A comparative study in the xanthone series Part I
A comparative study in the xanthone series Part I
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DOI：
10.1039/ct9201701053
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发表时间：
1920-01-01
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影响因子：
--
通讯作者：
Dhar, SN
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作者：
Dhar, SN
1054达尔：一项比较研究偶然提出了相同的quehon（“，天然有机着色物质，”页。126-127）。他们将茜素与3：4-二氢氧杂蒽酮进行了比较，但事实上，1：2-二羟基氧杂蒽酮而不是3：4-衍生物与茜素进行了比较。尝试6合成1：2-二羟基口山酮，并将其应用于二步反应中。同时，还对硝化、直接置换、硝化、硝化、直接置换、硝基被卤素、甲氧基等取代，还有其他重要的！与硝基化合物的关系，如Skraup的合成，Doebnes和米勒的合成，Knorr的合成等; (3)卤化;（4）卤原子的迁移率;（5）重氮基团的迁移。有趣的是，人们发现吨酮比蒽醌的反应活性要高得多。因此，仅用硝酸！氧杂蒽酮给出两个二硝基氧杂蒽酮（A和P），而蒽醌仅给出一个硝基衍生物（Bey.，1883，16，363）。此外，相当多的三硝基和四硝基氧杂蒽酮已很容易地被制备出来，而蒽醌的这种多硝基衍生物尚不为人所知，二硝基化合物的进一步硝化也尚未实现。氧杂蒽酮似乎不仅反应活性更高，而且也更稳定，虽然从它们的结构上看，这是完全没有预料到的。氧杂蒽酮与氢氧化钾熔融后分解为1：1 '-二羟基苯并吡喃酮，而其中一个羟基苯并吡喃酮与两个苯甲酸分子形成艾德。同样地，当用硝酸和硫酸的混合物进一步硝化1：5-或1：8-二硝基蒽醌时，它们完全分解，而α-和β-二硝基氧杂蒽酮都在硝化的早期转化为四硝基氧杂蒽酮，产物在随后的硝化中不分解。还可以注意到，四溴氧杂蒽酮被硝化并且不被这种混合物分解（达尔，T.，1916，109，740）。
1054 DHAR: A COMPARATIVE STUDY have incidentally raisd the same quehon (“The, Natural Organic Colouring Matters,” pp. 126-127). They compare1 alizarin with 3: 4-dihydrosyxanthone, but, rn a matter of fact, 1: 2-dihydroxyxanthonel, and not the) 3: 4-derivative, colrreaponds with alizarin. Attempt6 are being made tot synthesise 1: 2-dihydroxyxanthone, and the reaults will be uommunicated in duel course. At the same time, a systelmatia comparison is being attemptetd in the, following directions:(1) nitration;(2) direct displacetment? of nitro-groups by halogens, methaxy-group, etc., and certain other important! relaotions with nitro-compounds, such as Skraup’s synthesis, Doebnes and Miller’s and Knorr’s syntheses, etc.;(3) halogenation;(4) mobility of halogen atoms;(5) migration of diazogroups.It is interestling to notel that xanthonel has been found to he much more reactive than antthraquinone~. Thus with nitric acid alone!, xanthone giveis two dinitroxanthones (a and P), whereas anthraquinone gives a motnonitro-derivative only (Bey., 1883, 16, 363). Again, quite a number of tri-and tstra-nitroxanthones have very easily been prelpared, whilst no such polynitro-derivativea of anthraquinonel are known, and further nitration of the dinitro-compounds has not yet been effecteld. Xanthone seems notl only to be more reactivel, but, also more stable, altjhough from the structure of theisel compounds such a fact is quite unelxpected. It is well known that wheln fuseid with potassium hydroxide, xanthone decomposes into 1: 1’-dihydroxyb eln z op h e n o ne, wh elreas an th ra qu in on e is co m pl etd yd egr ad ed to two molecules of benzoic acid. Similarly, itl has beeln found that when furthelr nitration of 1: 5-or 1: 8-dinitroanthraquinone is attempted with mixtures of nitria and sulpliuric acids, they decom-pose completely, whilst both a-and P-dinit4rolxanthones are convelrted into tekranitroxanthones at an earlielr stage of such a treatr ment, and the products are not, decomposed on subsequent trelatment. It may also be nolted that tetrabromoxanthonel is nitrated and not decomposed by such a mixture (Dhar, T., 1916, 109, 740).