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.

中文翻译：

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通过铃木交叉偶联反应获得新的有效途径的苯和5-甲基苯酚的酚衍生物，即苯和苯甲基和5-甲基丙烯的二氢二醇和二醇环氧代谢物的前体

据报道，新合成了5-甲基（（17），2-羟基（（16），8-羟基-5-甲基ch（23）和2-羟基-5-甲基ch（24）。酚类衍生物16、23和24可以很容易地转化为致癌的二氢二醇和5-二甲基丙烯的二醇环氧化物代谢产物。该方法需要萘-2-硼酸（1）和/或6-甲氧基萘-2-硼酸（2）与2-溴-5-甲氧基苯甲醛（3）和2-溴苯基乙酸甲酯的初始Suzuki交叉偶联反应。 （4），2-溴苯基丙酮（5）和/或2-碘-5-甲氧基苯基丙酮（6）生成2-（2-萘基）-5-甲氧基苯甲醛（7），甲基2-（6-甲氧基-2 -萘基苯基乙酸酯（8），2-（2-萘基）苯基丙酮（9），2-（2-萘基）-5-甲氧基苯基丙酮（10）和2-（6-甲氧基-2-萘基）苯基丙酮（11 ），产率为55-98％。通过两种不同的方法以高区域选择性获得了2-甲氧基丙烯（15）。在第一个步骤中，在相转移条件下，用三甲基碘化碘延长7的醛官能度，生成环氧乙烷12，在甲磺酸处理后生成环氧乙烷12。第二个步骤涉及将酯8改性为其醛类似物14，随后对其进行处理用甲磺酸制备15。通过甲磺酸处理将苯丙酮10转化为具有90％区域选择性的8-甲氧基-5-甲基丙烯（18）。但是，类似的苯丙酮9和11环化成5-甲基丙烯（17）和2-甲氧基-5-甲基丙烯（19）的区域选择性只有33–50％。从色谱上相似的6-甲基苯中分离出17和19 [一个]蒽副产物20和22被容易地通过化学方法来实现。最终用三溴化硼将de的甲氧基衍生物脱甲基化为相应的酚类化合物，产率为90-98％。