4110-35-4

Basic information

• Product Name: 3,5-Dinitrobenzonitrile
• Synonyms: 3,5-Dinitrobenzonitrile 98+%;3,5-dinitro-benzonitril;3,5-DINITROBENZONITRILE;3,5-BISNITROBENZONITRILE;5-CYANO-1,3-DINITROBENZENE;3,5-DINITROBENZONITIRLE;3,5-Dinitrobenzonitrile,97%
• CAS NO: 4110-35-4
• Molecular Formula: C₇H₃N₃O₄
• Molecular Weight: 193.12
• EINECS: 223-889-9
• Product Categories: Nitrogen Compounds;Organic Building Blocks;Aromatic Nitriles;C6 to C7;Cyanides/Nitriles;Nitrogen Compounds;Building Blocks;C6 to C7;Chemical Synthesis
• Mol File: 4110-35-4.mol

Chemical Properties

• Melting Point: 126-130 °C(lit.)
• Boiling Point: 329.31°C (rough estimate)
• Flash Point: 136.855 °C
• Appearance: yellow crystals or crystalline powder
• Density: 1.6504 (rough estimate)
• Vapor Pressure: 0.000976mmHg at 25°C
• Refractive Index: 1.5500 (estimate)
• Storage Temp.: Sealed in dry,Room Temperature
• Water Solubility: Insoluble in water
• CAS DataBase Reference: 3,5-Dinitrobenzonitrile(CAS DataBase Reference)
• NIST Chemistry Reference: 3,5-Dinitrobenzonitrile(4110-35-4)
• EPA Substance Registry System: 3,5-Dinitrobenzonitrile(4110-35-4)

Safety Data

• Hazard Codes: Xn
• Statements: 20/21/22-36/37/38-36/38
• Safety Statements: 26-36
• RIDADR: 3276
• WGK Germany: 3
• RTECS: DI4365000
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 4110-35-4(Hazardous Substances Data)

Usage

Chemical Properties

yellow crystals or crystalline powder

Preparation

In a well-ventilated hood, diphosgene (2 mL) was added dropwise to a cold (0–5 C°), stirred solution of 3,5-dinitrobenzamide (2.1 g, 10 mmol) in trimethyl phosphate (6.3 mL). The reaction mixture was then slowly heated to 60 C° for 5 min to ensure completion of the reaction and also to distil off any generated phosgene. After cooling in an ice/water bath, the reaction mixture was vigorously stirred and iced water (10 mL) was added to destroy any traces of phosgene or chloroformate. The precipitated solid product was collected by filtration, washed with water to eliminate traces of HCl and trimethyl phosphate, and air-dried; yield: 1.88 g (96%), mp 127–129 C°. Recrystallization from diisopropyl ether gave an analytically pure product, mp 130–131 C°. The same authors also reported that alkyl, benzylic, aryl, and heteroaryl aldoximes bearing various functionalities could be readily converted to the corresponding nitriles using diphosgene in good yields of 82–96%.

Synthesis Reference(s)

Tetrahedron Letters, 27, p. 2203, 1986 DOI: 10.1016/S0040-4039(00)84487-1

InChI:InChI=1/C7H3N3O4/c8-4-5-1-6(9(11)12)3-7(2-5)10(13)14/h1-3H

Upstream product

• 98-10-2 benzenesulfonamide 
• 99-34-3 3,5-dinitrobenzoic acid 
• 121-81-3 3,5-dinitrobenzamide 
• 117-80-6 2,3-Dichloro-1,4-naphthoquinone 
• 153621-95-5 (3,5-dinitrophenyl)chlorodiazirine 
• 153621-98-8 3-Azido-3-(3,5-dinitro-phenyl)-3H-diazirine 
• 86475-51-6 methoxy(3,5-dinitrophenyl)methanimine 
• 14193-18-1 3,5-dinitrobenzaldehyde 
• 771579-30-7 3,5-dinitrobenzylamine 

Downstream Products

• 58010-15-4 6-(3,5-dinitro-phenyl)-[1,3,2,4,5]dioxadithiazine 2,2,4,4-tetraoxide 
• 86475-51-6 methoxy(3,5-dinitrophenyl)methanimine 
• 2702-58-1 methyl 3,5-dinitrobenzoate 
• 100-25-4 para-dinitrobenzene 
• 121-81-3 3,5-dinitrobenzamide 
• 146367-22-8 C₇H₃N₄O₄S₂⁽¹⁺⁾*AsF₆^(1-) 
• 71466-54-1 1-(1-Adamantyl)-3-cyano-5-nitrobenzol 
• 33786-93-5 3,5-diaminobenzonitrile 
• 64248-63-1 3,5-difluorobenzonitrile 
• 110882-60-5 3-fluoro-5-nitrobenzonitrile 

Relevant articles and documents

Anomalous Equilibrium and Kinetic α-Deuterium Secondary Isotope Effects Accompanying Hydride Transfer from Reduced Nicotinamide Adenine Dinucleotide

The kinetic α-deuterium secondary isotope effect on the second-order rate constant has been measured for the nonenzymatic direct hydride transfer reduction of 4-cyano-2,6-dinitrobenzenesulfonate by NADH (deuterium substitution of the hydrogen bonded to the 4 carbon of NADH which is not transferred to the acceptor).Values of 1.156 +/- 0.018 and 1.1454 +/- 0.0093 were obtained using direct and intramolecular competition methods, respectively.The corresponding (enzyme catalyzed) equilibrium isotope effects were found to be 1.013 +/- 0.020 and 1.0347 +/- 0.0087 as determined by direct and intermolecular competition methods, respectively.Thus, the value of the kinetic effect is significantly greater than that on the equilibrium.It is suggested that this may arise either from participation of the α hydrogen in a hyperconjugative stabilization of an early transition state or from its participation in the reaction coordinate motion of a nonlinear activated complex.The values of the equilibrium effect allow calculation of a fractional factor (relative to acetylene) for hydrogen bonded to the 4 carbon of NAD+ of 1.448 +/- 0.028 or 1.418 +/- 0.020.This is larger than expected based on comparison with hydrogen bound of sp2 carbon in propene (1.136) or benzene (1.368) but is consistent with the decreased aromatic character of pyridinium vibrational spectra.The lack of a significant inverse value for the equilibrium α-deuterium effect suggests complications in the interpretation of reported kinetic secondary effects of 0.85 and 1.2 for the forward (sp3 -> sp%&2) and reverse (sp2 -> sp3) rate constants for the nonenzymatic transhydrogenation of N-benzyl-1,4-dihydronicotinamide and its nicotinamide salt.

Synthesis of Nitriles from Primary Amides or Aldoximes under Conditions of a Catalytic Swern Oxidation

The preparation of nitriles from primary amides or aldoximes was achieved by using oxalyl chloride with a catalytic amount of dimethyl sulfoxide in the presence of Et3N. The reactions were complete within 1 h after addition at room temperature. A diverse range of cyano compounds were obtained in good to excellent yields, including aromatic, heteroaromatic, cyclic, and acyclic aliphatic species.

Double Dehydrogenation of Primary Amines to Nitriles by a Ruthenium Complex Featuring Pyrazole Functionality

A ruthenium(II) complex bearing a naphthyridine-functionalized pyrazole ligand catalyzes oxidant-free and acceptorless selective double dehydrogenation of primary amines to nitriles at moderate temperature. The role of the proton-responsive entity on the ligand scaffold is demonstrated by control experiments, including the use of a N-methylated pyrazole analogue. DFT calculations reveal intricate hydride and proton transfers to achieve the overall elimination of 2 equiv of H2.

Iodine-catalyzed, efficient, one-pot protocol for the conversion of araldehydes into 5-aryl-1H-tetrazoles

An easy access to various 5-aryl-1H-tetrazoles by a one-pot direct conversion of aldehydes to tetrazoles without the isolation of the intermediate nitriles using commercially available iodine as a catalyst is described. The protocol offers advantages in terms of good yields, mild reaction conditions, short reaction times, and use of readily available environmentally compatible catalyst. Copyright

Activated dimethyl sulfoxide dehydration of amide and its application to one-pot preparation of benzyl-type perfluoroimidates

Various types of primary amides were treated under an activated dimethyl sulfoxide (DMSO) species, (COCl)2-DMSO and Et3N, as a dehydrating agent to obtain nitriles in excellent yield. This dehydration system was extended to a one-pot preparation of perfluoroimidates via volatile perfluoronitriles from perfluoroamides. Fifteen benzyl-type perfluoroimidates can be prepared in 70-90% yield as more stable imidates than the trichloro analogue. MPM- and DMPM-perfluoroimidates can be used to protect alcohols in place of the trichloroacetimidate with excellent chemical properties and in comparable yields.

Preparation of nitriles from primary amides under Swern oxidation conditions

In order to establish a mild conversion method of primary amides to nitriles, various types of carboxamides were heated under Swern oxidation conditions, (COCl)2-DMSO and Et3N, as a dehydrating agent to obtain desired nitriles in 75-96% yields.

C-Azidodiazirines in the SRN1 Reaction of Azide Ion with Arylchlorodiazirines. Further Insights into Reaction Mechanism

Mixtures of arylchlorodiazirines and sodium azide in DMSO form visible charge transfer complexes.Irradiation of these solutions with fluorescent room light leads to SRN1 displacement of chloride and the transient formation of C-azidodiazirines.Relative reactivity studies (using competition experiments) show that nitro-substituted arylchlorodiazirines are substantially more reactive than other arylchlorodiazirines.This is attributed to facile electron transfer in the propagation cycle, involving the nitro-substituted aromatic ring.C-Azidodiazirines can be isolatedin solution and spectroscopically characterized when the SRN1 reaction is initiated by addition of catalytic amounts of the sodium salt of 2-nitropropane.These azidodiazirines readily decompose at room temperature by first order processes to give molecular nitrogen and benzonitriles.Solvent and substituent effects on decomposition rates are minimal.Computational studies on potential intermediate carbenes in the decomposition of azidodiazirines have been carried out at the HF/6-31-G* level.Singlet α-azidocarbenes RCN3, where R = NH2, OH, F, vinyl, phenyl, and CH3, are energy minima at this computational level.Isodesmic calculations show that the azido group is comparable to OH in its carbene stabilizing ability.Subsequent loss of N2 from α-azidocarbenes, leading to nitriles, is a highly exothermic process (126 kcal when R = vinyl and 128 kcal when R = phenyl).

Single-electron transfer in aromatic nucleophilic substitution on dinitrobenzonitriles

Reaction of OH- with 3,5-dinitrobenzonitrile in water or water-DMSO gives a mixture of unproductive 2- and 4-Meisenheimer complexes that equilibriate and eventually form 3,5-dinitrobenzamide and finally the benzoate ion. The corresponding reaction of 2,4-dinitrobenzonitrile gives the 5-Meisenheimer complex and then a mixture of 2,4-dinitrobenzamide and 2,4-dinitrophenoxide ion. The ratio amide:phenoxide ion increases with increasing [OH-]. These reactions appear to involve formation of charge-transfer complexes of the radical anion of the substrate and ?OH which collapse to give Meisenheimer complexes and final products. The rate constants of the various reaction steps can be estimated by simulation based on relaxation theory, which also fits the product mixture from 2,4-dinitrobenzonitrile. This reaction scheme is consistent with observations of exchange of arene hydrogen and of extensive broadening of 1H NMR signals of the substrates during reaction.

Entropy Changes and Electron Affinities from Gas-Phase Electron-Transfer Equilibria: A(-) + B = A + B(-)

By measuring the electron-transfer equilibria 1, A(-) + B = A + B(-), at 150 deg C with a pulsed electron high-pressure mass spectrometer we determined the ΔGo1 values involving 12 new compounds.Measurements of the temperature dependence of K1 for 21 reactions involving some of the new compounds and many compounds whose ΔGo1 had been determined previously led, via van't Hoff plots, to ΔHo1 and ΔSo1 values.These were interconnecting such that ΔHo and ΔSo continuous scales (ladders) were obtained.These were anchored to SO2 whose electron affinity is accurately known.Available geometries and vibrational frequencies for SO2 and SO2(-) permit the evaluation of So(SO2(-)) - So(SO2).Through the ΔSo scale the So(B(-)) - So(B) for the other compounds B could be obtained also.Certain regularities in the So(B(-)) - So(B) data permitted entropy estimates to be made also for compounds for which no van't Hoff plots were made.In this manner a table of ΔHo, ΔSo, and ΔGo data for the electron capture e + B = B(-) was obtained, which contains some 50 compounds B.Most of the compounds are substituted benzenes, quinones, conjugated acid anhydrides, and perfluorinated organics.

FACILE CONVERSION OF CARBOXAMIDES TO NITRILES

Alkyl, aralkyl, aryl, heteroaryl carboxamides bearing various functionalities are readily converted to the corresponding nitriles in good yields using the liquid "diphosgene", trichloromethyl chloroformate, as dehydrating agent.In many cases, the procedure does not require extraction, and hence offers a very simple work-up.