitro-2'-hydroxy-5'-methylazobenzene in the presence of acetic acid. Adding a base to the solvent during the hydrogenation of 2-nitro-2'-hydroxy-5'-methylazobenzene accelerates the rate of nitro group conversion and the intramolecular cyclization of the intermediate compound, increasing the selectivity towards the products containing the benzotriazole cycle (particularly 2-(2-hydroxy-5-methylphenyl)benzotriazole-N-oxide). The almost linear correlation between the selectivity of the catalytic hydrogenation of isomers of nitro-2'-hydroxy-5'-methylazobenzene and the kinetic characteristics of the hydrogenation of nitro and azo groups in compounds containing a single reactive substituent at different values of medium’s pH is estimated.

METHOD FOR PRODUCING AMINO AROMATIC COMPOUND

To provide a novel method for producing an amino aromatic compound.SOLUTION: A method for producing a compound (B) having at least one amino group on an aromatic ring, includes at least a step in which a compound (A) at least having an aromatic ring and one group represented by -CR=CH2 [R is a hydrogen atom or a C1-3 alkyl group] on the aromatic ring is reacted with sodium azide in the presence of acid.SELECTED DRAWING: None

Yeast supported gold nanoparticles: an efficient catalyst for the synthesis of commercially important aryl amines

Candida parapsilosisATCC 7330 supported gold nanoparticles (CpGNP), prepared by a simple and green method can selectively reduce nitroarenes and substituted nitroarenes with different functional groups like halides (-F, -Cl, -Br), olefins, esters and nitriles using sodium borohydride. The product aryl amines which are useful for the preparation of pharmaceuticals, polymers and agrochemicals were obtained in good yields (up to >95%) using CpGNP catalyst under mild conditions. The catalyst showed high recyclability (≥10 cycles) and is a robust free flowing powder, stored and used after eight months without any loss in catalytic activity.

UiO-66/btb/Pd as a stable catalyst reduction of 4-nitrophenol into 4-aminophenol

In order to synthesize highly sparse nanoparticles, UiO-66-NH2 can be utilized as an appropriate support. It has great surface area, which is functionalized by 1,3-bis(dimethylthiocarbamoyloxy)benzene compounds that can act as the powerful performers, hence, the Pd (II) is a complex without aggregate over the UiO-66-NH2 microspheres structures (UiO-66/btb/Pd). Nitro-aromatic pollution in industrial waste streams threat wellbeing of water resources. The produced UiO-66/btb/Pd nanocatalyst showed appropriate catalytic activity for reduce nitro-aromatic compounds in aqueous solution. XRD, EDS, SEM, FT-IR, and TEM were utilized for characterizing the nanostructures UiO-66/btb/Pd.