2-lithio-1,4-dimethoxybenzene | 39175-16-1

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: 2-lithio-1,4-dimethoxybenzene
• 英文别名: (2,5-dimethoxyphenyl)lithium
• CAS: 39175-16-1
• 化学式: C₈H₉LiO₂
• 分子量: 144.099
• InChiKey: GQSSYWCDFUFDSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.04
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 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-lithio-1,4-dimethoxybenzene 在 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 1,2-二氯乙烷 为溶剂， 反应 5.17h， 生成 (4aR,9aS)-5,8-Dimethoxy-1,2,3,4,4a,9a-hexahydro-fluoren-9-one
  参考文献：
  名称：

  Photo-Nazarov反应：范围和应用

  摘要：

  研究了芳基乙烯基酮的光-纳扎罗夫反应的反应条件和范围。与传统的酸催化方法相比，这种光解电环化反应在中性或碱性条件下进行。用紫外线（254 nm）照射带有各种芳族环，酸敏感基团，环己烯基，环庚烯基和不饱和吡喃的底物，可以平稳地产生六氢芴酮及其相关结构。这种光-纳扎罗夫反应也可能适用于在烯酮上带有β-烷基的底物，该底物产生了相应的含有季中心的多环。这些光电循环产物可能被证明可用于合成多种天然产物及其衍生物。

  DOI：

  10.1002/chem.201402993
• 作为产物：
  描述：

  对苯二甲醚 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 、 环己烷 、 正戊烷 为溶剂， 反应 0.33h， 生成 2-lithio-1,4-dimethoxybenzene
  参考文献：
  名称：

  ortho-Lithiations Reassessed: the Advantages of Deficiency Catalysis in Hydrocarbon Media

  摘要：

  Hydrocarbon media based metalation procedures involving "deficiency catalysis" are described for the ortho-lithiation of anisole (A), p-chloroanisole (p-ClA), o-, m-, p-methylanisoles (o-, m-, p-MA), the three dimethoxybenzenes (DMB's), dimethylaniline (DMA), dimethybenzylamine (DMBA), m-methoxydimethylaniline (m-MeODM.A), and tetramethyl-p-phenylenediamine (p-TMPDA). These procedures involve certain mechanistic considerations, which must be fine-tuned to maximize the extent of metalation (EoM). Our working hypothesis is that a controlled deoligomerization of the n-BuLi hexamer found in hydrocarbon media will afford a "sweet spot" of deoligomerization such that a maximally efficient metalation medium can be formed. In many eases, a substoichiometric ratio of equivalent TMEDA to n-BuLi is 0.1-0.2:1.0, but certain substrates suffer multiple sites of metalation under these conditions, so different promoted hydrocarbon media systems incorporating measured equivalents of an ether have been formulated. This paper represents the summary of our successful efforts to render ortho-lithiations safer, greener, and more atom-economical by use of hydrocarbon solvent media. EoM's of 11 of the 12 substrates under these atom-economical conditions range from 87 to 97%.

  DOI：

  10.1021/om301120e

文献信息

• An Approach to Anthracycline Synthetic Intermediate from Novel Glycerol-related Chiral Pool
  作者：Naoyuki Watanabe、Hiromichi Ohta

  DOI：10.1246/cl.1992.661

  日期：1992.4

  A key-intermediate of synthetic anthracycline, (+)-(1S,2S)-1,3-dihydroxy-3,3′-O-isopropiridene-3-(hydroxymethyl)-5,8-dimethoxy-1,2,3,4-tetrahydronaphthalene was synthesized from optically active 2-substituted glycerol monoacetate which was prepared via enantioselective enzymatic hydrolysis of a prochiral 2-substituted glycerol derivative.

  合成蒽环类药物的关键中间体，(+)-(1S,2S)-1,3-dihydroxy-3,3'-O-isopropiridene-3-(hydroxymethyl)-5,8-dimethoxy-1,2,3 ,4-四氢萘由旋光性 2-取代甘油单乙酸酯合成，该单乙酸酯通过前手性 2-取代甘油衍生物的对映选择性酶水解制备。
• Oxidation potential of benzylferrocenes and related compounds: effects of the ortho-methoxy substituent in the phenyl group
  作者：Masahiro Asahara、Satoko Natsume、Hideaki Kurihara、Takuya Yamaguchi、Tatsuo Erabi、Masanori Wada

  DOI：10.1016/s0022-328x(00)00075-9

  日期：2000.4

  reversible one-electron oxidation–reduction wave based on the ferrocene–ferrocenium redox couple with a wide range of shift. Compounds having ortho-methoxy groups showed lower redox potentials than those of compounds having para-methoxy groups. The X-ray crystal structure of FcCHΦ2a showed that the ortho-methoxy oxygens were situated very close to the central carbon, and there is a possibility that

  Fc的CHΦOH，FcCΦΦ'OH，FcCH类型的一些二茂铁衍生物的氧化电位2 Φ，FcCHΦΦ'[FC =铁（η 5 -C 5 H ^ 5）（η 5 -C 5 H ^ 4） ; Φ，Φ'= -2,4,6-（MEO）3 c ^ 6 ħ 2，2,6-（MEO）2 ·C 6 H ^ 3，2,5-（MEO）2 ·C 6 H ^ 3，2， 4-（MEO）2 ·C 6 H ^ 3，2-MEOC 6 H ^ 4，4-MEOC 6 H ^ 4，C 6在乙腈中测量H 5 ]。它们都显示出基于二茂铁-二茂铁氧化还原对的可逆的单电子氧化还原波，并且具有宽范围的位移。具有邻甲氧基的化合物显示出比具有对甲氧基的化合物更低的氧化还原电势。FcCHΦ的X射线晶体结构2一表明，邻-甲氧基氧被非常靠近中心碳，并且存在这样的可能性，与反键轨道CFc的氧孤对相互作用的一个σ键。还讨论了其他一些可能性。
• Facilemeso Functionalization of Porphyrins by Nucleophilic Substitution with Organolithium Reagents
  作者：Werner W. Kalisch、Mathias O. Senge

  DOI：10.1002/(sici)1521-3773(19980504)37:8<1107::aid-anie1107>3.0.co;2-z

  日期：1998.5.4

  ruffle of the porphyrin increases with the number of meso substituents. (Octaethylporphyrin)nickel(II) undergoes nucleophilic substitution reactions upon treatment with alkylating reagents such as butyllithium, hydrolysis with water, and oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone [DDQ; Eq. (a)]. Alkylation can be achieved at all four meso positions, and access is provided to new nonplanar

  卟啉的皱纹随着内消旋取代基的数量增加而增加。（Octaethylporphyrin）nickel（II）经过烷基化试剂（如丁基锂）处理，用水水解并用2,3-二氯-5,6-二氰基-1,4-苯醌氧化[DDQ]时，会发生亲核取代反应。等式 （一种）]。烷基化可以在所有四个内消旋位置上实现，并且可以使用新的非平面卟啉和不对称取代的系统。
• Reaction of β-formylporphyrins with organometallic reagents — A facile method for the preparation of porphyrins with exocyclic double bonds
  作者：Steffen Runge、Mathias O. Senge

  DOI：10.1016/s0040-4020(99)00579-7

  日期：1999.8

  various organolithium reagents to form porphyrins with exocyclic double bonds. The reaction involved conversion with LiR to the respective alcohol. Subsequence dehydratization of the alcohols yielded olefinic systems in which the double bond formed was located in the meso substituent neighboring the β position, i.e., the result of a 1,5-hydride shift. Depending on the organolithium reagent used various olefinic

  用各种有机锂试剂处理5,10,15,20-四烷基-2-甲酰基卟啉以形成具有环外双键的卟啉。该反应涉及用LiR转化成相应的醇。醇的子序列脱水产生烯烃体系，其中形成的双键位于β位附近的内消旋取代基中，即1，5-氢化物移位的结果。取决于所使用的有机锂试剂，只要中间碳正离子的稳定性足够高，就可以使用各种烯烃卟啉。此外，使用彼得森烯化允许2-乙烯基-5,10,15,20-四烷基卟啉的容易的合成，并且有机二锂试剂的使用使官能化的双卟啉的获得方便。
• Ring-metalated porphyrins
  申请人：The Trustees of the University of Pennsylvania

  公开号：US05493017A1

  公开（公告）日：1996-02-20

  Reaction products comprising ring-metalated porphyrins are provided that are useful in the synthesis of porphyrin polymers and porphyrins substituted with, for example, vinyl and acetylene groups.

  提供了包含环金属卟啉的反应产物，这些产物在卟啉聚合物和卟啉（例如乙烯和乙炔基团）的合成中很有用。