1,8-bis(diphenylhydroxymethyl)naphthalene | 96773-95-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 1,8-bis(diphenylhydroxymethyl)naphthalene
• 英文别名: 1,8-Bis-(hydroxy-diphenyl-methyl)-naphthalin；1,8-Bis-(diphenylhydroxymethyl)-naphthalin；[8-[Hydroxy(diphenyl)methyl]naphthalen-1-yl]-diphenylmethanol
• CAS: 96773-95-4
• 化学式: C₃₆H₂₈O₂
• 分子量: 492.617
• InChiKey: UZXNNANOLVAXON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  38
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,8-bis(diphenylhydroxymethyl)naphthalene 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 以2.7 g的产率得到1,1,3,3-tetraphenyl-1H,3H-benzo[d,e]isochromene
  参考文献：
  名称：

  1,8-Bis(diphenylmethylium)naphthalenediyl Dication as an Organic Oxidant:  Synthesis of Benzidines via Self-Coupling of N,N-Dialkylanilines

  摘要：

  1,8-Bis(diphenylmethylium)naphthalenediyl dications promoted oxidative coupling of various N,N-dialkylanilines to afford the corresponding para-coupled bisanilines, benzidines, in good to excellent yield. The dications were readily prepared from a cyclic ether precursor, derived from 1,8-dibromonaphthalene, via deoxygenation with a silylating reagent in 1,1,1,3,3,3-hexafluoro-2-propanol under anhydrous conditions.

  DOI：

  10.1021/ol048058w
• 作为产物：
  描述：

  8-溴-1-萘甲酸 生成 1,8-bis(diphenylhydroxymethyl)naphthalene
  参考文献：
  名称：

  Peri-Substituted Naphthalene Compounds. V.^1,2 1,8-Dilithionaphthalene

  摘要：

  DOI：

  10.1021/jo01049a534

文献信息

• Synthesis and Reactivity of a Chlorinated 1,8-Bis(diarylmethylium)naphthalenediyl Dication
  作者：Huadong Wang、François P. Gabbaï

  DOI：10.1021/ol0477071

  日期：2005.1.1

  8-Bis(bis(p-chlorophenyl)methylium)naphthalenediyl dication has been prepared by treatment of the corresponding diol with a mixture of [HBF4]aq and (CF3CO)2O. The proximity of the methylium centers leads to strong electrostatic repulsions that are exacerbated by the electron-withdrawing p-chloro substituents. As indicated by cyclic voltammetry, this dication is the strongest oxidant of the 1,8-bis(methy

  [反应：见正文]通过用[HBF4] aq和（CF3CO）2O的混合物处理相应的二醇，制备了1,8-双（双（对-氯苯基）甲基）萘二甲酸酯。甲基中心附近会导致强烈的静电斥力，这种斥力会因吸电子的对氯取代基而加剧。如循环伏安法所示，该指示剂是1,8-双（甲基）萘二烯基系列中最强的氧化剂。它经过氯化物的还原氯化作用，并与溴化物或碘化物反应，得到相应的。
• Naphthalene-1,8-diylbis(diphenylmethylium) as an Organic Two-Electron Oxidant:  Benzidine Synthesis via Oxidative Self-Coupling of <i>N,N</i>-Dialkylanilines
  作者：Terunobu Saitoh、Suguru Yoshida、Junji Ichikawa

  DOI：10.1021/jo060662s

  日期：2006.8.1

  Naphthalene-1,8-diylbis(diphenylmethylium) exhibits a unique electron-transfer reduction behavior due to the close proximity of the two triarylmethyl cations, which form a C-C bond while accepting two electrons, leading to 1,1,2,2-tetraphenylacenaphthene. The preparation of the dication was readily accomplished under anhydrous conditions starting from a cyclic bis(triarylmethyl) ether, derived from 1,8-dibromonaphthalene. The process proceeded via deoxygenation accompanying the formation of a disiloxane on treatment with a silylating agent (Me3SiClO4 or Me3SiOTf) in 1,1,1,3,3,3-hexafluoropropan-2-ol. The dication was successfully employed for oxidative coupling of N, N-dialkylanilines at the paraposition to afford the corresponding benzidines in good to excellent yield.
• Reaction of the 1,8-Bis(diphenylmethylium)naphthalenediyl Dication with Fluoride:  Formation of a Cation Containing a C−F→C Bridge
  作者：Huadong Wang、Charles Edwin Webster、Lisa M. Pérez、Michael B. Hall、François P. Gabbaï

  DOI：10.1021/ja048501y

  日期：2004.7.1

  Treatment of 1, 8-bis(diphenylhydroxymethyl) naphthalene with a mixture of [HBF4](aq) and (CF3CO)(2)O affords the corresponding clication, 1,8-bis(diphenylmethylium)naphthalenediyl (1(2+)), which was isolated as the [BF4](-) salt. This dication has been fully characterized, and its structure has been studied computationally. The C-13 NMR resonance of the methylium centers appears at 207.7 ppm. As indicated by an X-ray single-crystal analysis, the vicinal methylium centers are separated by 3.112(4) Angstrom. Dication (1(2+)) reacts with fluoride to afford [1-F](+) which has been isolated as the [BF4](-) salt. The fluorine atom of [1-F](+) is connected to one of the former methylium centers through a typical C-F bond of 1.424(2) Angstrom and forms a long interaction of 2.444(2) Angstrom with the other methylium center. While the structure of [1-F](+) can be largely accounted for by considering a simple methylium formulation, density functional calculations followed by an Atom In Molecules analysis as well as a calculation of the Boys localized orbitals indicate that the long C-F interaction of 2.444(2) Angstrom corresponds to a dative bond. Hence, formulation of [1-F](+) as an unsymmetrical fluoronium must also be considered. As indicated by H-1 NMR spectroscopy, the structure of this ion is fluxional; the fluorine atom oscillates between the former methylium centers with apparent activation parameters of DeltaH(double dagger) = 52(+/-3) kJ mol(-1) and DeltaS(double dagger) = -18(+/-9) J K-1 mol(-1) as derived from line shape analysis. This dynamic process, which has also been studied theoretically by B3LYP density functional theory and Moller-Plesset second-order perturbation theory methods, involves symmetrical fluoronium ions as low-energy transition states.