62-53-3 Usage
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).
Check Digit Verification of cas no
The CAS Registry Mumber 62-53-3 includes 5 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 2 digits, 6 and 2 respectively; the second part has 2 digits, 5 and 3 respectively.
Calculate Digit Verification of CAS Registry Number 62-53:
(4*6)+(3*2)+(2*5)+(1*3)=43
43 % 10 = 3
So 62-53-3 is a valid CAS Registry Number.
InChI:InChI=1/C6H7N/c7-6-4-2-1-3-5-6/h1-5H,7H2
62-53-3Relevant articles and documents
Magnetic Field Effects on and Mechanism of Photoredox Reaction of Aromatic Nitro Group
Mutai, Kiyoshi,Nakagaki, Ryoichi,Tukada, Hideyuki
, p. 920 - 926 (1993)
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
Srilakshmi, Chilukoti,Saraf, Rohit,Prashanth,Rao, G. Mohan,Shivakumara
, p. 4795 - 4805 (2016)
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
Sadjadi, Samahe,Akbari, Maryam,Monflier, Eric,Heravi, Majid M.,Leger, Bastien
, p. 15733 - 15742 (2018)
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
Mesoporous silica supported cobalt catalysts for gas phase hydrogenation of nitrobenzene: role of pore structure on stable catalytic performance
Kondeboina, Murali,Enumula, Siva Sankar,Gurram, Venkata Ramesh Babu,Yadagiri, Jyothi,Burri, David Raju,Kamaraju, Seetha Rama Rao
, p. 15714 - 15725 (2018)
Highly dispersed cobalt nanoparticles were prepared over mesoporous silica with different pore structures (2D-hexagonal COK-12 and 3D-cubic SBA-16). These catalysts were evaluated for gas phase hydrogenation of nitrobenzene to aniline at atmospheric H2 pressure. A combination of catalytic activity and characterization results were assessed to establish the role of the support pore structure on hydrogenation activity. XRD, N2-physisorption, SEM and TEM analysis confirmed the presence of mesoporous structures in the supported cobalt catalysts. H2-TPR, H2-pulse chemisorption and TEM studies demonstrated higher dispersion of cobalt nanoparticles in Co/SBA-16 than in the Co/COK-12 catalyst. During the time-on-stream study the Co/SBA-16 catalyst experienced a gradual deactivation whereas the Co/COK-12 catalyst exhibited constant catalytic performance with respect to the hydrogenation of nitrobenzene. The interconnected cage type pores in Co/SBA-16 catalyst allowed the product molecules to participate in further reactions. This resulted in the formation of condensed products and coke deposition. The Co/SBA-16 catalyst was rapidly deactivated due to pore blocking through coke deposition. N2-Physisorption, TGA, H2-TPR and CHNS elemental analysis of spent catalysts confirmed the severe coke deposition in the Co/SBA-16 catalyst compared to the Co/COK-12 catalyst.
Well-dispersed bimetallic nanoparticles confined in mesoporous metal oxides and their optimized catalytic activity for nitrobenzene hydrogenation
Liu, Juanjuan,Zou, Shihui,Xiao, Liping,Fan, Jie
, p. 441 - 446 (2014)
Well-dispersed bimetallic nanoparticles (BMNPs = PtPd/AuPd/AuPt) confined in mesoporous metal oxides (MMOs = TiO2/Al2O 3/SiO2/ZrO2) are synthesized by a general and mild one-step sol-gel strategy. Thi
Palladium nanoparticles supported on silicate-based nanohybrid material: highly active and eco-friendly catalyst for reduction of nitrobenzene at ambient conditions
Ebadati, Esmat,Aghabarari, Behzad,Bagheri, Mozhgan,Khanlarkhani, Ali,Martinez Huerta, Maria Victoria
, p. 569 - 578 (2021)
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
Efficient reduction catalysis of viologen-bound iron porphyrin and its application to six-electron reduction of nitrobenzene to aniline
Sakaki, Shigcyoshi,Koga, Hiroaki,Tao, Kou-Ichiro,Yamashita, Takafumi,Iwashita, Tetsuro,Hamada, Taisuke
, p. 1015 - 1017 (2000)
A newly synthesized methylviologen-bound iron porphyrin chloro(5-{4-[3-(1′-methyl-4,4′-bipyridinium)ethylcarboxyamidyl] phenyl}-10,15,20-triphenylporphyrin)iron dichloride, efficiently catalyzes six-electron reduction of nitrobenzene to aniline, a model reaction of NO2- conversion to NH4+ by nitrite reductase. The Royal Society of Chemistry 2000.
A Modification of the Sheverdina-Kocheshkov Amination: The Use of Methoxyamine-Methyllithium as a Convenient Synthetic Equivalent for NH2+
Beak, Peter,Kokko, Bruce J.
, p. 2822 - 2823 (1982)
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.
Transition Metal Catalyzed Reduction of Azidoarenes to Aminoarenes with Carbon Monoxide-Water System
Shim, Sang Chul,Choi, Kui Nam,Yeo, Young Kuk
, p. 1149 - 1150 (1986)
Azidoarenes were readily transformed to aminoarenes in good yields under mild conditions with carbon monoxide and water in the presence of a catalytic amount of rhodium(III) complex, which is more catalytically active than rhodium(I) or palladium(II) complexes.
Pd immobilized on polymeric network containing imidazolium salt, cyclodextrin and carbon nanotubes: Efficient and recyclable catalyst for the hydrogenation of nitroarenes in aqueous media
Sadjadi, Samahe,Koohestani, Fatemeh
, (2020)
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
