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首页> 外文期刊>Chemistry: A European journal >Sequential Formation of Yellow,Red,and Orange 1-Phenyl-3,3-Biphenylene-Allene Dimers Prior to Blue Tetracene Formation:Helicity Reversal in trans-3,4-Diphenyl-1,2-bis(fluorenylidene)cyclobutane
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Sequential Formation of Yellow,Red,and Orange 1-Phenyl-3,3-Biphenylene-Allene Dimers Prior to Blue Tetracene Formation:Helicity Reversal in trans-3,4-Diphenyl-1,2-bis(fluorenylidene)cyclobutane

机译：黄色，红色和橙色的1-苯基-3,3-联苯-丙二烯二聚体在蓝色四烯形成之前的顺序形成：反式-3,4-二苯基-1,2-双（芴基）环丁烷中的螺旋速率逆转

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1-Phenyl-3,3-biphenylene-allene (2),the base-catalyzed rearrangement product of 9-phenylethynylfluor-ene (1) yields a yellow,head-to-tail dimer 6 that,upon gentle warming,is converted to the red tail-to-tail isomer trans-3,4-diphenyl-1,2-bis(fluorenyl-idene)cyclobutane (7),in which the two fluorenylidene moieties severely overlap.The helical sense of the fluorenylidene moieties in 7 matches that of the phenyl substituents,and the interplanar angle between the fluorenylidene moieties is 41 deg.At 80 deg C,6 isomerizes to orange cis-3,4-diphenyl-1,2-bis(fluore-nylidene)cyclobutane (8),which at 110 deg C is converted to orange trans dia-stereomer 9,whereby the helicity of the overlapping fluorenylidene moieties is reversed from that in 7 such that they are aligned with the ring hydrogen atoms,and the interplanar angle between the fluorenylidene moieties is now 60 deg.At 180 deg C,6 rearranges to di-spirodihydrotetracene 3 and blue,electroluminescent diindenotetracene 4,which is readily oxidized to peroxide 5.In the solid state,both 3 and 4 adopt structures with C_i symmetry (only an inversion center) such that the central polycyclic framework is nonplanar.De-protonation of yellow head-to-tail allene dimer 6 with tBuOK in DMSO and reprotonation with HOAc yields the [1,3]-hydrogen migration product 10,in which the proton originally on the cyclobutane ring is now sited at C9 on the exocyclic fluorenyl substituent.Analogously,deprotonation and reprotonation of orange dimer 9 furnishes [1,3]-hydrogen migration product 11.Side product 17,formed during the synthesis of 1 from 9-phenylethynyl-fluoren-9-ol,BF_3 and Et_3SiH,was shown to be a silyl-indene spiro-linked to C9 of fluorene.All products were characterized by NMR spectroscopy and X-ray crystallography,and the mechanisms of these interconversions are discussed.
机译：1-苯基-3,3-联苯撑亚丙基（2），9-苯基乙炔基芴（1）的碱催化重排产物，产生黄色的头对尾二聚体6，该化合物在温和升温下转化为红色尾到尾异构体反式-3,4-二苯基-1,2-双（芴基-亚芳基）环丁烷（7），其中两个芴基基团严重重叠.7个匹配基团中的芴基的螺旋意义芴基部分之间的平面角为41度。在80摄氏度下，6异构化为橙色的顺式3,4-二苯基-1,2-双（氟-亚萘基）环丁烷（8），它在110℃转化为橙色的反式对-对映异构体9，从而重叠的芴基部分的螺旋度与7中的相反，使得它们与环氢原子对齐，并且芴基部分之间的平面角为60度，在180度，6重排为双螺并二茂铁3和蓝色，电致发光二茚四烯4，很容易被氧化被氧化为过氧化物5。在固态下，3和4都采用具有C_i对称性的结构（仅是一个反转中心），使得中心多环骨架是非平面的。tBuOK中的黄色头对尾异戊二烯二聚体6的去质子化DMSO和HOAc的质子化反应产生[1,3]氢迁移产物10，其中原来位于环丁烷环上的质子现在位于环外芴基取代基上的C9。类似地，橙色二聚体9的去质子化和质子化[1]。 ，3]-氢迁移产物11。由9-苯基乙炔基-芴-9-ol，BF_3和Et_3SiH合成1时形成的副产物17被显示为与芴的C9螺旋连接的甲硅烷基-茚。通过NMR光谱和X射线晶体学对所有产物进行了表征，并讨论了这些相互转化的机理。

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