Primary amines with phenanthrene

The nomenclature of amines is exceptional. By very long custom radical names may be attached to the ending amine, as in ethylamine but it is equally correct to add amine to the parent name, as indicated in Table 4, giving names such as phenanthren-1-amine, quinolin-8-amine, or even ethanamine. The latter practice is often reserved for more complex cases but that is not a necessary limitation. The same alternatives exist for ammonium salts. Secondary and tertiary amines are treated as substitution products of the most complex constituent primary amine, with N- prefixes when substitution elsewhere might be reasonable, as in triethylamine, dimethylamine,... 

Photosensitized animation of several aromatic compounds including phenanthrene, anthracene, naphthalene with ammonia or primary amines has also been investigated106 (equations 47-49). 

Yasuda et al. have used steady-state kinetics to investigate the reaction of the phenanthrene cation radical with ammonia and several primary amines. Rale constants were observed to increase from 0.3 x 10 M" s" for ammonia to 8.9 x I0 M s for /-butylamine. Correlation of these rates with the Taft o parameter (Table 4) indicates that there is substantial development of positive charge on nitrogen in the transition state for bond formation. 

The regioselective ET-sensitized addition of primary amines has been cleverly employed by Yasuda and co-woikers in the synthesis of isoquinolines and related alkaloids. For example, the DCNB-sensitized photoamination of stilbene with 2-hy-doxypropylamine in an acetonitrile-water solution yields the adduct 98, which is converted to the benzylisoquinoline 99 upon treatment with CFjSOjH, The P-hydroxyl group of ethano-lamine can be replaced with acetal or vinyl groups which also can serve as precursors of the carbocation required for the acid-catalyzed ring-forming reaction. Analogous reaction sequences have been used to convert phenanthrene to aporphines. ... 

Photoamination via Category III has been investigated in polycyclic arenes such as phenanthrene (la) and its derivatives (Ib-li), anthracene (Ij), and naphthalene derivatives (Ik-lv) [36-37], A typical example was photoamination of la with NHj, which was performed by the irradiation of an ammonia-saturated MeCN-H O solution containing la and m-DCB for 17 h to give the Type I aminated product, 9-amino-9,10-dihydrophenanthrene (10a), in 84% yield (Scheme 6.11). It was apphed to photoamination with primary amines such as alkylamines, ethanolamine, allylamine, and glycine ethyl ester and so on, which gave efficiently A-alkyl derivatives of 10a. But photoamination with secondary alkylamines such as dimethylamine and diethylamine were inefficient [38]. 

Tetraphenylethylene cyclizes anodically to 9,10-diphenylphenanthrene analogously to its photooxidative cyclization. The attempted anodic cyclization of cis- or frans-stilbene to phenanthrene however failed due to electrophilic reaction of the intermediate radical cation with the solvent 37S Primary aromatic amines are oxidized to radical cations which, depending on the pH of the electrolyte couple to aminodiphenylamines (C-N coupling (84) in Eq. (172) ), yield benzidines (85) at low pH (C-C coupling) or dimerize to hydrazobenzene (86) (N-N coupling) which is subsequently oxidized to azobenzene (Eq. (172) ) 2 5,376,377)... 

Introduction. The quinones are intermediate products in the oxidation of the aromatic nucleus. They may be prepared in some cases by the direct oxidation of aromatic hydrocarbons. For example, anthracene, naphthalene, and phenanthrene are oxidized to the corresponding quinones by chromic acid mixtures. Quinones are prepared more conveniently by oxidation of primary aromatic amines, particularly the p-substituted amines. p-Benzoquinone is obtained by the oxidation of aniline, p-toluidine, sulfanilic acid, p-aminophenol, and other similar compounds. Similarly the a-naph-thoquinone is obtained by oxidation of 1,4-aminonaphthol, and /9-naphthoquinone by the oxidation of 1,2-aminonaphthol. In the laboratory, although it is possible to prepare p-benzoquinone by the oxidation of aniline with acid-dichromate mixture, the method is tedious and the yield poor. Since hydroquinone is used extensively as a photographic developer and is made industrially, it is more convenient to prepare quinone by its oxidation. 

Bandyopadhyay et al. [50] synthesized a series of novel N-substituted pyrrole derivatives. The autiiors sought a simple and solvent-free ultrasound-assisted reaction for tiie synthesis of N-substituted pyrroles (12) by reacting 2,5-dime-thoxytetrahydrofuran (10) with aromatic, aliphatic, polyaromatic, and heteropolyaromatic amines (11) using bismuth nitrate pentahydrate as catalyst (Scheme 4). It should be mentioned that the addition of the bismuth salt, which is environmentally benign and nontoxic, increased tiie reaction yield from 55% to 99% and reduced the reaction time from 5h to 5 min. 5-(lH-Pyrrol-l-yl)-l,10-phenantiiroline and l-(phenanthren-2-yl)-lH-pyrrole have demonstrated cytotoxic specificity against liver cancer cell lines in vitro when compared with normal cultured primary hepatocytes. 

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