1 -Aminonaphthalene, formation

The formation of l-methyl-5-aminonaphthalene when dihydro-lysergic acid is fused with potassium hydroxide requires rings (A) and (Cb The presence of an indole nueleus (rings (A) and (B) ) is established by the formation of 3 4-dimethylindole, m.p. 115-7°, pierate, m.p. 185-7°, by decarboxylation of an indole acid obtained when dihydrolysergic acid is fused with potassium hydroxide. ... 

In addition, the formation of terminal metabolites may be adverse either for the organism itself, or for other organisms in the ecosystem. Microbial metabolites may also undergo purely chemical reactions to compounds that are terminal products. Examples include the formation of 5-hydroxyquinoline-2-carboxylate from 5-aminonaphthalene-2-sulfonate (Nortemann et al. 1993) or benzo[fc]naphtho[l,2- /]thiophene from benzothiophene (Kropp et al. 1994). Microbial metabolites may be toxic to both the bacteria producing them and to higher organisms. Illustrative examples of toxicity include the following ... 

The formation of complexes of the fluorescent tracer dye ammonium 1-phenyl-aminonaphthalene-8-sulphonate (10.41) with cyclodextrins has been investigated with favourable results, especially in environmental studies [33]. The ability of this dye to complex with cyclodextrins has been exploited mainly as an analytical tool in the study of cyclodextrin applications, since its fluorescence is easily measured. The interaction of a-, P-and y-cyclodextrins with azo acid dyes containing alkyl chains of different lengths has been reported [36,37]. The formation and isolation of solid complexes between P-cyclodextrin and Cl Acid Red 42, Cl Acid Blue 40 or Erionyl Bordeaux 5BLF (Ciba) have been reported [29]. 

Certain aromatic imines undergo a similar cyclodehydrogenation to the phenanthridine. Benzylideneaniline (330) yields phenanthridine (331) only in sulfuric acid,355 whereas diphenylmethyleneaniline cyclizes in the presence of oxygen or iodine.356 Cyclizations have also been reported in Schiff s bases formed from a- and /J-naphthylamine357 and from 4-aminoquinoline,358 and in the mesomeric betaine 4,5-diphenyl-2-mercapto-l,3,4-thiadiazolium hydroxide.359 Irradiation of the anil of 2-aminonaphthalene (332) in ethanol, however, leads to incorporation of ethanol and the formation of 3-phenylbenzo[/]-quinoline (333).860 Additional photoproducts are obtained when the photolysis is carried out in w-hexanol.361... 

When l-nitro-2-aminonaphthalene is treated with sodium nitrite and HCl, and then with warm water, there is obtained not only l-nitro-2-naphthol, but also l-chloro-2-naphthol. How do you account for the formation of the chloronaphthol Consider carefully the stage at which chlorine is introduced into the molecule. 

From a theoretical point of view this is an extremely interesting reaction. The displacement of a hydroxyl group from a saturated carbon atom appears to be unknown in basic solution. The fact that amino-methane sulfonic acid can be isolated from the bisulfite addition product of formaldehyde on treatment with ammonia does not prove, of course, that a direct displacement, such as is indicated in XVI to XVII, actually occurred. Furthermore, it is quite clear that preliminary formation of an imine (XVIII) is not necessary for the reaction of aromatic amines with sodium bisulfite (steps XIX to XVIII to XVII, etc.). 1-Dimethyl-aminonaphthalene-4-sulfonic acid (XX) and l-aminonaphthalene-4-sulfonic acid (XIX) show similar reaction kinetics 16a when treated with sodium bisulfite, yet with the tertiary amine (XX) it is not possible to write an imino structure corresponding to XVIII. 

Disulfide formation occurred when spiro[cyclopropane-l,5 -thiazole] 1 was refluxed in aqueous ethanol containing sodium hydroxide in addition 1-aminonaphthalene was obtained. ... 

In 1950, Boldyrev and Postovskii29 reported the heat of combustion and heat of formation of a series of naphthalenesulphonamides as a sequel to the series of benzenesulphonamides reported earlier by Pushkareva and Kokosho23. Table 7 presents the findings on these new species (28a-28c), 4-NH2C10H6SO2NHR. From these data, we find that the comparison of heats of combustion of 4-aminobenzenesulphonamides from Reference 23 and 4-aminonaphthalene-l-sulphonamides from Reference 27 is definitely problematic. In particular, the heats of combustion of the parent species (23b and 28a) differ by 460.6 kcal mol-1, but the iV-2-pyridyl species (23e and 28a) differ by 474.9 kcal mol-1. We know of no reason why these differences should be so unequal. Furthermore, using heat of combustion data from Reference 3, we find that differences for other corresponding naphthalene and benzene derivatives pairs (cf. Table 5) are ca... 

In addition to its importance in the mechanism of formation of naph-thalene-2-sulfonates, the desulfonation reaction has preparative utility in producing the dye intermediate 6-aminonaphthalene-l,3-disulfonic acid from the 1,3,5-trisulfonate. This is accomplished by refluxing at 125°C for 4 hr in dilute sulfuric acid. 

In addition to the light-induced reactions already reviewed elsewhere <1978HC(33)3>, the reductive degradation of 4 to 1-aminonaphthalene by irradiation in triethyl- or diethylamine as solvent should be mentioned <2002TH1>. 2-Methylnaphtho[l,8-r/i ]-l,2,3-triazin-2-ium-l-ide 5a is photostable toward broad-band UV or 254nm irradiation in ether (298 K) or in the crystal (303 and 213 K), but upon excimer laser excitation (351 nm) at 10 or 85 K the blue color of 5a is bleached with formation of the triaziridine 184 (Equation 60). The latter is stable in liquid methyltetra-hydrofuran (MTHF) at 110 K but is degraded upon 254 nm irradiation to several colorless products <1986AGE828> see also Section 9.01.3.4 and Table 11. 

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... 

Detection may be facilitated by preparation of colored or, more often, fluorescent derivatives prior to spotting and development. Examples include dansylation (reaction with 1-dimethyl aminonaphthalene-5-sulfonyl chloride) of amino acids and formation of 2,5-dinitrophenylhydrazones of amino acids and ketosteroids. Other reactions that have been used include oxidation, reduction, hydrolysis, ha-logenation, enzymatic, nitration, diazotization, esterification, and etherification (Szepesi and Nyiredy, 1996 Kovar and Morlock, 1996). Prechromatographic derivatization sometimes improves separation, stability, and/or quantification of the analytes in addition to providing visualization. 

The formation of l-methyl-5-aminonaphthalene when dihydro-lysergic acid is fused with potassium hydroxide requires rings (A) and (Cl. 

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