581-89-5

Usage

Uses

Naphthalene, 2-nitrois used as a chemical intermediate in the synthesis of various organic compounds and pharmaceuticals. Its specific applications may vary depending on the industry and the desired end product.

Synthesis Reference(s)

Journal of the American Chemical Society, 76, p. 6144, 1954 DOI: 10.1021/ja01652a083

Reactivity Profile

2-NITRONAPHTHALENE is non-flammable but combustible (flash point 160°C). Dust forms explosive mixtures with air. Heating or burning releases toxic and corrosive gases. Incompatible with strong oxidizing agents. Can serve as an oxidizing agent and so react with reducing agents such as hydrides, sulfides and nitrides. Such reactions may be vigorous and may culminate in a detonation. May explode in the presence of strong bases such as sodium or potassium hydroxide even in the presence of water or organic solvents.

Safety Profile

Confirmed carcinogen with experimental tumorigenic data. Moderately toxic by ingestion and intraperitoneal routes. Mutation data reported. A sktn and lung irritant. For explosion and disaster hazards, see NITRATES. Combustible when exposed to heat or flame. When heated to decomposition it emits toxic fumes of NOx. See also 1-NITRONAPHTHALENE.

Purification Methods

Distil it in a vacuum and/or crystallise it from aqueous EtOH and sublime in a vacuum. The 1:1 1,3,5-trinitrobenzene complex has m 75.5o (from EtOH). [Beilstein 5 H 555, 5 III 1596, 5 IV 1675.]

InChI:InChI=1/C10H7NO2/c12-11(13)10-6-5-8-3-1-2-4-9(8)7-10/h1-7H

Upstream product

• 75-52-5 nitromethane 
• 3947-77-1 2-methylisoquinolinium iodide 
• 19353-86-7 6-nitrotetralin 
• 607-23-8 2-nitro-1-naphthylamine 
• 3229-86-5 3-nitro-1-naphthalenamine 
• 91-59-8 naphthalen-2-ylamine 
• 67-56-1 methanol 
• 20937-86-4 2-azidonaphthalene 
• 91-20-3 naphthalene 
• 509-14-8 tetranitromethane 
• 151-50-8 potassium cyanide 
• 98-95-3 nitrobenzene 
• 141738-87-6 cis-1,4-dihydro-1-nitro-4-trinitromethylnaphthalene 
• 122520-10-9 7-nitro-3,4-dihydronaphthalene 

Downstream Products

• 132-53-6 2-Nitroso-1-naphthol 
• 67878-75-5 1-bromo-6-nitro-naphthalene 
• 4488-22-6 1,1'-binaphthalene-2,2'-diamine 
• 613-47-8 β-naphthylhydroxylamine 
• 7263-39-0 7,8-diaza[5]helicene N-oxide 
• 582-02-5 1,2-di(naphthalen-2-yl)diazene oxide 
• 91-59-8 naphthalen-2-ylamine 
• 10345-06-9 2-Naphthylamine-1-sulphonic acid 
• 85-02-9 benzo[f]quinoline 
• 163519-61-7 2-Amino-1-ethoxynaphthalin 
• 582-02-5 β,β'-Azoxynaphthalin 
• 606-41-7 2-amino-1-naphthol 
• 582-02-5 2,2'-Azoxynaphthalin 
• 98-95-3 nitrobenzene 

Relevant academic research and scientific papers

Lanthanide(III) nitrobenzenesulfonates as new nitration catalysts: The role of the metal and of the counterion in the catalytic efficiency

Lanthanide(III) complexes of p-nitrobenzenesulfonic acid, Ln(p-NBSA) 3, m-nitrobenzenesulfonic acid, Ln(m-NBSA)3, and 2,4-nitrobenzenesulfonic acid, Ln(2,4-NBSA)3, were prepared, characterized and examined as catalyst for the nitration of benzene, toluene, xylenes, naphthalene, bromobenzene and chlorobenzene. The initial screening of the catalysts showed that lanthanum(III) complexes were more effective than the corresponding ytterbium(III) complexes, and that catalysts containing the bulky 2,4-NBSA ligand were less effective than the catalyst containing p-NBSA (nosylate) or m-NBSA ligands. Examination of a series of Ln(p-NBSA)3 and Ln(m-NBSA)3 catalysts revealed that there is a clear correlation between the ionic radii of the lanthanide(III) ions and the yields of nitration, with the lighter lanthanides being more effective. The X-ray single crystal structure of Yb(m-NBSA)3·6H2O shows that two m-NBSA ligands are directly bound to the metal centre while the third ligand is not located in the first coordination sphere, but it is hydrogen bonded to one of the water molecules which is coordinated to ytterbium(III). NMR studies suggest that this structure is preserved under the conditions used in the nitration reaction. The structure of Yb(m-NBSA)3 is markedly different from the structure of the well-known ytterbium(III) triflate catalyst. The coordination of the nitrobenzenesulfonate counterion to the lanthanide(III) ion suggests that steric effects might play an important role in determining the efficiency of these novel nitration catalysts. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Catalysis of Nitration of Naphthalene by Lower Oxides of Nitrogen

Nitrous acid catalyzed nitration of naphthalene does not proceed through nitrosation, and the mechanism is best understood in terms of a chain reaction involving naphthalene radical cation.

Competitive Reactions of Trinitromethanide Ion and Nitrogen Dioxide with Radical Cations

From the species generated by photoexcitation of ArH-tetranitromethane charge transfer complexes, ArH radical cation, trinitromethanide ion and nitrogen dioxide, the reaction between ArH radical cation and trinitromethanide has been shown to be significantly faster than that between ArH radical cation and nitrogen dioxide.

Zeolite-assisted regioselective mononitration of naphthalene with nitrogen dioxide/molecular oxygen

The nitration process using nitrogen dioxide and oxygen instead of the classical nitric acid-sulfuric acid system appears to be attractive and promising in the selective preparation of nitro compounds. The ratio of 1-nitronaphthalene isomer to 2-nitronaphthalene can reach 11 in a moderate yield of 60 % when the reaction is carried out in acetonitrile with 5.0 mmol naphthalene, 10 mmol nitrogen dioxide, and 0.13 g HZSM-5 under molecular oxygen atmosphere at -15 C. The isomeric distribution of the product nitro-naphthalene was found to be superior to traditional methods. The zeolite could be easily regenerated and recycled and reused by simple work-up to give results similar to those obtained with the fresh catalyst.

Zeolite-assisted regioselective synthesis of dinitronaphthalene

The nitration selectivity of naphthalene was studied in different organic solvents with 95 % fuming nitric acid as nitration reagent. The yield of dinitronaphthalene can achieve 78 % in hexane. With nitrogen dioxide as nitration reagent in oxygen, the selectivity of dinitronaphthalene in different types of molecular sieve catalyst was studied. When HBEA zeolite catalyst was used, the yield of dinitronaphthalene was up to 61 %. This method is easy to carry out, environmentally benign, and economical.

NO2+ nitration mechanism of aromatic compounds: Electrophilic vs charge-transfer process

The nitration of methylnaphthalenes with NO2BF4 and NOBF4 was examined in order to shed light on the controversial aromatic nitration mechanism, electrophilic vs charge-transfer process. The NO2+ nitration of 1,8-dimethylnaphthalene showed a drastic regioselectivity change depending on the reaction temperature, where ortho-regioselectivity at -78 °C and para- regioselectivity at 0 °C were considered to reflect the electrophilic and the direct or alternative charge-transfer process, respectively, because the NO+ nitration through the same reaction intermediates as in the NO2+ nitration via a charge-transfer process resulted in para-regioselectivity regardless of the reaction temperature. The NO2+ nitration of redox potential methylnaphthalenes higher than 1,8-dimethylnaphthalene gave a similar ortho-regioselectivity enhancement to 1,8-dimethylnaphthalene at lower temperature, thus reflecting the electrophilic process. On the other hand, the NO2+ nitration of redox potential methylnaphthalenes lower than 1,8-dimethylnaphthalene showed para-regioselectivity similar to the NO+ nitration, indicating the direct or alternative charge-transfer process. In the presence of strong acids where the direct charge-transfer process will be suppressed by protonation, the ortho-regioselectivity enhancement was observed in the NO2+ nitration of 1,8-dimethylnaphthalene, suggesting that the direct charge-transfer process could be the main process to show para- regioselectivity. These experimental results imply that the NO2+ nitration proceeds via not only electrophilic but also direct charge-transfer processes, which has been considered to be unlikely because of the high energy demanding process of a bond coordination change between NO2+ and NO2. Theoretical studies at the MP2/6-31G(d) level predicted ortho- and para-regioselectivity for the NO2+ nitration via electrophilic and charge- transfer processes, respectively, and the preference of the direct charge- transfer process over the alternative one, which support the experimental conclusion.

Photochemical Nitration by Tetranitromethane. Part XIX. The Competitive Reactions of Trinitromethanide and Nitrogen Dioxide with Radical Cations and their Use for Selective Nitrations

The photolysis of the charge-transfer complex between an aromatic compound (ArH) and tetranitromethane is known to form initially a triad of the aromatic radical cation, trinitromethanide ion and NO2 .For reactive and moderately reactive radical cations, the chemical follow-up ion and (i) reactions from the species of the triad are fast at -60 deg C, as shown by the fact that the solutions are EPR-silent during photolysis.However, by conducting the photolysis in the presence of a protic acid, the trinitromethanide ion is rendered unreactive by protonation, resulting in the build-up of a detectable (EPR) concentration of ArH-radical cation or (ArH)2-radical cation.This shows that the initial chemical step from the triad is the nucleophilic attack of trinitromethanide ion upon ArH-radical cation, and that the rate of the reaction between the latter and NO2 must be significantly lower.Preparative experiments support this conclusion, in that the predominant adduct formation from ArH-tetranitromethane photolysis is diverted into nitro substitution in the presence of a protic acid, the latter reaction occurring via ArH-radical cation-NO2 coupling.These findings also establish that results obtained from the photonitration of aromatics by tetranitromethane are not relevant for judging the possible electron transfer nature of electrophilic aromatic nitration by nitronium ion.

The polyhedral nature of selenium-catalysed reactions: Se(iv) species instead of Se(vi) species make the difference in the on water selenium-mediated oxidation of arylamines

Selenium-catalysed oxidations are highly sought after in organic synthesis and biology. Herein, we report our studies on the on water selenium mediated oxidation of anilines. In the presence of diphenyl diselenide or benzeneseleninic acid, anilines react with hydrogen peroxide, providing direct and selective access to nitroarenes. On the other hand, the use of selenium dioxide or sodium selenite leads to azoxyarenes. Careful mechanistic analysis and 77Se NMR studies revealed that only Se(iv) species, such as benzeneperoxyseleninic acid, are the active oxidants involved in the catalytic cycle operating in water and leading to nitroarenes. While other selenium-catalysed oxidations occurring in organic solvents have been recently demonstrated to proceed through Se(vi) key intermediates, the on water oxidation of anilines to nitroarenes does not. These findings shed new light on the multifaceted nature of organoselenium-catalysed transformations and open new directions to exploit selenium-based catalysis.

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.

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.