2,7-di-tert-butyl-trans-11b,11c-dimethyl-11b,11c-dihydropyreno[4,5-c]furan

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: 2,7-di-tert-butyl-trans-11b,11c-dimethyl-11b,11c-dihydropyreno[4,5-c]furan
• 英文别名: 2,7-di-t-butyl-trans-11b,11c-dimethyl-11b,11c-dihydropyreno[4,5-c]furan；(18R,19R)-9,16-ditert-butyl-18,19-dimethyl-4-oxapentacyclo[9.6.2.02,6.07,19.014,18]nonadeca-1(17),2,5,7,9,11,13,15-octaene
• 化学式: C₂₈H₃₂O
• 分子量: 384.561
• InChiKey: SDNFOEXEXSRSEM-VSGBNLITSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.6
• 重原子数：
  29
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  13.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,7-di-tert-butyl-trans-11b,11c-dimethyl-11b,11c-dihydropyreno[4,5-c]furan 在 diiron nonacarbonyl 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 26.5h， 生成 2,7-di-tert-butyl-10,11-dicarbomethoxy-12c,12d-dimethyl-trans-12c,12d-dihydrobenzo[e]pyrene
  参考文献：
  名称：

  Photoelectric Signal Conversion by Combination of Electron-Transfer Chain Catalytic Isomerization and Photoisomerization on Benzodimethyldihydropyrenes

  摘要：

  Photochromic benzocyclophanediene showed oxidation-triggered isomerization to form benzodimethyldihydropyrene. The isomerization proceeded via an autocatalytic reaction system, which could be combined with the photochromic nature of the molecule to establish a new photoelectric signal conversion system.

  DOI：

  10.1021/ja412528d
• 作为产物：
  描述：

  以 氘代甲苯 为溶剂， 生成 2,7-di-tert-butyl-trans-11b,11c-dimethyl-11b,11c-dihydropyreno[4,5-c]furan
  参考文献：
  名称：

  含有 [e]-退火二氢芘的分子的合成和光致变色特性。基于二甲基二氢芘-间环芳二烯价异构化的二元和三元π-开关

  摘要：

  描述了几种新的简单负片、一个简单正片和多个负片光致变色材料的合成，这些光色素包含二氢芘-环芳二烯光致变色系统。母体 2,7-di-的 [e]-退火苯并 (7)、萘并 (9)、蒽 (11)、呋喃 (19) 和三苯并 (15) 衍生物的光开孔叔丁基-反式 10b,10c-二甲基-二氢芘 (5) 及其 4,5-二溴衍生物 (13) 被描述为提供相应的环芳二烯，以及它们的光封闭和热封闭二氢芘。将这些与正性光致变色二苯并[e，l]二氢芘（21）和双（二氢芘）芘（44）和（二氢芘苯并）（苯并）间环芘（47）光致变色的结果进行比较，它们具有多个光致变色开关，因此不仅仅是简单的“开-关”状态。获得热闭合反应的热力学数据。蒽二氢芘 (12) 的热闭合速度最快 (tau(1/2) = 20 分钟)，而呋喃二氢芘 (19') 的热闭合最慢 (tau(1/2) = 63 h) 在 46 摄氏度。对苯并二氢芘 (7)

  DOI：

  10.1021/ja0288136

文献信息

• The synthesis of benz-, naphth-, and anth-annelated dihydropyrenes as aids to measuring aromaticity by NMR
  作者：Reginald H. Mitchell、Timothy R. Ward

  DOI：10.1016/s0040-4020(01)00233-2

  日期：2001.4

  anthro[e]-fused 2,7-di-t-butyl-trans-10b,10c-dimethyldihydropyrenes are synthesized via an ‘aryne–furan’ Diels–Alder reaction and the series used to establish a relative aromaticity scale for estimating resonance energies (bond localization energies) using NMR chemical shift data of the internal methyl protons of the dihydropyrenes.

  苯并[e] - ，萘并[E] -和椐人体并[e] -融合2,7-二吨丁基-反式基硫代，10C-dimethyldihydropyrenes经由'芳炔呋喃' Diels-Alder反应和合成系列用于建立相对芳香度标度，以使用二氢py烯内部甲基质子的NMR化学位移数据估算共振能（键定位能）。
• An experimental estimate of the relative aromaticity of the cyclooctatetraene dianion by fusion to dimethyldihydropyrene
  作者：Reginald H. Mitchell、Pengrong Zhang、David J. Berg、Richard Vaughan Williams

  DOI：10.1039/c2cc33518b

  日期：——

  The synthesis of the cyclooctatetraene dianion (COT(2-)) fused at the [e]-position of trans-10b,10c-dimethyl-10b,10c-dihydropyrene (DHP) is described, and by comparison of (1)H NMR properties and NICSAv to the analogous benzene fused DHP, the relative aromaticity of the dianion is found to be at least as great as that of benzene, and substantially larger than that of the cyclopentadienide anion.

  描述了在反式10b，10c-二甲基-10b，10c-二氢py（DHP）[e]-位[e]-位融合的环辛酸酯二价阴离子（COT（2-））的合成，并通过（1）H NMR比较根据与类似的苯稠DHP的性质和NICSAv相比，发现二价阴离子的相对芳香性至少与苯的芳香度一样大，并且比环戊二烯阴离子的芳香度大得多。
• Experimental Verification of the Homoaromaticity of 1,3,5-Cycloheptatriene and Evaluation of the Aromaticity of Tropone and the Tropylium Cation by Use of the Dimethyldihydropyrene Probe
  作者：Richard Vaughan Williams、W. Daniel Edwards、Pengrong Zhang、David J. Berg、Reginald H. Mitchell

  DOI：10.1021/ja306868r

  日期：2012.10.10

  shifts and nucleus-independent chemical shifts (NICS) support these conclusions. These estimates were obtained by synthesis of the annelated dihydropyrenes 7 (tropone fused), 9 (1,3,5-cycloheptatriene fused), and 10 (tropylium fused). [4 + 3] Cycloaddition of the isofuran 5 with an oxyallyl cation (prepared from 2,4-dibromopentan-3-one) gave the C7 fused dihydropyrene 6 in 77% yield. Elimination of water

  通过使用二甲基二氢芘实验探针检测芳香性，1,3,5-环庚三烯 (16) 被证明是一种中性的同芳烃！根据 (1)H NMR 结果，16 被判断为 ~30%，托酮 18 ~20%，和 tropylium 22 ~50% 与苯一样芳香。由于电荷离域，后一个结果可能被低估。B3LYP/6-31G* 计算的几何形状和 GIAO-HF/6-31G*//B3LYP/6-31G* 计算的 NMR 化学位移和与核无关的化学位移 (NICS) 支持这些结论。这些估计值是通过合成退火二氢芘 7（稠合的托酮）、9（稠合的 1,3,5-环庚三烯）和 10（稠合的芘）而获得的。[4 + 3] 异呋喃 5 与氧烯丙基阳离子（由 2,4-二溴戊烷-3-酮制备）的环加成得到 C7 稠合二氢芘6，产率为 77%。
• Multistate π Switches:  Synthesis and Photochemistry of a Molecule Containing Three Switchable Annelated Dihydropyrene Units
  作者：Reginald H. Mitchell、Cornelia Bohne、Yunxia Wang、Subhajit Bandyopadhyay、Chelsea B. Wozniak

  DOI：10.1021/jo052153g

  日期：2006.1.1

  The synthesis of the multistate photochromic switch 3 is described. This switch contains three dihydropyrene (DHP) units in the most conjugated fully closed form 3-c,c,c. The thermally stable form has the central DHP unit open and is 3-c,o,c. NMR and laser flash photolysis experiments were used to characterize the multiple states in the photoswitching of 3 by visible and UV light. Three of the possible five isomeric states of 3-c,o,c were observed. Irradiation of 3-c,o,c by visible light led to the formation of 3-o,o,o via the isomer 3-c,o,o as an intermediate, which were observed by NMR. Irradiation by UV light led to the formation of 3-c,c,c, which decays with a lifetime of 7.5 ms.
• Stable Ion NMR and GIAO-DFT Study of Novel Cations from 8,16-Dicyano[2.2]metacyclophanedienes and from Strategically Substituted/Benzannelated Dihydropyrenes:  Charge-Induced Tropicity Modulation and π-Switching
  作者：Kenneth K. Laali、Takao Okazaki、Reginald H. Mitchell、Khurshid Ayub、Rui Zhang、Stephen G. Robinson

  DOI：10.1021/jo701932j

  日期：2008.1.1

  [GRAPHICS]The dicyanometacyclophanediene 1 is diprotonated at the cyano groups (1H(2)(2+)) in various superacid media. Upon quenching, intact 1 and the ring-closed CPD 2 were obtained in a 3:2 or 3:1 ratio, depending on the superacid system. Compound 2 undergoes ring opening in the superacid to give the ipso-monoprotonated 2H(+), which on quenching furnishes 1-cyanopyrene as a major product together with 2 and 1. The dication 3(2+), with strongly deshielded internal methyls, was generated from the epoxyannulene 3. Ketones 4-6 and ester 7 are O/C diprotonated to give paratropic carboxonium-annulenium dications (4H(2)(2+), 5H(2)(2+), 6H(2)(2+), and -7H(2)(2+), respectively). Ester 8 gives a trication by two-electron oxidation and O-protonation. Conjugated carboxylic acid 9 gives a mixture of two dications by CO and ring protonation. The dibromo derivatives 10 and 11 form carboxoniurn ions, whereas the monobromo derivative 12 is O/C diprotonated to give an oxonium-annulenium dication. Charge delocalization modes and tropicity in the resulting species are evaluated by NMR and GIAO-DFT. Facile formation of 2 from I in quenching experiments indicates that thermal closing can be achieved with the diprotonated dinitrile, without imposing skeletal rearrangement.