3-bromo-1,4-dimethoxynaphthalen-2-yl acetate | 182875-78-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: 3-bromo-1,4-dimethoxynaphthalen-2-yl acetate
• 英文别名: 3-acetoxy-2-bromo-1,4-dimethoxynaphthalene；(3-Bromo-1,4-dimethoxynaphthalen-2-yl) acetate
• CAS: 182875-78-1
• 化学式: C₁₄H₁₃BrO₄
• 分子量: 325.159
• InChiKey: VXETWMBMVCLELK-UHFFFAOYSA-N

物化性质

• 沸点：
  405.0±45.0 °C(Predicted)
• 密度：
  1.442±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-bromo-1,4-dimethoxynaphthalen-2-yl acetate 在 甲醇 、 potassium carbonate 、 cesium fluoride 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 6.75h， 生成 6,11-dimethoxy-5H-benzo[4,5]cyclohepta[1,2-b]naphthalene-5,13(12H)-dione
  参考文献：
  名称：

  通过Aryne插入环状1,3-二酮中的苯环环化中环碳氢化合物的多用途路线：在合成Radermachol中的应用

  摘要：

  描述了一种通用方法，该方法涉及将原位生成的芳烃插入环状1,3-二酮的C–C键中，以快速组装官能化的苯并稠合的中环碳环化合物。该方法的有效性已通过简明的五环天然产物雷德马胆全合成方法得到了证明。

  DOI：

  10.1021/acs.orglett.6b01078
• 作为产物：
  描述：

  2-(1,3-dioxolan-2-yl)-1,4-dimethoxynaphthalene 在 三甲基溴硅烷 、 碘苯二乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 3-bromo-1,4-dimethoxynaphthalen-2-yl acetate
  参考文献：
  名称：

  Hypervalent Iodine Chemistry:  Mechanistic Investigation of the Novel Haloacetoxylation, Halogenation, and Acetoxylation Reactions of 1,4-Dimethoxynaphthalenes

  摘要：

  Treatment of 1,4-dimethoxynaphthalenes with iodosobenzene diacetate and trimethylsilyl chloride or bromide furnished the haloacetoxylated, acetoxylated, and halogenated 1,4-dimethoxynaphthalenes in excellent yield. The reaction pathway for each transformation was shown to be a function of reagent stoichiometry. A mechanistic hypothesis is presented that rationalizes the reaction pathways and explains the subtle differences in the halogenation reactions. The acetoxylation, for example, is thought to involve the formation of an iodonium ion that promotes the nucleophilic addition of acetate ion and subsequent 1,2-acetyl migration. Bromination occurs as a direct result of the oxidation of trimethylsilyl bromide to bromine, followed by electrophilic aromatic substitution. Chlorination is thought to proceed via a radical process and not the formation of molecular chlorine from the dissociation of iodosobenzene dichloride. The haloacetoxylation reaction also appears to be fairly specific for 1,4-dimethoxynaphthalenes, since the analogous reaction with a 1,4-dimethoxybenzene derivative was unsuccessful.

  DOI：

  10.1021/jo970525i

文献信息

• Synthesis of 2,3-Dihydro-3-hydroxy-2-hydroxylalkylbenzofurans from Epoxy Aldehydes. One-Step Syntheses of Brosimacutin G, Vaginidiol, Vaginol, Smyrindiol, Xanthoarnol, and Avicenol A. Biomimetic Syntheses of Angelicin and Psoralen
  作者：Yefen Zou、Mercedes Lobera、Barry B. Snider

  DOI：10.1021/jo047974k

  日期：2005.3.1

  [GRAPHICS]We have developed two practical one-step syntheses of 2,3-dihydro-3-hydroxy-2-hydroxyalkylbenzofurans from readily available optically pure alpha,beta-epoxy aldehydes. Electron-deficient resorcinols react with epoxy aldehydes using either Cs2CO3 in DMF or KOH/CaCl2 in MeOH to give adducts 13, 16, 18, 20, 21, and brosimacutin G (6t). Grignard reagents prepared by low-temperature halogen-metal exchange of acetoxy iodocoumarins 35d and 40 and acetoxy bromonaphthalene 41 add to epoxy aldehyde (S)-26 to complete the first syntheses of vaginidiol (7c), vaginol (7t), smyrindiol (8c), xanthoarnol (8t), and avicenol A (9t). Acid-catalyzed fragmentation of vaginidiol or vaginol provides angelicin, while that of smyrindiol or xanthoarnol affords psoralen. In both cases, the trans isomers fragment only twice as fast as the cis isomers, possibly through the intermediacy of a common benzylic cation. This may have implications for the biosynthesis of angelicin and psoralen.
• Novel haloacetoxylation of 1,4-dimethoxynaphthalenes using hypervalent iodine chemistry
  作者：P.Andrew Evans、Thomas A. Brandt

  DOI：10.1016/0040-4039(96)01427-x

  日期：1996.9

  Treatment of 1,4-dimethoxynaphthalenes with iodosobenzene and trimethylsilyl chloride or bromide furnished the corresponding 2,3-haloacetoxylated-1,4-dimethoxynaphthalenes. Copyright (C) 1996 Elsevier Science Ltd
• Versatile Route to Benzoannulated Medium-Ring Carbocycles via Aryne Insertion into Cyclic 1,3-Diketones: Application to a Synthesis of Radermachol
  作者：Ramesh Samineni、Pabbaraja Srihari、Goverdhan Mehta

  DOI：10.1021/acs.orglett.6b01078

  日期：2016.6.17

  involving the insertion of in situ generated aryne into the C–C bond of cyclic 1,3-diketones for rapidly assembling functionalized benzo-fused medium ring carbocycles is delineated. The efficacy of the methodology has been demonstrated through a concise total synthesis of pentacyclic natural product radermachol.

  描述了一种通用方法，该方法涉及将原位生成的芳烃插入环状1,3-二酮的C–C键中，以快速组装官能化的苯并稠合的中环碳环化合物。该方法的有效性已通过简明的五环天然产物雷德马胆全合成方法得到了证明。
• Hypervalent Iodine Chemistry:  Mechanistic Investigation of the Novel Haloacetoxylation, Halogenation, and Acetoxylation Reactions of 1,4-Dimethoxynaphthalenes
  作者：P. Andrew Evans、Thomas A. Brandt

  DOI：10.1021/jo970525i

  日期：1997.8.1

  Treatment of 1,4-dimethoxynaphthalenes with iodosobenzene diacetate and trimethylsilyl chloride or bromide furnished the haloacetoxylated, acetoxylated, and halogenated 1,4-dimethoxynaphthalenes in excellent yield. The reaction pathway for each transformation was shown to be a function of reagent stoichiometry. A mechanistic hypothesis is presented that rationalizes the reaction pathways and explains the subtle differences in the halogenation reactions. The acetoxylation, for example, is thought to involve the formation of an iodonium ion that promotes the nucleophilic addition of acetate ion and subsequent 1,2-acetyl migration. Bromination occurs as a direct result of the oxidation of trimethylsilyl bromide to bromine, followed by electrophilic aromatic substitution. Chlorination is thought to proceed via a radical process and not the formation of molecular chlorine from the dissociation of iodosobenzene dichloride. The haloacetoxylation reaction also appears to be fairly specific for 1,4-dimethoxynaphthalenes, since the analogous reaction with a 1,4-dimethoxybenzene derivative was unsuccessful.