99-65-0

Usage

Uses

1,3-Dinitrobenzene is used in various applications across different industries, including:
Used in Dye and Explosive Manufacturing:
1,3-Dinitrobenzene is used as a chemical intermediate in the production of dyes and explosives due to its reactivity and ability to form various compounds.
Used in Organic Syntheses:
1,3-Dinitrobenzene is used as a reagent or starting material in various organic syntheses, enabling the creation of a wide range of chemical products.
Used in Munitions Plants:
As an impurity in the manufacture of 2,4,6-trinitrotoluene, 1,3-DNB is indirectly involved in the production of munitions, posing potential exposure risks to workers in these plants.

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.

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

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.

InChI:InChI=1/C6H4N2O4/c9-7(10)5-2-1-3-6(4-5)8(11)12/h1-4H

Upstream product

• 37049-86-8 benzenesulfonic acid-[N'-(2,4-dinitro-phenyl)-hydrazide] 
• 606-22-4 2,6-dinitroaniline 
• 1940-55-2 1-iodyl-2,4-dinitro-benzene 
• 603-33-8 triphenylbismuthane 
• 23351-89-5 m-nitrodiphenyliodonium bromide 
• 108-45-2 m-phenylenediamine 
• 98-95-3 nitrobenzene 
• 97-00-7 1-chloro-2,4-dinitro-benzene 
• 99-09-2 3-nitro-aniline 
• 56224-53-4 1,3-dihydrazino-4,6-dinitrobenzene 
• 71-43-2 benzene 
• 97-02-9 2,4-Dinitroanilin 
• 100-42-5 styrene 
• 108030-46-2 (E,E)-1-(N,N-dimethylamino)-4-nitro-1,3-butadiene 

Downstream Products

• 98-01-1 furfural 
• 119-61-9 benzophenone 
• 5392-40-5 (E/Z)-3,7-dimethyl-2,6-octadienal 
• 115-11-7 isobutene 
• 89-98-5 2-chloro-benzaldehyde 
• 552-89-6 2-nitro-benzaldehyde 
• 104-55-2 3-phenyl-propenal 
• 38469-85-1 2-methoxy-6-nitrobenzonitrile 
• 123241-34-9 2-nitro-6-propoxybenzonitrile 
• 4832-38-6 naphthalene; compound with 1,3-dinitro-benzene 
• 91-20-3 naphthalene 
• 123241-32-7 2-ethoxy-6-nitro-benzonitrile 
• 855757-55-0 2-sec-butoxy-6-nitro-benzonitrile 
• 69877-21-0 2-nitro-6-pentyloxy-benzonitrile 

Relevant academic research and scientific papers

Electron transfer within 1,3-dinitrobenzene radical anions: Electron hopping or superexchange?

The intramolecular electron transfer on several 1,3-dinitrobenzene radical anions with different substituents on position 5 was studied by electron paramagnetic resonance and optical spectroscopies in MeCN. The radical anions are all charge-localized mixed valence species, as is common for meta-substituted dinitrobenzenes. Rate constants for the electron transfer reaction were obtained by the Marcus-Hush analysis of the intervalence optical bands assuming quartic-augmented energy surfaces and solvent-controlled dynamics. These calculated rate constants match quite well the experimental ones obtained by simulation of the electron paramagnetic resonance spectra, which rules out bridge-reduced states as intermediates in the reaction path and confirms the superexchange mechanism. Copyright

Exploiting a silver-bismuth hybrid material as heterogeneous noble metal catalyst for decarboxylations and decarboxylative deuterations of carboxylic acids under batch and continuous flow conditions

Herein, we report novel catalytic methodologies for protodecarboxylations and decarboxylative deuterations of carboxylic acids utilizing a silver-containing hybrid material as a heterogeneous noble metal catalyst. After an initial batch method development, a chemically intensified continuous flow process was established in a simple packed-bed system which enabled gram-scale protodecarboxlyations without detectable structural degradation of the catalyst. The scope and applicability of the batch and flow processes were demonstrated through decarboxylations of a diverse set of aromatic carboxylic acids. Catalytic decarboxylative deuterations were achieved on the basis of the reaction conditions developed for the protodecarboxylations using D2O as a readily available deuterium source.

Photoinduced Iron-Catalyzed ipso-Nitration of Aryl Halides via Single-Electron Transfer

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.

Nitration of deactivated aromatic compounds via mechanochemical reaction

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.

Nitration of aromatics with dinitrogen pentoxide in a liquefied 1,1,1,2-tetrafluoroethane medium

Regardless of the sustainable development path, today, there are highly demanded chemical productions still operating that bear environmental and technological risks inherited from the previous century. The fabrication of nitro compounds, and nitroarenes in particular, is traditionally associated with acidic wastes formed in nitration reactions exploiting mixed acids. However, nitroarenes are indispensable for industrial and military applications. We faced the challenge and developed a greener, safer, and yet effective method for the production of nitroaromatics. The proposed approach comprises the application of an eco-friendly nitrating agent, namely dinitrogen pentoxide (DNP), in the medium of liquefied 1,1,1,2-tetrafluoroethane (TFE) - one of the most non-hazardous Freons. Importantly, the used TFE is not emitted into the atmosphere but is effortlessly recondensed and returned into the process. DNP is obtainedviathe oxidation of dinitrogen tetroxide with ozone. The elaborated method is characterized by high yields of the targeted nitro arenes, mild reaction conditions, and minimal amount of easy-to-utilize wastes.

Synthesis, Biological Evaluation, and Computational Analysis of Biaryl Side-Chain Analogs of Solithromycin

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.

N-Nitroheterocycles: Bench-Stable Organic Reagents for Catalytic Ipso-Nitration of Aryl- And Heteroarylboronic Acids

Photocatalytic and metal-free protocols to access various aromatic and heteroaromatic nitro compounds through ipso-nitration of readily available boronic acid derivatives were developed using non-metal-based, bench-stable, and recyclable nitrating reagents. These methods are operationally simple, mild, regioselective, and possess excellent functional group compatibility, delivering desired products in up to 99% yield.

Direct Stereoselective β-Arylation of Enol Ethers by a Decarboxylative Heck-Type Reaction

Despite remarkable advances to promote regio- and stereoselective decarboxylative arylation of inactivated olefins with benzoic acid derivatives, methodologies involving hetero-substituted alkenes are still lacking. Herein, PdII-catalyzed decarboxylative Heck coupling of α-alkoxyacrylates with (hetero)aryl carboxylic acids for the stereocontrolled production of (Z)-β-heteroarylated vinyl ethers is reported. This methodology offers a rational and step-economical route to the synthesis of attractive β-arylated α-alkoxy α,β-unsaturated carboxylates family which emerged as a relevant class of building blocks with different applications. Mechanistically, whereas electron rich benzoic acids undergo a PdII-catalyzed decarboxylation, electron-deficient substrates proceed through silver(I)-mediated decarboxylation, explaining thus the formation of stereoisomers (E) and (Z) of β-arylated vinyl ethers in presence of these latter.

Mass production method of phenylenediamine from high purity dinitrobenzene

The present invention relates to a method for producing phenylenediamine using the high purity of dinitrobenzene, which may manufacture meta-phenylenediamine having a high yield since dinitrobenzene can be produced without aniline as a byproduct. Meta-phenylenediamine is manufactured based on a cost effective raw material by using a process as above without a separate purification process, thereby drastically reducing a manufacturing cost compared to an existing process. Therefore, stable reaction can be induced in a synthetic process, thereby easily and safely manufacturing meta-phenylenediamine.COPYRIGHT KIPO 2020

Electrochemical dehydrogenation of hydrazines to azo compounds

A strategy for the electrochemical dehydrogenation of hydrazine compounds is disclosed under ambient conditions. This protocol proceeded smoothly in ethanol by employing electrons as clean oxidants. Its synthetic value is well demonstrated by the highly efficient synthesis of symmetric and unsymmetric azo compounds. It is an environmentally friendly transformation and the present protocol was effective on a large scale.