Anthraquinone (AQ) derivatives play a prominent role in medicine and also in textile industry. Bromaminic acid (1-amino-4-bromoanthraquinone-2-sulfonic acid) is an important precursor for obtaining dyes as well as biologically active compounds through the replacement of the C4-bromo substituent with different (ar)alkylamino residues. Here we report methods for the synthesis of bromaminic acid analogues bearing different substituents at the 2-position of the anthraquinone core. 1-Aminoanthraquinone was converted to its 2-hydroxymethyl-substituted derivative which, under different reaction conditions, yielded the corresponding carbaldehyde, carboxylic acid, and nitrile derivatives. The latter was further reacted to obtain 1-amino-2-tetrazolylanthraquinone. Subsequent bromination using bromine in DMF led to the corresponding bromaminic acid derivatives in excellent isolated yields (>90%) and high purities. Alternatively, 1-amino-4-bromo-2-hydroxymethylanthraquinone could be directly converted to the desired 2-substituted bromaminic acid analogues in high yields (85-100%). We additionally report the preparation of bromaminic acid sodium salt and 1-amino-2,4-dibromoanthraquinone directly from 1-aminoanthraquinone in excellent yields (94-100%) and high purities. The synthesized brominated AQs are valuable precursors for the preparation of AQ drugs and dyes.

中文翻译：

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2-取代的1-氨基-4-溴代蒽醌（溴酸类似物）的合成-染料和药物的前体。

蒽醌（AQ）衍生物在医学和纺织工业中起着重要作用。溴酸（1-氨基-4-溴蒽醌-2-磺酸）是通过将C4-溴取代基替换为不同的（芳）烷基氨基残基而获得染料以及生物活性化合物的重要前体。在这里，我们报告了在蒽醌核心的2位带有不同取代基的溴酸类似物的合成方法。将1-氨基蒽醌转化为其2-羟甲基取代的衍生物，在不同的反应条件下，得到相应的甲醛，羧酸和腈衍生物。后者进一步反应以获得1-氨基-2-四唑基蒽醌。随后在DMF中使用溴进行溴化，可得到具有优异分离产率（> 90％）和高纯度的相应溴酸衍生物。或者，可以高产率（85-100％）将1-氨基-4-溴-2-羟基甲基蒽醌直接转化为所需的2-取代的溴酸类似物。我们还报告了直接从1-氨基蒽醌制备溴代乙酸钠盐和1-氨基2,4-二溴蒽醌的方法，收率很高（94-100％），纯度很高。合成的溴化AQ是制备AQ药物和染料的有价值的前体。我们还报告了直接从1-氨基蒽醌制备溴代乙酸钠盐和1-氨基2,4-二溴蒽醌的方法，收率很高（94-100％），纯度很高。合成的溴化AQ是制备AQ药物和染料的有价值的前体。我们还报告了直接从1-氨基蒽醌制备溴代乙酸钠盐和1-氨基2,4-二溴蒽醌的方法，收率很高（94-100％），纯度很高。合成的溴化AQ是制备AQ药物和染料的有价值的前体。