1-溴-2-(溴甲基)-4-甲氧基-6-甲基苯 | 164513-49-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-溴-2-(溴甲基)-4-甲氧基-6-甲基苯
• 英文名称: 2-bromo-1-(bromomethyl)-5-methoxy-3-methylbenzene
• CAS: 164513-49-9
• 化学式: C₉H₁₀Br₂O
• 分子量: 293.986
• InChiKey: XBEAMDITEJRHPE-UHFFFAOYSA-N

物化性质

• 沸点：
  319.0±37.0 °C(Predicted)
• 密度：
  1.676±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  12
• 可旋转键数：
  2
• 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

安全信息

• 储存条件：
  室温密封，干燥保存。

反应信息

• 作为反应物：
  描述：

  1-溴-2-(溴甲基)-4-甲氧基-6-甲基苯 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 生成 2-bromo-1,3-bis(bromomethyl)-5-methoxybenzene
  参考文献：
  名称：

  Nuclear versus Side-Chain Bromination of Methyl-Substituted Anisoles by N-Bromosuccinimide

  摘要：

  The reactions of methyl-substituted anisoles with N-bromosuccinimide in CCl4 are reported. In the absence of a catalyst and under irradiation, some of these substrates undergo nuclear bromination in competition with the well-known side-chain bromination. With 2-methylanisole and with 2,6-dimethylanisole, nuclear bromination is not observed, whereas with 3,5-dimethylanisole, nuclear bromination at the 4-position is the dominating reaction. Investigation of the reactivity of several other methyl-substituted anisoles revealed the following general trend: methyl-substituted anisoles are attacked at the position para to the methoxy group rather than at the side chain when (at least) two methyl groups are present at positions 3 and 5. When positions 2 and 6 are both occupied, nuclear bromination is retarded; in 2,6-dimethylanisole and in 2,3,6-trimethylanisole, only side-chain bromination is observed. In contrast, in 2,3,5,6-tetramethylanisole, the 4-position is sufficiently reactive to be brominated, because the decrease in reactivity by the presence of two methyl groups at positions 2 and 6 is overruled by the two additional methyl groups at positions 3 and 5; as a result, both nuclear and side-chain bromination occur. The observed chemospecificity can be rationalized by a difference in mechanism: the side-chain bromination is a radical reaction, while the nuclear bromination is an electrophilic aromatic substitution reaction, which is so far contrary to expectation, as irradiation had been expected to favor radical processes.

  DOI：

  10.1021/jo00095a023
• 作为产物：
  描述：

  3,5-二甲基苯酚 在 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 溴 作用下， 以 甲醇 、 四氯化碳 为溶剂， 反应 5.0h， 生成 1-溴-2-(溴甲基)-4-甲氧基-6-甲基苯
  参考文献：
  名称：

  新的2,2'-取代的4,4'-二甲氧基-6,6'-二甲基[1,1'-联苯]，在液晶中产生很强的螺旋扭曲力。

  摘要：

  基于手性残基稳定分子运动，开发了用于向列型液晶的新型光学活性联苯手性掺杂剂。通过在手性联苯的2,2'-位引入介晶残基来获得这种分子拥塞。这导致了一种新颖的分子结构，该结构被认为是有效的。当用作向列型液晶中的手性掺杂剂时，合成的光学活性联苯具有很短的胆甾型节距特征。描述了对映体纯联苯掺杂剂的合成及其初步的物理化学特征。

  DOI：

  10.1002/chem.200400035

文献信息

• [EN] NOVEL THIOPHENE AMIDINES, COMPOSITIONS THEREOF, AND METHODS OF TREATING COMPLEMENT-MEDIATED DISEASES AND CONDITIONS<br/>[FR] NOUVELLES AMIDINES DE THIOPHENE, COMPOSITIONS DE CES AMIDINES ET PROCEDE POUR TRAITER DES MALADIES ET DES ETATS MEDIES PAR LE COMPLEMENT
  申请人：DIMENSIONAL PHARM INC

  公开号：WO2003099805A1

  公开（公告）日：2003-12-04

  Disclosed is a method for treating the symptoms of an acute or chronic disorder mediated by the classical pathway of the complement cascade, comprising administering to a mammal in need of such treatment a therapeutically effective amount of a compound of Formula (I) or a solvate, hydrate or pharmaceutically acceptable salt thereof; wherein R1, R2, R3, R4 and R7 are defined in the specification, Z is SO or SO2, and Ar is an aromatic or heteroaromatic group as defined herein.

  揭示了一种治疗急性或慢性疾病症状的方法，该方法通过补体级联的经典途径介导，包括向需要此类治疗的哺乳动物施用化合物I的治疗有效量或其溶剂化合物、水合物或药用可接受盐；其中规范中定义了R1、R2、R3、R4和R7，Z为SO或SO2，Ar为本规范中定义的芳香族或杂环芳基。
• Novel thiophene amidines, compositions thereof, and methods of treating complement-mediated diseases and conditions
  申请人：3-Dimensional Pharmaceuticals, Inc.

  公开号：US20040009995A1

  公开（公告）日：2004-01-15

  Disclosed is a method for treating the symptoms of an acute or chronic disorder mediated by the classical pathway of the complement cascade, comprising administering to a mammal in need of such treatment a therapeutically effective amount of a compound of Formula I 1 or a solvate, hydrate or pharmaceutically acceptable salt thereof; wherein R 1 , R 2 , R 3 , R 4 and R 7 are defined in the specification, Z is SO or SO 2 , and Ar is an aromatic or heteroaromatic group as defined herein.

  揭示了一种治疗急性或慢性疾病症状的方法，该方法通过补体级联的经典途径介导，包括向需要此类治疗的哺乳动物施用公式I的化合物的治疗有效量或其溶剂化合物、水合物或药用可接受盐；其中在规范中定义了R1、R2、R3、R4和R7，Z为SO或SO2，Ar为本文中定义的芳香族或杂环芳基。
• Regioselectivity in free radical bromination of unsymmetrical dimethylated pyridines
  作者：Rajesh Thapa、Jordan Brown、Thomas Balestri、Richard T. Taylor

  DOI：10.1016/j.tetlet.2014.08.069

  日期：2014.12

  literature review some curious inconsistencies in the free radical bromination of picolines were noted. To achieve a better understanding of the mechanisms and regioselectivity we reran these reactions, extending our work to unsymmetrical lutidines using N-bromosuccinimide in limiting amount. Characterization of the products was done with GC/MS and H NMR. The regioselectivity of bromination in unsymmetrical

  在一篇文献综述中，人们注意到甲基吡啶的自由基溴化过程中存在一些奇怪的矛盾之处。为了更好地理解其机理和区域选择性，我们重新进行了这些反应，并使用有限量的N-溴代琥珀酰亚胺将工作扩展到不对称的二甲基吡啶。用GC / MS和1 H NMR对产物进行表征。在不对称的二甲基吡啶中溴的区域选择性表明环中的氮被感应失活。2,3、2,4和2,5二甲基吡啶对溴的竞争导致溴化在距离环中N最远的甲基中进行。3,4-亮氨酸仅显示4,4-二溴化产物。
• Reactions of [2-(2-Naphthyl)phenyl]acetylenes and 2-(2-Naphthyl)benzaldehyde<i>O</i>-Phenyloximes: Synthesis of the Angucycline Tetrangulol and 1,10,12-Trimethoxy-8-methylbenzo[<i>c</i>]phenanthridine
  作者：Kennedy J. Ngwira、Amanda L. Rousseau、Myron M. Johnson、Charles B. de Koning

  DOI：10.1002/ejoc.201601373

  日期：2017.3.17

  Suzuki-Miyaura coupling reaction between 1,4,5-(trimethoxynaphthalen-2-yl)boronic acid and 2-iodo-3-methoxy-5-methylbenzaldehyde afforded intermediate, 3-methoxy-5-methyl-2-(1,4,5-trimethoxynaphthalen-2-yl)benzaldehyde. Conversion of this benzaldehyde into the alkyne, 2-(2-ethynyl-6-methoxy-4-methylphenyl)-1,4,5-trimethoxynaphthalene was accomplished utilizing the Corey-Fuchs reaction. Exposure of the derived

  1,4,5-(三甲氧基萘-2-基)硼酸和2-碘-3-甲氧基-5-甲基苯甲醛之间的铃木-宫浦偶联反应得到中间体3-甲氧基-5-甲基-2-(1, 4,5-三甲氧基萘-2-基）苯甲醛。该苯甲醛转化为炔烃，2-(2-乙炔基-6-甲氧基-4-甲基苯基)-1,4,5-三甲氧基萘是利用 Corey-Fuchs 反应完成的。将衍生的乙炔暴露于催化铂 (II) 介导的闭环产生所需的四环芳烃产物 1,7,8,12-四甲氧基-3-甲基四苯，其转化为四丁醇。将相关的 3-甲氧基-5-甲基-2-(1,4,5-三甲氧基萘-2-基)苯甲醛邻苯基肟在离子液体中暴露于微波辐射下产生 1,10,12-三甲氧基-8-甲基苯并[c]菲啶，
• Practical Synthesis of the Trisubstituted Naphthalene Carboxylic Acid from Neocarzinostatin Chromophore
  作者：Mark Rucker、Reinhard Brückner

  DOI：10.1055/s-1997-983

  日期：1997.10

  Neocarzinostatin carboxylic acid (5) has been synthesized in 33% overall yield by a nine-step sequence which is operationally easy enough to be carried out by second-year chemistry students. 3,5-dimethylanisole was brominated in the para and in one benzylic position so that an SN2 reaction with sodium cyanide led to the cyanated aryl bromide 15. Heck-coupling with ethyl acrylate gave the α,β-unsaturated ester 14. It was converted into the saturated diester 18 through dissolving-metal reduction, saponification of nitrile and ester groups, and re-esterification with MeOH. Dieckmann cyclization and dehydroaromatization furnished ester 19 whose hydrolysis to the title compound 5 has been known.

  新制癌菌素羧酸 (5) 通过九个步骤合成，总产率为 33%，操作简单，二年级化学学生即可完成。 3,5-二甲基苯甲醚在对位和一个苄基位置被溴化，以便与氰化钠发生 SN2 反应，生成氰化芳基溴 15。与丙烯酸乙酯进行 Heck 偶联，得到 α,β-不饱和酯 14。通过溶解金属还原、腈基和酯基的皂化、再酯化，转化为饱和二酯18甲醇。 Dieckmann环化和脱氢芳构化得到酯19，其水解成标题化合物5是已知的。

表征谱图