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本文报告脱二甲胺地霉红(Ⅰ)合成工作中两种有用中间体4-甲基-8-甲氧基萘酚-[1](Ⅵ)和1,8-二甲氧基-4-甲基萘甲酸-[2](Ⅶ)的合成以及其结构的证明。 4-甲基-8-甲氧基萘酚-[1](Ⅳ)可从两条途径合成:其一由8-甲氧基萘酚-[1](Ⅱ)经Gattermann醛合成及黄鸣龙改良Kishner-Wolff还原法而得。另一途径由2-氯-5-甲氧基苯甲酰氯(Ⅷ)经八步反应,首先获得4-甲基-5-氯-8-甲氧基四氢萘酮-[1](ⅩⅥ),其中每步反应都分离得到纯粹的产物。将ⅩⅥ经溴化,脱溴化氢及氢解反应便生成化合物(Ⅳ)。从这两途径所得的最后产物(Ⅳ)性质完全相同。 1,8-二甲氧基-4-甲基萘甲酸-[2](Ⅶ)乃由化合物Ⅳ引入溴原子,甲基化后,经金属-卤素的交换及羧基化而得。Ⅶ的结构证明如下;化合物(ⅩⅥ)经二溴化及脱溴化氢、甲基化后,生成1,8-二甲氧基-2-溴-4-甲基-5-氯萘(ⅩⅩ),另一方面,将Ⅵ氯化以期获得ⅩⅩ,却得到2,4-二氯-5-甲基-7-溴-8-甲氧基萘酚-[1](ⅩⅪ)。由于将ⅩⅩ氯化亦得到ⅩⅪ,化合物Ⅵ中溴的位置得到证明,因此Ⅶ的结构也予以肯定。
In this paper, two useful intermediates 4-methyl-8-methoxynaphthol- [1] (Ⅵ) and 1,8-dimethoxy-4 - methylnaphthoic acid - [2] (Ⅶ) and its structure proved. 4-Methyl-8-methoxynaphthol- [1] (IV) can be synthesized in two ways: one is synthesized from 8-methoxynaphthol- [1] (II) via Gatter- Kishner-Wolff reduction derived. The other way is to obtain 4-methyl-5-chloro-8-methoxytetralone [1] (XVI) from 8-chloro-5-methoxybenzoyl chloride ), Where each reaction separates to give pure product. Bromination of XVI, dehydrobromination and hydrogenolysis yields compound (IV). The final products (IV) obtained from these two approaches are of the same nature. 1,8-Dimethoxy-4-methylnaphthoic acid - [2] (VII) is the introduction of bromine atom from compound Ⅳ, after methylation, it is obtained through metal-halogen exchange and carboxylation. The structure of VII is shown below. The compound (XVI) is methylated by dibromination and dehydrobromination to give 1,8-dimethoxy-2-bromo-4-methyl-5-chloronaphthalene (XX ), On the other hand, chlorination of VI to obtain XX gives 2,4-dichloro-5-methyl-7-bromo-8-methoxynaphthol- [1] (XXI). Since XX is also chlorinated to give XXI, the position of bromine in compound VI is evidenced, and the structure of VII is also affirmed.