86-57-7 1-Nitronaphthalene

Prepare a mixture of 40 ml. of concentrated nitric acid and 40 ml. of concentrated sulphuric acid as detailed in the previous Section. Introduce 50 g. of findy-powdered naphthalene in small quantities at a time and with vigorous shaking maintain the temperature at 45-50° and cool in ice water if necessary. When all the naphthalene has been added, warm the mixture on a water bath at 55-60° for 30-40 minutes or until the smell of naphthalene has disappeared. Pom the mixture into 500 ml. of cold water the nitronaphtlialene will sink to the bottom. Decant the liquid. Boil the solid cake with 200 ml. of water for 20 minutes and pour the water away. Transfer the oil to a large flask and subject it to steam distillation (Fig. II, 40, 1) any unattacked naphthalene will thus be removed. Pour the warm contents of the flask into a beaker containing a large volume of water which is vigorously stirred. Filter off the granulated a-nitro-naphthalene at the pump, press it well, and recrystallise it from dilute alcohol. The yield of a-nitronaphthalene, m.p. 61°, is 60 g. 

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Colourless crystals m.p. 50 C, b.p. 301 C. Basic and forms sparingly soluble salts with mineral acids. Prepared by the reduction of 1-nitronaphthalene with iron and a trace of hydrochloric acid or by the action of ammonia upon l-naphlhol at a high temperature and pressure. 

In the nitration of benzene, wj-dinilro- and sym-trinitrobenzenes are obtained under more vigorous conditions. With naphthalene, 1-nitronaphthalene is the first product and further nitration gives a mixture of 1,5- and 1,8-dinitronaphthalenes 2-nitronaphthalene is never obtained. 

Nitration. Naphthalene is easily nitrated with mixed acids, eg, nitric and sulfuric, at moderate temperatures to give mostly 1-nitronaphthalene and small quantities, 3—5%, of 2-nitronaphthalene. 2-Nitronaphthalene [581-89-5] is not made in substantial amounts by direct nitration and must be produced by indirect methods, eg, the Bucherer reaction starting with 2-naphthalenol (2-naphthol [135-19-3]). However, the 2-naphthylamine [91-59-8] made using this route is a carcinogen thus the Bucherer method is seldom used in the United States. 

Nitronaphthalene. 1-Nitronaphthalene is manufactured by nitrating naphthalene with nitric and sulfuric acids at ca 40—50°C (37). The product is obtained in very high yield and contains ca 3—10 wt % 2-nitronaphthalene and traces of dinitronaphthalene the product can be purified by distillation or by recrystaUization from alcohol. 1-Nitronaphthalene is important for the manufacture of 1-naphthalenearnine. Photochemical nitration of naphthalene by tetranitromethane in dichioromethane and acetonitrile to give 1-nitronaphthalene has been described (38). 

Nitronaphthalenesulfonic Acids. Nitronaphthalenesulfonic acids can be obtained either by the sulfonation of 1-nitronaphthalene or by the nitration of 1- or 2-naphthalenesulfonic acid. Thus the sulfonation of 1-nitronaphthalene with oleum at ca 25°C gives mainly 5-nitro-l-naphthalenesulfonic acid/77521-00-5]. The mononitration of 1-naphthalenesulfonic acid gives mainly 5- and 8-nitro-l-naphthalenesulfonic acid/717-41-9] and mononitration of 2-naphthalenesulfonic acid gives mainly 5-nitro-2-naphthalenesulfonic acid [86-69-1] and 8-nitro-2-naphthalenesulfonic acid [18425-74-6]. These... 

Naphthaleneamine. 1-Naphthylamine or a-naphth5iamine/7i5 -i2- can be made from 1-nitronaphthalene by reduction with iron—dilute HCl, or by catalytic hydrogenation it is purified by distillation and the content of 2-naphthylamine can be reduced as low as 8—10 ppm. Electroreduction of 1-nitronaphthalene to 1-naphthylamine using titania—titanium composite electrode has been described (43). Photoinduced reduction of 1-nitronaphthalene on semiconductor (eg, anatase) particles produces 1-naphthylamine in 77% yield (44). 1-Naphthylamine/7J4-J2-. can also be prepared by treating 1-naphthol with NH in the presence of a catalyst at elevated temperature. The sanitary working conditions are improved by gas-phase reaction at... 

The oxidation of 1-nitronaphthalene by ceric ammonium nitrate has been reported (16). The resulting 1-iiitronaphthoquinone condenses with 1,3-butadiene followed by air oxidation under alkaline conditions to form 1-nitroanthraquinone, or l-aminoanthraquinone is formed direcdy by an intramolecular redox reaction. 

Nitronaphthalene [86-57-7] M 173.2, m 57.3-58.3 , b 30-40 /0.01mm. Fractionally distd under reduced pressure, then crystd from EtOH, aqueous EtOH or heptane. Chromatographed on alumina from benzene/pet ether. Sublimes in vacuo. 

Resonance activation in the 8-substituted-isoquinolines (344) or -2-nitronaphthalenes is predicted to be greater than that in 5-substituted-quinolines (345) or -1 -nitronaphthalenes due to the lower energy charge-... 

Line 1-Nitronaphthalene No. substituents Nucleophile (solvent) Rate constant (temp. °C) 106A liter mole" sec" Activation energy kcal mole" Frequency factor logioA Ref. 

The deoxygeneration of nitroarenes by trivalent phosphorus compounds in the presence of amines is a useful route to 3/f-azepin-2-amines (cf. compounds 32, Section 3.1.1.4.2.2.). Subsequently, it has been shown, by carrying out the reaction in strongly basic solution, that the process can be extended to the synthesis of 1H-. 3H- and 5//-2-benzazepines from nitronaph-thalenes 43 For example, 1-nitronaphthalenes 3 with dimethyl phosphite in the presence of sodium methoxide and a primary or secondary aliphatic amine, yield the dimethyl 5//-2-ben-zazepin-3-yl phosphonates 4 accompanied, in some cases, by the isomeric 3//-2-bcnzazepin-3-yl phosphonates 5. 

Likewise with 2-nitronaphthalcne (6), 1 //-2-benzazepin-l -yl phosphonates 7 are formed in good yields, and the method can also be used to synthesize pyridoazepines from nitroquinolines (see Section 3.2.1.4.1.5.). The reaction fails, however, with 2-substituted 1-nitronaphthalenes. 

A zido-1 -nitronaphthalene (1 -Nitro-2-naphthyl azide). Yel needles from acet, mp 116—17°... 

Subsequently577b, the naphthalene values were changed to 30,000 and 600, other values (lO7 ) being 1-nitronaphthalene, 0.7 falling to 0.6 1-cyano-naphthalene, 6 falling to 0.8 2-naphthoic acid, 0.9 falling to 0.6 1-chloronaph-thalene, 850 and 1-bromonaphthalene, 700, though little can be deduced from these results. 

Tetranitromethane is thought to be relatively stable in the pure state. Mixing it with nitrobenzene (which is stable), 1- or4-nitrotoluene, nitroxylene, 1,3-dinitrobenzene or 1-nitronaphthalene leads to mixtures that detonate with extreme violence. 

Tetranitronaphthalene was prepared by adding nitric acid/sulphuric acid mixture to 1-nitronaphthalene. A solid residue formed after a valve had broken down. The medium was heated to try to melt the residue. This operation gives rise to a precipitate present in large quantities that blocked the stirrer and caused the reactor to detonate violently. 

Figure 1.4 Low- and high-resolution STM images of a decanter of 1-nitronaphthalene, together with the minimum structure optimized from a force model, showing individual enantiomers in a 6 4 ratio. (Reprinted with permission from Ref. [7]. Copyright 1999, American Physical Society.)...

I, 4-benzoquinone.4 Other methods that have been employed include the oxidation of naphthalene with hydrogen peroxide,5 the oxidation of 1,4-naphthalenediamine 6 and naphthylamine sulfonic acid 7 and the oxidation of 4-amino-1-naphthol prepared by electrolytic reduction of 1-nitronaphthalene.8... 

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