65945-06-4Relevant articles and documents
Intramolecular gold(III) catalysed Diels-Alder reaction of 1-(2-furyl)-hex-1-en-5-yn-3-ol derivatives: A short and generalised route for the synthesis of hydroxyphenanthrene derivatives
Samanta, Khokan,Kar, Gandhi K.,Sarkar, Achintya K.
, p. 1376 - 1379 (2012/04/04)
Gold(III) catalysed intramolecular Diels-Alder reaction of various 1-(2-furyl)-hex-1-en-5-yn-3-ol derivatives has been studied to synthesise hydroxyphenanthrenes and other polynuclear aromatic hydroxyl compounds. The required precursors were synthesised by indium mediated propargylation of suitable β-furyl-α,β-unsaturated aldehydes.
A new efficient route to the phenolic derivatives of chrysene and 5-methylchrysene, precursors to dihydrodiol and diol epoxide metabolites of chrysene and 5-methylchrysene, through Suzuki cross-coupling reaction
Kumar, Subodh
, p. 3157 - 3161 (2007/10/03)
A new, abbreviated synthesis of 5-methylchrysene (17), 2-hydroxychrysene (16), 8-hydroxy-5-methylchrysene (23), and 2-hydroxy-5-methylchrysene (24) is reported. The phenolic derivatives 16, 23, and 24 can easily be converted to carcinogenic dihydrodiol and diol epoxide metabolites of chrysene and 5-methylchrysene. The method entails the initial Suzuki cross-coupling reaction of naphthalene-2-boronic acid (1) and/or 6-methoxynaphthalene-2-boronic acid (2) with 2-bromo-5-methoxybenzaldehyde (3), methyl 2-bromophenylacetate (4), 2-bromophenylacetone (5), and/or 2-iodo-5-methoxyphenylacetone (6) to produce 2-(2-naphthyl)-5-methoxybenzaldehyde (7), methyl 2-(6-methoxy-2-naphthyl)phenylacetate (8), 2-(2-naphthyl)phenylacetone (9), 2-(2-naphthyl)-5-methoxyphenylacetone (10), and 2-(6-methoxy-2-naphthyl)phenylacetone (11) in 55-98% yields. 2-Methoxychrysene (15) was obtained with high regioselectivity by two different procedures. In the first procedure, the aldehyde function of 7 was elongated with trimethylsulfonium iodide under phase transfer conditions to generate the ethylene oxide 12 which after methanesulfonic acid treatment produced 15. The second procedure involved modification of ester 8 to its aldehyde analogue 14 which was subsequently treated with methanesulfonic acid to produce 15. Phenylacetone 10 was converted by methanesulfonic acid treatment into 8-methoxy-5-methylchrysene (18) with 90% regioselectivity. However, the similar cyclization of phenylacetones 9 and 11 to 5-methylchrysene (17) and 2-methoxy-5-methylchrysene (19) occurred with only 33-50% regioselectivity. The separation of 17 and 19 from their chromatographically similar 6-methylbenz[a]anthracene byproducts 20 and 22 was readily achieved by a chemical method. The methoxy derivatives of chrysene were finally demethylated with boron tribromide to the corresponding phenolic compounds in 90-98% yields.
Synthesis of the Dihydrodiol and Diol Epoxide Metabolites of Chrysene and 5-Methylchrysene
Harvey, Ronald G.,Pataki, John,Lee, Hongmee
, p. 1407 - 1412 (2007/10/02)
Carcinogenic polycyclic aromatic hydrocarbons are known to undergo enzymatic activation to diol epoxide metabolites bearing an epoxide ring in a bay molecular region.Introduction of a methyl group into a nonbenzo bay region position generally enhances carcinogenic activity.We now report efficient syntheses of the diasteromeric anti and syn bay region diol epoxide derivatives of both chrysene and 5-methylchrysene (5-MC) in both bay regions.The anti- and syn-1,2-diol-3,4-epoxide derivatives of 5-MC (1b and 2b) are the first examples of synthetic diol epoxides with a methyl group in the same bay region as the epoxide ring.NMR analysis indicates that these diol epoxide derivatives and the related dihydrodiols, with the exception of 2b and the syn-7,8-diol-9,10-epoxide of 5-methylchrysene (2c), exist preferentially in the diequational conformation in solution; 2b and 2c show a slight predominance of the diaxial conformer.All the synthetic diol epoxides were sufficiently stable to conduct biological experiments on tumorigenicity and DNA binding on mouse skin; the results confirm that 1b is the major active carcinogenic form of 5-methylchrysene which binds covalently to DNA in vivo.
