Naphthalene, addition

Figure 1. Visible and 11V spectra of (A) naphthalene radical anion (NRA) (THF, 25°C) (B) naphthalene dianion (OD values shifted upward by 0.2 unit) (C) naphthalene dianion after neutral naphthalene addition (OD values shifted upward by 1 unit the NRA concentration is the same in A and ).

Anthracene reacts with all of the trinitrotoluenes similarly to naphthalene, addition compounds being formed. 

Further experimentation showed that no complex formed when dispersed sodium was added to dimethoxyethane that had been carefully dried and purified by distillation from a sodium-naphthalene addition compound, yet ferric chloride was reduced almost as readily as when the so-called complex had been preformed (12). This was taken as evidence that the ether was acting also as a solvent for the ferric chloride and that the complex must have been dependent on impurities in the commercial-grade ether, which either reacted with sodium or acted as a catalyst for complex formation. Nevertheless, the ether was used as the medium for all iron powder runs because of its solvent action for ferric chloride and the smaller particle sizes which were obtained as a result of its use. 

Disubstituted butadienes are good Diels-Alder partners for benzyne. The method affords, after dehydrogenation, a 6+4 carbon assembly route to naphthalenes. Addition of benzyne to 173 affords naphthalene containing 98+2% D, whereas the resulting naphthalene from 174 contained only 2 2% D. Thus not only is the cycloaddition stereoselective, but the elimination from dihydronaphthalene 175 is almost exclusively syn. 

The effects of adding nonpolymerizable and polymerizable electron donors, such as anthracene, naphthalene, cyclohexene, and dihydrofuran, to the styrene-MA copolymerization system has received substantial study by Tsuchida and coworkers.The ability of these additives and styrene to complex with MA follows the order anthracene > naphthalene > styrene > cyclohexene > dihydrofuran. Naphthalene addition reduced the overall activation energy, increased the rate of thermal initiation and propagation slightly, and increased the rate of copolymerization. In addition, the rate maxima shifted from compositions poor in styrene toward equivalence. Because... 

When we reinvestigated the base-induced reaction of 1-naphthol with formaldehyde we isolated and identified three isomeric tetrameric compounds [2] which we named calix[4]naphthalenes by analogy with the calix[4]arenes and cal-ix[4]resorcinarenes. However, unlike the latter which are derived fromp-substituted phenols and resorcinol respectively, several different isomers can theoretically exist for the calix[4]naphthalenes. Additionally, the conformations that are possible for some of these isomers are further complicated due to the dissymmetry that is introduced by the naphthalene rings. In this contribution we will describe some properties of this new class of compounds. 

NiMo and NiW catalysts supported on Zr-SBA-15 and y-alumina were characterized and tested in simultaneous hydrodesulfurization of DBT and 4,6-DMDBT in absence and presence of quinoline or naphthalene. NiMo and NiW catalysts supported on Zr-SBA-15 showed higher HDS activity than those supported on y-Al203. In presence of quinoline, all catalysts lost their activity for HDS of 4,6-DMDBT. Naphthalene addition had a small effect on NiMo/Zr-SBA-15 catalyst and almost none on NiW/Zr-SBA-15. 

Identification of Aromatic Hydrocarbons. Picric acid combines with many aromatic hydrocarbons, giving addition products of definite m.p. Thus with naphthalene it gives yellow naphthalene picrate, C oHg,(N08)jCeHiOH, m.p. 152°, and with anthracene it gives red anthracene picrate, C 4Hio,(NOj)jCeHjOH, m.p. 138 . For practical details, see p. 394. 

Effect of impurities upon the melting point. Let us take a specific example and examine the effect of the addition of a small quantity of naphthalene to an equilibrium mixture of pure solid and liquid a-naphthol at the temperature of the true melting point (95 5°) at atmospheric pressure. 

Davies and Warren have investigated the nitration of naphthalene, ace-naphthene and eight dimethylnaphthalenes in acetic anhydride at o °C. Rates relative to naphthalene were determined by the competition method, and the nitro-isomers formed were separated by chromatographic and identified by spectrophotometric means. The results, which are summarised in the table, were discussed in terms of various steric effects, and the applicability of the additivity rule was examined. For the latter purpose use was made of the data of Alcorn and Wells (table 10.2) relating to the nitration of monomethyl-naphthalenes at 25 °C. The additivity rule was found to have only limited utility, and it was suggested that the discrepancies might be due in part to the... 

In addition to benzene and naphthalene derivatives, heteroaromatic compounds such as ferrocene[232, furan, thiophene, selenophene[233,234], and cyclobutadiene iron carbonyl complexpSS] react with alkenes to give vinyl heterocydes. The ease of the reaction of styrene with sub.stituted benzenes to give stilbene derivatives 260 increases in the order benzene < naphthalene < ferrocene < furan. The effect of substituents in this reaction is similar to that in the electrophilic aromatic substitution reactions[236]. 

Dimethyl acetylenedicarboxylate (DMAD) (125) is a very special alkyne and undergoes interesting cyclotrimerization and co-cyclization reactions of its own using the poorly soluble polymeric palladacyclopentadiene complex (TCPC) 75 and its diazadiene stabilized complex 123 as precursors of Pd(0) catalysts, Cyclotrimerization of DMAD is catalyzed by 123[60], In addition to the hexa-substituted benzene 126, the cyclooctatetraene derivative 127 was obtained by the co-cyclization of trimethylsilylpropargyl alcohol with an excess of DMAD (125)[6l], Co-cyclization is possible with various alkenes. The naphthalene-tetracarboxylate 129 was obtained by the reaction of methoxyallene (128) with an excess of DMAD using the catalyst 123[62],... 

The unit Kureha operated at Nakoso to process 120,000 metric tons per year of naphtha produces a mix of acetylene and ethylene at a 1 1 ratio. Kureha s development work was directed toward producing ethylene from cmde oil. Their work showed that at extreme operating conditions, 2000°C and short residence time, appreciable acetylene production was possible. In the process, cmde oil or naphtha is sprayed with superheated steam into the specially designed reactor. The steam is superheated to 2000°C in refractory lined, pebble bed regenerative-type heaters. A pair of the heaters are used with countercurrent flows of combustion gas and steam to alternately heat the refractory and produce the superheated steam. In addition to the acetylene and ethylene products, the process produces a variety of by-products including pitch, tars, and oils rich in naphthalene. One of the important attributes of this type of reactor is its abiUty to produce variable quantities of ethylene as a coproduct by dropping the reaction temperature (20—22). 

The in, uv, mass, nmr, and C-nmr spectral data for naphthalene and other related hydrocarbons have been reported (7—11). Additional information regarding the properties of naphthalene has been pubUshed (3,6,12,13). 

Addition. The most important addition products of naphthalene are the hydrogenated compounds. Of less commercial significance are those made by the addition of chlorine. 

Hyd.rogena.tlon. Hydrogen is added to the naphthalene nucleus by reagents that do not affect ben2ene. Two, four, six, eight, or ten hydrogen atoms may add. Of these, only the tetra- and decahydronaphthalenes are commercially significant. In addition to the commercially important... 

Chlorine Addition. Chlorine addition and some chlorine substitution occurs at normal or slightly elevated temperatures in the absence of catalysts. The chlorination of molten naphthalene under such conditions yields a mixture of naphthalene tetrachlorides, a monochloronaphthalene tetrachloride, and a dichloronaphthalene tetrachloride, as well as mono- and dichloronaphthalenes (35). Sunlight or uv radiation initiates the addition reaction of chlorine and naphthalene resulting in the production of the di- and tetrachlorides (36). These addition products are relatively unstable and, at ca 40—50°C, they decompose to form the mono- and dichloronaphthalenes. 

The coal tar first is processed through a tar-distillation step where ca the first 20 wt % of distillate, ie, chemical oil, is removed. The chemical oil, which contains practically all the naphthalene present in the tar, is reserved for further processing, and the remainder of the tar is distilled further to remove additional creosote oil fractions until a coal-tar pitch of desirable consistency and properties is obtained. 

However, since the naphthalene produced from petroleum is of high purity and quaUty, the production of refined naphthalene by such chemical treatments essentially has ceased in the United States. Not only are such treatments expensive, but they also generate a significant amount of waste sludge, which creates additional costs for appropriate waste-disposal faciUties. 

In additional EPA studies, subchronic inhalation was evaluated ia the rat for 4 and 13 weeks, respectively, and no adverse effects other than nasal irritation were noted. In the above-mentioned NTP chronic toxicity study ia mice, no chronic toxic effects other than those resulting from bronchial irritation were noted. There was no treatment-related increase ia tumors ia male mice, but female mice had a slight increase in bronchial tumors. Neither species had an increase in cancer. Naphthalene showed no biological activity in other chemical carcinogen tests, indicating Htde cancer risk (44). No incidents of chronic effects have been reported as a result of industrial exposure to naphthalene (28,41). 

Naphthalenesulfonic Acid. The sulfonation of naphthalene with excess 96 wt % sulfuric acid at < 80°C gives > 85 wt % 1-naphthalenesulfonic acid (a-acid) the balance is mainly the 2-isomer (P-acid). An older German commercial process is based on the reaction of naphthalene with 96 wt % sulfuric acid at 20—50°C (13). The product can be used unpurifted to make dyestuff intermediates by nitration or can be sulfonated further. The sodium salt of 1-naphthalenesulfonic acid is required, for example, for the conversion of 1-naphthalenol (1-naphthol) by caustic fusion. In this case, the excess sulfuric acid first is separated by the addition of lime and is filtered to remove the insoluble calcium sulfate the filtrate is treated with sodium carbonate to precipitate calcium carbonate and leave the sodium l-naphthalenesulfonate/7J(9-/4-J7 in solution. The dry salt then is recovered, typically, by spray-drying the solution. 

Sulfonation can be conducted with naphthalene—92 wt % H2SO4 in a 1 1.1 mole ratio with staged acid addition at 160°C over 2.5 h to give a 93% yield of the desired product (20). Continuous mono sulfonation of naphthalene with 96 wt % sulfuric acid in a cascade reactor at ca 160°C gives... 

Naphthalenesulfonic Acid—Formaldehyde Condensates. The sodium salts of the condensation products of naphthalenesulfonic acid with formaldehyde constitute an important class of compounds which are mainly used in the area of concrete additives (32,33), agricultural formulations, mbber formulations, and synthetic tanning agents. They are also used in photographic materials (34). Hampshire Chemical Co. and Henkel of America, Inc., are the largest suppHers of naphthalene sulfonate in concrete additives (superplasticizer) and reportedly hold 75—80% of this market. It was estimated that naphthalene sulfonate demand from U.S. producers would reach approximately... 

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