ethyl-(α-chloro-benzyl)-ether | 27975-74-2

• 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: ethyl-(α-chloro-benzyl)-ether
• 英文别名: Aethyl-(α-chlor-benzyl)-aether；(Chloro-ethoxymethyl)benzene；[chloro(ethoxy)methyl]benzene
• CAS: 27975-74-2
• 化学式: C₉H₁₁ClO
• 分子量: 170.639
• InChiKey: QGIXSMXIYQMWDB-UHFFFAOYSA-N

物化性质

• 沸点：
  211.3±20.0 °C(Predicted)
• 密度：
  1.085±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  11
• 可旋转键数：
  3
• 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：

  ethyl-(α-chloro-benzyl)-ether 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 生成 2-(4-氯苯基)-1-苯乙酮
  参考文献：
  名称：

  Schaumann,E.; Grabley,F.-F., Justus Liebigs Annalen der Chemie, 1977, p. 88 - 100

  摘要：

  DOI：
• 作为产物：
  描述：

  苯甲醛二乙缩醛 在 氯化亚砜 、 乙酰氯 作用下， 生成 ethyl-(α-chloro-benzyl)-ether
  参考文献：
  名称：

  与有机磷化合物合成，II。PO活化的烷氧基烯化

  摘要：

  α-酮羧酸酯，α-酮甲酰胺，1，2-二酮和苯基酮的烯醇醚是通过醛和酮的“ PO-活化的烷氧基烯化”而合成的。

  DOI：

  10.1002/jlac.19666990106

文献信息

• Dimensiosolvatic Effects. IV. Topomerization in Alkyl<b><i>α</i></b>-Chlorobenzyl Ethers and Insights into Mechanisms of Their Thermolyses
  作者：Michinori Oki、Hiroshi Ikeda、Hiromichi Miyake、Hirohito Mishima、Shinji Toyota

  DOI：10.1246/bcsj.71.915

  日期：1998.4

  Rates of topomerization in α-chlorobenzyl ethyl ether and its p-methyl as well as p-methoxy derivatives were determined in various solvents by the dynamic NMR method. The topomerization process was deduced to be ionic because the rates are enhanced in polar solvents as well as by electron-donating substituents. Concentration dependence study of the topomerization in carbon tetrachloride revealed that the observed process is unimolecular; the rates are not affected by concentration of the substrate if the concentration is lower than 0.2 mol L−1. The rates of topomerization are smaller for solutions in bulky solvents than in small solvents, the effects being clear for compounds with electron-donating substituents. The key feature of the kinetic parameters is that the entropy of activation is large and negative for all the solvents examined. The reaction mechanisms are discussed on the basis of these data. The effects of the molecular size of the solvent, dimensiosolvatic effects, are attributed to the effectiveness of the solvation in the formation of ion pairs. The results show that thermolyses of alkyl α-chlorobenzyl ethers are much slower reactions than the ionization. The nature of the reaction is discussed.

  利用动态NMR方法，在不同溶剂中测定了α-氯苄基乙基醚及其对甲基和对甲氧基衍生物的异构化速率。推断异构化过程为离子型，因为在极性溶剂中以及电子供体取代基的存在下，异构化速率得到增强。通过在四氯化碳中对异构化的浓度依赖性研究揭示，观察到的过程是单分子的；如果底物浓度低于0.2 mol L−1，异构化速率不受浓度的影响。在大体积溶剂中溶液的异构化速率比在小体积溶剂中小，对于具有电子供体取代基的化合物，这种效应很明显。动力学参数的关键特征是，对于所有检测的溶剂，活化熵都是大且负值。基于这些数据讨论了反应机理。溶剂分子大小、溶剂维度效应的影响归因于离子对形成中的溶剂化效果。结果表明，烷基α-氯苄基醚的热分解反应比电离反应慢得多。讨论了反应的性质。
• Studies on hypolipidemic agents. I. Synthesis of 1,3-dioxolanes and 1,3-dioxanes.
  作者：AKASHI ERIGUCHI、TOSHIO TAKEGOSHI

  DOI：10.1248/cpb.30.428

  日期：——

  2-Aryl-substituted 3a, 4, 5, 9b-tetrahydronaphtho [1, 2-d]-1, 3-dioxolanes (4), 5-phenyl-(6), 5-(1, 2, 3, 4-tetrahydro-2-naphthyl)-(7) and 5-(2-naphthyl)-1, 3-dioxanes (8) and 3-aryl-substituted 1H-naphtho [2, 1-d] [1, 3] dioxins (5) were synthesized. Among them, the 1, 3-dioxanes (6-8) were each obtained as a mixture of the trans and cis isomers. Two stereoisomers of the 2-(3-pyridyl)-substituted derivatives (6c and 7c) and the trans isomers of the other 1, 3-dioxanes (6-8) were isolated and their stereostructures are discussed. Most of the trans isomers of 6-8 showed potent hypolipidemic activity, while the cis isomers were inactive. The most active compound was the trans isomer of 7c.

  2-芳基取代的3a, 4, 5, 9b-四氢萘并[1, 2-d]-1, 3-二氧杂环戊烷（4）、5-苯基衍生物（6）、5-（1, 2, 3, 4-四氢-2-萘基）衍生物（7）和5-（2-萘基）-1, 3-二氧杂环戊烷（8）以及3-芳基取代的1H-萘并[2, 1-d][1, 3]二氧辛英（5）被合成。其中，1, 3-二氧杂环戊烷（6-8）各自以反式和顺式异构体的混合物形式获得。两种立体异构体的2-（3-吡啶基）取代衍生物（6c和7c）以及其它1, 3-二氧杂环戊烷（6-8）的反式异构体被分离出来，并讨论了它们的立体结构。大多数6-8的反式异构体表现出强大的降血脂活性，而顺式异构体则无活性。活性最高的化合物是7c的反式异构体。
• [EN] CONJUGATES OF HETEROAROMATIC NITROGEN-COMPRISING COMPOUNDS<br/>[FR] CONJUGUÉS DE COMPOSÉS HÉTÉROAROMATIQUES CONTENANT DE L'AZOTE
  申请人：ASCENDIS PHARMA AS

  公开号：WO2020254606A1

  公开（公告）日：2020-12-24

  The present invention relates to conjugates of ΤΓ-electron-pair-donating heteroaromatic nitrogen-comprising drugs and pharmaceutically acceptable salts thereof, pharmaceutical compositions comprising said conjugates and the use of said conjugates as medicaments.

  本发明涉及ΤΓ-电子对供体杂芳氮含药物及其药用盐的结合物，包括所述结合物的药物组合物以及将所述结合物用作药物的用途。
• Azobisisobutyronitrile-Initiated Oxidative C–H Functionalization of Simple Alcohols with Diaryl(arylethynyl)phosphine Oxides: A Metal-Free Approach toward Hydroxymethyl Benzo[<i>b</i>]phosphole Oxides and 6<i>H</i>-Indeno[2,1-<i>b</i>]phosphindole 5-Oxide Derivatives
  作者：Jiami Guo、Chenlu Mao、Bin Deng、Liyi Ye、Yingwu Yin、Yuxing Gao、Song Tu

  DOI：10.1021/acs.joc.0c00118

  日期：2020.5.15

  described with azobisisobutyronitrile as a radical initiator, affording an efficient and one-pot procedure to access a new class of hydroxymethyl benzo[b]phosphole oxides and 6H-indeno[2,1-b]phosphindole 5-oxides for potential application in organic materials via sequential C(sp3)-H/C(sp2)-H functionalization. The method employs easily accessible starting materials and is endowed with high regioselectivity

  用偶氮二异丁腈作为自由基引发剂，已经描述了用二芳基（芳基乙炔基）膦氧化物对简单的醇进行的首次无金属且容易的自由基加成/环化反应，并提供了一种有效的单罐方法来获得一类新的羟甲基苯并[b]。磷氧化物和6H-茚并[2,1-b]磷吲哚5-氧化物可通过连续的C（sp3）-H / C（sp2）-H官能化潜在地应用于有机材料。该方法采用易于获得的原料，并具有较高的区域选择性和宽泛的官能团耐受性。
• A New Type of P–C and C–C Bond Cleavage Reactions in α-Trimethylsilyloxy-β-oxo Phosphonates and α-Ethoxy-β-oxo Phosphonates. The Synthesis of Unsymmetrical α-Hydroxy Ketones Utilizing 1:1 Carbonyl Adducts of Diethyl Trimethylsilyl Phosphite with Benzaldehyde
  作者：Mitsuo Sekine、Masashi Nakajima、Tsujiaki Hata

  DOI：10.1246/bcsj.55.218

  日期：1982.1

  α-Lithiated diethyl α-(trimethylsilyloxy)benzylphosphonate underwent facile acylation with various acylating agents to afford the corresponding α-acylated products in good yields. On treatment of the α-acylated products with 1 M NaOH–EtOH (1:1, v/v) the P–C bond was cleaved with elimination of diethyl phosphate to give α-hydroxy ketones predominantly. On the other hand, when diethyl α-acyl-α-ethoxybenzylphosphonates

  α-锂化的 α-（三甲基甲硅烷氧基）苄基膦酸二乙酯与各种酰化剂进行轻松酰化，以良好的收率得到相应的 α-酰化产物。在用 1 M NaOH-EtOH (1:1, v/v) 处理 α-酰化产物时，P-C 键断裂并消除磷酸二乙酯，主要得到 α-羟基酮。另一方面，当 α-酰基-α-乙氧基苄基膦酸二乙酯在相同条件下处理时，它们相当稳定并且可以回收。然而，长时间的碱处理或使用 4 M NaOH-EtOH (1:1, v/v) 导致 C-C 键断裂，分别以定量产率得到羧酸和 α-乙氧基苄基膦酸二乙酯。结合Perkow反应和相关反应提出并讨论了上述两个反应的机理。