Novel annulene dications from methylated [2.2]metacyclophane monoenes and [e]-ring benzannelated dimethyldihydropyrene.
Novel annulene dications from methylated [2.2]metacyclophane monoenes and [e]-ring benzannelated dimethyldihydropyrene.
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来自甲基化[2.2]偏环芳单烯和[e]-环苯并二甲基二氢芘的新型轮烯双键。
DOI：
10.1021/jo0100594
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
Ward,TR
中科院分区：
文献类型：
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作者：
Laali,KK;Okazaki,T;Mitchell,RH;Ward,TR
以SO2ClF或SO2为溶剂，在FSO3H·SbF5(4：1)和FSO3H·SbF5(1：1)中，将四甲基和六甲基取代的[2，2]偏环芳烃单烯(10和11)转化为correspondingtrans-dimethyldihydroethanophenanthrenium式(142+和152+)，这10个π式相当于反式-DMDHP3a的2，7-二甲基衍生物的C-4/C-5二质子化反应。Thetrans-12c，12d-dimethyl-12c，12d-dihydrobenzo[e]pyrene(6)与FSO_3H/SO_2ClF在非常温和的条件下反应，首先得到持久的双质子化阳离子(6H22+)，然后是氧化阳离子(62+)，低温一周后，62+：6H22+的比例达到4：1。还考察了反偏环膦(13)的质子化反应。通过500 MHz下详细的核磁共振研究，测量了结果中的电荷离域模式和热带性。
Tetramethyl- and hexamethyl-substituted [2.2]metacyclophane monoenes (10and11) are transformed into their correspondingtrans-dimethyldihydroethanophenanthrenium dications (142+and152+)in FSO3H·SbF5(4:1) and FSO3H·SbF5(1:1) with SO2ClF or SO2as the solvent; these 10π-dications are equivalent to the C-4/C-5 diprotonated dications of the 2,7-dimethyl derivative oftrans-DMDHP,3a. Thetrans-12c,12d-dimethyl-12c,12d-dihydrobenzo[e]pyrene (6) reacts with FSO3H/SO2ClF under surprisingly mild conditions to give initially a persistent diprotonated dication (6H22+) and, subsequently, the oxidation dication (62+); the62+:6H22+ratio reaches 4:1 after 1 week at low temperature. Protonation of theanti-metacyclophane (13) was also examined. Charge delocalization mode and tropicity in the resulting dications are gauged via detailed NMR studies at 500 MHz.