62-53-3

Basic information

• Product Name: Aniline
• Synonyms: ai3-03053;amino-benzen;Aminophen;Anilin;anilin(czech);Anilina;anilina(italian,polish);Aniline reagent
• CAS NO: 62-53-3
• Molecular Formula: C₆H₇N
• Molecular Weight: 93.13
• EINECS: 200-539-3
• Product Categories: Industrial/Fine Chemicals;Aniline;ACS GradeNitrogen Compounds;C2 to C6;Essential Chemicals;Routine Reagents;A;A-BAlphabetic;Alpha Sort;AM to AQAnalytical Standards;Amines;Aromatics;AromaticsChemical Class;Chemical Class;Volatiles/ Semivolatiles;Alphabetic;AM to AQ;Pesticides&Metabolites;Reagent Plus;AM to AQChemical Class;A-B, Puriss p.a.Nitrogen Compounds;Analytical Reagents for General Use;Puriss p.a.
• Mol File: 62-53-3.mol
• Article Data: 1669

Chemical Properties

• Melting Point: -6.2 °C
• Boiling Point: 184 °C(lit.)
• Flash Point: 76 °C
• Appearance: APHA: ≤250/Liquid
• Density: 1.022 g/mL at 25 °C(lit.)
• Vapor Density: 3.22 (185 °C, vs air)
• Vapor Pressure: 0.7 mm Hg ( 25 °C)
• Refractive Index: n20/D 1.586(lit.)
• Storage Temp.: 2-8°C
• Solubility: water: soluble
• PKA: 4.63(at 25℃)
• Relative Polarity: 0.42
• Explosive Limit: 1.2-11%(V)
• Water Solubility: 36 g/L (20 ºC)
• Stability: Stable. Incompatible with oxidizing agents, bases, acids, iron and iron salts, zinc, aluminium. Light sensitive. Combustible.
• Merck: 14,659
• BRN: 605631
• CAS DataBase Reference: Aniline(CAS DataBase Reference)
• NIST Chemistry Reference: Aniline(62-53-3)
• EPA Substance Registry System: Aniline(62-53-3)

Safety Data

• Hazard Codes: T,N,F
• Statements: 23/24/25-40-41-43-48/23/24/25-50-68-48/20/21/22-39/23/24/25-11
• Safety Statements: 26-27-36/37/39-45-46-61-63-36/37-16
• RIDADR: UN 1547 6.1/PG 2
• WGK Germany: 2
• RTECS: BW6650000
• F: 8-9
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 62-53-3(Hazardous Substances Data)

Usage

Description

Different sources of media describe the Description of 62-53-3 differently. You can refer to the following data:
1. Aniline is the simplest primary aromatic amine and a compound formed by the substitution of a hydrogen atom in the benzene molecule with an amino group. It is colorless oil like flammable liquid with strong odor. When heated to 370 C, it is slightly soluble in water and soluble in ethanol, ether, chloroform and other organic solvents. It becomes brown in the air or under the sun. It can be distilled by steam. A small amount of zinc powder is added to prevent oxidation when it is distilled. The purified aniline can be added 10 ~ 15ppm NaBH4 to prevent oxidation deterioration. The solution of aniline is alkaline. It is easy to produce salt when it reacts with acid. The hydrogen atoms on its amino groups can be substituted by alkyl or acyl groups to produce second or third grade aniline and acyl aniline. When substitution reaction occurs, the products of ortho and para substituted products are mainly produced. It reacts with nitrite to form diazonium salts, which can be used to produce a series of benzene derivatives and azo compounds.
2. First produced in 1826 by Otto Unverdorben through destructive distillation of indigo, the first industrial use was as a purple dye, Mauveine, formulated by William Henry Perkin accidentally in an attempt to isolate quinone. The name aniline was given in deference to the indigoyielding plant, Indigofera suffruticosa, commonly named anil.

Uses

Different sources of media describe the Uses of 62-53-3 differently. You can refer to the following data:
1. Aniline is an important industrial chemical for many decades. Currently, it is most widely used for the manufacture of polyurethanes and rubber, with lesser amounts consumed in the production of pesticides (herbicides, fungicides, insecticides, animal repellants), defoliants, dyes, antioxidants, antidegradants, and vulcanization accelerators. It is also an ingredient of some household products, such as polishes (stove and shoe), paints, varnishes, and marking inks.
2. Aniline is used in the manufacture of dyes,pharmaceuticals, varnishes, resins, photo graphic chemicals, perfumes, shoe blacks,herbicides, and fungicides. It is also usedin vulcanizing rubber and as a solvent. Itoccurs in coal tar and is produced from thedry distillation of indigo. It is also producedfrom the biodegradation of many pesticides.Aniline is a metabolite of many toxic com pounds, such as nitrobenzene, phenacetin,and phenylhydroxylamine.
3. Rubber accelerators and antioxidants, dyes and intermediates, photographic chemicals (hydro- quinone), isocyanates for urethane foams, pharma- ceuticals, explosives, petroleum refining, dipheny- lamine, phenolics, herbicides, fungicides.
4. A thin, colorless oil prepared by reducing benzene with iron filings in the presence of hydrochloric or acetic acid and then separating the aniline formed by distillation. It is slightly soluble in water but dissolves easily in alcohol, ether, and benzene. Aniline is the base for many dyes used to increase the sensitivity of emulsions.

Reaction

A primary aromatic amine, aniline is a weak base and forms salts with mineral acids such as aniline hydrochloride. PKb = 9.30, 0.2mol aqueous solution PH value 8.1. In acidic solution, nitrous acid converts aniline into a diazonium salt that is an intermediate in the preparation of a great number of dyes and other organic compounds of commercial interest. When aniline is heated with organic acids, it gives amides, called anilides, such as acetanilide from aniline and acetic acid. Monomethylaniline and dimethylaniline can be prepared from aniline and methyl alcohol. Catalytic reduction of aniline yields cyclohexylamine. Various oxidizing agents convert aniline to quinone, azobenzene, nitrosobenzene, p-aminophenol, and the phenazine dye aniline black. Amino groups can undergo acylation, halogenation, alkylation and diazotization, and the presence of amino groups makes it nucleophiles capable of many nucleophilic reactions, and at the same time activates the electrophilic substitution on aromatic rings.

Production

Aniline was first obtained in 1826 by the destructive distillation of indigo. It is named because of the specific indigo-yielding plant “Indigofera anil” (Indigofera suffruticosa); In 1857, W.H.Jr. Perkin made aniline from reduction of nitrobenzene with iron filings using hydrochloric acid as catalyst which is still being used. At present, the methods of aniline production include catalytic vapor phase reduction of nitrobenzene with hydrogen, catalytic reaction of chlorobenzene and ammonolysis of phenol (Japan). Before 1960s, aniline production was based on coal tar benzene, and now petroleum benzene has been used. At the end of 1990s, the world's aniline production capacity was above 2.5 million t. 50% of the aniline is used in the production of dye intermediates. About 25% aniline is used to produce isocyanate and its copolymers. The remaining (25%) is used for pesticides, gasoline antiknock agents, and photographic materials etc.

Hazards

The toxicity of Aniline is LD50500mg/kg (dog oral administration), and is a common pollutant in the environment. Aniline has strong toxicity to blood and nerves. It can be absorbed by skin or by respiratory tract to cause toxicity. The acute (short-term) and chronic (long-term) effects of aniline in humans consist mainly of effects on the lung, such as upper respiratory tract irritation and congestion. Chronic exposure may also result in effects on the blood. Human cancer data are insufficient to conclude that aniline is a cause of bladder tumors while animal studies indicate that aniline causes tumors of the spleen. EPA has classified aniline as a Group B2, probable human carcinogen. Evidence reported by the National Institute for Occupational Safety and Health (NIOSH) clearly associates the occupational exposure to o-toluidine and aniline with an increased risk of bladder cancer among workers. The risk of bladder cancer is greatest among workers with possible and definite exposures to o-toluidine and aniline, and the risk increases with the duration of exposure.

Chemical Properties

Aniline,C6H5NH2, is slightly soluble in water,miscible in alcohol and ether,and turns yellow to brown in air. Aniline may be made(1) by the reduction, with iron or tin in HCI, of nitrobenzene, and(2) by the amination of chlorobenzene by heating with ammonia to a high temperature corresponding to a pressure of over 200 atmospheres in the presence of a catalyst(a mixture of cuprous chlorideandoxide).Aniline is the end point of reduction of most mononitrogen substituted benzene nuclei,as nitro benzene beta-phenyl hydroxylamine, azoxybenzene, azobenzene, hydrazobenzene. Aniline is detected by the violet coloration produced by a small amountof sodium hypochlorite. Aniline is used as a solvent, in the preparation of compound in the manufacture of dyes and their intermediates, and in the manufacture of medicinal chemicals.

Physical properties

Colorless, oily liquid with a faint ammonia-like odor and burning taste. Gradually becomes yellow to reddish-brown on exposure to air or light. The lower and upper odor thresholds are 2 and 128 ppm, respectively (quoted, Keith and Walters, 1992). An odor threshold of 1.0 ppmv was reported by Leonardos et al. (1969).

Production Methods

Aniline was obtained in 1826 by Unverdorben from distillation of indigo and was given the name aniline in 1841 by Fritzsche (Windholz et al 1983). The chemical was manufactured in the U. S. by the Bechamp reaction involving reduction of nitrobenzene in the presence of either copper/silica or hydrochloric acid/ferrous chloride catalysts; but in 1966, amination of chlorobenzene with ammonia was introduced (IARC 1982; Northcott 1978). Currently, aniline is produced in the U.S., several European countries and Japan by the catalytic hydrogenation of nitrobenzene in either the vapor phase or solvent system. This chemical is also produced by reacting phenol with ammonia (HSDB 1989). Production in 1982 amounted to 331,000 tons (HSDB 1989).

Definition

ChEBI: A primary arylamine in which an amino functional group is substituted for one of the benzene hydrogens.

Synthesis Reference(s)

Chemical and Pharmaceutical Bulletin, 29, p. 1159, 1981 DOI: 10.1248/cpb.29.1159The Journal of Organic Chemistry, 58, p. 5620, 1993 DOI: 10.1021/jo00073a018

General Description

A yellowish to brownish oily liquid with a musty fishy odor. Melting point -6°C; boiling point 184°C; flash point 158°F. Denser than water (8.5 lb / gal) and slightly soluble in water. Vapors heavier than air. Toxic by skin absorption and inhalation. Produces toxic oxides of nitrogen during combustion. Used to manufacture other chemicals, especially dyes, photographic chemicals, agricultural chemicals and others.

Air & Water Reactions

Darkens on exposure to air and light. Polymerizes slowly to a resinous mass on exposure to air and light. Slightly soluble in water.

Reactivity Profile

Aniline is a heat sensitive base. Combines with acids to form salts. Dissolves alkali metals or alkaline earth metals with evolution of hydrogen. Incompatible with albumin, solutions of iron, zinc and aluminum, and acids. Couples readily with phenols and aromatic amines. Easily acylated and alkylated. Corrosive to copper and copper alloys. Can react vigorously with oxidizing materials (including perchloric acid, fuming nitric acid, sodium peroxide and ozone). Reacts violently with BCl3. Mixtures with toluene diisocyanate may ignite. Undergoes explosive reactions with benzenediazonium-2-carboxylate, dibenzoyl peroxide, fluorine nitrate, nitrosyl perchlorate, peroxodisulfuric acid and tetranitromethane. Violent reactions may occur with peroxyformic acid, diisopropyl peroxydicarbonate, fluorine, trichloronitromethane (293° F), acetic anhydride, chlorosulfonic acid, hexachloromelamine, (HNO3 + N2O4 + H2SO4), (nitrobenzene + glycerin), oleum, (HCHO + HClO4), perchromates, K2O2, beta-propiolactone, AgClO4, Na2O2, H2SO4, trichloromelamine, acids, FO3Cl, diisopropyl peroxy-dicarbonate, n-haloimides and trichloronitromethane. Ignites on contact with sodium peroxide + water. Forms heat or shock sensitive explosive mixtures with anilinium chloride (detonates at 464° F/7.6 bar), nitromethane, hydrogen peroxide, 1-chloro-2,3-epoxypropane and peroxomonosulfuric acid. Reacts with perchloryl fluoride form explosive products.

Hazard

An allergen. Toxic if absorbed through the skin. Combustible. Skin irritant. Questionable car- cinogen.

Health Hazard

Aniline is a moderate skin irritant, a moderate to severe eye irritant, and a skin sensitizer in animals. Aniline is moderately toxic via inhalation and ingestion. Symptoms of exposure (which may be delayed up to 4 hours) include headache, weakness, dizziness, nausea, difficulty breathing, and unconsciousness. Exposure to aniline results in the formation of methemoglobin and can thus interfere with the ability of the blood to transport oxygen. Effects from exposure at levels near the lethal dose include hypoactivity, tremors, convulsions, liver and kidney effects, and cyanosis. Aniline has not been found to be a carcinogen or reproductive toxin in humans. Some tests in rats demonstrate carcinogenic activity. However, other tests in which mice, guinea pigs, and rabbits were treated by various routes of administration gave negative results. Aniline produced developmental toxicity only at maternally toxic dose levels but did not have a selective toxicity for the fetus. It produces genetic damage in animals and in mammalian cell cultures but not in bacterial cell cultures.

Fire Hazard

Combustion can produce toxic fumes including nitrogen oxides and carbon monoxide. Aniline vapor forms explosive mixtures with air. Aniline is incompatible with strong oxidizers and strong acids and a number of other materials. Avoid heating. Hazardous polymerization may occur. Polymerizes to a resinous mass.

Flammability and Explosibility

Aniline is a combustible liquid (NFPA rating = 2). Smoke from a fire involving aniline may contain toxic nitrogen oxides and aniline vapor. Toxic aniline vapors are given off at high temperatures and form explosive mixtures in air. Carbon dioxide or dry chemical extinguishers should be used to fight aniline fires.

Chemical Reactivity

Reactivity with Water No reaction; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Flush with water and rinse with dilute acetic acid; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.

Safety Profile

Suspected carcinogen with experimental neoplastigenic data. A human poison by an unspecified route. Poison experimentally by most routes incluhng inhalation and ingestion. Experimental reproductive effects. A skin and severe eye irritant, and a rmld sensitizer. In the body, aniline causes formation of methemoglobin, resulting in prolonged anoxemia and depression of the central nervous system; less acute exposure causes hemolysis of the red blood cells, followed by stimulation of the bone marrow. The liver may be affected with resulting jaundice. Long-term exposure to a d n e dye manufacture has been associated with malignant bladder growths. A common air contaminant, A combustible liquid when exposed to heat or flame. To fight fire, use alcohol foam, CO2, dry chemical. It can react vigorously with oxidizing materials. When heated to decomposition it emits highly toxic fumes of NOx. Spontaneously explosive reactions occur with benzenediazonium-2-carboxylate, dibenzoyl peroxide, fluorine nitrate, nitrosyl perchlorate, red fuming nitric acid, peroxodisulfuric acid, and tetranitromethane. Violent reactions with boron trichloride, peroxyformic acid, dhsopropyl peroxydicarbonate, fluorine, trichloronitromethane (145℃), acetic anhydride, chlorosulfonic acid, hexachloromelamine, (HNO3 + N2O4 + H2SO4), (nitrobenzene + glycerin), oleum, (HCHO + HClO4), perchromates, K2O2, ppropiolactone, AgClO4, Na2On, H2SO4, trichloromelamine, acids, peroxydisulfuric acid, F03Cl, diisopropyl peroxy-dicarbonate, n-haloimides, and trichloronitromethane. Ignites on contact with sodium peroxide + water. Forms heator shock-sensitive explosive mixtures with anhnium chloride (detonates at 240°C/7.6 bar), nitromethane, hydrogen peroxide, 1 -chloro-2,3- epoxypropane, and peroxomonosulfuric acid. Reactions with perchloryl fluoride, perchloric acid, and ozone form explosive products.

Carcinogenicity

The IARC has classified aniline as a Group 3 carcinogen, that is, not classifiable as to its carcinogenicity. However, NIOSH has determined that there is sufficient evidence to recommend that OSHA require labeling this substance a potential occupational carcinogen. This position followed an evaluation of a high-dose feeding study of aniline hydrochloride in F344 rats and B6C3F1 mice (3000 or 6000 ppm and 6000 or 12,000 ppm, respectively). The test was negative in both sexes of mice; however, hemangiosarcomas of the spleen and combined incidence of fibrosarcomas and sarcomas of the spleen were statistically significant in the male rats; the number of female rats having fibrosarcomas of the spleen was also significant.

Source

Detected in distilled water-soluble fractions of regular gasoline (87 octane) and Gasohol at concentrations of 0.55 and 0.20 mg/L, respectively (Potter, 1996). Aniline was also detected in 82% of 65 gasoline (regular and premium) samples (62 from Switzerland, 3 from Boston, MA). At 25 °C, concentrations ranged from 70 to 16,000 μg/L in gasoline and 20 to 3,800 μg/L in watersoluble fractions. Average concentrations were 5.8 mg/L in gasoline and 1.4 mg/L in watersoluble fractions (Schmidt et al., 2002). Based on laboratory analysis of 7 coal tar samples, aniline concentrations ranged from ND to 13 ppm (EPRI, 1990). Aniline in the environment may originate from the anaerobic biodegradation of nitrobenzene (Razo-Flores et al., 1999).

InChI:InChI=1/C6H7N/c7-6-4-2-1-3-5-6/h1-5H,7H2

Synthetic route

bromobenzene (108-86-1) → aniline (62-53-3)

Conditions	Yield
With copper(I) oxide; ammonium hydroxide In 1-methyl-pyrrolidin-2-one at 80℃; for 15h;	100%
With ammonia; copper In water at 100℃; for 24h; Ullmann reaction;	99.1%
With copper(l) iodide; 2-carboxyquinoline N-oxide; potassium carbonate; ammonium hydroxide In dimethyl sulfoxide at 80℃; for 23h; Inert atmosphere;	98%

nitrobenzene (98-95-3) → aniline (62-53-3)

Conditions	Yield
With hydrogen; platinum In water at 20℃; Product distribution; other temp.;	100%
With ethanol; water; tetrabutylammonium hypophosphite; benzene; palladium on activated charcoal for 5h; Product distribution; Heating; hydrogenation in a biphasic solvent system;	100%
With hydrogen; Pd in AV-17-8-Pd In ethanol at 40℃; under 760 Torr; Rate constant;	100%

nitrobenzene (98-95-3) → aniline (62-53-3) + diphenyl hydrazine (122-66-7)

Conditions	Yield
With ammonia borane; gold on titanium oxide In ethanol at 20℃; for 0.5h; Inert atmosphere;	A 92% B 100%
With samarium; iodine; ammonium chloride In tetrahydrofuran; water at 20℃; for 4h; Reduction;	A 56% B 20%
Electrolysis;

Nitrosobenzene (586-96-9) → aniline (62-53-3)

Conditions	Yield
With hydrazine hydrate In ethanol; water at 80℃; chemoselective reaction;	100%
With ammonium hydroxide; nickel boride at 40℃; for 0.5h; Product distribution; further medium: 3N HCl;	94.4%
With copper(I) chloride; potassium borohydride In methanol for 0.416667h; Product distribution; Ambient temperature; reduction of aromatic nitro compounds, nitrozobenzene, azobenzene and azoxybenzene with potassium borohydride-copper(I) chloride to primary amines;	94%

Phenyl azide (622-37-7) → aniline (62-53-3)

Conditions	Yield
With sodium hydrogen telluride In diethyl ether; ethanol for 0.25h; Ambient temperature;	100%
With iron(III)-acetylacetonate; hydrazine hydrate In methanol at 150℃; for 0.05h; Microwave irradiation; chemoselective reaction;	99%
With dibutyltin In benzene at 15℃; for 5h; other reagents;	98%

benzene (71-43-2) → aniline (62-53-3)

Conditions	Yield
With tris-(2-chloro-ethyl)-amine; trifluorormethanesulfonic acid; trifluoroacetic acid In chloroform at 40℃; for 12h; Product distribution; Mechanism; various acids, various substrates;	100%
With trifluorormethanesulfonic acid; trimethylsilylazide at 55℃; for 0.833333h; Product distribution; Mechanism; other arenes or substituted arenes; var. temperatures and time;	95%
With trifluorormethanesulfonic acid; trimethylsilylazide In chloroform at 90℃; under 5250.53 Torr; for 0.0466667h; Flow reactor;	86%

carbamic acid, phenyl-, 1-methylethyl ester (122-42-9) → aniline (62-53-3)

Conditions	Yield
With sodium hydroxide In ethanol; water at 100℃; for 0.666667h; Product distribution;	100%

3-(4-nitro-phenoxy)-benz[d]isothiazole-1,1-dioxide (132636-65-8) → aniline (62-53-3) + saccharin (81-07-2)

Conditions	Yield
With sodium hypophosphite; palladium on activated charcoal In water; benzene for 0.25h; Heating;	A 100% B n/a

benzamide (55-21-0) → aniline (62-53-3)

Conditions	Yield
With sodium hypochlorite; sodium hydroxide In 1,4-dioxane; water at 80℃; for 0.25h; Hofmann degradation;	100%
With sodium hydroxide; benzyltrimethylazanium tribroman-2-uide In water for 2h; Ambient temperature;	72%
With water; bromine; sodium hydroxide Hofmann Rearrangement; Cooling with ice;

N-Phenylhydroxylamine (100-65-2) → aniline (62-53-3)

Conditions	Yield
With hydrazine hydrate In ethanol; water at 80℃; chemoselective reaction;	100%
With sodium tetrahydroborate; meso-tetraphenylporphyrin iron(III) chloride In methanol; diethylene glycol dimethyl ether at 25℃; for 3h; Product distribution; Further Variations:; Reagents;	98%
With hydrogen In ethanol at 30℃; under 1875.19 Torr; for 1h; Irradiation; Autoclave;	95%

isobutyric acid-(N'-phenyl-hydrazide) (5461-50-7) → ISOPROPYLAMIDE (563-83-7) + aniline (62-53-3)

Conditions	Yield
With hydrogen; palladium In ethanol; acetic acid under 2585.7 Torr;	A 100% B n/a

As,As-bis(p-bromophenyl)-N,N'-diphenylarsinimidic amide → bis(p-bromophenyl)arsinic acid (113827-90-0) + aniline (62-53-3)

Conditions	Yield
With water In diethyl ether	A 100% B n/a

t-butyl N-phenyl sulfinamoyl acetate (82185-52-2) + benzylamine (100-46-9) → Benzylamino-thioxo-acetic acid tert-butyl ester (130293-09-3) + aniline (62-53-3)

Conditions	Yield
In diethyl ether for 72h; Ambient temperature;	A 63% B 100%
In diethyl ether for 72h; Mechanism; Ambient temperature; reaction of other substituted t-butyl sulfinamoyl acetates;	A 63% B 100%

azoxybenzene (495-48-7) → aniline (62-53-3)

Conditions	Yield
With copper(I) chloride; potassium borohydride In methanol for 0.25h; Product distribution; Ambient temperature; reduction of aromatic nitro compounds , nitrosobenzene, azobenzene and azoxybenzene with potassium borohydride-copper(I) chloride to primary amines;	100%
With N-doped TiO2 In methanol at 20℃; for 3h; UV-irradiation; Inert atmosphere;	92%
With 4,4'-di-tert-butylbiphenyl; lithium; nickel dichloride In tetrahydrofuran at 20℃; for 10h; Reduction; deoxygenation;	66%

(HRu3(CO)9((C6H5)N))(1-) + carbon monoxide (201230-82-2) → aniline (62-53-3)

Conditions	Yield
With H2 In not given Ru compound heated at 80°C under CO-H2 (1:1);	100%

(((C6H5)3P)2N)(1+)*(HRu3(CO)9((C6H5)NCO))(1-)=(((C6H5)3P)2N)(HRu3(CO)9((C6H5)NCO)) + carbon monoxide (201230-82-2) → aniline (62-53-3)

Conditions	Yield
With H2 In not given Ru compound heated at 80°C under CO-H2 (1:1);	100%

iodobenzene (591-50-4) → aniline (62-53-3)

Conditions	Yield
With iron(III) oxide; sodium hydroxide; copper(l) iodide; ammonia In ethanol; water at 90℃; for 16h;	100%
With copper(I) oxide; ammonium hydroxide In 1-methyl-pyrrolidin-2-one at 80℃; for 15h;	99%
With ammonia; triethylamine In water at 20℃; for 2.5h; Reagent/catalyst; Solvent; Time;	98%

anilino(tert-butyldimethyl)silane (53742-62-4) → aniline (62-53-3)

Conditions	Yield
With silica gel In ethanol; water at 20℃; for 2h;	100%

2-methyl-1,2,3,4-tetrahydroquinolin-4-yl-(phenyl)amine (1026-05-7) → 2-methylquinoline (91-63-4) + aniline (62-53-3)

Conditions	Yield
With palladium dichloride In acetonitrile	A 100% B 100%

4-chloro-aniline (106-47-8) → aniline (62-53-3)

Conditions	Yield
With ammonium formate In water; isopropyl alcohol at 20℃; for 3h;	99%
With hydrogen; triethylamine In water at 120 - 140℃; under 22502.3 - 37503.8 Torr;	99%
With hydrogen; NiCl2-Li-[poly(2-vinyl-naphthalene)-co-(divinylbenzene)] In tetrahydrofuran at 20℃; under 760.051 Torr; for 2h;	98%

3-chloro-aniline (108-42-9) → aniline (62-53-3)

Conditions	Yield
With hydrogen; triethylamine In water at 120 - 140℃; under 22502.3 - 37503.8 Torr;	99%
With lithium at 230℃; Zersetzen der Reaktionsprodukte mit Wasser;
With potassium fluoride; polymethylhydrosiloxane; palladium diacetate In tetrahydrofuran at 20℃; for 0.75h;	94 % Spectr.

4-chlorobenzonitrile (100-00-5) → aniline (62-53-3)

Conditions	Yield
With ammonium formate In water at 20℃; for 3h;	99%
With ammonium formate; PdMCM-41 In methanol at 69.84℃; for 0.666667h;	95%
With palladium on activated charcoal; formic acid; N,N-dimethyl-formamide for 3h; Heating;	90%

4-bromo-aniline (106-40-1) → aniline (62-53-3)

Conditions	Yield
With hydrogen; triethylamine In water at 120 - 140℃; under 22502.3 - 37503.8 Torr; Temperature;	99%
With methanol; gold; hydrogen; caesium carbonate at 100℃; under 3800.26 Torr; for 155h;	80%
Stage #1: 4-bromo-aniline With palladium dichloride In water at 20℃; for 0.0333333h; Stage #2: With 1,1,3,3-Tetramethyldisiloxane for 0.383333h;	79%

tert-butyl phenylcarbamate (3422-01-3) → aniline (62-53-3)

Conditions	Yield
With water at 100℃; for 10h; Inert atmosphere;	99%
HY-Zeolite In dichloromethane for 1.5h; Heating;	92%
With 3-butyl-l-methyl-1H-imidazol-3-iumtrifloroacetate In 1,4-dioxane; water at 70 - 72℃; for 1h;	92%

styrene (292638-84-7) + nitrobenzene (98-95-3) → ethylbenzene (100-41-4) + aniline (62-53-3)

Conditions	Yield
With hydrogen; 5% rhodium-on-charcoal; tris(acetylacetonato)cobalt In tetrahydrofuran at 20℃; for 16h;	A 99% B 89%
With hydrogen; 5% rhodium-on-charcoal; iron(II) acetate In tetrahydrofuran at 20℃; for 16h;	A 98% B 80%
With hydrogen; 5% rhodium-on-charcoal In tetrahydrofuran at 20℃; for 16h; Product distribution / selectivity;	A 93% B 31%
With hydrogen at 110℃; under 4560.31 Torr; for 24h; Autoclave; chemoselective reaction;

4-nitrobenzanilide (3460-11-5) → aniline (62-53-3) + 4-nitro-benzoic acid (62-23-7)

Conditions	Yield
With 40% potassium fluoride/alumina for 0.0666667h; Microwave irradiation; Neat (no solvent);	A 90% B 99%

3,5-Dichloroaniline (626-43-7) → aniline (62-53-3)

Conditions	Yield
With ammonium formate In water; isopropyl alcohol at 20℃; for 3h;	99%
With Raney aluminium-nickel alloy; water; sodium hydroxide In dimethoxymethane at 25℃; for 17h;

2,4-Dichloroaniline (554-00-7) → aniline (62-53-3)

Conditions	Yield
With ammonium formate In water; isopropyl alcohol at 20℃; for 3h;	99%
With methylene blue; sodium hydroxide Kinetics; Concentration; pH-value; Temperature; Irradiation;

nitrobenzene (98-95-3) + 12percent nickel/Al-SBA-15 fiber → aniline (62-53-3)

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

Cyclopentene oxide (285-67-6) + aniline (62-53-3) → trans-2-(phenylamino)cyclopentanol (77924-49-3, 101593-89-9)

Conditions	Yield
With zirconium(IV) chloride at 20℃; for 0.25h;	100%
With lithium bromide at 20℃; for 5h;	100%
With sulfated zirconia In neat (no solvent) at 20℃; for 0.5h; regioselective reaction;	98%

furfural (98-01-1) + aniline (62-53-3) → N-(2-furylmethylene)aniline (3237-23-8)

Conditions	Yield
With copper(II) bis(trifluoromethanesulfonate) In water at 20℃; for 0.0166667h;	100%
With aluminum oxide for 5h; Milling;	100%
sodium hydrogen sulfate; silica gel at 56 - 58℃; for 0.0244444h; microwave irradiation;	98%

maleic anhydride (108-31-6) + aniline (62-53-3) → N-phenylmaleamic acid (555-59-9, 4437-08-5, 37902-58-2)

Conditions	Yield
In diethyl ether Ring cleavage; Substitution;	100%
In dichloromethane at 20℃; for 1h;	100%
at 20℃; for 2h;	99%

phthalic anhydride (85-44-9) + aniline (62-53-3) → N-phenylphthalimide (520-03-6)

Conditions	Yield
Stage #1: phthalic anhydride; aniline In N,N-dimethyl acetamide at 20℃; for 24h; Stage #2: In N,N-dimethyl acetamide; xylene at 140℃; for 48h;	100%
In 1,2-dichloro-benzene at 180 - 190℃; for 5h; Dean-Stark;	100%
In 1,2-dichloro-benzene at 180 - 190℃; for 5h; Dean-Stark;	100%

Phenyl glycidyl ether (122-60-1) + aniline (62-53-3) → N-(2-hydroxy-3-phenoxypropyl)aniline (16112-55-3, 113279-34-8)

Conditions	Yield
With zirconium(IV) chloride at 20℃; for 0.25h;	100%
With lithium bromide at 20℃; for 5h;	100%
silica gel at 20℃; for 3h;	100%

cyclohexane-1,2-epoxide (286-20-4) + aniline (62-53-3) → 2-(phenylamino)cyclohexan-1-ol (75907-11-8, 110716-75-1, 118457-60-6, 131234-75-8, 38382-30-8)

Conditions	Yield
In water at 60℃; for 18h;	100%
With acetic acid at 20 - 25℃; for 1h; Temperature; Reagent/catalyst;	100%
With PhCNAl(OC(CF3)2PhCH3)3 at 25℃; for 4h; Inert atmosphere; Neat (no solvent);	99%

cyclohexane-1,2-epoxide (286-20-4) + aniline (62-53-3) → trans-(2-(phenylamino)cyclohexanol) (38382-30-8, 75907-11-8, 110716-75-1, 118457-60-6, 131234-75-8)

Conditions	Yield
With bis(trifluoromethane)sulfonimide lithium at 20℃; for 20h; without solvent;	100%
With zirconium(IV) chloride at 20℃; for 0.25h;	100%
Montmorillonite K 10 at 20℃; for 3h; Product distribution; Further Variations:; Catalysts; reaction times;	100%

acetic anhydride (108-24-7) + aniline (62-53-3) → Acetanilid (103-84-4)

Conditions	Yield
With pyridine; aluminum oxide at 93 - 95℃; for 1h; microwave irradiation;	100%
In dichloromethane at 20℃; Inert atmosphere;	100%
In dichloromethane at 21℃; Inert atmosphere;	100%

4-chlorobenzaldehyde (104-88-1) + aniline (62-53-3) → N-(4-chlorobenzylidene)aniline (2362-79-0)

Conditions	Yield
With acetic acid In 1,2-dichloro-ethane at 20℃; for 24h; Inert atmosphere;	100%
With formic acid In ethanol; water at 20℃; for 0.0166667h; Green chemistry;	99%
at 20℃; for 14h; Molecular sieve;	98%

cinnamoyl chloride (102-92-1) + aniline (62-53-3) → cinnamanilide (3056-73-3, 25775-89-7, 52393-67-6)

Conditions	Yield
With pyridine In toluene for 12h;	100%
With triethylamine In dichloromethane at 20℃; Inert atmosphere;	100%
With triethylamine In ethyl acetate at 0 - 20℃;	94%

1-naphthaldehyde (66-77-3) + aniline (62-53-3) → [1]naphthylmethylen-aniline (890-50-6)

Conditions	Yield
In chloroform Ambient temperature;	100%
In benzene Heating;	74%
In water at 20℃; for 2h;	69%

2-ethoxycarbonyl-1-cyclopentanone (611-10-9) + aniline (62-53-3) → 2-(N-phenylcarbamoyl)cyclopentanone (4874-65-1)

Conditions	Yield
In neat (no solvent) at 180℃; for 0.75h; Microwave irradiation; Green chemistry;	100%
In 5,5-dimethyl-1,3-cyclohexadiene at 160℃; Inert atmosphere;	90%
With dmap In toluene for 9.5h; Reflux; Inert atmosphere;	39%

3,4,5-trimethoxy-benzaldehyde (86-81-7) + aniline (62-53-3) → N-(3,4,5-trimethoxybenzylidene)aniline (114468-30-3, 32349-41-0)

Conditions	Yield
In chloroform Ambient temperature;	100%
sodium hydrogen sulfate; silica gel at 60 - 62℃; for 0.025h; microwave irradiation;	94%
In ethanol at 20℃;	87%

trityl chloride (76-83-5) + aniline (62-53-3) → Phenyl-trityl-amine (4471-22-1)

Conditions	Yield
Stage #1: trityl chloride; aniline at 190℃; for 0.5h; Stage #2: With hydrogenchloride In methanol for 0.5h; Reflux;	100%
at 50℃; for 1.5h;	63%
With pyridine at 20℃; for 24h; Substitution;	44%

benzaldehyde (100-52-7) + aniline (62-53-3) → N-Benzylaniline (758640-21-0)

Conditions	Yield
With tri-n-butyl-tin hydride; silica gel at 20℃; for 1h;	100%
With sodium tetrahydroborate; triethylamine In methanol	100%
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 18℃; for 1h; Solvent; Reagent/catalyst; Green chemistry;	100%

benzaldehyde (100-52-7) + aniline (62-53-3) → benzylidene phenylamine (538-51-2)

Conditions	Yield
In chloroform Ambient temperature;	100%
In toluene at 120℃; for 24h;	100%
With alumina-entrapped Ag at 120℃; under 750.075 Torr; for 1h; Inert atmosphere; Autoclave;	100%

benzaldehyde (100-52-7) + aniline (62-53-3) → (E)-N-benzylidenebenzenamine (1750-36-3, 33993-35-0, 538-51-2, 137431-97-1, 137432-04-3)

Conditions	Yield
In ethanol for 6h; Reflux;	100%
In toluene Inert atmosphere; Schlenk technique; Molecular sieve;	100%
With silica gel In ethanol at 20℃; Ultrasound irradiation;	99%

4-methoxy-benzaldehyde (123-11-5) + aniline (62-53-3) → p-methoxybenzylidene-phenylamine (836-41-9)

Conditions	Yield
In chloroform Ambient temperature;	100%
In toluene for 1h; Ambient temperature;	100%
In benzene for 4h; Reflux; Dean-Stark;	100%

salicylaldehyde (90-02-8) + aniline (62-53-3) → N-phenylsalicylaldimine (779-84-0)

Conditions	Yield
at 50℃; for 4h;	100%
With sodium sulfate In dichloromethane for 4h; Reflux;	100%
In methanol at 20℃; for 1h;	98%

benzoyl chloride (98-88-4) + aniline (62-53-3) → N-phenyl benzoyl amide (93-98-1)

Conditions	Yield
With pyridine; aluminum oxide at 92 - 94℃; for 0.0166667h; microwave irradiation;	100%
With triethylamine In dichloromethane at 0 - 20℃; for 16h; Inert atmosphere;	100%
With triethylamine In tetrahydrofuran at 0 - 20℃; for 2.5h; Inert atmosphere; Schlenk technique; Glovebox;	99.5%

phenyl isocyanate (103-71-9) + aniline (62-53-3) → bis(diphenyl)urea (102-07-8)

Conditions	Yield
With triethylamine In dichloromethane	100%
In acetic acid for 0.0833333h;	98%
In hexane	95%

vanillin (121-33-5) + aniline (62-53-3) → N-(4-hydroxy-3-methoxybenzylidene)aniline (17696-53-6)

Conditions	Yield
With aluminum oxide for 5h; Milling;	100%
sodium hydrogen sulfate; silica gel at 58 - 60℃; for 0.0208333h; microwave irradiation;	96%
With aqueous extract of pericarp of Sapindus trifoliatus fruits at 20℃; for 0.333333h;	93%

4-nitro-benzoyl chloride (122-04-3) + aniline (62-53-3) → 4-nitrobenzanilide (3460-11-5)

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 2.5h;	100%
With pyridine Reflux;	95%
With pyridine at 20℃; Inert atmosphere; Reflux;	91%

3,4-dimethoxy-benzaldehyde (120-14-9) + aniline (62-53-3) → N-(3,4-dimethoxybenzylidene)aniline (27895-67-6)

Conditions	Yield
In toluene Heating;	100%
sodium hydrogen sulfate; silica gel at 56 - 58℃; for 0.0222222h; microwave irradiation;	95%
magnesium(II) perchlorate In 1,2-dichloro-ethane at 20℃; for 4h;	94%

formamide (77287-34-4, 77287-35-5, 60100-09-6) + aniline (62-53-3) → Formanilid (103-70-8)

Conditions	Yield
With iron(III) chloride hexahydrate In toluene for 6.5h; Solvent; Reagent/catalyst; Reflux;	100%
at 20 - 120℃; for 15h;	99%
at 120℃; for 15h;	99%

acetic acid (64-19-7) + aniline (62-53-3) → Acetanilid (103-84-4)

Conditions	Yield
With dmap; 2-chloro-1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecyl)pyridinium trifluoromethanesulfonate; triethylamine In N,N-dimethyl-formamide at 20℃; for 1h;	100%
With dmap; 2-chloro-1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-henicosafluorododecyl)pyridinium trifluoromethanesulfonate; triethylamine In N,N-dimethyl-formamide at 20℃; for 1h;	100%
With zinc(II) oxide for 2.33h; Reflux; chemoselective reaction;	99%

methyl vinyl ketone (78-94-4) + aniline (62-53-3) → 4-phenylamino-butan-2-one (6220-79-7)

Conditions	Yield
In water at 20℃; for 24h; Michael condensation;	100%
With Nafion(R) SAC-13 In acetonitrile at 20℃; for 12h;	98%
With bis(trifluoromethanesulfonyl)amide In acetonitrile for 4h; Michael addition;	98%

chloroacetonitrile (107-14-2) + aniline (62-53-3) → N-phenylglycinonitrile (3009-97-0)

Conditions	Yield
With potassium carbonate; sodium iodide In acetonitrile for 3h; Reflux;	100%
With potassium carbonate; sodium iodide In acetonitrile for 3h; Reflux;	100%
With triethylamine In ethanol for 4h; Heating;	22%

butyraldehyde (123-72-8) + aniline (62-53-3) → N-(n-butyl)aniline (1126-78-9)

Conditions	Yield
With ammonium formate; palladium on activated charcoal In water; isopropyl alcohol at 20℃; for 0.5h;	100%
With 1.1 wt% Pd/NiO; hydrogen In ethanol at 25℃; under 760.051 Torr; for 10h;	98%
With sodium tetrahydroborate In tetrahydrofuran at 20℃;	96%

Upstream product

• 591-50-4 iodobenzene 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 19964-97-7 N-bromobenzamide 
• 64-19-7 acetic acid 
• 102-07-8 bis(diphenyl)urea 
• 1007476-32-5 sodium ethyl acetylacetate enolate 
• 88-73-3 2-Chloronitrobenzene 
• 100-00-5 4-chlorobenzonitrile 
• 222851-56-1 N-phenylsulfinylamine 
• 106-45-6 para-thiocresol 
• 98-95-3 nitrobenzene 
• 71-36-3 butan-1-ol 
• 106-97-8 n-butane 
• 6921-34-2 benzylmagnesium chloride 

Downstream Products

• 33345-17-4 N,N-diphenylbenzamidine 
• 5608-83-3 5-anilino-penta-2,4-dienal-phenylimine 
• 1497-49-0 glutacondianil hydrochloride 
• 102-08-9 N,N-diphenylthiourea 
• 103-70-8 Formanilid 
• 3336-59-2 5-anilino-penta-2,4-dienal-phenylimine; hydrobromide 
• 1886-29-9 N-(2-methyl-4-amino-5-pyrimidinyl)methylaniline 
• 2908-73-8 (4-amino-2-methylpyrimidin-5-yl)methanesulfonic acid 
• 102-02-3 1-phenylbiguanide 
• 4478-04-0 2-(3-phenyl-triazenyl)-benzoic acid 
• 106978-87-4 3-ethyl-5-anilino-penta-2,4-dienal-phenylimine; hydrobromide 
• 100957-27-5 N-[2-(4,6-dimethyl-[2]pyridyl)-ethyl]-aniline 
• 100957-31-1 N-[2-(5-ethyl-[2]pyridyl)-ethyl]-aniline 
• 61973-96-4 (E)-1-(5-methylfuran-2-yl)-N-phenylmethanimine 

Relevant articles and documents

Magnetic Field Effects on and Mechanism of Photoredox Reaction of Aromatic Nitro Group

Photoredox reaction mechanism of a homologous series p-O2NC6H4O(CH2)nNHPh (1) in acetonitrile and benzene is studied.The major products are p-ONC6H4O(CH2)n-1CHO (3) and aniline derived from intramolecular reaction, but the presence of minor amounts of intermolecular reaction products, p-O2NC6H4O(CH2)n-1CHO (4) and p-ONC6H4O(CH2)nNHPh (5) is confirmed in the reaction mixture.In the presence of an external magnetic field, the yield of 3 is suppressed and those of 4 and 5 are correspondingly increased, while the rates of the disappearance of 1 and of the formation of aniline remain unchanged, suggesting the presence of biradical recombination process accompanied by intersystem crossing in a rate-determining step.On the basis of these observations, two reaction schemes are proposed.The magnetic field effects provide strong evidence for the presence of a transient species with (nitro)N(OH)-O-CHN group generally supposed for nitro oxygen transfer process in this type photoreaction.

Structure and Catalytic Activity of Cr-Doped BaTiO3 Nanocatalysts Synthesized by Conventional Oxalate and Microwave Assisted Hydrothermal Methods

In the present study synthesis of BaTi1-xCrxO3 nanocatalysts (x = 0.0 ≤ x ≤ 0.05) by conventional oxalate and microwave assisted hydrothermal synthesis methods was carried out to investigate the effect of synthesis methods on the physicochemical and catalytic properties of nanocatalysts. These catalysts were thoroughly characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), N2 physisortion, and total acidity by pyridine adsorption method. Their catalytic performance was evaluated for the reduction of nitrobenzene using hydrazine hydrate as the hydrogen source. Structural parameters refined by Rietveld analysis using XRD powder data indicate that BaTi1-xCrxO3 conventional catalysts were crystallized in the tetragonal BaTiO3 structure with space group P4mm, and microwave catalysts crystallized in pure cubic BaTiO3 structure with space group Pm3μm. TEM analysis of the catalysts reveal spherical morphology of the particles, and these are uniformly dispersed in microwave catalysts whereas agglomeration of the particles was observed in conventional catalysts. Particle size of the microwave catalysts is found to be 20-35 nm compared to conventional catalysts (30-48 nm). XPS studies reveal that Cr is present in the 3+ and 6+ mixed valence state in all the catalysts. Microwave synthesized catalysts showed a 4-10-fold increase in surface area and pore volume compared to conventional catalysts. Acidity of the BaTiO3 catalysts improved with Cr dopant in the catalysts, and this could be due to an increase in the number of Lewis acid sites with an increase in Cr content of all the catalysts. Catalytic reduction of nitrobenzene to aniline studies reveals that BaTiO3 synthesized by microwave is very active and showed 99.3% nitrobenzene conversion with 98.2% aniline yield. The presence of Cr in the catalysts facilitates a faster reduction reaction in all the catalysts, and its effect is particularly notable in conventional synthesized catalysts.

Pd nanoparticles immobilized on halloysite decorated with a cyclodextrin modified melamine-based polymer: a promising heterogeneous catalyst for hydrogenation of nitroarenes

For the first time, a hybrid system composed of halloysite (Hal) and a cyclodextrin modified melamine-based polymer is developed and employed for immobilization of Pd(0) nanoparticles. The resulting catalytic hybrid system, Pd@HTMC, was then applied as a

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Palladium nanoparticles supported on silicate-based nanohybrid material: highly active and eco-friendly catalyst for reduction of nitrobenzene at ambient conditions

In this study, spent bleaching earth (SBE), a hazardous industrial waste was used as raw material to synthesis carbon/silicate nanohybrid material (CSNH) as support for mono and bimetallic palladium and nickel nanoparticles. The synthesized catalysts were

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A Modification of the Sheverdina-Kocheshkov Amination: The Use of Methoxyamine-Methyllithium as a Convenient Synthetic Equivalent for NH2+

Direct stoichiometric amination of organolithiums can be achieved in high yields by methoxyamine and methyllithium in hexane-ether.The synthetic advantages of this approach are noted.

Pd immobilized on polymeric network containing imidazolium salt, cyclodextrin and carbon nanotubes: Efficient and recyclable catalyst for the hydrogenation of nitroarenes in aqueous media

A novel polymeric network benefiting from the chemistry of imidazolium salt (IL), cyclodextrin (CD) and carbon nanotube (CNT) is fabricated through a multi-step process, in which silica coated CNTs were vinyl functionalized and polymerized with poly (ethy

Synthesis of PVP-stabilized Pt/Ru colloidal nanoparticles by ethanol reduction and their catalytic properties for selective hydrogenation of ortho-chloronitrobenzene

Stable poly(N-vinyl-2-pyrrolidone)-stabilized Pt/Ru colloidal nanoparticles (PVP-Pt/Ru) were prepared via ethanol reduction of H2PtCl 66H2O and RuCl3nH2O. The average diameters of the nanoparticles with different molar ratio of Pt/Ru were in a range of 2.1-2.8 nm with narrow size distributions. X-ray photoelectron spectroscopy verified that both Pt and Ru were in the metallic state and Ru was rich on the surface. These nanoparticles were employed to selectively hydrogenate ortho-chloronitrobenzene at 298 K and 0.1 MPa hydrogen pressure. They showed high activity [TOF was in the range of 0.8-5.3 × 10 -2 molo-CNB/(molM,surface atom) s] and high selectivity (93-99%) to ortho-chloroaniline (o-CAN) for the reaction, which were composition-dependent. The selectivity to o-CAN monotonously increased, but the activity of the catalyst decreased with the increasing proportion of Ru in Pt/Ru colloidal catalysts. PVP-1Pt/4Ru nanoparticles exhibited the highest selectivity of 99.0% to o-CAN at a complete conversion.

Thermolysis of azobenzene

Thermolysis of azobenzene in a melt and in solution results in the formation of aniline.The possible directions of the reaction are considered.Comparison of the enthalpies of the reaction proves that the cleavage of a ?-bond in the N=N group to form a biradical intermediate is thermodynamically more favorable than that of a C-N ?-bond.

Photochemical locking and unlocking of an acyl nitroso dienophile in the Diels-Alder reaction

Photochromic Diels-Alder cycloadducts consisting of acyl nitroso dienophiles, which are known nitroxyl (HNO) donors, and dithienyldienes are presented. The dithienylethene-type photochromic cycloadducts were found to exhibit reversible electrocyclic ring closing and ring opening reactions to 'lock' or 'unlock' the retro Diels-Alder reaction, respectively. The release of an acyl nitroso dienophile via a retro Diels-Alder reaction at 92 °C was shown to occur only from the open or 'unlocked' form of a photochromic dithienylcyclopentene and not from the closed or 'locked' isomer.

Oxidation-reduction conversions of derivatives of 1,4-dihydropyridine and 4H-pyran on interaction of alicyclic 1,5-diketones with 4-aminoazobenzene

The interaction of 2,2′-methylenedicyclohexanone and 2,2′-methylenedicyclopentanone with 4-aminoazobenzene in acetic acid leads to reduction of the azo group of 1,4-dihydropyridine and 4H-pyran derivatives formed as intermediates. The reduction products were isolated as the corresponding pyridinium salts.

Methylene blue sensitized photodechlorination of isomeric mono- and dichloroanilines via molecular complex formation mechanism

The photosensitized dechlorination of isomeric mono- and dichloroanilines has been studied using methylene blue as photosensitizer in alkaline medium. The dechlorination products have been identified and formation of molecular complex between aniline and methylene blue has been observed. The effects of the pH, concentration of the sensitizer, concentration of the substrate, the intensity of the light and the temperature on the rate of the reaction have been studied. The quantum efficiency of the photodechlorination has been evaluated. The mechanism of the photodechlorination has been suggested.

Trimethylsilyl Azide/Triflic Acid, a Highly Efficient Electrophilic Aromatic Amination Reagent

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Features of the phenylhydroxylamine catalytic hydrogenation in water solutions of 2-propanole on skeletal nickel

The kinetics of phenylhydroxylamine hydrogenation reaction on skeletal nickel catalyst in 2-propanole aqueous solutions was studied. It was shown that the value of phenylhydroxylamine and aniline adsorption increases with an increase in the molar fraction of water in the binary solvent 2-propanole-water. It was found experimentally that the hydrogenation reaction is of the first order with phenylhydroxilamine and of the zero order with hydrogen. It is noted that the amount of hydrogen absorbed in the reduction of phenylxydroxylamine in the initial phase of the reaction is considerably lower than the stehiometry of the reaction would indicate. The reasons for the effect of solvent on the features of phenylhydroxilamine hydrogenation are discussed.

Vilsmeier-Haack reagent-promoted formyloxylation of α-chloro-N-arylacetamides by formamide

In this study, a Vilsmeier-Haack reagent-promoted formyloxylation of α-chloro-N-arylacetamides by formamide was developed. The reaction successfully provided the desired α-formyloxy-N-arylacetamides 4 and 7a-n in moderate to excellent yields (70-96%) by use of 3.0 equivalents of PBr3 at 80-90 °C and was applicable to substrates bearing electron-donating or withdrawing groups at the aryl moiety. For α-chloro-N-(naphthalenyl)acetamide (8a), α-chloro-N-(quinolin-8-yl)acetamide (8b), and α-chloro-N-(thiazol-2-yl)acetamide (8c) possessing the α-chloro group, the reaction also provided the desired formyloxylated products 9a-c in 70-87% yields. A plausible mechanism was proposed through the activation of α-chloroacetamide by the Vilsmeier-Haack reagent to account for the new transformation.

o-Phenylenediamine from sulfur, ammonia, and cyclohexane

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METAL-ASSISTED REACTIONS. PART 24: THE IMPORTANCE OF SOLVENTS IN LIQUID-PHASE HETEROGENEOUS CATALYTIC TRANSFER REDUCTION

In liquid-phase catalytic transfer reduction in which a hydrogen donor is used to effect hydrogenation of a substrate, reaction often proceeds sluggishly in single phase solvents but goes rapidly in biphasic solvent systems in which the catalyst usually resides in one or other of the phases.Depending on the nature of the substrate and donor, an excess of either can lead to the catalyst surface becoming saturated with one component, thereby preventing reaction.It is shown that the biphasic solvent system is, in practice, a simple means of controlling access to the catalyst by either the substrate or donor such that both are present on the surface in comparable amounts, leading to optimum or near optimum reaction rates.

NN bond cleavage of azobenzene: Via photocatalytic hydrogenation with Dy-doped Zn(O,S): The progress from hydrogen evolution to green chemical conversion

Hydrogen-evolved Dy-doped Zn(O,S) photocatalysts with different amounts of Dy precursor have been synthesized, characterized and further utilized for hydrogenation reactions. The Dy catalysts are first examined using electrochemical impedance spectroscopy, photo responsivity, and the hydrogen evolution reaction. Dy-doped Zn(O,S) with 10% Dy precursor shows the best photocatalyst performance with the highest H2 production rate of 8.160 mmol g-1 h-1. This catalyst is chosen for conducting the hydrogenation reaction. It is our intention to confirm the correlation between the photocatalytic H2 production rate and the hydrogenation reactions of 4-nitrophenol to 4-aminophenol and azobenzene to aniline, which is a step further in the hydrogenation reaction to challenge the NN bond cleavage of azobenzene. A 100% photo conversion of 60 ppm azobenzene to aniline in 6 h was confirmed under a low-power UV light illumination in a 10% ethanol solution. Kinetic steps and kinetic mechanisms are proposed, which involve the important reaction steps of solvation, adsorption, pinning, and surface hydrogenation reaction operating together.

7-Bromo-5-phenyl-1,2-dihydro-3H-1,3,5-benztriazepin-2-one

7-Bromo-5-phenyl-1,2-dihydro-3H-1,4-benztriazepin-2-one was obtained by thermolysis of the syn-4-phenylsemicarbazone of 2-aminobenzophenone. Its molecular and crystal structure were established by X-ray crystallography. The nature of the hydrogen bonds be

Study of dehalogenation of halogenoanilines using Raney Al-Ni alloy in aqueous medium at room temperature

Dehalogenation of halogenated anilines by action of powdered aluminium-nickel alloy in aqueous alkaline solution at room temperature has been studied. The reaction course was monitored by means of1H nuclear magnetic resonance (NMR) spectroscopy. The rates of dehalogenation of 4-bromo-, 4-chloro-, 4-fluoro-and 3-chloroaniline were compared under conditions of minimum necessary excess of Al-Ni alloy as reducing agent in edetane buffer medium at pH 10.9. The dehalogenation rates of halogenated anilines decreased in the following order: 3-chloroaniline > 4-bromoaniline ≥ 4-chloroaniline >4-fluoroaniline. On the basis of the results obtained in buffers, the dehalogenation method of aqueous solutions of halogenoanilines was verified using NaOH as the base. Springer-Verlag 2010.

Synthesis of palladium nanoparticles over graphite oxide and carbon nanotubes by reduction in ethylene glycol and their catalytic performance on the chemoselective hydrogenation of para-chloronitrobenzene

Pd nanoparticles have been synthesized over carbon nanotubes (CNT) and graphite oxide (GO) by reduction with ethylene glycol and by conventional impregnation method. The catalysts were tested on the chemoselective hydrogenation of p-chloronitrobenzene and the effect of the synthesis method and surface chemistry on their catalytic performance was evaluated. The catalysts were characterized by N2 adsorption/desorption isotherms at 77 K, TEM, powder X-ray diffraction, thermogravimetry, infrared and X-ray photoelectron spectroscopy and ICP-OES. It was observed that the synthesis of Pd nanoparticles employing ethylene glycol resulted in metallic palladium particles of smaller size compared to those prepared by the impregnation method and similar for both supports. The presence of oxygen groups on the support surface favored the activity and diminished the selectivity. It seems that ethylene glycol reacted with the surface groups of GO, this favoring the selectivity. The activity was higher over the CNT-based catalysts and both catalysts prepared by reduction in ethylene glycol were quite stable upon recycling.

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Functionalization of a plasmonic Au/TiO2 photocatalyst with an Ag co-catalyst for quantitative reduction of nitrobenzene to aniline in 2-propanol suspensions under irradiation of visible light

A functionalized plasmonic Au/TiO2 photocatalyst with an Ag co-catalyst was successfully prepared by the combination of two types of photodeposition methods, and it quantitatively converted nitrobenzene and 2-propanol to aniline and acetone under irradiation of visible light.

Kinetics of the hydrogenation of a mixture of nitrobenzene and azoxybenzene on skeletal nickel in an aqueous solution of propan-2-ol

The sequence of the reduction of nitro and azoxy groups in the combined hydrogenation of nitrobenzene and azoxybenzene on skeletal nickel in an aqueous azeotropic solution of propan-2-ol is considered. The time dependences of the rates and concentrations of the initial compound and reaction product for the hydrogenation of individual compounds (nitrobenzene and azoxybenzene) in the solvent of the indicated composition are discussed for comparative analysis. In all cases, the reactions proceed selectively to aniline without accumulating side products. The reduction of the nitro and azoxy groups involves hydrogen bound by the active sites of the catalyst surface. The competitive character of adsorption between the initial compounds and formed aniline is observed. Nitrobenzene is characterized by the highest adsorbability, whereas azoxybenzene and aniline are less adsorbable.

Palladated composite of Cu-BDC MOF and perlite as an efficient catalyst for hydrogenation of nitroarenes

A novel composite of metal-organic framework and perlite is prepared through hydrothermal treatment of terephthalic acid and Cu(NO3)2·3H2O in the presence of perlite. The resulting composite was then utilized as a support for the immobilization of Pd nanoparticles. The obtained compound was characterized via XRD, TGA, ICP, FTIR, TEM, FE-SEM/EDS and elemental mapping analysis and applied as a catalyst for the hydrogenation of nitroarenes under mild reaction condition. The results approved that the catalyst could efficiently promote hydrogenation of various nitroarenes with different electronic densities and steric properties. Moreover, the catalyst showed high selectivity towards hydrogenation of nitro groups. Hot filtration test affirmed heterogeneous nature of catalysis. Furthermore, the present catalytic composite was highly recyclable with low Pd leaching. A comparative study also approved superior activity of the composite compared to palladated perlite and metal-organic framework.

Synthesis, thermal behavior in oxidative and pyrolysis conditions, spectroscopic and DFT studies of some alkaline earth metals p-aminobenzoate complexes using TG-DTA, DSC, PXRD and EGA (TG-FTIR) techniques

p-aminobenzoic acid is a substance widely used in several areas, such as catalysis, biomarkers, magnetic materials, luminescent materials and biological applications. p-aminobenzoate complexes with alkaline earth metal were synthesized and the thermal and pyrolysis behavior was studied using thermoanalytical and spectroscopic techniques. Based on TG/DTG-DTA and EGA results, the thermal decomposition mechanisms of the compounds were proposed under both atmospheres studied. The main gaseous products identified by EGA in both study conditions were H2O, Aniline, CO and CO2. From DSC analysis, it was possible to measure the enthalpies of dehydration and evaluate the phase transitions of the magnesium complex. FTIR data suggest that metal-ligand coordination occurs through carboxylate group by different ways. The coordination modes suggested by experimental FTIR data were supported by DFT study. The X-ray diffraction powder patterns show that the barium compound was obtained in amorphous state, while the other compounds have a crystalline structure.

2-(4-Nitrophenyl)-1H-indolyl-3-methyl Chromophore: A Versatile Photocage that Responds to Visible-light One-photon and Near-infrared-light Two-photon Excitations

Due to cell damage caused by UV light, photoremovable protecting groups (PPGs) that are removed using visible or near-infrared light are attracting attention. A 2-(4-nitrophenyl)- 1H-indolyl-3-methyl chromophore (NPIM) was synthesized as a novel PPG. Various compounds were caged using this PPG and uncaged using visible or near-infrared light. Low cytotoxicity of NPIM indicates that it may be applied in physiological studies.