triphenylmethanol-d15 | 6922-92-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: triphenylmethanol-d15
• 英文别名: Tris(2,3,4,5,6-pentadeuteriophenyl)methanol
• CAS: 6922-92-5
• 化学式: C₁₉H₁₆O
• 分子量: 275.216
• InChiKey: LZTRCELOJRDYMQ-KLHTYYPYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  triphenylmethanol-d15 在 乙酰氯 作用下， 以 甲苯 为溶剂， 反应 0.67h， 生成 chloro-tris(d5-phenyl)methane
  参考文献：
  名称：

  通过 Cu/Mn 促进的分子内 C-H 胺化/电环反应级联将苄胺氧化重排为 4H-3,1-苯并恶嗪

  摘要：

  We have developed a copper/manganese-mediated oxidative rearrangement of benzylamines to 4H-3,1-benzoxazines of potent interest in medicinal applications. The reaction proceeds uniquely through the initial copper/manganese-promoted intramolecular C-H amination giving benzazetidine intermediates and subsequent 4n electrocyclic ring opening/6 pi electrocyclic ring closing cascade. The key to success is the introduction of picolinamide-based N,N-bidentate directing group. The obtained benzoxazines can also be readily hydrolyzed to the corresponding 2-aminobenzyl alcohols, thus indicating that the overall transformations is regarded as the ortho-aminative rearrangement of benzylarnines to benzylic alcohols.

  DOI：

  10.3987/com-18-s(t)27
• 作为产物：
  描述：

  氘代溴苯 、 碳酸二乙酯 在 碘 、 magnesium 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以52%的产率得到triphenylmethanol-d15
  参考文献：
  名称：

  Longer polyenyl cations in relation to soliton theory

  摘要：

  合成了类胡萝卜素多烯物质：十环烯-β-胡萝卜素（C50）、C54-β-胡萝卜素（C54，首次合成）和十二环烯-β-胡萝卜素（C60），它们分别具有15、17和19个共轭双键，采用双威提反应合成。未能在烯丙位引入离去基团，通过氢离子消除反应获得了阳离子，该反应由以下两种方法实现：i）通过一种新方法制备的三苯基卡宾四氟硼酸盐-d15，或ii）用三氟醋酸-d处理。采用氘代试剂进行产物分析，使用1H NMR进行表征。与β,β-胡萝卜素（C40）进行了平行实验。使用室温和-15°C的近红外光谱（NIR）对阳离子产物进行了特征化和稳定性研究。在CH2Cl2中记录了900–1350 nm波段的最大波长。通过两种新制备方法获得的β,β-胡萝卜素阳离子产物的NMR数据与先前表征的两个单阳离子一致。较长多烯的阳离子产物提供了向下偏移和宽化的信号，与C50单阳离子、混合C54单阳离子和双阳离子以及C60双阳离子相兼容。综合NIR和NMR数据表明，由于大约20个sp2杂化碳原子的线性多烯产生的阳离子的电荷离域程度受到最大孤子宽度的限制。

  DOI：

  10.1039/b706212e

文献信息

• Rhodium- and Iridium-Catalyzed Dehydrogenative Cyclization through Double C–H Bond Cleavages To Produce Fluorene Derivatives
  作者：Masaki Itoh、Koji Hirano、Tetsuya Satoh、Yu Shibata、Ken Tanaka、Masahiro Miura

  DOI：10.1021/jo4000465

  日期：2013.2.15

  The rhodium-catalyzed cyclization of a series of 2,2-diarylalkanoic acids in the presence of copper acetate as an oxidant smoothly proceeded through double C-H bond cleavages and subsequent decarboxylation to produce the corresponding fluorene derivatives. The direct cyclization of triarylmethanols also took place efficiently by using an iridium catalyst in place of the rhodium, while the hydroxy function was still intact.
• Longer polyenyl cations in relation to soliton theory
  作者：Geir Kildahl-Andersen、Thorleif Anthonsen、Synnøve Liaaen-Jensen

  DOI：10.1039/b706212e

  日期：——

  The carotene-like polyenes decapreno-β-carotene (C50), C54-β-carotene (C54, first synthesis) and dodecapreno-β-carotene (C60) with 15, 17 and 19 conjugated double bonds, respectively, were synthesized by double Wittig reactions. Introduction of a leaving group in allylic position failed, and cations were obtained by hydride elimination effected by i) triphenylcarbenium tetrafluoroborate-d15, prepared by a new method, or ii) treatment with trifluoroacetic acid-d. Deuterated reagents were employed for product analysis by 1H NMR. Parallel experiments were performed with β,β-carotene (C40). NIR spectra at room temperature and at –15 °C were employed for characterisation and stability studies of the cationic products. In CH2Cl2λmax in the 900–1350 nm region was recorded. NMR data for the cationic product of β,β-carotene obtained by the two new preparation methods were consistent with the two monocations previously characterised. The cationic products of the longer polyenes provided downfield-shifted, broadened signals, compatible with C50-monocation, mixed C54-mono- and dication and C60-dication. Combined NIR and NMR data suggest that the extent of charge delocalisation is limited by the maximum soliton width for cations obtained from linear polyenes with more than ca. 20 sp2-hybridized carbon atoms.

  合成了类胡萝卜素多烯物质：十环烯-β-胡萝卜素（C50）、C54-β-胡萝卜素（C54，首次合成）和十二环烯-β-胡萝卜素（C60），它们分别具有15、17和19个共轭双键，采用双威提反应合成。未能在烯丙位引入离去基团，通过氢离子消除反应获得了阳离子，该反应由以下两种方法实现：i）通过一种新方法制备的三苯基卡宾四氟硼酸盐-d15，或ii）用三氟醋酸-d处理。采用氘代试剂进行产物分析，使用1H NMR进行表征。与β,β-胡萝卜素（C40）进行了平行实验。使用室温和-15°C的近红外光谱（NIR）对阳离子产物进行了特征化和稳定性研究。在CH2Cl2中记录了900–1350 nm波段的最大波长。通过两种新制备方法获得的β,β-胡萝卜素阳离子产物的NMR数据与先前表征的两个单阳离子一致。较长多烯的阳离子产物提供了向下偏移和宽化的信号，与C50单阳离子、混合C54单阳离子和双阳离子以及C60双阳离子相兼容。综合NIR和NMR数据表明，由于大约20个sp2杂化碳原子的线性多烯产生的阳离子的电荷离域程度受到最大孤子宽度的限制。
• Oxidative Rearrangement of Benzylamines to 4H-3,1-Benzoxazines via Cu/Mn-Promoted Intramolecular C–H Amination/Electrocyclic Reaction Cascade
  作者：Masahiro Miura、Koji Hirano、Chiaki Yamamoto、Kazutaka Takamatsu

  DOI：10.3987/com-18-s(t)27

  日期：——

  We have developed a copper/manganese-mediated oxidative rearrangement of benzylamines to 4H-3,1-benzoxazines of potent interest in medicinal applications. The reaction proceeds uniquely through the initial copper/manganese-promoted intramolecular C-H amination giving benzazetidine intermediates and subsequent 4n electrocyclic ring opening/6 pi electrocyclic ring closing cascade. The key to success is the introduction of picolinamide-based N,N-bidentate directing group. The obtained benzoxazines can also be readily hydrolyzed to the corresponding 2-aminobenzyl alcohols, thus indicating that the overall transformations is regarded as the ortho-aminative rearrangement of benzylarnines to benzylic alcohols.