(+/-)-7-methyldinaphtho<2,1-b;1',2'-d>phosphole | 149639-51-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (+/-)-7-methyldinaphtho<2,1-b;1',2'-d>phosphole
• 英文别名: 12-Methyl-12-phosphapentacyclo[11.8.0.02,11.03,8.016,21]henicosa-1(13),2(11),3,5,7,9,14,16,18,20-decaene
• CAS: 149639-51-0；156854-47-6
• 化学式: C₂₁H₁₅P
• 分子量: 298.324
• InChiKey: YOGYACOGGCKPLR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (+/-)-7-methyldinaphtho<2,1-b;1',2'-d>phosphole 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以92%的产率得到7-methyldinaphtho<2,1-b:1',2'-d>phosphole oxide
  参考文献：
  名称：

  Synthesis, Crystal Structure, Dynamic Behavior and Reactivity of Dinaphtho[2,1-b:1',2'-d]phospholes and Related Atropisomeric Phosphacyclic Derivatives

  摘要：

  7-Phenyldinaphtho[2,1-b:1',2'-d]phosphole (1b) has been prepared by reaction of dichlorophenylphosphine either with 2,2'-dilithio-1,1'-binaphthalene or with bis-dialin 7. In the latter case the relevant tetrahydro derivative 8 is formed at the same time. Displacement of the phenyl substituent in Ib by alkyl groups can be accomplished through a dephenylation-alkylation protocol involving a lithium-promoted phosphole anion formation. By this way the unsubstituted phosphole la and a variety of alkyl-substituted derivatives have been prepared. The X-ray crystal structure of Ib shows an intracyclic C-P-C angle of 89.3 degrees indicating that phosphole ring is strained. Alkylphospholium iodides 4 undergo ready ring opening by reaction with LiAlH4 or other nucleophiles under mild conditions affording with fair diastereoselectivities (2-(1,1'-binaphthylyl))substituted phosphines 5 or phosphines oxides 6, respectively. Dinaphthophospholes 1 are fluxional at ambient temperature because of the rapid interconversion of the atropisomeric conformers. Line shape analysis of the variable temperature NMR spectra lead to estimation of an energy barrier of 55-60 kJ mol(-1) for this process. Fluxionality is maintained both when the phosphorus center is tetrasubstituted, like in the relevant oxides 2, and when it is coordinated to a transition metal, like in the Pd-complexes 10. On the contrary, P-substituted dinaphthophosphepines 9 do not undergo atropisomerization even well above room temperature and can be successfully resolved under ambient conditions. The crystal structures of the P-phenyl-substituted derivatives 1b, 8 and 9a, as determined by X-ray diffraction, show remarkable differences in the relative disposition of the naphthalene rings.

  DOI：

  10.1021/jo00100a044
• 作为产物：
  描述：

  2,2-二溴-1,1-联萘 在 正丁基锂 、 lithium 作用下， 生成 (+/-)-7-methyldinaphtho<2,1-b;1',2'-d>phosphole
  参考文献：
  名称：

  Dinaphtho[2,1-b; 1′,2′-d]phospholes: a new class of atropisomeric phosphorus ligands

  摘要：

  母体和一些烷基和芳基取代的二萘并[2,1-b； 1-,2-d]磷化合物 1 已被合成并显示在室温以下具有阻转异构性稳定。

  DOI：

  10.1039/c39930001124

文献信息

• Atropisomerism in (±)-7-methyl- and -phenyl-substituted dinaphtho[2,1-b;1′,2′-d]phospholes and dinaphth[2,1-b;1′,2′-d]arsoles
  作者：Andrew A. Watson、Anthony C. Willis、S.Bruce Wild

  DOI：10.1016/0022-328x(93)80189-i

  日期：1993.2

  dinaphtho[2,1-b;1′,2′-d]phospholes and dinaphth[2,1-b:1′,2′-d]arsoles. The molecules are fluxional on the NMR time scale with similar barriers between the conformational isomers (atropisomers) for the four compounds, vis. †G‡ = 56 ± 1 (243 K, ER = PMe), 56 ± 1 (254 K, ER = PPh), 65 ± 1 (287 K, ER = AsMe), 59 ± 1 (259 K, ER = AsPh) kJ mol−1. An X-ray diffraction study of (S)-7-phenyldinaphth[2,1-b;1′,2′-d]arsole

  2，2'-二硫代-1,1'-联萘与RECl 2（E = P或As； R = Me或Ph）反应，得到相应的（±）-7-取代的萘并[2,1- b]； 1'，2'- d ]磷脂和dinaphth [2,1- b：1'，2'- d ]鞋底。该分子可用于四种化合物fluxional上与构象异构体（阻转异构体）之间类似屏障的NMR时间尺度，可见。† G ‡= 56±1（243 K，ER = PMe），56±1（254 K，ER = PPh），65±1（287 K，ER = AsMe），59±1（259 K，ER = AsPh） ）kJ mol -1。（S）-7-苯基二萘酚[2,1- b ; 1'，2'- d的X射线衍射研究通过自发析出结晶的] arsole揭示了扭曲的萘基残基彼此明显弯曲。不对称unidentates（±）-L坐标中的类型的复合物的铁（II）[（η 5 -C 5 H ^ 5）〔1,2-C
• Gladiali Serafino, Dore Antonio, Fabbri Davide, De Lucchi Ottorino, Valle+, J. Org. Chem, 59 (1994) N 21, S 6363-6371
  作者：Gladiali Serafino, Dore Antonio, Fabbri Davide, De Lucchi Ottorino, Valle+

  DOI：——

  日期：——
• KOMPLEXVERBINDUNGEN MIT ANIONISCHEN LIGANDEN MIT ZWEI P-DONOREN UND IHRE VERWENDUNG IM OPTO-ELEKTRONISCHEN BEREICH
  申请人：Merck Patent GmbH

  公开号：EP2737004B1

  公开（公告）日：2016-05-04
• US7704912B2
  申请人：——

  公开号：US7704912B2

  公开（公告）日：2010-04-27
• [DE] KOMPLEXVERBINDUNGEN MIT VIERZÄHNIGEN LIGANDEN UND IHRE VERWENDUNG IM OPTO-ELEKTRONISCHEN BEREICH<br/>[EN] COMPLEX COMPOUNDS HAVING TETRADENTATE LIGANDS AND USE THEREOF IN THE OPTOELECTRONIC FIELD<br/>[FR] COMPOSÉS DE TYPE COMPLEXES COMPORTANT DES LIGANDS TÉTRADENTÉS ET LEUR UTILISATION DANS LE DOMAINE DE L'OPTOÉLECTRONIQUE
  申请人：UNIV EBERHARD KARLS

  公开号：WO2013014048A1

  公开（公告）日：2013-01-31

  Beschrieben werden elektronische Vorrichtungen, enthaltend eine Metallkomplexverbindung mit mindestens einem vierzahnigen Liganden mit N- und/ oder P-Donoren, insbesondere einen Liganden mit PPPP-, NNNN-, PNNP- oder NPPN-Struktur, sowie Verwendungen eines solchen Komplexes im elektronischen Bereich sowie zur Erzeugung von Licht.