Naphthalene dependence

Figure 14 shows the circular dichroism spectra for the LB films of p-CDNH C12-H25 including Naph-SOsNa molecules under the initial surface pressure of 30 mN/m. Different induced circular dichro-isms are clearly observed at1 Bbband of naphthalene, depending on the substituted position the negative and positive Cotton effects occur for 1 - and 2-Naph-SOaNa included in the cavity of the CD... 

Of the polycondensed benzenoid compounds, naphthalene itself is metallated by n-BuLi in THF in the 1 and 2 positions only in poor yields. Polymetallation occurs using n-BuLi TMED, but t-BuLi alkylates naphthalene. Depending on the conditions and... 

The dissociation energy of the /3-C—H bond is critical to the rate of this process since it affects the value of kh. Howard and Ingold [74] found that 1,4-dihydronaphthalene gave organic peroxide as well as naphthalene depending on the hydrocarbon concentration, viz. 

In the sohd state, jr-surfaces tend to self-organize into either a stacked or herringbone motif. Desiraju and Gavez-zoti have shown that the assembly of fused-ring aromatics (e.g., naphthalene) depends on the number and positioning of C- and H-atoms within a molecule. The predictive nature is, thus, based on topological and shape considerations of molecules. The relative ability of molecules to participate in C- C and C- H forces was also a... 

Much of our knowledge of the frequency dependence of VER rates in polyatomic molecules stems from low-temperature studies of molecular crystals [2] such as pentacene (PTC 221 4) guest molecules in a crystalline naphthalene (N C,., H ) host. In naphthalene, the phonon cut-off frequency is -180 cm [97]. At low temperature,... 

Figure C3.5.10. Frequency-dependent vibronic relaxation data for pentacene (PTC) in naphthalene (N) crystals at 1.5 K. (a) Vibrational echoes are used to measure VER lifetimes (from [99]). The lifetimes are shorter in regime I, longer in regime II, and become shorter again in regime III. (b) Two-colour pump-probe experiments are used to measure vibrational cooling (return to the ground state) from [1021.

Tetrahydronaphthalene is produced by the catalytic treatment of naphthalene with hydrogen. Various processes have been used, eg, vapor-phase reactions at 101.3 kPa (1 atm) as well as higher pressure Hquid-phase hydrogenation where the conditions are dependent upon the particular catalyst used. Nickel or modified nickel catalysts generally are used commercially however, they are sensitive to sulfur, and only naphthalene that has very low sulfur levels can be used. Thus many naphthalene producers purify their product to remove the thionaphthene, which is the principal sulfur compound present. Sodium treatment and catalytic hydrodesulfuri2ation processes have been used for the removal of sulfur from naphthalene the latter treatment is preferred because of the ha2ardous nature of sodium treatment. 

The economics of naphthalene recovery from coal tar can vary significantly, depending on the particular processiag operation used. A significant factor is the cost of the coal tar. As the price of fuel oil increases, the value of coal tar also increases. The price history of naphthalene from 1975 to 1993 is given in Table 7. 

Acid-cataly2ed hydroxylation of naphthalene with 90% hydrogen peroxide gives either 1-naphthol or 2-naphthiol at a 98% yield, depending on the acidity of the system and the solvent used. In anhydrous hydrogen fluoride or 70% HF—30% pyridine solution at — 10 to + 20°C, 1-naphthol is the product formed in > 98% selectivity. In contrast, 2-naphthol is obtained in hydroxylation in super acid (HF—BF, HF—SbF, HF—TaF, FSO H—SbF ) solution at — 60 to — 78°C in > 98% selectivity (57). Of the three commercial methods of manufacture, the pressure hydrolysis of 1-naphthaleneamine with aqueous sulfuric acid at 180°C has been abandoned, at least in the United States. The caustic fusion of sodium 1-naphthalenesulfonate with 50 wt % aqueous sodium hydroxide at ca 290°C followed by the neutralization gives 1-naphthalenol in a ca 90% yield. 

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

In the Sulser-MWB process the naphthalene fractions produced by the crystallisation process are stored in tanks and fed alternately into the crystalliser. The crystalliser contains around 1100 cooling tubes of 25-mm diameter, through which the naphthalene fraction passes downward in turbulent flow and pardy crystallises out on the tube walls. The residual melt is recycled and pumped into a storage tank at the end of the crystallisation process. The crystals that have been deposited on the tube walls are then pardy melted for further purification. Following the removal of the drained Hquid, the purified naphthalene is melted. Four to six crystallisation stages are required to obtain refined naphthalene with a crystallisation point of 80°C, depending on the quaHty of the feedstock. The yield is typically between 88 and 94%, depending on the concentration of the feedstock fraction. 

Most coal chemicals are obtained from high temperature tar with an average yield over 5% of the coal which is carbonized. The yields in coking are about 70% of the weight of feed coal. Tars obtained from vertical gas retorts have a much more uniform chemical composition than those from coke ovens. Two or more coals are usually blended. The conditions of carbonization vary depending on the coals used and affect the tar composition. Coal-tar chemicals include phenols, cresols, xylenols, benzene, toluene, naphthalene, and anthracene. 

In the benzene and naphthalene series there are few examples of quinone reductions other than that of hydroquinone itself. There are, however, many intermediate reaction sequences in the anthraquinone series that depend on the generation, usually by employing aqueous "hydros" (sodium dithionite) of the so-called leuco compound. The reaction with leuco quinizarin [122308-59-2] is shown because this provides the key route to the important 1,4-diaminoanthtaquinones. 

The rate of amination and of alkoxylation increases 1.5-3-fold for a 10° rise in the temperature of reaction for naphthalenes (Table X, lines 1, 2, 7 and 8), quinolines, isoquinolines, l-halo-2-nitro-naphthalenes, and diazanaphthalenes. The relation of reactivity can vary or be reversed, depending on the temperature at which rates are mathematically or experimentally compared (cf. naphthalene discussion above and Section III,A, 1). For example, the rate ratio of piperidination of 4-chloroquinazoline to that of 1-chloroisoquino-line varies 100-fold over a relatively small temperature range 10 at 20°, and 10 at 100°. The ratio of rates of ethoxylation of 2-chloro-pyridine and 3-chloroisoquinoline is 9 at 140° and 180 at 20°. Comparison of 2-chloro-with 4-chloro-quinoline gives a ratio of 2.1 at 90° and 0.97 at 20° the ratio for 4-chloro-quinoline and -cinnoline is 3200 at 60° and 7300 at 20° and piperidination of 2-chloroquinoline vs. 1-chloroisoquinoline has a rate ratio of 1.0 at 110° and 1.7 at 20°. The change in the rate ratio with temperature will depend on the difference in the heats of activation of the two reactions (Section III,A,1). 

The effect of solvent on the rate, E, and dS can be derived from the data on haloquinolines and their A-oxides (Tables X and XI), on halonitronaphthalenes (Tables XII and XIII), and on halodinitro-naphthalenes (Table XVI). Depending on the nature of the reaction, the relative reactivity of two compounds can be substantially different in different solvents. For example, piperidination of 2-chloroquinoline (Table X, lines 3 and 4) compared to 2-chloroquinoxaline (Table XV,... 

Either ring of an alkyl-substituted naphthalene may be reduced and the rate ratio depends both on the position of R and its size 2S). Naphthalenes... 

The diastereomeric ratio of the trimethylsilyl triflate catalyzed amidoalkylation of a number of silyl enol ethers at — 40 CC appears to be dependent on the substituents in the substrate87. At — 40 °C the diastereomeric ratio is shown to be kinetically controlled. On allowing the reaction mixture to warm to 20 "C slow epimerization, increasing the amount of the minor isomer, is observed. In the case of the naphthalene derivative, sodium methoxide catalyzed epimerization of the kinetic mixture [(antijsyn) 88 12] produces the thermodynamic mixture [(antijsyn) 9 91]. 

Berliner et a/.284-8 have examined kinetics of bromination in aqueous acetic acid in an attempt to find the acid concentration at which the change in kinetic order principally occurs, though it follows from the earlier work that this will depend upon the aromatic reactivity. In 50 % acid the bromination of naphthalene was second-order overall284, and at constant ionic strength the rate coefficient showed a dependence on [Br-] according to equation (140)... 

Hatta T, G Mukleijee-Dhar, J Damborsky, H Kiyohara (2003) Characterization of a novel thermostable Mn(ll)-dependent 2,3-dihydroxybiphenyl 1,2-dioxygenase from polychlorinated biphenyl- and naphthalene-degrading Bacillus sp. JE8. J Biol Chem 278 21483-21492. 

It has been shown that for naphthalene contained in coal tar globules, the area-dependent mass transfer coefficient for globules was 10 greater than when the substrate was coated on microporous silica beads, and that this was an important factor in determining the rate of mineralization (Ghoshal and Luthy 1996). 

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