4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 1-naphthyl ketone

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 1-naphthyl ketone
• 英文别名: [(10bR,10cS)-4,9-dibromo-7-tert-butyl-10b,10c-dimethylpyren-2-yl]-naphthalen-1-ylmethanone
• 化学式: C₃₃H₂₈Br₂O
• 分子量: 600.393
• InChiKey: ZYLLUHGFZSMMLS-JHOUSYSJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.6
• 重原子数：
  36
• 可旋转键数：
  3
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 1-naphthyl ketone 在 氯氟磺酰 、 氟磺酸 作用下， 生成
  参考文献：
  名称：

  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

  摘要：

  [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.

  DOI：

  10.1021/jo701932j
• 作为产物：
  描述：

  以 氘代氯仿 为溶剂， 生成 4,9-dibromo-7-tert-butyl-10b,10c-dihydro-trans-10b,10c-dimethylpyren-2-yl 1-naphthyl ketone
  参考文献：
  名称：

  抑制热偏环二烯到二氢py异构化：8,16-二氰基[2.2]元环烷-1,9-二烯的合成和重排以及支持拟议的双自由基机理的证据

  摘要：

  由1,3-双（溴甲基）苄腈分五个步骤完成了8,16-二氰基-抗-[[2.2] metacyclophane -1,9-diene，1b的合成。与大多数易被热异构化（在20°C时τ1 /2 =分钟至数天）变为二氢吡啶2的metacyclophanedienes不同，二腈1b在室温下（τ1 /2 > 30年）没有热转化为2b的趋势基于激活壁垒计算的预测。用紫外光照射环庚二烯1b容易形成二硝二氢吡啶2b，这出乎意料地表明，内部腈基的1，5-σ重排更容易（50°C），得到二氢py 9b，然后是10b，而内部甲基取代基2a在190°C以上时形成9a C。还描述了2-甲酰基衍生物1c和2-萘甲酰基衍生物1d的合成。预测这些取代基会降低热闭环反应生成相应二氢吡啶的活化势垒，并且实验证据支持了这些计算。

  DOI：

  10.1021/jo7019459

文献信息

• Oligothiophene Functionalized Dimethyldihydropyrenes I: Syntheses and Photochromicity
  作者：Stephen G. Robinson、Vittorio A. Sauro、Reginald H. Mitchell

  DOI：10.1021/jo901070y

  日期：2009.9.4

  The syntheses of 2,7-di-tert-butyldimethyldihydrobenzo[e]pyrenes with thienyl (6), terthienyl (7), and pentathienyl (14) side chains at the 4,5- positions, ter- and pentathienyl side chains at the 4-position with ter- (39) and pentathienylcarbonyl (40) side chains at the 10- and 11-positions, 2-naphthoyl-7-tert-butyldimethyldihydropyrenes with ter- (53), penta- (54), and septithienyl (55) side chains at the 4,9-positions are described. These compounds are all photochromic and open to the corresponding cyclophanedienes with long wavelength ( > 490 nm) light, and as such, the conjugative path could change considerably, making them suitable to investigate as potentially switchable conducting molecules. In this paper, the syntheses and the photochemical and thermal isomerizations are studied in the accompanying paper, the electrochemical and conductive properties are studied. Here, a comparison of the relative opening rates to that of the benzo[e]pyrene 4 (with no thienyl substituents) is made, and all of the above photochromes show considerably enhanced photo-opening of the DHPs to the CPDs. As examples, 14, 40, and 54 were cycled between the open and closed forms, and no decomposition was observed; however, when 54 was irradiated for 40 h with 254 nm light, some radicals did form, which enhanced the thermal closing rate, and so extensive irradiation with short wave UV is better avoided. The thermal closing reactions were also studied, and all of the above compounds close faster than benzo-CPD 4', though for the highly photochromic ter- and pentathienyl benzo-CPDs 39' and 40', the rate was not too enhanced from that of 4' and so are probably the best compromise between fast photochromicity and slow thermal reversion.
• Oligothiophene Functionalized Dimethyldihydropyrenes II: Electrochemical and Conductive Properties
  作者：Stephen G. Robinson、Mark C. Lonergan、Reginald H. Mitchell

  DOI：10.1021/jo901071q

  日期：2009.9.4

  Three different types of oligothiophene functionalized dihydropyrene photoswitches, (A) 2-naphthoyl-dimethyldihydropyrenes functionalized at the 4,9-positions with oligothiophenes, (B) benzodimethyl-dihydropyrenes functionalized at the 4-positions with oligothiophenes and the 10(11)-position with oligothienylcarbonyl groups, and (C) benzodimethyldihydropyrenes functionalized at the 4,5-positions with oligothiophenes, were studied with the goal of using the change in pi-conjugation between the open and the closed forms of the dihydropyrene (DHP)-metacyclophane (CPD) switch to control electrical conductivity. UV-vis absorption studies were performed to measure the extent to which the attached thienyl oligomers were conjugated with the switch and the ability of the switch when opened or closed to affect conjugation. Of the three types of switches studied, those of type A showed the greatest effect. Solution cyclic voltammetry (CV) for the closed isomers indicated that the First few oxidation peaks were quasi-reversible, but that later ones were irreversible, leading to polymerization. Solution CV experiments on the open CPD form led to elect rochemically induced closing to the DHP form. Conductivity studies were performed oil undoped thin films of the A-type compound 4 and showed that opening the switch caused a decrease in electrical conductivity, and closing the switch caused an increase in electrical conductivity through the film. Doped films were studied by dual-electrode voltammetry and spectroelectrochemistry and showed that while doping led to an increase in the conductivity of the Film it also led to the closing of the open form, preventing the conductivity of the open doped form from being measured.
• Suppressing the Thermal Metacyclophanediene to Dihydropyrene Isomerization:  Synthesis and Rearrangement of 8,16-Dicyano[2.2]metacyclophane-1,9-diene and Evidence Supporting the Proposed Biradicaloid Mechanism
  作者：Khurshid Ayub、Rui Zhang、Stephen G. Robinson、Brendan Twamley、Richard Vaughan Williams、Reginald H. Mitchell

  DOI：10.1021/jo7019459

  日期：2008.1.1

  Synthesis of 8,16-dicyano-anti-[2.2]metacyclophane-1,9-diene, 1b, was achieved in five steps from 1,3-bis(bromomethyl)benzonitrile. Unlike most metacyclophanedienes which easily thermally isomerize (τ1/2 = minutes to days at 20 °C) to dihydropyrenes 2, dinitrile 1b shows no tendency to convert thermally to 2b at room temperature (τ1/2 > 30 years), consistent with predictions based on calculation of

  由1,3-双（溴甲基）苄腈分五个步骤完成了8,16-二氰基-抗-[[2.2] metacyclophane -1,9-diene，1b的合成。与大多数易被热异构化（在20°C时τ1 /2 =分钟至数天）变为二氢吡啶2的metacyclophanedienes不同，二腈1b在室温下（τ1 /2 > 30年）没有热转化为2b的趋势基于激活壁垒计算的预测。用紫外光照射环庚二烯1b容易形成二硝二氢吡啶2b，这出乎意料地表明，内部腈基的1，5-σ重排更容易（50°C），得到二氢py 9b，然后是10b，而内部甲基取代基2a在190°C以上时形成9a C。还描述了2-甲酰基衍生物1c和2-萘甲酰基衍生物1d的合成。预测这些取代基会降低热闭环反应生成相应二氢吡啶的活化势垒，并且实验证据支持了这些计算。
• 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.