1.4.5- Tris naphthalenes

Sulfonation. Sulfonation of naphthalene with sulfuric acid produces mono-, di-, tri-, and tetranaphthalenesulfonic acids (see Naphthalene derivatives), ah of the naphthalenesulfonic acids form salts with most bases. Naphthalenesulfonic acids are important starting materials in the manufacture of organic dyes (15) (see Azo dyes). They also are intermediates used in reactions, eg, caustic fusion to yield naphthols, nitration to yield nitronaphthalenesulfonic acids, etc. 

Physical properties for naphthalene mono-, di-, tri-, and tetracarboxyhc acids are summari2ed in Table 9. Most of the naphthalene di- or polycarboxyLic acids have been made by simple routes such as the oxidation of the appropriate dior polymethylnaphthalenes, or by complex routes, eg, the Sandmeyer reaction of the selected antinonaphthalenesulfonic acid, to give a cyanonaphthalenesulfonic acid followed by fusion of the latter with an alkah cyanide, with simultaneous or subsequent hydrolysis of the nitrile groups. 

Two different all-aromatic crowns have been reported ". In 1975, de Jong, Siegel and Cram reported the synthesis of a tri-binaphthyl system in which each oxygen was bound to a naphthalene ring, but aliphatic bridges were used to join the binaphthyl units. Relatives of this compound are discussed further in Sect. 3.13. The synthesis of this molecule (Structure 17, below) was not simple, but was relatively straightforward. An interesting feature of it was the use of ethyl chloroacetate followed by LAH reduction to attach ethyleneoxy units to the naphthol unit. 

Tri nitro-1 -N aphthol (2,4,7 -Trinitro-1 -oxy-naphthalene). Yellow prisms from AcOH or benz, mp 145° (decompn). Sol in AcOH glac AcOH. Prepn from 2,4-dinitro-l-naphthol by mixed acid (nitric-sulfuric-acetic) nitration. The compound is extracted as the Na salt from... 

A distinction between a solid and liquid is often made in terms of the presence of a crystalline or noncrystalline state. Crystals have definite lines of cleavage and an orderly geometric structure. Thus, diamond is crystalline and solid, while glass is not. The hardness of the substance does not determine the physical state. Soft crystals such as sodium metal, naphthalene, and ice are solid while supercooled glycerine or supercooled quartz are not crystalline and are better considered to be supercooled liquids. Intermediate between the solid and liquid are liquid crystals, which have orderly structures in one or two dimensions,4 but not all three. These demonstrate that science is never as simple as we try to make it through our classification schemes. We will see that thermodynamics handles such exceptions with ease. 

Tri-(l-naphthyl)phosphine is cleaved by alkali metals in THF solution. " Reaction with sodium gives the naphthalene radical-ion, with lithium the perylene radical-ion, and with potassium the radical-ion (22). Hydrocarbon radical-ion formation was thought to occur via naphthalene derived from the metal naphthalenide. E.s.r. spectra of further examples of phosphorus-substituted picrylhydrazyl radicals have been reported. ... 

The results of this study are presented in Table 4.7. As can be seen from the data in Table 4.7, decarbonylation with hydrogen or deuterium transfer to the resulting radical is a relatively efficient process. The failure to observe this reaction using acetone or acetophenone as photosensitizer would suggest a singlet pathway for the direct photolysis of the aldehyde. In agreement, decarbonylation could not be quenched by naphthalene, piperylene, or 1,3-cyclohexadiene when the aldehyde was excited directly. The reaction could, however, be somewhat quenched by the addition of tri-n-butylstannane. The products in this case were... 

Firstly, the electronic effect of the substituents would be a dominant factor in the determination of the thermal stability of the thiepins. Thermal stability was found to decrease sharply with decreasing substitution. For example, the tri-substituted benzo-[6]thiepin (16 d) extrudes sulfur only when heated while the non-substituted benzo[ >]-thiepin (4) is readily converted into naphthalene and sulfur at 40 °C with a half-life of 80 min 41 >. 

In addition to CN and ON, the smoke point (SP), which is the maximum smoke-free laminar diffusion flame height, has been employed widely to evaluate the tendency of different fuels to form soot. This tool was first applied to kerosenes, later diesel, and then jet engine fuels.19,20 Researchers have tried to relate smoke points of pure compounds to their molecular structure. It was found that the inverse of smoke point, which measures the potential of a fuel to form soot, increases from n-paraffins to iso-paraffins to alkylbenzenes to naphthalenes.21,22 Since smoke points vary with experimental conditions, the concept of a threshold soot index (TSI), which is calculated from the smoke point, molecular weight, and experimental constants, has been used to compare the soot-formation tendencies of different fuel molecules.23... 

Fig. 8. Separation of polyaromatic hydrocarbons using commercial stationary phases. (Reprinted with permission from [56]. Copyright 1997 VCH-Wiley). Conditions voltage 20 kV,capillary column 100 pm i. d., total length 33.5 cm, active length 25 cm, isocratic separation using 80 20 acetonitrile-50 mmol/1 TRIS buffer pH=8. Peaks thiourea (1), naphthalene (2), and flu-oranthrene (3)...

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

This is remarkable, since the reduction potential of Th(IV) to Th(III) recently has been estimated as —3.7 volts 73) and direct reduction of U(C5H5)4 and Pu(C5Hs)3 with potassium metal produces the actinide metals. The ei/z for naphthalene in acetonitrile is —2.63 V (nearly the same as the aLkaJi metals). Since this is much smaller than the Th(IV) to Th(III) reduction potential, it would seem to imply substantial stabilization of the +3 state by cyclopentadienide. The observed room temperature magnetic moment of Th(C 5115)3 (0.403 BM) is consistent with the Th(III) (5/ ) assignment. Thorium triscyclopentaxhenide is similar in behavior to U(C5H5)3, forms adducts with both THF and cyclohexyhso-nitrile and has been shown to be isostructural with the other tris (cyclopentadienyl) actinides and lanthanides. 

There is no information on systemic effects in humans. In animals, systemic toxicity from chlorinated naphthalenes appears to be limited to liver injury characterized as acute yellow atrophy. In general the tri- to hexa-chlorinated range shows the highest toxicity, with octachlorinated naphthalene significantly less toxic than the others, presumably reflecting poor uptake of octachloronaphthalene by organisms. ... 

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