FULVENE,FULVALENE .50. SYNTHESIS OF PENTAFULVALENE BY OXIDATIVE COUPLING OF CYCLOPENTADIENIDE WITH COPPER(II) CHLORIDE
FULVENE,FULVALENE .50. SYNTHESIS OF PENTAFULVALENE BY OXIDATIVE COUPLING OF CYCLOPENTADIENIDE WITH COPPER(II) CHLORIDE
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DOI：
10.1002/hlca.19860690719
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发表时间：
1986-01-01
影响因子：
1.8
通讯作者：
NEUENSCHWANDER, M
中科院分区：
文献类型：
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作者：
ESCHER, A;RUTSCH, W;NEUENSCHWANDER, M
环壬四烯与氯化铜氧化偶联合成五富瓦烯从环壬四烯7与1，1 ′-二氢壬富瓦烯8在AgBF 4作用下的近定量偶联反应出发，提出了一种简单的合成五富瓦烯的一般思路（方案2），包括用Ag（I）或Cu（II）盐将"Hückelanions"如2和7氧化偶联成1，1 ′-二氢富瓦烯10，随后是去质子化（→ 11）和氧化（→ 1,2）;在五富瓦烯（1;总产率61%;方案3）和1，2：5，6-二苯并五富瓦烯（18;总产率66%，方案4）的情况下已经实现。NMR光谱研究表明1是一种非芳香族化合物，具有强烈的交替键长，其π系统比简单的五富烯更局域化。事实上，1在− 50 °以上的浓溶液中具有极强的反应性。除了聚合反应，还发生Diels-Alder二聚反应1 → 19，随后发生再聚合反应19 → 20（方案5）。
Synthesis of Pentafulvalene by Oxidative Coupling of Cyclopentadienide with Copper(II) ChlorideStarting with a nearly quantitative coupling of cyclononatetraenide7to 1, 1′‐dihydrononafulvalene8by means of AgBF4, a simple general synthetic concept for fulvalenes is outlined (Scheme 2), consisting in an oxidative coupling of ‘Hückelanions’ like2and7to 1, 1′‐dihydrofulvalenes10with Ag(I) or Cu(II) salts, followed by deprotonation (→11) and oxidation (→12); it has been realised in the case of pentafulvalene (1; overall yield 61%;Scheme 3) and 1,2:5,6‐dibenzopentafulvalene (18; overall yield 66%,Scheme 4). NMR‐spectroscopic investigations show that1is a non‐aromatic compound with strongly alternating bond‐lengths, its π‐system being even more localised than that of simple pentafulvenes. In fact,1is extremely reactive in concentrated solutions above −50°. Besides of polymerisations,Diels‐Alderdimerisation1→19followed by a rearrangement19→20takes place (Scheme 5).