Naphthalene amines

From the published reports, there are few aromatic amines found that can be mineralized under anaerobic conditions, such as naphthalene amines, which can be utilized as the sole organic carbon source by bacterial cultures [58]. Furthermore, it was reported that 2-aminonaphthyl sulfonate can be degraded or used as sulfur source by pure cultures [59, 60]. In many reports, however, it was found that sulfo-nated aromatic amines cannot be degraded under anaerobic conditions [61]. 

The intramolecular ortho-arylation of aryl amide ions with aryl iodides has been recently applied to the synthesis of phenanthridines 25 in excellent yields (Scheme 10.49) [66], By applying the same procedure, N-(2-iodobenzyl) naphthalene-amine and N-(2-chlorobenzyl) naphthalen-1-amine yield benzo[a]- andbenzo[c] phenanthridines in 98% and 84% yields, respectively [66]. 

C11H9N03 3-hydroxy-2-methyl-4-quinolinecarboxylic acid 117-57-7 523.15 46.113 2 21726 C11H11N N-methyl-2-naphthalen amine 2216-67-3 590.15 52.610 1,2... 

Commonly used aromatic frothers are phenols, cresols, pyridines. These are mixtures of various methylphenols, naphthols, quinolines, anilines, naphthalene, amines, etc. extracted from coal tars. These frothers have been widely used in the flotation of coal. Apart from the frothability, these reagents have certain ability as collector especially with the increase in their molecular size. 

Pischel U, Abad S, Miranda MA (2003) Stereoselective fluorescence quenching by photoin-duced electron transfer in naphthalene-amine dyads. Chem Commun 1088-1089 Xu M H, Lin J, Hu Q et al (2002) Fluorescent sensors for the enantioselective recognition of mandeUc acid signal amplification by dendritic branching. J Am Chem Soc 124 14239-14246... 

Fischer-Hepp rearrangement The nitros-amines of aromatic secondary amines when treated with hydrochloric acid give nuclear substituted nitrosoamines. Among the benzene derivatives, if the para position is free the -NO group displaces the hydrogen atom there in naphthalene derivatives it enters the 1-position ... 

Naphthalimides are prepared from naphthaUc anhydride obtained from naphthalene-1,8-dicarboxyhc acid, ie, the oxidation product of acenaphthene or its derivatives, by reaction with amines. They are utilized for synthetic fibers such as polyesters. 

Naphthalenesulfonic acids are important chemical precursors for dye intermediates, wetting agents and dispersants, naphthols, and air-entrainment agents for concrete. The production of many intermediates used for making a2o, a2oic, and triphenylmethane dyes (qv) involves naphthalene sulfonation and one or more unit operations, eg, caustic fusion, nitration, reduction, or amination. 

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

Generally, phenols (as the phenolate anion) couple more readily than amines, and members of the naphthalene series more readily than the members of the benzene series. 

Manufacturing procedures for producing dye dispersions are generally not disclosed. The principal dispersants in use include long-chain alkyl sulfates, alkaryl sulfonates, fatty amine—ethylene oxide condensates, fatty alcohol—ethylene oxide condensates, naphthalene—formaldehyde—sulfuric acid condensates, and the lignin sulfonic acids. 

This leaction is lesorted to for the reason that naphthalene forms only the n-nitro-compound with niti icacid. The method, similar to that used for prepaiing aniline from nitiobenzene, cannot, therefore, be employed for the production of /3-n.tphtliyl-.amine. u-Naphthol is mainly used foi the manufacture of yellow and orange colours (Martins and naphthol yellow) by the action of nitric acid, and are similai m constitution to picric acid (see Prep. 107). 

IV-substituted and B-substituted borazines are readily prepared by suitable choice of amine and borane starting materials or by subsequent reaction of other borazines with Grignard reagents, etc. Thermolysis of monocyclic borazines leads to polymeric materials and to polyborazine analogues of naphthalene, biphenyl, etc. ... 

The rate of amination and of alkoxylation increases 1.5-3-fold for a 10° rise in the temperature of reaction for naphthalenes (Table X, lines 1, 2, 7 and 8), quinolines, isoquinolines, l-halo-2-nitro-naphthalenes, and diazanaphthalenes. The relation of reactivity can vary or be reversed, depending on the temperature at which rates are mathematically or experimentally compared (cf. naphthalene discussion above and Section III,A, 1). For example, the rate ratio of piperidination of 4-chloroquinazoline to that of 1-chloroisoquino-line varies 100-fold over a relatively small temperature range 10 at 20°, and 10 at 100°. The ratio of rates of ethoxylation of 2-chloro-pyridine and 3-chloroisoquinoline is 9 at 140° and 180 at 20°. Comparison of 2-chloro-with 4-chloro-quinoline gives a ratio of 2.1 at 90° and 0.97 at 20° the ratio for 4-chloro-quinoline and -cinnoline is 3200 at 60° and 7300 at 20° and piperidination of 2-chloroquinoline vs. 1-chloroisoquinoline has a rate ratio of 1.0 at 110° and 1.7 at 20°. The change in the rate ratio with temperature will depend on the difference in the heats of activation of the two reactions (Section III,A,1). 

As previously described, a mixture of and J -octalins can be prepared by the reduction of naphthalene or Tetralin. Another route to this mixture is the dehydration of a mixture of 2-decalol isomers. This latter route has certain advantages in that one can avoid the handling of lithium metal and low-boiling amines. Moreover, 2-decalol is available commercially or can be prepared by the hydrogenation of 2-naphthol (5). In either case a comparable mixture of octalins is obtained, which can be purified by selective hydroboration to give the pure J -octalin (Chapter 4, Section III). 

Benzene- 1,2-diacetonitriles e.g. 19, in the presence of hydrogen bromide in acetic acid, or in diethyl ether, cyclize to 4-bromo-l //-3-benzazepin-2-amines, e.g. 20a.41,42 l//-Naphtho[2,3-t/]azepines, e.g. 22a, are prepared in a similar manner from naphthalene-2,3-diacetonitriles, e.g. 21.41 Replacement of hydrogen bromide by hydrogen iodide yields the corresponding 4-iodo derivatives, e.g. 20b and 22b. 

The isomeric naphthalene-1,2-diacetonitrile (23) behaves differently in that with hydrogen bromide in acetic acid a mixture of 4-bromo-l //-naphtho[2,l-r/]azepin-2-amine (24) and 4-bromo-l//-naphtho[l, 2-r/]azepin-2-amine (25) is formed, from which only one isomer (32% mp 232-238 °C dec.), of undetermined structure, was isolated and purified.41... 

Analysis. 1-MNN is best identified by redn to the amine with Sn and 10% HC1, which is converted to the benzenesulfonamide, mp 167° or the benzamide, mp 160° (Ref 36). The picrate, CA Registry No 29754-26-5, is also known (Ref 37). It has been found in cn de TNT recovered from Comp B (probably anCng from the presence of naphthalene in coml toluene), from which it was isolated by gas chromatography and identified by mass spec (Ref 40). Standard anal procedures for Mil grade 1-MNN are given in Ref 35 Flash Point. Closed Cup, 327°F (Ref 42)... 

MNN is obtained in 3—5% yield by the nitration of naphthalene and is present at this level in coml MNN. It is best prepd by indirect methods for example, by the removal of an amino group from an appropriately substituted nitro-naphthylamine. The amine is treated with Na nitrite and acid to form the diazonium salt which is replaced with a H atom by redn with EtOH (Ref 7). It may also be prepd by treatment of 6-nitro-l, 2,3,4-tetrahydronaphthalene with Br to form a dibromo compn (probably the 1,4-isomer), followed by removal of two moles of H bromide by distn in the presence of base (Ref 10). 2-Naphthalenediazonium fluoroborate... 

Including aromatic amines (to be discussed below) the order of reactivities for substituted benzene and naphthalene coupling components is therefore O" > NR2 > NHR > NH2 > OR = OH > CH3 > unsubstituted (R = alkyl). 

---