2,3-bis(bromomethyl)-1,4-dimethoxynaphthalene | 196880-79-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 2,3-bis(bromomethyl)-1,4-dimethoxynaphthalene
• CAS: 196880-79-2
• 化学式: C₁₄H₁₄Br₂O₂
• 分子量: 374.072
• InChiKey: LTAKPRGIRDGULR-UHFFFAOYSA-N

物化性质

• 熔点：
  118 °C
• 沸点：
  437.6±40.0 °C(Predicted)
• 密度：
  1.622±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,3-bis(bromomethyl)-1,4-dimethoxynaphthalene 在 ammonium cerium(IV) nitrate 作用下， 以 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 0.5h， 以87%的产率得到2,3-bis(bromomethyl)-1,4-naphthoquinone
  参考文献：
  名称：

  苯并[f]异吲哚-4，9-二酮的合成。

  摘要：

  从2，3-双（溴甲基）-1，4-二甲氧基萘15与伯胺的反应开始，给出苯并[f]异吲哚-4，9-二酮1的合成，得到2，3-双（氨基甲基）-。 1,4-二甲氧基萘14可以通过CAN介导的一步氧化反应转化为苯并[f]异吲哚-4,9-二酮1。苯并[f]异吲哚-4,9-二酮1的另一种合成方法开始由2，3-双（溴甲基）-1，4-萘醌9经2，3-二氢苯并[f]异吲哚10自动氧化。

  DOI：

  10.1021/jo801056e
• 作为产物：
  描述：

  2,3-二甲基-1,4-二甲氧基萘 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 作用下， 以 四氯化碳 为溶剂， 反应 2.0h， 以97%的产率得到2,3-bis(bromomethyl)-1,4-dimethoxynaphthalene
  参考文献：
  名称：

  Reaction of C₆₀ with Sultines:  Synthesis, Electrochemistry, and Theoretical Calculations of Organofullerene Acceptors

  摘要：

  The [4 + 2] cycloaddition reaction of o-quinodimethanes, generated in situ from 4,5-benzo-3,6-dihydro-1,2-oxathiin 2-oxides (10a,b, 13, and 19) (sultines), to [60]fullerene is described. Sultines are readily accesible from the commercially available rongalite and smoothly generate o-quinodimethanes, by extrusion of sulfur dioxide, which are efficiently trapped by the active dienophile C-60. The cycloadducts formed (21a-d) were further oxidized to the respective p-benzoquinone-containing fullerenes 23a-c. The temperature dependent H-1 NMR spectra show a dynamic process of the methylene protons. The activation free energy determined for the boat-to-boat inversion (11.3-11.6 kcal/mol) is remarkably lower than that obtained for other related carbocyclic or heterocyclic analogues. Semiempirical PM3 calculations show that the geometrical features and not the electronic properties of the organic addend in 23 are responsible for the low activation energy barriers. A linear correlation is found between the activation energy barriers and the length of the C62-C63 bond. The electrochemical properties of 23a-c have been rationalized on the basis of DFT-B3P86/3-21G calculations. The attachment of the first electron in the reduction process takes place in either the C-60 cage or the organic addend depending upon the nature of the substituents on the p-benzoquinone ring, which controls the relative energy of the LUMO of the p-benzoquinone moiety. A full agreement between the theoretical predictions and the electrochemical measurements is found.

  DOI：

  10.1021/jo9706436

文献信息

• A four-step route to synthetic equivalents of ortho-xylylenes: Dötz benzannulation, desilylation, bromo-dehydroxylation, and sultine formation. A concise approach to oxygenated linearly fused polycyclic aromatics
  作者：Sambasivarao Kotha、Vikas R. Aswar、Amarender Manchoju

  DOI：10.1016/j.tet.2016.03.047

  日期：2016.5

  A new route has been reported for the synthesis of densely oxygenated polycyclic aromatic compounds via cycloaddition approach. This strategy involves the Dötz benzannulation and Diels-Alder reaction as key steps. Naphthalene synthons required here were generated by Dötz benzannulation between aryl chromium carbene complexes and symmetrical internal alkyne.

  已经报道了通过环加成法合成高氧合多环芳族化合物的新途径。该策略涉及Dötz苯环和Diels-Alder反应作为关键步骤。此处所需的萘合成子是通过芳族铬卡宾配合物和对称内部炔烃之间的Dötz苯并环生成的。
• A New Synthesis of Benzo[f]isoindole-4,9-diones by Radical Alkylation and Bromomethylation of 1,4-Naphthoquinones
  作者：Jurgen Deblander、Sam Van Aeken、Jan Jacobs、Norbert De Kimpe、Kourosch Abbaspour Tehrani

  DOI：10.1002/ejoc.200900562

  日期：2009.10

  of 1-alkylbenzo[f]isoindole-4,9-diones by bromomethylation and subsequent N-deprotection. Further functionalization by N-alkylation and bromination resulted in completely and asymmetrically substituted benzo[f]isoindole-4,9-diones. The second synthesis is based on a reductive amination of 3-(bromomethyl)-1,4-dimethoxynaphthalene-2-carbaldehyde and subsequent oxidation. (© Wiley-VCH Verlag GmbH & Co.

  已开发出两种取代苯并[f]异吲哚-4,9-二酮的合成路线。一种策略依赖于通过 Kochi-Anderson 氧化脱羧方法从 1,4-萘醌和 N-三氟乙酰基-α-氨基酸开始合成 N-三氟乙酰基保护的 2-(1-氨基烷基)-1,4-萘醌。此外，已证明 2-(1-氨基烷基)-1,4-萘醌是通过溴甲基化和随后的 N-脱保护合成 1-烷基苯并[f]异吲哚-4,9-二酮的合适前体。通过 N-烷基化和溴化进一步官能化导致完全和不对称取代的苯并[f]异吲哚-4,9-二酮。第二个合成基于 3-(溴甲基)-1,4-二甲氧基萘-2-甲醛的还原胺化和随后的氧化。(© Wiley-VCH Verlag GmbH & Co. KGaA,
• Synthesis and electrochemistry of soluble double-bridged tetrathiafulvalene (TTF)-p-benzoquinone dyads
  作者：Mar González、Beatriz Illescas、Nazario Martín、JoséL. Segura、Carlos Seoane、Michael Hanack

  DOI：10.1016/s0040-4020(98)83022-6

  日期：1998.3

  unsymmetrically substituted TTF derivatives as precursor for the preparation of novel TTF-based donor-bridge-acceptor dyads is reported. Substitution on the acceptor p-benzoquinone moiety has a strong influence on the reduction potentials in compounds 18 which, however, do not show the presence of a charge transfer band in the electronic spectra. The cyclic voltammetry measurements reveal two oxidation waves

  据报道，新型可溶性不对称取代的TTF衍生物作为前体，用于制备新型的基于TTF的供体-桥-受体二元体。受体对-苯醌部分上的取代对化合物18中的还原电位有很大的影响，然而，在电子光谱中没有显示出电荷转移带的存在。循环伏安法测量揭示了16和17中TTF部分的两个氧化波和分配给氢醌部分的第三个氧化波。化合物18除了TTF氧化波，还显示存在与醌部分相对应的还原波。光谱电化学研究表明阳离子自由基的逐步形成和TTF片段的阳离子化。
• A non-lithiation route towards facile synthesis of bioactive 4, 9-dimethoxynaphthalide
  作者：Raju M. Walunj、Arun D. Natu、Rajeev C. Chikate、Madhusudan V. Paradkar、Santosh C. Narwade、Gunderao H. Kathwate、Deepti D. Deobagkar

  DOI：10.1080/00397911.2020.1794656

  日期：2020.10.17

  Abstract A simple, facile, and convenient route is adopted for the synthesis of 4,9-dimethoxynaphthalide (4,9-DMN); an analog of naturally occurring naphthalene lactone family. It is achieved without involving a tedious and hazardous lithiation step using 3-(bromomethyl)-1,4-dimethoxy-2-naphthaldehyde as key intermediate through base catalyzed oxidative cyclization resulting in a five-membered lactone

  摘要 采用一条简单、简便、方便的路线合成4,9-二甲氧基萘(4,9-DMN)；一种天然存在的萘内酯家族的类似物。它的实现不涉及使用 3-(溴甲基)-1,4-二甲氧基-2-萘醛作为关键中间体通过碱催化氧化环化产生五元内酯环的繁琐和危险的锂化步骤。该化合物对白色念珠菌表现出显着的抗真菌活性，同时发现它对 MCF-7 癌细胞系的毒性较小，IC50 值小于 250 µM。图形概要
• Synthesis of Hexahydropyrazino[1,2-b]isoquinolines as Simplified Saframycin Analogues
  作者：Norbert De Kimpe、Tuyen Nguyen Van、Pieter Claes

  DOI：10.1055/s-0033-1340070

  日期：——

  Various hexahydropyrazino[1,2-b]isoquinolines were synthesised as simplified saframycin analogues. Construction of this core proceeded through a tetrahydroisoquinoline synthesis followed by acylation/alkylation of the tetrahydroisoquinoline nitrogen and subsequent ring closure using various aliphatic and aromatic amines. The resulting piperazinones were reacted with LiAlH4 or LiAlH(OEt)(3) to synthesise further analogues.