Naphthalene nitric acid reaction

Fluoronaphthalene [321-38-0] is prepared from 1-naphthylamine by the Balz-Schiemaim reaction in 52% yield or by diazotization in anhydrous hydrogen fluoride in 82% yield. Electrophilic substitution occurs at the 4-position, eg, nitration with fuming nitric acid in acetic acid gave 88% yield of l-fluoro-4-nitro-naphthalene [341 -92-4]. 

Nitro-3,4,6-Tribromo-2-Naphthol (1-Nitio-3,4,6-tribromo-2-oxy-naphthalene). 02N.CloH3Br3.OH, mw 425.87, N 3.29%, OB toC02 -71.38%, turns black at 135°, mp 136° (decompn). Prepn from l,3,4,6 tetrabromo-l-nitro-2-naphthol by reaction with nitric acid, then alkali Ref Beil 6,655... 

Di n itr o-8- Hyd roxy 1 -Acetoxy-Naphtha bob (2,4-Dinitro-8-acetoxy-naphthol-(l), acetic acid-r >.7-dinit.ro-8-hvdrnxv-nanhthv14r1 V tf rl f5 7. dinitro-8-hydroxy-naphthyl-(l)-acetate]. H0.(O2N)2C10H4.OCOCH3, mw 292.22, N 9.59%, OB to C02 —149.81%, gold prisms from AcOH, mp 200° (decompn). Sol in ale boiling AcOH. Prepn from 1,8-diacetoxy-naphthalene by reaction with dil nitric acid (d 1.4g/cc) at 25-30°... 

Anthraquinone itself is traditionally available from the anthracene of coal tar by oxidation, often with chromic acid or nitric acid a more modern alternative method is that of air oxidation using vanadium(V) oxide as catalyst. Anthraquinone is also produced in the reaction of benzene with benzene-1,2-dicarboxylic anhydride (6.4 phthalic anhydride) using a Lewis acid catalyst, typically aluminium chloride. This Friedel-Crafts acylation gives o-benzoylbenzoic acid (6.5) which undergoes cyclodehydration when heated in concentrated sulphuric acid (Scheme 6.2). Phthalic anhydride is readily available from naphthalene or from 1,2-dimethylbenzene (o-xylene) by catalytic air oxidation. 

A kinetic study of nitrous acid-catalyzed nitration of naphthalene with an excess of nitric acid in aqueous mixture of sulfuric and acetic acids (Leis et al. 1988) shows a transition from first-order to second-order kinetics with respect to naphthalene. (At this acidity, the rate of reaction through the nitronium ion is too slow to be significant the amount of nitrous acid is sufficient to make one-electron oxidation of naphthalene as the main reaction path.) The reaction that initially had the first-order in respect to naphthalene becomes the second-order reaction. The electron transfer from naphthalene to NO+ has an equilibrium (reversible) character. In excess of the substrate, the equilibrium shifts to the right. A cause of the shift is the stabilization of cation-radical by uncharged naphthalene. The stabilized cation-radical dimer (NaphH)2 is just involved in nitration ... 

The cerium(IV) oxidation of lactyllactic acid49 and of 4-oxopentanoic acid50 in aqueous nitric acid solutions shows first-order dependence of the reaction on both cerium(IV) and substrate. A 1 1 complex formation between manganese(III) and amine, which later decomposes in the rate-limiting step, best explains the kinetics of oxidation of aliphatic amines by cerium(IV) in nitric acid medium in the presence of manganese(II).51 The kinetics of oxidation of naphthalene, 2-methyhiaphthalene, and a-naphthol with cerium(IV) in perchloric acid solutions have been studied.52 Use of a 50-fold molar excess of cerium(IV) perchlorate results in complete oxidation of fluorophenols to CO2, HCO2H, and HF in 48 h at 50 °C.53... 

Cognate preparation. 1-Nitronaphthalene. Use 40 ml of concentrated nitric acid and 40 ml of concentrated sulphuric acid with 50 g (0.39 mol) of finely powdered naphthalene as detailed for nitrobenzene. The subsequent heating at 60 °C should be for 30-40 minutes or until the smell of naphthalene has disappeared. Pour the reaction mixture into 500 ml of water decant the washings from the product and then boil the solid with 200 ml of water for 20 minutes. Decant the water and subject the oil to steam distillation (Fig. 2.102) to remove unreacted naphthalene. Pour the warm residue into a large volume of water with vigorous stirring. Filter and recrystallise from dilute alcohol to give pure 1-nitronaphthalene (60 g, 89%), m.p. 61 °C. 

Into a suitable flask equipped with motorized stirrer, thermometer and powder funnel, add 185 milliliters of 70% nitric acid, followed by carefully adding 350 milliliters of 98% sulfuric acid. Thereafter, place this flask into a water bath at room temperature, and then slowly add in small portions, 450 grams of dry powdered naphthalene over a period of 6 hours while rapidly stirring the acid mixture and maintaining its temperature below 30 Celsius. After the addition of the naphthalene, remove the powder funnel and replace it with a condenser and then reflux the entire reaction mixture for 2 hours at 60 Celsius with constant stirring. After refluxing for 2 hours, remove the heat source, and allow the reaction mixture to cool to room temperature. Thereafter, drown the entire reaction mixture into 1000 milliliters of ice water, and then filter-off the precipitated crystals. Then wash these crystals with three 250-milliliter portions of cold water, and then vacuum dry or air-dry the crystals. The dry solid product will be a mixture of para, ortho, and meta isomers. 

In general, naphthalene reacts much more easily than benzene, and nitration of naphthalene takes place so energetically that polynitro compounds are formed easily. On the other hand, since the reaction is carried out at a temperature below the melting point of naphthalene, the larger particles may not be attacked by the nitric acid under the... 

Dinitro-5-methoxy-naphthol-(l), methyl-[4,6-dinitro-5-hydroxy-naphthyl-(l)] -ether). (02N)2CioH4(OH).O.CH3, mw 278.24, N 10.07%, OB to CO2 -132.26%, gold needles from ale, mp 183° (decompn). Sol in ale. Prepn from 5-methoxy-l-acetoxy-naphthalene by reaction with an excess of nitric acid (d 1.42 g/cc) at 0°... 

The nitro substitution products of naphthalene are easily prepared by the action of nitric acid on the hydrocarbon. By such direct nitration the product obtained is alpha-nitro naphthalene. This is proven by the following series of reactions. Nitro-naphfhalene by reduction yields amino naphthalene, naphthylamine, which by the diazo reaction yields hydroxy naphthalene, naphthol. Now the naphthol so obtained is identical with the one resulting from the phenyl vinyl acetic acid synthesis (p. 768) and this must be the alpha compound. 

The two phase nature of the reaction mixture (aqueous nitric acid/lanthanide salt and solvent/substrate) poses a number of questions. Foremost amongst these is the following in which phase does the actual nitration occur Comparison of the nitration rates using 1,2-dichloroethane (b.p. 83 °C) versus cyclohexane (b.p. 80 °C) as the solvents (both reactions performed at reflux) allows speculation on this matter. For the nitration of naphthalene with 10 mol% ytterbium(III) triflate a 78% conversion of naphthalene to mononitronaphthalenes occurred over 0.5h in 1,2-dichloroethane whereas for cyclohexane only a 24% conversion was observed. Based on this result it seems reasonable to conclude that the electrophilic substitution process transpires in the organic phase. 

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