4-(allyloxy)-1,2-dimethoxybenzene | 6906-64-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-(allyloxy)-1,2-dimethoxybenzene
• 英文别名: Allyl (3,4-dimethoxyphenyl) ether；1,2-dimethoxy-4-prop-2-enoxybenzene
• CAS: 6906-64-5
• 化学式: C₁₁H₁₄O₃
• 分子量: 194.23
• InChiKey: APBVQAHSAWNALZ-UHFFFAOYSA-N

物化性质

• 沸点：
  114 °C(Press: 2 Torr)
• 密度：
  1.024±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(allyloxy)-1,2-dimethoxybenzene 生成 4,5-二甲氧基-2-(2-丙烯基)苯酚
  参考文献：
  名称：

  合成苯并稠合双环化合物的开环易位

  摘要：

  闭环复分解（RCM）用于合成五个4 H-色烯，萘酚和茚满醇。这些是应用于此类苯并稠合双环化合物合成的RCM的第一个实例。

  DOI：

  10.1016/s0040-4039(02)02522-4
• 作为产物：
  描述：

  (3,4-Dimethoxyphenyl) (1-propenyl) ether 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 生成 4-(allyloxy)-1,2-dimethoxybenzene
  参考文献：
  名称：

  Thermodynamic, spectroscopic, and density functional theory studies of allyl aryl and prop-1-enyl aryl ethers. Part 1. Thermodynamic data of isomerization

  摘要：

  通过对70对异构化的烯丙基苯基醚（a）和（Z）-丙-1-烯基苯基醚（b）在DMSO溶液中的化学平衡研究，考察了它们相对热力学稳定性的变化。从平衡常数随温度的变化中，评估了在298.15 K下的异构化吉布斯自由能、焓和熵。由于其低焓值，（Z）-丙-1-烯基苯基醚在平衡状态下具有显著优势，a→b异构化的吉布斯自由能范围从-12至-23 kJ/mol。在大多数反应中，熵的贡献可以忽略不计，但偶尔会发现小于+10 J/K·mol的正值。平衡研究还扩展到涉及两对在烯键C(2)位置带有甲基取代基的相关异构化醚。甲基取代基可以增加烯丙基醚的相对热力学稳定性约3.4 kJ/mol。

  DOI：

  10.1039/b101837j

文献信息

• Investigating the microwave-accelerated Claisen rearrangement of allyl aryl ethers: Scope of the catalysts, solvents, temperatures, and substrates
  作者：Zi Hui、Songwei Jiang、Xiang Qi、Xiang-Yang Ye、Tian Xie

  DOI：10.1016/j.tetlet.2020.151995

  日期：2020.6

  The microwave-accelerated Claisen rearrangement of allyl aryl ethers was investigated, in order to gain insight into the scope of the catalysts, solvents, temperatures, and substrates. Among the catalysts examined, phosphomolybdic acid (PMA) was found to greatly accelerate the reaction in NMP, at temperatures ranging from 220 to 300 °C. This method was found to be useful for preparing several intermediates

  对微波加速烯丙基芳基醚的克莱森重排进行了研究，以便深入了解催化剂，溶剂，温度和底物的范围。在所考察的催化剂中，发现磷钼酸（PMA）在220至300°C的温度下可大大促进NMP中的反应。发现该方法对于使用贵金属催化剂例如Au（I），Ag（I）和Pt（II）制备先前在文献中报道的几种中间体是有用的。另外，在芳基部分带有溴和硝基的底物需要仔细调整反应条件，以避免复杂的产物分布。
• An improved method for the conversion of oxiranes to thiiranes and the discrimination of their base peaks in EI-MS
  作者：Hsing-Ming Chen、Po-Yuan Chen、Chih-Feng Wang、Jui-Chi Tsai、Eng-Chi Wang

  DOI：10.3998/ark.5550190.0013.815

  日期：——

  An efficient method for the conversion of oxiranes to thiiranes by treatment with excess ammonium thiocyanate in aqueous media under reflux or by microwave irradiation is reported.

  报道了一种将环氧乙烷转化为硫杂丙环的有效方法，该方法是在水介质中回流或微波照射下用过量的硫氰酸铵处理。
• A Biomimetic Approach to Dihydrobenzofuran Synthesis
  作者：John W. Benbow、Reeti Katoch-Rouse

  DOI：10.1021/jo000696e

  日期：2001.7.1

  precursors 10 is presented. The putative oxonium ion intermediate 17 formed by an intramolecular hydroxyl cyclization followed by dehydration is reduced in situ by an added dihydroquinone source. Good to excellent yields of cyclized products are realized in all cases except for highly electron deficient systems, and these suffer reduction prior to oxonium ion formation. All products are monomeric and

  提出了一种由2-（2'-羟乙基）醌前体10酸催化构造二氢苯并呋喃杂环（14）的方法。通过分子内羟基环化然后脱水形成的假定的氧鎓离子中间体17通过添加的二氢醌源原位还原。除高度缺乏电子的系统外，在所有情况下均实现了良好至优异的环化产物收率，并且这些化合物在形成氧离子之前遭受还原。除10克外，所有产物均为单体，均来自两电子转移，可得到二聚二氢苯并呋喃。环化或还原产物的量取决于醌底物与二氢醌添加剂之间的HOMO / LUMO间隙，
• Metabolism of Methylisoeugenol in Liver Microsomes of Human, Rat, and Bovine Origin
  作者：Alexander T. Cartus、Karl-Heinz Merz、Dieter Schrenk

  DOI：10.1124/dmd.111.038851

  日期：2011.9

  Methylisoeugenol (1,2-dimethoxy-4-propenylbenzene, 1) is a minor constituent of essential oils, naturally occurring as a mixture of cis/trans isomers. 1 is a U.S. Food and Drug Administration-approved food additive and has been given “Generally Recognized as Safe” status. Previously, metabolism of 1 has been studied in the rat, revealing mainly nontoxic cinnamoyl derivatives as major metabolites. However, data concerning the possible formation of reactive intermediary metabolites are not available to date. In this study, the oxidative metabolism of 1 was studied using liver microsomes of rat [not induced, rat liver microsomes (RLM); Aroclor1254 induced RLM (ARLM)], bovine, and human (pooled from 150 donors) origin. Incubations of these microsomes with 1 provided phase I metabolites that were separated by high-performance liquid chromatography (HPLC) and identified by NMR and UV-visible spectroscopy and/or liquid chromatography-mass spectrometry. Identity was confirmed by comparison with 1H NMR spectra of synthesized reference compounds. Formation of metabolites was quantified by HPLC/UV using dihydromethyleugenol (10) synthesized as the internal standard. From incubations of ARLM with 1, seven metabolites could be detected, with 3′-hydroxymethylisoeugenol (2), isoeugenol and isochavibetol (3 + 4), and 6-hydroxymethylisoeugenol (5) being the main metabolites. Secondary metabolites derived from 1 were identified as the α,β-unsaturated aldehyde 3′-oxomethylisoeugenol (6) and 1′,2′-dihydroxy-dihydromethylisoeugenol (7). We were surprised to find that formation of allylic 6-hydroxymethyleugenol (8) was observed starting at approximately 30 min after the beginning of incubations with ARLM. HLM did not form ring-hydroxylated metabolites but were most active in the formation of 6 and 7. ARLM incubations displayed the highest turnover rate and broadest metabolic pattern, presumably resulting from an increased expression of cytochrome P450 enzymes. In conclusion, we present a virtually complete pattern of nonconjugated microsomal metabolites of 1 comprising reactive metabolites and suggest the formation of reactive intermediates that need more investigation with respect to their possible adverse properties.

  美克尔异香豆烯（1,2-二甲氧基-4-丙烯基苯，1）是精油中的次要成分，自然以顺式/反式异构体的混合物存在。1是美国食品药品管理局批准的食品添加剂，并已被认定为“普遍认为安全”。此前，已经在大鼠中研究了1的代谢，主要发现无毒的肉桂酸衍生物作为主要代谢物。然而，目前尚无关于可能形成反应性中间代谢物的数据。在本研究中，我们使用大鼠（未诱导的大鼠肝微粒体；Aroclor1254诱导的大鼠肝微粒体（ARLM））、牛和人类（来自150名供体的 pooled）肝微粒体研究了1的氧化代谢。将这些微粒体与1共同孵育后，获得了第一相代谢物，这些代谢物通过高效液相色谱（HPLC）分离，并通过核磁共振（NMR）和紫外-可见光谱分析和/或液相色谱-质谱法（LC-MS）进行鉴定。通过与合成的对照化合物的1H NMR光谱进行比较来确认其身份。代谢物的形成通过使用合成的内标二氢美克尔异香豆烯（10）进行HPLC/UV定量。从ARLM与1的孵育中，可以检测到七种代谢物，主要代谢物包括3′-羟甲基美克尔异香豆烯（2）、美克尔异香豆烯及异香豆醇（3 + 4），以及6-羟甲基美克尔异香豆烯（5）。从1衍生的次级代谢物被确定为α,β-不饱和醛3′-氧甲基美克尔异香豆烯（6）和1′,2′-二羟基-二氢美克尔异香豆烯（7）。我们惊讶地发现，观察到烯丙基6-羟甲基美克尔异香豆烯（8）的形成，起始于与ARLM孵育约30分钟后。人类肝微粒体（HLM）未形成环羟基化代谢物，但在6和7的形成方面最为活跃。ARLM的孵育显示出最高的周转率和最广泛的代谢模式，这可能是由于细胞色素P450酶的表达增加。总之，我们呈现了1的几乎完整的非结合微粒体代谢物谱，包含反应性代谢物，并建议形成需要更多研究以了解其潜在不良性质的反应性中间体。
• Total Synthesis of (−)-Haouamine B Pentaacetate and Structural Revision of Haouamine B
  作者：Yuichi Momoi、Kei-ichiro Okuyama、Hiroki Toya、Kenji Sugimoto、Kentaro Okano、Hidetoshi Tokuyama

  DOI：10.1002/anie.201407686

  日期：2014.11.24

  The enantiocontrolled total synthesis of (−)‐haouamine B pentaacetate was accomplished via an optically active indane‐fused β‐lactam, which was prepared by a newly developed Friedel–Crafts reaction. Subsequent cleavage of the β‐lactam and an intramolecular McMurry coupling reaction provided the core indane‐fused tetrahydropyridine, which led to the elucidation of the structure, as proposed by Trauner

  对映体控制的（-）-haouamine B五乙酸酯的全合成是通过光学活性的茚满-β-内酰胺完成的，这是由新开发的Friedel-Crafts反应制备的。随后β-内酰胺的裂解和分子内McMurry偶联反应提供了核心的茚满融合的四氢吡啶，从而阐明了结构，正如Trauner和Zubia所提出的那样。