1-bromo-3-methoxy-2,5-dimethylbenzene | 72623-20-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 1-bromo-3-methoxy-2,5-dimethylbenzene
• CAS: 72623-20-2
• 化学式: C₉H₁₁BrO
• 分子量: 215.09
• InChiKey: IMXCSFMBLJCPMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-bromo-3-methoxy-2,5-dimethylbenzene 在 吡啶 、 dipotassium peroxodisulfate 、 copper(II) sulfate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.25h， 以35%的产率得到2-bromo-6-methoxy-4-methylbenzaldehyde
  参考文献：
  名称：

  Synthesis of putative intermediates in the biosynthesis of the kinamycin antibiotics: total synthesis of phenanthroviridin aglycon and related compounds

  摘要：

  Phenanthroviridin aglycon, 14, recently isolated from Streptomyces viridiochromogenes DSM 3972, and the corresponding pyridone 10 have been synthesized from the common intermediate (bromoaryl)naphthamide 42. This was prepared by condensation of a (trimethylsilyl)ethyl (bromoaryl)cinnamate 36 and a methoxy-substituted cyanophthalide anion 15, providing the ABD rings of the target benzo[b]phenanthridine skeleton. The aglycon 14 was obtained by a sequence of metal-halogen exchange and formylation, Hofmann rearrangement, cyclization, and deprotection. The pyridone was obtained by Hofmann rearrangement, metal-halogen exchange, cyclization, and deprotection. In addition, a route to cinnamate 36 via coumarin 49 was developed which would allow selective protection of the 1-hydroxyl group for synthesis of glycosidic analogues of phenanthroviridin, 13. The methodology developed is useful for preparation of 10, 14, and analogues specifically labeled at C-5 for study of biosynthesis of the kinamycin antibiotics.

  DOI：

  10.1021/jo00036a005
• 作为产物：
  描述：

  2,4,5-三溴-3,6-二甲基苯酚 在 氢碘酸 、 potassium carbonate 作用下， 以 水 、 丙酮 为溶剂， 反应 40.0h， 生成 1-bromo-3-methoxy-2,5-dimethylbenzene
  参考文献：
  名称：

  Pd 0催化的不对称C（sp 3）–H活化不同（Nor）illudalane倍半萜烯的对映体选择性合成

  摘要：

  通过使用Pd 0催化的不对称C（sp 3）-H芳基化作为控制目标分子离体的，高度对称的四元立体中心的关键步骤，设计了（正）伊拉达拉烷倍半萜的不同对映体选择性合成。手性底物和催化剂的匹配组合被证明是最佳的，可以达到良好的立体选择性。该方法使得能够合成三种（去甲）illudalanes，包括首次以对映体富集形式合成的（S）-地苯醌和（S）-鲁su香酚F。

  DOI：

  10.1021/acs.orglett.8b04086

文献信息

• Synthetic Study on Acremoxanthone A: Construction of Bicyclo [3.2.2]nonane CD Skeleton and Fusion of AB Rings
  作者：Keisuke Suzuki、Yoichi Hirano、Kensei Tokudome、Hiroshi Takikawa

  DOI：10.1055/s-0036-1588600

  日期：——

  Toward the total synthesis of acremoxanthone A, a model study has revealed a convergent approach to construct the ABCDE ring system. The key steps include: (1) an effective construction of the bicyclo[3.2.2]nonane skeleton, (2) protocol for generating the bridgehead anion and trapping, and (3) 1,3-dipolar cycloaddition of a nitrile oxide to the internal alkene.

  对于 acremoxanthone A 的全合成，一项模型研究揭示了一种构建 ABCDE 环系统的收敛方法。关键步骤包括：(1) 双环 [3.2.2] 壬烷骨架的有效构建，(2) 生成桥头阴离子和捕获的协议，以及 (3) 腈氧化物的 1,3-偶极环加成反应内部烯烃。
• [EN] DERIVATIVES OF QUINOLINES AND QUINOXALINES AS PROTEIN TYROSINE KINASE INHIBITORS<br/>[FR] DÉRIVÉS DE QUINOLÉINES ET DE QUINOXALINES EN TANT QU'INHIBITEURS DE PROTÉINE TYROSINE KINASES
  申请人：NOVARTIS AG

  公开号：WO2009141386A1

  公开（公告）日：2009-11-26

  The invention relates to compounds of Formula (I), wherein the substituens are as defined in the specification, in free form or in the form of a pharmaceutically acceptable salt, solvate, ester, N-oxide thereof; processes for the preparation thereof; to pharmaceuticals containing such compounds, in particular for the use in one or more Protein tyrosine kinase mediated diseases.

  该发明涉及式（I）的化合物，其中取代基如规范中定义的那样，以自由形式或作为药用盐、溶剂合物、酯、其N-氧化物的形式存在；其制备方法；含有这种化合物的药物，特别是用于治疗一个或多个蛋白酪氨酸激酶介导的疾病。
• Enantioselective Approach to (−)-Hamigeran B and (−)-4-Bromohamigeran B via Catalytic Asymmetric Hydrogenation of Racemic Ketone To Assemble the Chiral Core Framework
  作者：Han Lin、Li-Jun Xiao、Min-Jie Zhou、Hong-Ming Yu、Jian-Hua Xie、Qi-Lin Zhou

  DOI：10.1021/acs.orglett.6b00369

  日期：2016.3.18

  A new strategy featuring an iridium-catalyzed asymmetric hydrogenation of a racemic ketone via dynamic kinetic resolution to generate a cyclopentanol with three contiguous stereocenters and a SmI2-promoted pinacol coupling to install the six-membered ring with correct stereochemistry has been described for the enantioselective total synthesis of (−)-hamigeran B (19 steps, 10.6% overall yield) and

  已经描述了一种新的策略，该方法通过动态动力学拆分通过铱催化外消旋酮的不对称氢化，生成具有三个连续立体中心的环戊醇，并通过SmI 2促进的频哪醇偶联以正确的立体化学方式安装六元环，从而实现了对映选择性（-）-hamigeran B（19步，总产率的10.6％）和（-）-4-bromohamigeran B（19步，总产率的12.3％）的总合成。
• Fukuyama Cross-Coupling Approach to Isoprekinamycin: Discovery of the Highly Active and Bench-Stable Palladium Precatalyst POxAP
  作者：Shuang-Qi Tang、Jacques Bricard、Martine Schmitt、Frédéric Bihel

  DOI：10.1021/acs.orglett.9b00031

  日期：2019.2.1

  identified for use in Fukuyama cross-coupling reactions. Suitable for storage under air, the POxAP precatalyst allowed reaction between thioesters and organozinc reagents with turnover numbers of ∼90000. A series of 23 ketones were obtained with yields ranging from 53 to 99%. As proof of efficacy, an alternative approach was developed for the synthesis of a key precursor of the natural product isoprekinamycin

  确定了一种有效且用户友好的钯（II）预催化剂POxAP（后氧化加成预催化剂）可用于福山交叉偶联反应。POxAP预催化剂适合在空气中储存，它可使硫代酯与有机锌试剂之间的反应发生反应，其周转数约为90000。获得了一系列23种酮，产率为53％至99％。作为功​​效的证明，开发了另一种方法来合成天然产物异普瑞霉素的关键前体。
• Total Synthesis of (Nor)illudalane Sesquiterpenes Based on a C(sp³)–H Activation Strategy
  作者：Romain Melot、Marcus V. Craveiro、Olivier Baudoin

  DOI：10.1021/acs.joc.9b01669

  日期：2019.10.18

  Three (nor)illudalane sesquiterpenes were synthesized from a common intermediate in racemic and enantioenriched forms using Pd0-catalyzed C(sp3)-H arylation as a key step. The configuration of the isolated, highly symmetric quaternary stereocenter of the target molecules was controlled through a matched combination of chiral substrate and catalyst. Moreover, the recently developed Ir-catalyzed C-H

  使用Pd0催化的C（sp3）-H芳基化为关键步骤，从外消旋和对映体富集形式的一种常见中间体合成了三（正）伊拉达拉烷倍半萜。通过手性底物和催化剂的匹配组合来控制靶分子的分离的，高度对称的四元立体中心的构型。此外，采用最近开发的Ir催化的CH硼化/ Cu催化的甲基化方法将甲基安装在苯环上。这种策略允许高效合成外消旋和（S）构型的嘌呤奎尼酸，地喹醌和russujaponol F.