Of 2-naphthylamine

Naphthaleneamine is a dye intermediate and is used as the starting material in the manufacture of the rodenticide, Antii (8), l-naphthalenethiourea/5 %< < -4/, which is prepared by heating a mixture of 1-naphthylamine hydrochloride, NH SCN, and a large amount water for 14—16 h while keeping its volume constant by a dding an additional amount of water, to give a 97% yield. Its LD q is 600 mg in squirrels (46). 

Table 3-1. Equilibrium constants Kxno (Scheme 3-28) and rate constants for diazotization of aniline (Ar2, Scheme 3-29) and of 1-naphthylamine (k2 and k-2/k Scheme 3-34) in water by nitrosyl chloride, nitrosyl bromide, nitrosyl thiocyanate, S-nitrosothiuronium ion [(NH2)2CSNO], and dinitrogen trioxide at 25 °C.

Structure 12.148 was already supported by results from Stamm and Zollinger s investigation (1957) in which activation entropies were determined. The mechanism was corroborated by further activation entropy studies (Demian, 1972, 1973 Demian et al., 1983) and investigations on the 2/4-ratio of coupling of 1-naphthylamine carried out by Hashida et al. (1975 b). 

Time Percentage degradation of 1-naphthylamine under different experimental conditions... 

A marginal hydrogenation of the benzenic ring of 1-naphthylamine leading to 5,6,7,8-tetrahydro-l-naphthylamine [72] was explained as due to a weaker adsorption of the benzene part than of the aniline part of the naphthylamine. However, this reaction was disregarded for the HDN of 1-naphthylamine, as the minor role it could play under the studied conditions. 

The oxidation of primary and secondary alcohols in the presence of 1-naphthylamine, 2-naphthylamine, or phenyl-1-naphthylamine is characterized by the high values of the inhibition coefficient / > 10 [1-7], Alkylperoxyl, a-ketoperoxyl radicals, and (3-hydroxyperoxyl radicals, like the peroxyl radicals derived from tertiary alcohols, appeared to be incapable of reducing the aminyl radicals formed from aromatic amines. For example, when the oxidation of tert-butanol is inhibited by 1-naphthylamine, the coefficient /is equal to 2, which coincides with the value found in the inhibited oxidation of alkanes [3], However, the addition of hydrogen peroxide to the tert-butanol getting oxidized helps to perform the cyclic chain termination mechanism (1-naphthylamine as the inhibitor, T = 393 K, cumyl peroxide as initiator, p02 = 98 kPa [8]). This is due to the participation of the formed hydroperoxyl radical in the chain termination ... 

Chemical/Physical. Kanno et al. (1982) studied the aqueous reaction of 1-naphthylamine and other substituted aromatic hydrocarbons (aniline, toluidine, 2-naphthylamine, phenol, cresol, pyrocatechol, resorcinol, hydroquinone, and 1-naphthol) with hypochlorous acid in the presence of ammonium ion. They reported that the aromatic ring was not chlorinated as expected but was cleaved by chloramine forming cyanogen chloride. The amount of cyanogen chloride that formed increased as the pH was lowered (Kanno et al., 1982). 

For each 9 mg of 1-naphthylamine, add 10 mL of 0.1 M hydrochloric acid (prepared by cautiously adding 1 mL of concentrated acid to 119 mL of cold water). Mix to dissolve. For each 10 mL of the solution, add 5 mL of 0.2 M potassium permanganate solution (0.3 g of solid potassium permanganate dissolved in 10 mL of water) and 5 mL of 2.0 M sulfuric acid (prepared by cautiously adding 1 mL of concentrated acid to 8 mL of cold water). Mix and let stand overnight (at least 10 hours). Decolorize if necessary with sodium metabisulfite or ascorbic acid. Neutralize by careful addition of 5 M sodium hydroxide solution (20 g of NaOH dissolved in 100 mL of cold water). Discard the remaining solution into the drain.7... 

Figure 4. Liquid chromatogram of 1-naphthylamine and 2-naphthylamine flow rate, 90 mL/hr eluent, 0.080M HCIO (a) impurity, (b) 10 ppm 1-naphthylamine, (c) 5 ppm 2-naphthylamine.

Recently a similar analysis has been done for the diazotisation of 1-naphthylamine in hydrochloric acid (Woppmann, 1980). Here again the initial N-nitrosation is reversible and the corresponding Arj-value measured as 1.9 X 10 dm mol" s" at 0°C. 

Mononitration of naphthalene with mixed acid at a temperature of 35 to 50°C gives a good yield of 1-nitronaphthalene this is the main source of 1-naphthylamine and its derivatives. 

In the laboratory of S. Gupta, the synthesis of novel heterocyclic ring systems was accomplished utilizing the Combes reaction The condensation of 1-naphthylamine with 2-acylindan-1,3-diones produced the corresponding anils in good yield. The anils were cyclodehydrated to benz[/ ]indeno[2,1-c]quinoline-7-ones in the presence of polyphosphoric acid. Subsequent Wolff-Kishner reduction gave rise to the novel 7H-benzo[/ ]indeno[2,1-c]quinolines. 

Although not strictly an arylated aniline but rather a benzannelated species, the two isomeric naphthylamines are the simplest polynuclear aromatic hydrocarbon counterparts of aniline. Unfortunately, they are the only such examples with enthalpy of formation data known to the authors. No less than five sets of measurements23,44 - 47 with a range of 29 kJmol-1 have been reported for the enthalpy of combustion, and thus of formation, of 1-naphthylamine. Likewise, for the enthalpy of combustion of 2-naphthylamine... 

Though the toxicity of xenobiotics is generally decreased by metabolism, some xenobiotic metabolites are more toxic than their parent compounds. As noted earlier, the metabolite of benzo (a) pyrene is a lung carcinogen. Similarly, it is the metabolite of 1-naphthylamine and not the parent compound that is a bladder carcinogen. 

Derivation Decomposition of 1-naphthylamine-4,8-disulfonic acid by diazotization and acidifying with heat. 

The reaction of 1-naphthylamine, however, has been written in the form of an ene reaction, and two reasonable mechanisms, apart from the above electrophilic substitution, can be proposed for the ortho-amination of 2-(tri-n-butylstannyloxy)naphthalene. First, it could follow a metalloene mechanism, as shown in Scheme 6.3.12. 

Metabolism of foreign compounds is not necessarily detoxication. This has already been indicated in examples and will become more apparent later in this book. This may involve activation by a phase 1 or phase 2 pathway or transport to a particular site followed by metabolism. Thus, sulphate conjugation and acetylation may be involved in the metabolic activation of /V-hydroxy aromatic amines, glutathione conjugation may be important in the nephrotoxicity of compounds, methylation in metal toxicity, glucuronidation in the carcinogenicity of /1-naphthylamine and 3, 2 -dimethyl-4-aminobiphenyl. 

The yield of 1-naphthylamine decreases as the temperature is lowered. In contrast, the yield of 9 increases steadily on cooling and reaches a maximum between 213 and 195 K (Table 5). A mixture of the isomeric diamines 9 and 10 is obtained at lower temperature (173-203 K). However, upon further cooling to 113 or 77 K, the yields of adducts are tremendously reduced and azonaphthalene predominates. The photochemical reactions run between 173 and 77 K used a solvent mixture of 4 1 isopentane/cyclopentane which is much less viscous than methylcyclohexane at these temperatures. 

Blangey314 obtained direct C-nitration of some primary amines when he added the amine to an ice-cold solution of sodium nitrite in concentrated sulfuric acid with exclusion of moisture. After complete consumption of the nitrous acid the products were precipitated by ice-water and proved in each case to be the / -nitroso amine. Thus were obtained the 4-nitroso derivatives of 1-naphthylamine and its 2-, 6-, 7-, and 8-monosulfonic acids, and in the benzene series those of m-anisidine, m-toluidine (NH2 = 1), etc. The sulfo group was split off from naphthionic acid, which gave a good yield of the product obtained from 1-naphthylamine. For the preparation of C-nitroso derivatives of primary amines from nitrosophenols see page 529. 

Amino-l-naphthalenesulfonic acid 153 Preparation of the acid sulfate 70% Sulfuric acid (73.5 g) is heated to 120-125° in a three-necked flask fitted with a dropping funnel, stirrer, and descending condenser. A warm (50°) solution of 1-naphthylamine (75 g) in benzene (about 15 g) is then dropped in, with stirring, in 0.5 h the benzene distils off continuously. The solid residue is dried for 18 h at 120°. 

Naphtho-l,4-dioxepine 32 was prepared using classical cyclocondensation approach. The reaction of 1-naphthylamine 31 with ethyleneglycol resulted in the high yield formation of 32 (Fig. 10.14). 

The hypercrosslinked sorbent NDA-150 prepared according to a similar protocol of treating initial material with nitrobenzene and FeCls was tested for adsorption of 1-naphthylamine [93]. On a direct contact of dry NDA-150 beads with the sorbate aqueous solution, this sorbent extracts more than 4mmol/g of the aromatic amine, while the pre-wetted XAD-4 absorbs only 3mmol/g of 1-naphthylamine. Under dynamic conditions the breakthrough capacity and total capacity were found to be 1.49 and 1.82 mmol per cm of the NDA-150 resin (after percolating 100 and 350 bed volumes of diluted feed solution), respectively. A 100% recovery of... 

Several studies have been carried out in sulphate media. The mechanism of oxidation of 1-naphthylamine and 8-aminonaphthalene-l-sulphonic acid has been described and complex formation invoked in the reactions with benzilic acid and formaldehyde. Hydrochloric acid reduces cerium(iv) at a measurable rate at room temperature and silver(i) acts as a catalyst for the reaction. The activated complex is considered to involve both sulphatocerate and chloride anions. The large overall heats of reaction with a-thiolocarboxylic acids and thioureas have been... 

Naphthalene - production and uses 3. Pressure hydrolysis of 1-naphthylamine... 

The most important process to obtain 1-naphthol has been developed by Union Carbide via tetralin to 1-naphthol (see Chapter 9.3.6). Processes applying alkali fusion of naphthalene-1-sulfonic acid, manufactured at 180 °C by selective sulfo-nation, and by pressure hydrolysis of 1-naphthylamine at 185 °C with 20% sulfuric acid are of less importance in terms of quantities. 

Ohsaka et al. [393] reported on the preparation by electrochemical oxidation and properties of thin films of 1-naphthylamine in acetonitrile solutions. These films had conductivities of 10 to 10" S cm". Aminocoronene, which consists of seven fused aromatic rings and an amino group, has also been polymerized [394]. Eaves et al. [395] polymerized perfluorocyclopentene in dimethyl formamide in the presence of tetrabutlyammonium perchlorate. The fluorocarbon polymers could exhibit enhanced environmental stability in comparison with hydrocarbon polymers. 

A copper-mediated biaryl coupHng of 1-naphthylamine 75 and thia-zole 76 via double C-H cleavage provides (thiazolyl)naphthalene 77 in moderate yield (13JOC11045). The key to the success of this reaction is the introduction of the N,N-double coordination strategy based on a picolinamide system. The directing group is readily removable after the coupling reaction. 

The solvation process in alcoholic solutions of molecular species has been examined by picosecond measurements on the time-dependence of the Stokes shift , i.e., of the frequency difference between the maxima of the absorption and fluorescence spectra. The time-constant for this quantity for solutions of 1-naphthylamine in propanol is 52 ps, which agrees as regards order of magnitude with the result of an electrostatic calculation from a model in which the solvent is represented by a dielectric continuum and the solute by a spherical cavity of dielectric constant c- This model predicts the relaxation time of the reactive field to be not x but the longitudinal relaxation time tl which equals Ti ( c + 2 oo)/( c -f 2 q), and can be much smaller than td for highly-polar solvents (cf. Section 4.3.4). 

A glassy carbon electrode is modified with an electropolymerized film of 1-naphthylamine in aqueous solution... 

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