153-78-6 Usage
Description
Occupational exposure to polycyclic aromatic amines (PAA) has
occurred historically in the rubber, textile, and dye industries.
Some sources of nonoccupational exposure to PAAs include
inhalation of tobacco smoke, emissions from heated cooking oil
and diesel engine exhaust, and dermal exposure to hair dyes.
During the 1870s, the first aromatic amine dyes were
manufactured in Germany (dyes of natural origin were used
prior to the synthesis of dyes). In 1895, a physician by the name
Rehn reported a cluster of patients who had developed bladder
cancer. He observed that all of the affected workers were
employed at a site in Germany that manufactured fuschsin dye.
The workers had all been exposed to large amounts of intermediate
arylamines. The United States first started manufacturing
dyes in the early 1900s when trade between the
United States and Germany was halted during the First World
War. DuPont was the first company to begin manufacturing
synthetic dyes in the United States, and shortly thereafter
(1930s) the physicians employed by DuPont also started
reporting an increased incidence of workers who had developed
bladder cancer. During 1947, a physician by the name of
Mengellsdorf who was employed by DuPont reported that
100% of the workers who handled the chemical betanaphthylamine
had developed bladder cancer. By the 1950s,
Chinese dye manufacturers reported the development of
bladder cancer in workers who handled benzidine. Evidence of
the development of bladder cancer associated with the manufacture
of dyes continued to mount, and during the 1970s dye
manufacturing was discontinued in the United States and was
taken over by developing nations. During the early 1970s, the
US Occupational Safety and Health Administration (OSHA)
began regulating aromatic amines that had been associated
with the development of bladder cancers. During the 1980s,
DuPont reported retrospectively that 316 of their dye
manufacturing workers had developed bladder cancer prior to
the discontinuation of dye manufacturing in the United States.
During the 1990s, the first reports of bladder cancer in the
Chinese dye manufacturing industry became public.
Hair dye products manufactured prior to the mid-1970s
contained chemicals that were shown to produce cancer in rodents. Some of these chemical included aromatic amines.
The manufacturers of hair coloring products began reformulating
their products to remove these potentially carcinogenic
compounds from their products beginning in the mid-1970s. It
is not clear if some of the ingredients in contemporary hair
products can cause an increased risk of cancer. The US National
Cancer Institute reported that there may be an increased risk of
developing non-Hodgkin’s lymphoma in people who used hair
dyes prior to the 1980s; however, the data are limited and often
inconsistent.
Chemical Properties
WHITE TO SLIGHTLY BROWN CRYSTALLINE POWDER
Uses
PAAs are used in the rubber, textile, and dye industries. They are
used as intermediates in the manufacture of plastics, drugs, and
carbamate pesticides. The aromatic amines 2-aminofluorene
and N-acetyl aminofluorene were being developed during the
1930s for use as pesticides; however, they were found to be
carcinogenic in laboratory animals. They were never marketed
as pesticides.
General Description
Brown crystal powder.
Air & Water Reactions
2-Aminofluorene is sensitive to prolonged exposure to air. Insoluble in water.
Reactivity Profile
2-AMINO FLUORENE forms salts with acids and can react with oxidizing materials.
Health Hazard
ACUTE/CHRONIC HAZARDS: When heated to decomposition 2-Aminofluorene emits toxic fumes.
Fire Hazard
Flash point data for 2-Aminofluorene are not available, but 2-Aminofluorene is probably combustible.
Safety Profile
Suspected carcinogen
with experimental carcinogenic,
neoplastigenic, and tumorigenic data. Poison
by intraperitoneal route. Mutation data
reported. When heated to decomposition it
emits toxic fumes of NOx. See also AMINES.
Environmental Fate
PAAs may be transported as vapor or adsorbed onto particulates.
Due to low water solubility, PAAs are not transported in
water but adsorb onto soil and sediments. Leaching is negligible.
Bioaccumulation is not considered a concern.
Purification Methods
Wash the amine well with H2O and recrystallise it from Et2O or 50% aqueous EtOH (25g with 400mL), and dry it in a vacuum. Store it in the dark. [Bavin Org Synth Coll Vol V 30 1973, Beilstein 12 H 1331, 12 IV 337.]
Toxicity evaluation
N-hydroxy metabolites within the gastrointestinal tract transform
fluoren-2-amine into a mutagen or carcinogen. A number
of PAAs are potent bladder carcinogens. As noted previously,
sequential hydroxylation and glucuronidation lead to urinary
excretion, with metabolites in the urinary bladder. While glucuronidation
enhances excretion via the urine, a glucuronidase
in the bladder hydrolyzes the glucuronide and under acidic
conditions N-hydroxylarylamines are formed. Subsequent conversion of the amine leads to an aryl nitrenium ion, which
can initiate tumor formation. Sulfate esters can degrade to
electrophilic nitronium ion–carbonium ion, which can form
adducts with macromolecules.
Check Digit Verification of cas no
The CAS Registry Mumber 153-78-6 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,5 and 3 respectively; the second part has 2 digits, 7 and 8 respectively.
Calculate Digit Verification of CAS Registry Number 153-78:
(5*1)+(4*5)+(3*3)+(2*7)+(1*8)=56
56 % 10 = 6
So 153-78-6 is a valid CAS Registry Number.
InChI:InChI=1/C13H11N/c14-13-7-3-6-11-10-5-2-1-4-9(10)8-12(11)13/h1-7H,8,14H2
153-78-6Relevant articles and documents
A new and efficient pyridine-2,6-dicarboxamide-based fluorescent and colorimetric chemosensor for sensitive and selective recognition of Pb2+ and Cu2+
Hosseinzadeh, Rahman,Rahimi, Hannaneh,Tajbakhsh, Mahmood
, (2021)
A new fluorene-bearing pyridine-2,6-dicarboxamide (3) as an effectint fluorescent and colorimetric cation sensor was successfully synthesized and well-characterized using FT-IR, NMR, ESI+-MS and elemental analysis. The metal ion binding ability of the chemosensor 3 in the presence of different metal ions was investigated using UV–vis, fluorescence experiments and results exhibited a desirable selectivity and significant sensitivity of the chemosensor 3 for the detection of Cu2+ and Pb2+ ions. The association constant (Ka) of 3-Cu2+ and 3-Pb2+ complexes were determined to be 8.89 × 103 M?1 and 5.65 × 108 M-2, respectively. The obtained limit of detection (LOD) values (1.49 × 10?6 M for Cu2+ and 2.31 × 10?6 M for Pb2+) clearly revealed the considerable sensitivity of the chemosensor 3.
Ultrasound-promoted highly efficient reduction of aromatic nitro compounds to the aromatic amines by samarium/ammonium chloride
Basu, Manas K.,Becker, Frederick F.,Banik, Bimal K.
, p. 5603 - 5606 (2000)
Ultrasound-promoted, highly efficient reduction of several aromatic nitro compounds to the aromatic amines was achieved by samarium/ammonium chloride mediated reaction. (C) 2000 Elsevier Science Ltd.
Route to the tritiation of carbon atom 9 of carcinogenic fluorenylhydroxamic acids
Gutmann,Bell
, p. 255 - 270 (1974)
-
Non-specific tritiation of some carcinogenic aromatic amines
Breeman,Kaspersen,Westra
, p. 741 - 750,748,749 (1978)
2-Aminofluorene, 4-amino-3-methylbiphenyl, 4-amino-biphenyl and 4-amino-4'-fluorobiphenyl were tritiated by acid catalyzed exchange of the corresponding nitro compounds followed by catalytic reduction. The exchange reactions were carried out by heating the nitro compounds in [3H]-trifluoroacetic acid with a catalytic amount of trifluoromethanesulphonic acid (TFMS). No loss of tritium could be detected during the conversion of the tritiated nitro compounds into the corresponding amines by catalytic hydrogenation. Incorporation into the ortho position is very low (4%). During the metabolic activation and binding of the tritiated N-acetyl-2-aminofluorene to rat liver DNA in vivo, no tritium exchange occurred.
Amidofluorene-appended lower rim 1,3-diconjugate of calix[4]arene: Synthesis, characterization and highly selective sensor for Cu2+
Hosseinzadeh, Rahman,Nemati, Mohammad,Zadmard, Reza,Mohadjerani, Maryam
, p. 1749 - 1757 (2016)
Functionalization of calix[4]arene with amidofluorene moieties at the lower rim led to formation of the 1,3-diconjugate of calix[4]arene L as a novel fluorescent chemosensor for Cu2+. The receptor molecule L exhibited a pronounced selectivity towards Cu2+ over other mono and divalent ions. The formation of the complex between L and Cu2+ was evaluated by absorption, fluorescence and 1H NMR spectroscopy. The sensor L showed a remarkable color change from colorless to purple and a fluorescence quenching only upon interaction with Cu2+. The 1:1 stoichiometry of the obtained complex has been determined by Job's plot. The association constant determined by fluorescence titration was found to be 1.8 × 106 M-1. The sensor showed a linear response toward Cu2+ in the concentration range from 1 to 10 μM with a detection limit of 9.6 × 10-8 M.
Half-Sandwich Ruthenium Complexes of Amide-Phosphine Based Ligands: H-Bonding Cavity Assisted Binding and Reduction of Nitro-substrates
Pachisia, Sanya,Kishan, Ram,Yadav, Samanta,Gupta, Rajeev
, p. 2009 - 2022 (2021/02/06)
We present synthesis and characterization of two half-sandwich Ru(II) complexes supported with amide-phosphine based ligands. These complexes presented a pyridine-2,6-dicarboxamide based pincer cavity, decorated with hydrogen bonds, that participated in the binding of nitro-substrates closer to the Ru(II) centers, which is further supported with binding and docking studies. These ruthenium complexes functioned as the noteworthy catalysts for the borohydride mediated reduction of assorted nitro-substrates. Mechanistic studies not only confirmed the intermediacy of [Ru-H] in the reduction but also asserted the involvement of several organic intermediates during the course of the catalysis. A similar Ru(II) complex that lacked pyridine-2,6-dicarboxamide based pincer cavity substantiated its unique role both in the substrate binding and the subsequent catalysis.
Hydrogenation of nitroarenes catalyzed by a dipalladium complex
Hung, Ming-Uei,Yang, Shu-Ting,Ramanathan, Mani,Liu, Shiuh-Tzung
, (2017/09/06)
A dipalladium complex [Pd2(L)Cl2](PF6)2 (2), via the substitution of (PhCN)2PdCl2 with 5-phenyl-2,8-bis(6′-bipyridinyl)-1,9,10-anthyridine (L) followed by the anion exchange, was found to be a good pre-catalyst for the reduction of nitroarenes to yield the corresponding anilines under atmospheric pressure of hydrogen in methanol. This method provides a straightforward access to a diverse array of functionalized anilines, exhibiting a possible application in synthetic chemistry. The catalytic activity of this complex is enhanced by the di-metallic system via the synergistic effect.
