Magnesium Adducts of Substituted Anthracenes – Preparation and Properties
Magnesium Adducts of Substituted Anthracenes – Preparation and Properties
复制标题
取代蒽的镁加合物 – 制备和性能
DOI：
10.1002/cber.19901230713
复制
发表时间：
1990
期刊：
影响因子：
--
通讯作者：
J. Treber
中科院分区：
文献类型：
--
作者：
B. Bogdanovic;Nikolaus Janke;Hans‐Georg Kinzelmann;K. Seevogel;J. Treber
2-甲基-、1，4-二甲基-、9-甲基-、9-乙基-、9，10-二甲基-和9-苯基蒽（1a-f）与镁在THF中在室温下反应，得到相应的取代镁蒽2a-i。然而，9，10-二苯基蒽（1g）在相同条件下与镁反应生成深蓝色的双（9，10-二苯基蒽）镁· 6 THF（4g）。在THF中加热至60°C时，4g可逆地解离以得到镁9，10-二苯基蒽· 3 THF（2g）和Ig，而在60°C下长时间加热导致2g分解成活性镁（Mg*）和Ig。在THF中，2a-c、e和f与1a-c、e和f以及镁表现出依赖于温度的平衡。与蒽镁· 3 THF（2）相比，这些平衡强烈地向取代的蒽和镁移动，并且仅在0°C下实现高转化率。实验证实了2与取代蒽1a、B和f在THF中的镁交换。2a、e和f与有机卤化物以与2相同的方式反应，然而，在烯丙基、炔丙基和苄基氯的情况下，格氏化合物的产率低于2;与溴苯一起，自由基转移反应的趋势比2强。9，10-二甲基蒽镁（2 e）与乙酸乙酯通过分子内C-C偶联反应生成双环叔醇9。
2-Methyl-, 1,4-dimethyl-, 9-methyl-, 9-ethyl-, 9,10-dimethyl-, and 9-phenylanthracene (1a–f) react with magnesium in THF at room temperature to afford the corresponding substituted magnesium anthracenes 2a-i. 9,10-Diphenylanthracene (1g), however, reacts with magnesium under the same conditions to produce the deep-blue magnesium bis(9,10-diphenylanthracenide) · 6 THF (4g). Upon heating to 60°C in THF, 4g reversibly dissociated to give magnesium 9,10-diphenylanthracene · 3 THF (2g) and 1g, while prolonged heating at 60°C causes decomposition of 2g to active magnesium (Mg*) and 1g. In THF 2a–c, e, and f exhibit temperature-dependent equilibria with 1a–c, e, and f and magnesium. Compared with magnesium anthracene · 3 THF (2), these equilibria are strongly shifted toward substituted anthracenes and magnesium, and only at 0°C high conversions are achieved. The magnesium exchange between 2 and the substituted anthracenes 1a,b, and f in THF has been experimentally verified. 2a,e, and f react with organic halides in the same way as 2, however, in the case of allyl, propargyl, and benzyl chloride the yields of Grignard compounds are lower than for 2; with bromobenzene, the tendency for the radical transfer reaction is stronger than for 2. Magnesium 9,10-dimethylanthracene (2e) reacts with ethyl acetate to give the bicyclic tertiary alcohol 9 by an intramolecular C–C coupling reaction.