ARENE SYNTHESIS BY EXTRUSION REACTION. PART 8. SYNTHESIS OF 1,2:7,8-DIBENZO(2.2)PARACYCLOPHANE AND 1,2-BENZO-7,8-NAPHTHO(2.2)PARACYCLOPHANE
ARENE SYNTHESIS BY EXTRUSION REACTION. PART 8. SYNTHESIS OF 1,2:7,8-DIBENZO(2.2)PARACYCLOPHANE AND 1,2-BENZO-7,8-NAPHTHO(2.2)PARACYCLOPHANE
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通过挤出反应合成芳烃。
DOI：
10.1002/chin.198547168
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发表时间：
1985
期刊：
影响因子：
--
通讯作者：
H. Wong
中科院分区：
文献类型：
--
作者：
Chin;H. Wong
作为一种理论上有趣但未知的物质。在结构上，环烷1具有正交苯环，因此有望表现出有趣的化学和物理性质。此外，它可能作为金属络合的新型配体，也可能在笼形物包合现象中作为宿主分子。1978年，Jacobson和boekelheided报道了2,5的分离和鉴定，1982年，Psiorz和Hopf报道了一种难以识别的中间体3.6的鉴定。在他们的策略的基础上，我们在这里报道了1和1,2 -苯并- 7,8 -萘[2.2]对环己烷的成功合成（11）。用大量过量的iv -溴代琥珀酰亚胺处理已知的环烷45" 8，得到二溴5，产率为30%（方案一），分离为白色晶体，9mp 223-225℃；* H NMR 4.71 (s, 2), 6.50-6.70 (m, 4), 6.70-7.30 (AA' xx ', 4 H), 7.30-7.70 （A2B2, 4 H）。在THE中，5与-Bu的脱氢溴化可能导致逸出的环苯6与呋喃(7)在原位捕获，以15%的产率生成内氧化物8（方案II）： mp 203-205 C, H NMR 5.83 (s, 2), 6.10-6.60，中心为6.36
1 2 3 as a theoretically interesting but unknown substance. 3 Struc-turally, cyclophane 1 possesses orthogonal benzene rings and therefore is expected to exhibit interesting chemical as well as physical properties. Moreover, it may serve as a novel ligand for metal complexation and it is also possible that it may behave as a host molecule in clathrate inclusion phenomenon. 4 In 1978, Jacobson and Boekelheidereported the isolation and characterization of 2, 5 and in 1982, Psiorz and Hopf reported the identification of an elusive intermediate 3.6 7On the basis of their strategies, we here report the successful synthesis of 1 as well as l, 2-benzo-7, 8-naphtho [2.2] paracyclophane (11). Treatment of the known cyclophane 45" 8 with a large excess of iV-bromosuccinimide gave thedibromide 5 in 30% yield (Scheme I), isolated as white crystals, 9 mp 223-225 C;* H NMR 4.71 (s, 2), 6.50-6.70 (m, 4), 6.70-7.30 centered at 7.00 (AA'XX', 4 H), 7.30-7.70 (A2B2, 4 H). Dehydrobromination of 5 with--Bu in THE led presumably to the fugitive cyclophyne 6 which was trapped in situ with furan (7) to yield the endoxide8 in 15% yield (Scheme II): mp 203-205 C,’H NMR 5.83 (s, 2), 6.10-6.60 centered at 6.36