Naphthalen acidity constant

It is not only p-substituted phenols that have been connected by methylene groups an extended calixarene based on naphthalene units [57] has also been synthesized and its acidity constants have been measured (see Table 25 Poh and Lim, 1989, 1990). In contrast to the calix[4]arenes, the pKa of the expanded calixarene [57] did not differ much from the of the analogue [58]. This may have two explanations (i) the conformation of the expanded calixarene is different from phenol-based calix[4]arenes and a special stabilization of the anion does not occur, (ii) this stabilization occurs but it is also present in the analogue. A stabilization by the neighbouring... 

The above generalities apply particularly to palladium. Hydrogenation over platinum or rhodium are far less sensitive to the influence of steric crowding. Reduction of 1-t-butylnaphthalene over platinum, rhodium, and palladium resulted in values of /ci//c2 of 0.42, 0.71, and 0.024, respectively. Also, unlike mononuclear aromatics, palladium reduces substituted naphthalenes at substantially higher rates than does either platinum or rhodium. For example, the rate constants, k x 10 in mol sec" g catalyst", in acetic acid at 50 C and 1 atm, were (for 1,8-diisopropylnaphthalene) Pd (142), Pt(l8.4), and Rh(7.1)(25). 

To determine the purity of a sample of arsenic(III) oxide follow the general procedure outlined in Section 10.127 but when the 25 mL sample of solution is being prepared for titration, add 25 mL water, 15 mL of concentrated hydrochloric acid and then two drops of indicator solution (xylidine ponceau or naphthalene black 12B see Section 10.125). Titrate slowly with the standard 0.02M potassium bromate with constant swirling of the solution. As the end point approaches, add the bromate solution dropwise with intervals of 2-3 seconds between the drops until the solution is colourless or very pale yellow. If the colour of the indicator fades, add another drop of indicator solution. (The immediate discharge of the colour indicates that the equivalence point has been passed and the titration is of little value.)... 

Salts of diazonium ions with certain arenesulfonate ions also have a relatively high stability in the solid state. They are also used for inhibiting the decomposition of diazonium ions in solution. The most recent experimental data (Roller and Zollinger, 1970 Kampar et al., 1977) point to the formation of molecular complexes of the diazonium ions with the arenesulfonates rather than to diazosulfonates (ArN2 —0S02Ar ) as previously thought. For a diazonium ion in acetic acid/water (4 1) solutions of naphthalene derivatives, the complex equilibrium constants are found to increase in the order naphthalene < 1-methylnaphthalene < naphthalene-1-sulfonic acid < 1-naphthylmethanesulfonic acid. The sequence reflects the combined effects of the electron donor properties of these compounds and the Coulomb attraction between the diazonium cation and the sulfonate anions (where present). Arenediazonium salt solutions are also stabilized by crown ethers (see Sec. 11.2). 

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)... 

At constant PBT/PTMO composition, when the molar mass of PTMO block is >2000, partial crystallization of the polyether phase leads to copolymer stiffening. The properties of polyesterether TPEs are not dramatically different when PTMO is replaced by polyethers such as poly(oxyethylene) (PEO) or poly(oxypropylene). PEO-based TPEs present higher hydrophilicity, which may be of interest for some applications such as waterproof breathable membranes but which also results in much lower hydrolysis resistance. Changing PBT into a more rigid polymer by using 2,6-naphthalene dicarboxylic acid instead of terephthalic acid results in compounds that exhibit excellent general properties but poorer low-temperature stiffening characteristics. 

Photolytic. Based on data for structurally similar compounds, acenaphthylene may undergo photolysis to yield quinones (U.S. EPA, 1985). In a toluene solution, irradiation of acenaphthylene at various temperatures and concentrations all resulted in the formation of dimers. In water, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, and 1-naphthoic acid. In methanol, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, methyl 8-formyl-1-naphthoate, and dimethoxyacetal 1,8-naphthalene dialdehyde (Chen et al., 1979). Acenaphthylene reacts with photochemically produced OH radicals and ozone in the atmosphere. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with OH radicals (500,000/cm ) at 25 °C are 8.44 x lO " cmVmolecule-sec and 5 h, respectively. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with ozone at 25 °C are... 

Rate constants for deuterium or tritium exchange of benzene, naphthalene, and other aromatic molecules have been measured in concentrated solutions of sulfuric or perchloric acid. Conveniently, Cox has extrapolated values to aqueous solution from plots of log/cx against Xa and corrected them for isotope effects (e.g., k /kp) to yield kA.72... 

Streitwieser40 pointed out that the correlation which exists between relative rates of reaction in deuterodeprotonation, nitration, and chlorination, and equilibrium constants for protonation in hydrofluoric acid amongst polynuclear hydrocarbons (cf. 6.2.3) constitutes a relationship of the Hammett type. The standard reaction is here the protonation equilibrium (for which p is unity by definition). For convenience he selected the 1 -position of naphthalene, rather than a position in benzene as the reference position (for which er is zero by definition), and by this means was able to evaluate p -values for the substitutions mentioned, and cr -values for positions in a number of hydrocarbons. The p -values (for protonation equilibria, x for deuterodeprotonation, 0-47 for nitration, 0-26 and for chlorination, 0-64) are taken to indicate how closely the transition states of these reactions resemble a er-complex. 

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