Naphthalene alkylation

Naphthalene (qv) from coal tar continued to be the feedstock of choice ia both the United States and Germany until the late 1950s, when a shortage of naphthalene coupled with the availabihty of xylenes from a burgeoning petrochemical industry forced many companies to use o-xylene [95-47-6] (8). Air oxidation of 90% pure o-xylene to phthaUc anhydride was commercialized ia 1946 (9,10). An advantage of o-xylene is the theoretical yield to phthaUc anhydride of 1.395 kg/kg. With naphthalene, two of the ten carbon atoms are lost to carbon oxide formation and at most a 1.157-kg/kg yield is possible. Although both are suitable feedstocks, o-xylene is overwhelmingly favored. Coal-tar naphthalene is used ia some cases, eg, where it is readily available from coke operations ia steel mills (see Steel). Naphthalene can be produced by hydrodealkylation of substituted naphthalenes from refinery operations (8), but no refinery-produced napthalene is used as feedstock. Alkyl naphthalenes can be converted directiy to phthaUc anhydride, but at low yields (11,12). 

DMN can be produced by alkylating naphthalene or 2-methylnaphthalene at 250—450°C over ZeoHte catalysts (102,103). However, no commercial technology by this synthetic route had been developed as of 1991, primarily because of low catalytic selectivity. 

There are three main uses for naphthalene sulfonic acid derivatives (75—79) as naphthalenic tanning material alkyl naphthalene sulfonates for industrial appHcations as nondetergent wetting agents and as dye intermediates. Consumption of naphthalene sulfonates as surfactants accounts for a large portion of usage. Naphthalene sulfonate—formaldehyde condensates are also used as concrete additives to enhance flow properties. Demand for naphthalene sulfonates in surfactants and dispersent appHcations, particularly in concrete, was expected to increase into the twenty-first century. Consumption as of 1995 was 16 x 10 kg/yr. 

Naphthalenes [C1LH9 (alkyl naphthalenes should also have m/z 91)]... 

The reaction has been applied to nonheterocyclic aromatic compounds Benzene, naphthalene, and phenanthrene have been alkylated with alkyllithium reagents, though the usual reaction with these reagents is 12-20, and Grignard reagents have been used to alkylate naphthalene. The addition-elimination mechanism apparently applies in these cases too. A protected form of benzaldehyde (protected as the benzyl imine) has been similarly alkylated at the ortho position with butyl-lithium. ... 

The most common hydrophobes used as the basis for surfactants are those containing eight to eighteen carbon atoms, such as those listed as carboxylates in Table 9.1. Some hydrophobes are aromatic (benzene or naphthalene) moieties, often containing lower alkyl substituents dodecylbenzene (9.1) is a common example. Alkyl-substituted toluenes, xylenes and phenols, and mono- and di-alkylated naphthalenes (9.2 and 9.3), are also used. 

AT-Alkyl methanesulfonamides, 23 685 Alkyl monoperoxycarbonic acid, 18 466 Alkylnaphthalenes, 17 84-85 dispersant moieties, 8 706t Alkyl naphthalene sulfonates, 24 146 Alkylnickel, re-complexes of, 17 116 Alkyl nitrites, formation of, 17 165-166 Alkylonium salt hydrates, 14 171... 

Thomas et al. (43) showed that phenanthrene is actively metabolized in salmonTds and Lee et al. (41) have shown that benzo[a]pyrene is biodegraded in three species of marine fish. Varanasi et al. (VI ) demonstrated for the first time that the skin of fish exposed to aromatic hydrocarbons via either force-feeding, intraperitoneal injection, or in flowing seawater accumulate substantial concentrations of metabolic products. This is of particular interest since studies of mammalian systems have shown that some alkyl naphthalenes can be accelerators of skin carcinogenesis (32). Varanasi et al. (11) also demonstrated that the mucus of rainFow trout exposed to radiolabeled naphthalene... 

Photolytic. Fukuda et al. (1988) studied the photodegradation of acenaphthene and alkylated naphthalenes in distilled water and artificial seawater using a high-pressure mercury lamp. Based upon a rate constant of 0.23/h, the photolytic half-life of acenaphthene in water is 3 h. Behymer and Hites (1985) determined the effect of different substrates on the rate of photooxidation of acenaphthene using a rotary photoreactor equipped with a 450-W medium pressure mercury lamp (X = 300-410 nm). The photolytic half-lives of acenaphthene absorbed onto silica gel, alumina, and fly ash were 2.0, 2.2, and 44 h, respectively. The estimated photooxidation half-life of acenaphthene in the atmosphere via OH radicals is 0.879 to 8.79 h (Atkinson, 1987). 

Photolytic. Fukuda et al. (1988) studied the photodegradation of 2-methylnaphthalene and other alkylated naphthalenes in distilled water and artificial seawater using a high-pressure mercury lamp. Based upon an experimentally rate constant of 0.042/h, the photolytic half-life of 2-methylnaphthalene in water is 16.4 h. 

Quaternary ammonium salts and salts of alkyl naphthalene sulfonic acid were some of the first compounds to be used effectively as fuel demulsifiers and dehazers. Today, a wide range of monomeric and polymeric demulsifiers and dehazers exist. 

Explosive Mixtures of High Density. A method of prepn, patented by Cook 8i Davis, involves subjecting two solid chem compds, at least one of which is a nitrated org compd (such as a mixt of TNT, An and (other compds), to a temperature at which at least a portion of one of the compds is in molten condition. To this molten mass is added a dispersing agent (such as a Na alkyl naphthalene sulfonate or other suitable org sulfonate or fatty acid soap) and then, after thorough blending, the mass is cooled and solidified. Several examples with details are given... 

M.A, Cook C.O. Davis, USP 2353147 (1944) CA 38, 6098(1944) (Explosive of high density is prepd by heating a mixt of TNT, AN and a dispersing agent such as Na alkyl naphthalene sulfonate to a temp at which. at least a portion of TNT is In molten condition)... 

The analogous alkyl derivatives of toluene, xylene, and lower alkyl naphthalenes are included in the vast number of alkyl aromatics which are also described in the literature as sulfonation stocks (16). While several sulfonates derived from such products have enjoyed partial success, they have limitations with respect to yield, sudsing, and handling characteristics which place them at a disadvantage with respect to the alkyl benzenes described above. 

Comparison with Alkyl Naphthalene Model Compounds 38... 

Alkylation. Naphthalene can be easily alkylated, Isopropvlnaphthalenes produced by alkylation of naphthalene with propylene have gained commercial importance as chemical intermediates. e.g., 2-isopropylnaphthalene, and as multipurpose solvents, e.g, mixed isopropylnaphthalenes. 

Vanderbilt Darvan 1 polymerized Na alkyl naphthalene sulfonate NaOH... 

Pyrolysis results for the inertinite concentrates are fairly inconclusive due to the high concentration of vitrinite except for the 111 2 fusinite which is quite unreactive. Pyrolysis MS of this fusinite shows mostly alkylated naphthalenes and phenanthrenes. What may be interesting is the Kentucky inertinite fraction which is thought to contain 50% pseudo-vitrinite. This maceral which is usually categorized... 

Wasserman, H.H. and Larsen, D.L. (1972) Formation of 1,4-endoperoxides from the dye-sensitized photo-oxygenation of alkyl-naphthalenes. Journal of the Chemical Society, Chemical Communications, (5), 253-254. 

Wettable powders Sodium di-alkyl naphthalene Sulphonates Fatty alcohol ethoxylates Wetting agents... 

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