99-65-0 Usage
Description
1,3-Dinitrobenzene (1,3-DNB) is an impurity present in the
manufacture of 2,4,6-trinitrotoluene. Workers in munitions
plants are at risk of exposure. While it does not bioaccumulate, it
persists in the environments (air, water, and soil) with slow rates
of degradation. Metabolism in animals (rabbits) results in
reduction of the nitro functionalities to amine functionalities to
produce 2,4-diaminophenol, m-nitroaniline, m-phenylenediamine,
and 2-amino-4-nitrophenol. Human exposure is generally
dermal contact or inhalation of vapor.
Chemical Properties
orange to yellow crystalline powder. Freely soluble in benzene, chloroform, ethyl acetate, soluble in alcohol, slightly soluble in water. Can evaporate with water vapour.
Uses
1,3-Dinitrobenzene (1,3-DNB) is an impurity present in the manufacture of 2,4,6-trinitrotoluene. Dinitrobenzene (as a mixture of 1,2-dinitro- 1,3-dinitro- and 1,4-dinitro-isomers) is used in the manufacture of dyes and explosives, and in organic syntheses.
Preparation
1,3-Dinitrobenzene is accessible by nitration of nitrobenzene. The reaction proceeds under acid catalysis using sulfuric acid. The directing effect of the nitro group of nitrobenzene leads to 93% of the product resulting from nitration at the meta-position. The ortho- and para-products occur in only 6% and 1%, respectively.
Definition
ChEBI: 1,3-dinitrobenzene is a dinitrobenzene that is benzene disubstituted at positions 1 and 3 with nitro groups. It has a role as a neurotoxin.
Synthesis Reference(s)
The Journal of Organic Chemistry, 38, p. 4243, 1973 DOI: 10.1021/jo00964a007Synthesis, p. 1085, 1992 DOI: 10.1055/s-1992-26309
General Description
1,3-Dinitrobenzene is a yellow solid with a slight odor. Sinks in water. (USCG, 1999)
Health Hazard
Inhalation or ingestion causes loss of color, nausea, headache, dizziness, drowsiness, and collapse. Eyes are irritated by liquid. Stains skin yellow; if contact is prolonged, can be absorbed into blood and cause same symptoms as for inhalation.
Safety Profile
Suspected carcinogen.
Human poison by ingestion. Experimental
poison by ingestion, intraperitoneal, and
intravenous routes. Human systemic effects
by skin contact: cyanosis and motor activity
changes. Experimental reproductive effects.
An eye irritant. Mutation data reported.
Mixture with nitric acid is a high explosive.
Mixture with tetranitromethane is a hgh
explosive very sensitive to sparks. When
heated to decomposition it emits toxic
fumes of NOx. See also 0and pDINITROBENZENE.
Environmental fate
Biological. Under anaerobic and aerobic conditions using a sewage inoculum, 1,3-
dinitrobenzene degraded to nitroaniline (Hallas and Alexander, 1983). In activated sludge
inoculum, following a 20-d adaptation period, no degradation was observed (Pitter, 1976).
Photolytic. Low et al. (1991) reported that the nitro-containing compounds (e.g., 2,4-
dinitrophenol) undergo degradation by UV light in the presence of titanium dioxide yielding
ammonium, carbonate, and nitrate ions. By analogy, 1,3-dinitrobenzene should degrade forming
identical ions.
Chemical/Physical. Releases toxic nitrogen oxides when heated to decomposition (Sax and
Lewis, 1987). 1,3-Dinitrobenzene will not hydrolyze in water (Kollig, 1993).
Solubility in organics
Soluble in acetone, ether, pyrimidine (Weast, 1986), alcohol (27 g/L), pyridine (3,940 g/kg at 20–25 °C) (Dehn, 1917); freely soluble in benzene, chloroform, ethyl acetate (Windholz et al., 1983),
and toluene.
Purification Methods
Crystallise 1,3-dinitrobenzene from alkaline EtOH solution (20g in 750mL 95% EtOH at 40o, plus 100mL of 2M NaOH) by cooling and adding 2.5L of H2O. The precipitate, after filtering off, is washed with H2O, sucked dry, and crystallised from 120mL, then 80mL of absolute EtOH [Callow et al. Biochem J 32 1312 1938]. Alternatively crystallise it from MeOH, CCl4 or EtOAc. It can be sublimed in a vacuum. [Tanner J Org Chem 52 2142 1987, Beilstein 5 IV 739.]
Toxicity evaluation
Cultured astrocytes and brain capillary endothelial cells were
exposed to 1 mM concentrations for 1 day in an in vitro
blood–brain barrier (BBB) model, resulting in cell death.
Check Digit Verification of cas no
The CAS Registry Mumber 99-65-0 includes 5 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 2 digits, 9 and 9 respectively; the second part has 2 digits, 6 and 5 respectively.
Calculate Digit Verification of CAS Registry Number 99-65:
(4*9)+(3*9)+(2*6)+(1*5)=80
80 % 10 = 0
So 99-65-0 is a valid CAS Registry Number.
InChI:InChI=1/C6H4N2O4/c9-7(10)5-2-1-3-6(4-5)8(11)12/h1-4H
99-65-0Relevant articles and documents
Ciaccio,Marcus
, p. 1838 (1962)
Nitration of deactivated aromatic compounds via mechanochemical reaction
Wu, Jian-Wei,Zhang, Pu,Guo, Zhi-Xin
supporting information, (2021/05/05)
A variety of deactivated arenes were nitrated to their corresponding nitro derivatives in excellent yields under high-speed ball milling condition using Fe(NO3)3·9H2O/P2O5 as nitrating reagent. A radical involved mechanism was proposed for this facial, eco-friendly, safe, and effective nitration reaction.
Synthesis, Biological Evaluation, and Computational Analysis of Biaryl Side-Chain Analogs of Solithromycin
Daher, Samer S.,Lee, Miseon,Jin, Xiao,Teijaro, Christiana N.,Wheeler, Steven E.,Jacobson, Marlene A.,Buttaro, Bettina,Andrade, Rodrigo B.
supporting information, p. 3368 - 3373 (2021/09/06)
There is an urgent need for new antibiotics to mitigate the existential threat posed by antibiotic resistance. Within the ketolide class, solithromycin has emerged as one of the most promising candidates for further development. Crystallographic studies of bacterial ribosomes and ribosomal subunits complexed with solithromycin have shed light on the nature of molecular interactions (π-stacking and H-bonding) between from the biaryl side-chain of the drug and key residues in the 50S ribosomal subunit. We have designed and synthesized a library of solithromycin analogs to study their structure-activity relationships (SAR) in tandem with new computational studies. The biological activity of each analog was evaluated in terms of ribosomal affinity (Kd determined by fluorescence polarization), as well as minimum inhibitory concentration assays (MICs). Density functional theory (DFT) studies of a simple binding site model identify key H-bonding interactions that modulate the potency of solithromycin analogs.
Photoinduced Iron-Catalyzed ipso-Nitration of Aryl Halides via Single-Electron Transfer
Wu, Cunluo,Bian, Qilong,Ding, Tao,Tang, Mingming,Zhang, Wenkai,Xu, Yuanqing,Liu, Baoying,Xu, Hao,Li, Hai-Bei,Fu, Hua
, p. 9561 - 9568 (2021/08/06)
A photoinduced iron-catalyzed ipso-nitration of aryl halides with KNO2 has been developed, in which aryl iodides, bromides, and some of aryl chlorides are feasible. The mechanism investigations show that the in situ formed iron complex by FeSO4, KNO2, and 1,10-phenanthroline acts as the light-harvesting photocatalyst with a longer lifetime of the excited state, and the reaction undergoes a photoinduced single-electron transfer (SET) process. This work represents an example for the photoinduced iron-catalyzed Ullmann-type couplings.