Cyclic amidines. Part 26. The reported syntheses of 7-anilino-6-aryl-5,12-diazabenz[a]anthracenes are reinvestigated and their correct structures identified

Upton, Christopher

doi:10.1039/p19860001225

Cited by 8 publications

(7 citation statements)

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“…Ultraviolet data are given in Table 2 and analytical data are given in Table 1. (Upton 1986 Biology. Spot tests were performed as described by Bridges (1972).…”

Section: -Ethyl-7-methyl-58-diazabenzo[c]phenanthrenementioning

confidence: 99%

“…quinazolines (Kroon & van der Plas 1974) supported the contention that the introduced amino group is derived, in part at least, from one of the two endocyclic nitrogens and so indirect methods of replacement of oxygen by nitrogen have been developed on the basis of previously prepared compounds. We have shown (Upton 1986) that the halogen in 6-chloro-7-phenyl-5,8-diazabenzo[c]phenanthrene can undergo nucleophilic displacement by aromatic amines and have extended this reactivity to include aliphatic amines by reaction with 2-aminoethanol. These derivatives represent…”

Section: Compoundmentioning

confidence: 99%

“…More recently it has been shown that diaza derivatives are particularly pertinent in this context (Pai & Ranadive 1965;Buu-Hoi et a1 1967, 1968. To extend our studies of such polycyclic compounds (Bloomfield et a1 1986;Upton 1986Upton , 1992Tucker et a1 1993a, b), a series of diazabenzo[c]phenanthrenes has been prepared and screened, prompted by the isosteric relationship between benzo[c]phenanthrene 1 and its diaza analogue 2. The carbocycle 1 has been shown to be an epidermal carcinogen (Barry et a1 1935), to be present in cigarette tars (Severson et a1 1977(Severson et a1 , 1978 occur as an airborne pollutant in industrialized countries (Lunde 1976;Lunde & Bjorseth 1977).…”

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confidence: 99%

“…In another report (Gulland & Robinson 1925) the preparation of 3,l O-diamino-6,7-dimethyl-5,8-diazabenzo [ c]phenanthrene from the corresponding tetraamine was described. We have adopted the method reported earlier (Upton 1986) which offers access to the required range of target compounds.…”

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confidence: 99%

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Novel 5,8-Diazabenzo[c]phenanthrenes: Synthesis and Mutagenicity

Upton

Jaeda

Upton

1998

Journal of Pharmacy and Pharmacology

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The polycyclic aromatic hydrocarbons have been recognized as carcinogens and mutagens since the early part of this century. More recently their aza and polyaza derivatives have been shown to have the same biological activity. A major source of these compounds is the combustion of fresh or metamorphosed plant materials; this contributes to the environmental burden of, and exposure to, these carcinogens. We report the synthesis and characterization of a series of novel 5,8-diazabenzo[c]phenanthrenes which are isosteric with the known epidermal carcinogen benzo[c]phenanthrene but have not yet been reported as components of soot or diesel particulate matter. The synthesis of the compounds exploits a versatile, double Friedlander reaction between the appropriately substituted 2,2'-diaminobenzophenone and beta-diketones, with yields of purified product ranging from 30-90%. The nucleophilic substitution of these diazabenzophenanthrenes with ethanolamine is also described. This strategy will enable further elaboration of these heterocyclic nuclei at a later date. Mutagenicity testing of these agents was performed using spot tests and in Ames plate-incorporation assays using Escherichia coli WP2 and WP2uvrA as test organisms. The plate-incorporation assays were performed in the presence or absence of metabolic enzymes contained in the S9 liver fraction from Aroclor 1254-induced rats, to investigate whether bioactivation of the diazabenzophenanthrenes contributed to their toxicity. No differences between these two protocols were observed, with neither test showing reversion to prototrophic behaviour. Furthermore, the compounds were not toxic to the test organism. These initial results suggest that these compounds are not mutagenic in the Ames tests employed.

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“…Ultraviolet data are given in Table 2 and analytical data are given in Table 1. (Upton 1986 Biology. Spot tests were performed as described by Bridges (1972).…”

Section: -Ethyl-7-methyl-58-diazabenzo[c]phenanthrenementioning

confidence: 99%

Section: Compoundmentioning

confidence: 99%

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Novel 5,8-Diazabenzo[c]phenanthrenes: Synthesis and Mutagenicity

Upton

Jaeda

Upton

1998

Journal of Pharmacy and Pharmacology

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“…[29][30][31] Moreover, compounds comprised of a dibenzo-[b,g] [1,8]naphthyridine system are reported to exhibit intriguing biological activities. 21,22) Although a number of efficient synthetic methods for dibenzo [b,g] [1,8]naphthyridines have been reported, [38][39][40][41] the present method via the thermal isomerization of nonconjugated AYCs may alternatively be favored, because of the mildness of the conditions and the simple short-step procedure, which lead to a higher total yield of the product.…”

Section: Notesmentioning

confidence: 99%

Thermal Cyclization of Nonconjugated Aryl-Yne-Carbodiimide Furnishing a Dibenzonaphthyridine Derivative

Kimura

Torikai

Ueda

2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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NotesConjugated enyne compounds have received considerable attention in the broad field of chemistry, because of their unique cyclization reactions affording aromatized products by way of radical intermediates capable of DNA cleavage. [2][3][4][5][6][7][8] To date, a number of polyenyne compounds, including both natural 2,4,7) and artificial products, 3,7,8) have been synthesized to evaluate their reactivity and to develop more potent and selective antitumor agents, however, modification of the conjugated enyne core structures has not been well investigated. We focused on nonconjugated polyenyne systems and found that nonconjugated aryl-ynes and aryl-yne-allenes undergo thermal cycloaromatization (CA) reactions [9][10][11][12][13][14] while cleaving DNA. [15][16][17] Thus, as a next goal, we set a reagent-free thermal isomerization of nonconjugated aryl-yne systems, which involves homolyses of carbon-nitrogen (C-N) unsaturated bonds to afford useful azaaromatic compounds via a domino radical reaction. 18)As target polycyclic aromatic compounds, we focused on dibenzonaphthyridine derivatives, which have never been synthesized via thermal isomerization of aryl-ynes, despite their fascinating and intriguing pharmacological properties. [19][20][21][22][23] In order to provide a novel synthetic methodology of dibenzonaphthyridines, we planned to examine the CA reactions of nonconjugated aryl-yne-carbodiimides (AYCs). Carbodiimide is considered to be an aza-equivalent of allene, and more importantly, canceled dipole moments of C-N bonds are expected to facilitate the homolytic cleavage of the C-N bond to form radical species. The Wang [24][25][26][27][28] and the Schmittel 29-31) groups have recently reported the thermal CA of AYCs, but their scopes are limited to conjugated systems, whose electronic and steric environments are far different from nonconjugated ones, and which would be unable to provide dibenzonaphthyridine derivatives. Herein, we report the synthesis and the CA reactions of AYCs 1 and 2.As AYC substrates, we selected two compounds (Fig. 1). One possesses a conjugated aryl-yne and a dependent carbodiimide moiety (1) and the other is equipped with a conjugated aryl-carbodiimide and a dependent alkyne moiety (2).Synthesis of AYC 1 commenced with 2-bromobenzylamine hydrochloride 3 (Chart 1). After tert-butoxycarbonyl (Boc) protection of 3 (98%), the resulting bromobenzene 4 was coupled with ethynylbenzene 5 under Sonogashira-Hagihara conditions 32,33) to give 6 in good yield (90%). 34) After removal of the Boc group with trifluoroacetic acid (TFA), amine 7 was converted to the corresponding thiourea 8 by the action of phenyl isothiocyanate in refluxing acetone (69%).35) Desulfurization of 8 by treatment with methanesulfonyl chloride (MsCl) in the presence of triethylamine and 4-dimethylaminopyridine (DMAP) 36) successfully furnished carbodiimide 1 (84%). As for AYC 2, the synthesis was initiated with 2-aminobenzylalcohol 9. Oxidation of alcohol 9 with MnO 2 into aldehyde, followed by addition of phenyleth...

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1992

Chemistry of Heterocyclic Compounds: A Series of Monographs

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Cyclic amidines. Part 26. The reported syntheses of 7-anilino-6-aryl-5,12-diazabenz[a]anthracenes are reinvestigated and their correct structures identified

Cited by 8 publications

References 3 publications

Novel 5,8-Diazabenzo[c]phenanthrenes: Synthesis and Mutagenicity

Novel 5,8-Diazabenzo[c]phenanthrenes: Synthesis and Mutagenicity

Thermal Cyclization of Nonconjugated Aryl-Yne-Carbodiimide Furnishing a Dibenzonaphthyridine Derivative

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