0-Naphthylamine, 4-derivative

Stilben-4-yl)naphthotriazoles (2) are prepared by diazotization of 4-amino-stilbene-2-sulfonic acid or 4-amino-2-cyano-4 -chlorostilbene, coupling with an ortho-coupling naphthylamine derivative, and finally, oxidation to the triazole. 

Also recently, Liao and collaborators [89] proposed a homogeneous noncompetitive assay of a protein in biological samples based on FRET by using its tryptophan residues as intrinsic donors and its specific fluorescent ligand as the FRET acceptor, which was defined as an analytical FRET probe. To evaluate this method, a naphthylamine derivative, namely /V-biotinyl-/V -(l -naphthylj-ethylene-diamine (BNEDA) 33 was used as an analytical FRET probe for the homogeneous noncompetitive assay of streptavidin. 

When we perform experiment in such way that there is no interference of H-bonds or these bonds are stable and structure of solvent also does not varies essentially, solvatochromic plot demonstrates very good linearity as shown, for example, for some naphthylamine derivatives in ethanol-water mixtures. The linearity of solvatochromic plots is often regarded as an evidence for the dominant importance of nonspecific universal intermolecular interaction in the spectral shifts. Specific solvent effects lead to essential deviation of measured points from this linear plot. 

Aryl naphthylamine derivatives are good general antioxidants with moderate volatility and negligible effect on cure. These give a small degree of fatigue protection in natural and polyisoprene rubbers, but little in styrene-butadiene and butadiene vulcanisates. 

It should be noted that the 1 1 adducts of benzyne with pyrrylmag-nesium iodide, and A -methyl- and iV-benzylpyrrole were isolated and characterized only as the hydrobromide (113), the methiodide (115), and the picrate of 102, respectively. The low yields of all these derivatives are due in part to further reactions of thenaphthalen-l,4-imines with benzyne (see Section III, F and G). Yields are better where the starting pjnrole has an electron-withdrawing N-substituent. Some analogous naphthalen-l,4-imines expected from 1,2,5-trisubstituted pyrroles apparently rearrange spontaneously to j3-naphthylamine derivatives under the conditions for their formation (see Section III, F). The related adducts 107 and 108 are formed from tetrahalobenzynes and N-methy Ipyrrole. 

The palladium catalysed ring closure of the A-(2 -bromobcnzyl)-naphthylamine derivative shown in 5.18. could in principle occur either in the 2-position or in the 8-position of the naphthalene ring giving rise to the formation of a six or a seven membered ring respectively. Surprisingly the latter case is favoured in most cases, unless there is a bulky substituent in position 7 of the naphthalene ring. This finding, where preference of the observed reaction path is explained by the intramolecular coordination of the benzylamino function to the palladium, has been successfully exploited in the preparation of a series of naphthobenzazepines.17... 

Reaction Lx x ill. Direct Replacement of the Aromatic Amino-group by Hydroxyl. (B., 7, 77, 809 D.R.P., 109102.)—The simple primary amino-groups in the benzene series are not easily replaced directly by hydroxyl unless an activating group (e.g., N02) be present in the o- or p-position. a-Naphthols, however, are readily obtained by heating a-naphthylamine derivatives with fairly concentrated acid under pressure. 

Monoazo dyes with heterocyclic coupling components, such as pyrazolone or pyridone, are yellow to greenish yellow. Other suitable coupling components include aniline and naphthylamine derivatives. Substituted anilines or amino-naphthalenesulfonic acids are employed as diazo components. Examples are C.I. Reactive Yellow4, C.I. Reactive Yellow 17 (see Section 3.1.5). 

The most important dyes of the type D->M->K are black and navy blue wool dyes, which contain as the middle component M chiefly 1-naphthylamine or 1-naphthylamine-7-sulfonic acid and as the coupling component K A-phenyl peri acid (A-phe ny 1 a m i n o n a p h th a 1 c n c - 8 - s u 1 fo n i c acid), A-tolyl peri acid, and naphthol or 1-naphthylamine derivatives. Examples of these high-yield and very wash- and lightfast dyes are C.I. Acid Black 24, 26370 (see Section 3.9.3), which is manufactured by coupling diazotized 1-naphthylamine-5-sulfonic acid to 1-naphthylamine, further diazotization of the aminomonoazo dye, and coupling to iV-phenylperi acid and C.I. Acid Blue 113, 26360 [3351-05-1] (20). This blue dye is very important in the dyeing of wool and polyamide. 

Scheme 31. Proposed mechanism for both carbazole and binaphthyl formation upon exposure of naphthylamine derivatives to copper(ll) and an amine base.

Tab. 38. Enantioselective dimerization of 2-naphthol (and 2-naphthylamine) derivatives promoted by vanadium complexes 219 and 220.

The naphthylamine derivative 59 was investigated115 by X-ray diffraction analysis of a single crystal, by dipole moment measurements, by H NMR and by infrared spectral data. 

Diels-Alder adducts (e.g., 81-84) have been prepared from N-substituted pyrroles with tetrafluoro- and tetrachlorobenzyne.55-66,69,70 These adducts are less readily isomerized to naphthylamine derivatives and less prone to react further with benzyne. A minor product of the reaction of tetrachlorobenzyne with iV-tm-butylpyrrole is the 1,2-cycloadduct 85 (2%), for which... 

Van Overbeke, A. Baeyens, W. Van Der Weken, G. Van de Voorde, I. Dewaele, C. Comparative chromatographic study on the chiral separation of the 1-naphthylamine derivative of ketoprofen on cellulose-based columns of different sizes. Biomed.Chromatogr., 1995, 9, 289-290... 

Naphthylamine derivatives (strongly discoloring) djlauryl-p,p-11iiodipr( ionate DLTDP... 

The synthesis of substituted naphthylamine derivatives from propargyl esters by way of a carboannulation via a Pd(0)-catalysed [l,5]-sigmatropic hydrogen shift and cyclization has been reported (Scheme 134). ... 

Asymmetric derivatives can be synthesized by 4-amino-4 -nitrostilbene-2,2 -disulfonic acid however, their preparation is more expensive, and they show little advantage over the symmetrical compounds. The principal effects of structural variations are changes in solubility, substrate affinity, acid fastness, etc. The bistriazinyl brighteners are anployed principally on cellulosics such as cotton or paper. 2-(Stilben-4-yl)-naphthotriazoles (34, 35) are prepared by diazotization of 4-aminostilbene-2-sulfonic acid or 4-amino-2-cyano-4 -chlorostilbene, coupling with an orthocoupling naphthylamine derivative, and finally, oxidation to the triazole. 

The direct addition of electrophilic radicals such as fluoroalkyl radicals, without previous electron transfer, leads to substitution in positions 4 and 2 [55]. Recently, such a reaction was carried out using the photochemical electron transfer from an electronically excited naphthylamine derivative similar to that one shown in Scheme 29.10 to induce a radical chain reaction [56]. 

SCHEME 29.10 Photochemical electron transfer-mediated a-selective addition of a naphthylamine derivative to an a,p-unsaturated lactone. 

Reduced by liver microsomes to benzidine and naphthylamine derivatives... 

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