2-(2-甲基-1,3-二噁烷-2-基)乙酸乙酯 | 90293-83-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 中文名称: 2-(2-甲基-1,3-二噁烷-2-基)乙酸乙酯
• 英文名称: 2-<(ethoxycarbonyl)methyl>-2-methyl-1,3-dioxane
• 英文别名: methyl-2 dioxanne-1,3 acetate-2 d'ethyle；2-Methyl-2-aethoxycarbonylmethyl-1,3-dioxan；(2-methyl-[1,3]dioxan-2-yl)-acetic acid ethyl ester；(2-Methyl-[1,3]dioxan-2-yl)-essigsaeure-aethylester；Ethyl 2-(2-methyl-1,3-dioxan-2-yl)acetate
• CAS: 90293-83-7
• 化学式: C₉H₁₆O₄
• 分子量: 188.224
• InChiKey: XMLLBDKQPQZGDP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 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：

  2-(2-甲基-1,3-二噁烷-2-基)乙酸乙酯 在 盐酸 、 sodium hydroxide 、 三乙胺 、 氯甲酸甲酯 作用下， 生成 2-(3'-diazo-2'-oxopropyl)-2-methyl-1,3-dioxane
  参考文献：
  名称：

  Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides

  摘要：

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.

  DOI：

  10.1021/jo961844x
• 作为产物：
  描述：

  乙酰乙酸乙酯 、 1,3-丙二醇 在 对甲苯磺酸 作用下， 生成 2-(2-甲基-1,3-二噁烷-2-基)乙酸乙酯
  参考文献：
  名称：

  Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides

  摘要：

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.

  DOI：

  10.1021/jo961844x

文献信息

• Bioinspired Collective Syntheses of Iboga-Type Indole Alkaloids
  作者：Gaoyuan Zhao、Xingang Xie、Haiyu Sun、Ziyun Yuan、Zhuliang Zhong、Shouchu Tang、Xuegong She

  DOI：10.1021/acs.orglett.6b00989

  日期：2016.5.20

  We present the application of a bioinspired collective synthesis strategy in the total syntheses of seven iboga-type indole alkaloids: (±)-tabertinggine, (±)-ibogamine, (±)-ibogaine, (±)-ibogaine hydroxyindolenine, (±)-3-oxoibogaine hydroxyindolenine, (±)-iboluteine, and (±)-ervaoffines D. In particular, tabertinggine and its congeners serve as iboga precursors for the subsequent biomimetic transformations

  我们提出了一种生物启发性的集体合成策略在七个iboga型吲哚生物碱的总合成中的应用：（±）-他汀丁，（±）-ibogamine，（±）-ibogaine，（±）-ibogaine羟基吲哚肾上腺素，（±） -3-氧代bogaine羟吲哚胺，（±）-iboluteine和（±）-ervaoffinesD。特别是，他培他汀及其同类物可作为iboga前体，用于随后的仿生转化为其他iboga型生物碱。
• Synthese electrochimique de methoxy-2 dioxa-1,4 cyclanes par oxydation anodique de cetals cycliques de β-ceto-carboxylates
  作者：Daniel Lelandais、Cathy Bacquet、Jacques Einhorn

  DOI：10.1016/s0040-4020(01)98845-3

  日期：1981.1

  Anodic oxidation of β-oxocarboxylate cyclic acetals in anhydrous methanol gives 2-methoxy-1,4-diox-acycloalkanes in 40–60% yields. The mechanism is discussed.

  β-氧代羧酸环缩醛在无水甲醇中的阳极氧化以40-60％的收率得到2-甲氧基-1,4-二氧-无环烷烃。讨论了该机制。
• Oxygen-containing hererocyclic compound, processes for their preparation and pharmaceutical compositions comprising them
  申请人：FUJISAWA PHARMACEUTICAL CO., LTD.

  公开号：EP0346511A1

  公开（公告）日：1989-12-20

  A compound of the formula : wherein R¹ is hydrogen or lower alkyl, R² is carboxy(lower)alkyl or protected carboxy(lower)alkyl and R³ is -CH₂NH-R⁴, -CH=N-R⁴ or -CH₂-R⁵ in which R⁴ is acyl, acylamino, heterocyclic amino, heterocyclic(lower)alkyl or ar(lower)alkoxy and R⁵ is acyloxy or heterocyclic(lower)alkoxy and X is -O- or -CH₂-, or pharmaceutically acceptable salt thereof, processes for their preparation and pharmaceutical compositions comprising them as an active ingredient.

  一种化合物的公式为：其中R¹为氢或较低的烷基，R²为羧基(较低)烷基或保护羧基(较低)烷基，R³为-CH₂NH-R⁴、-CH=N-R⁴或-CH₂-R⁵，其中R⁴为酰基、酰胺基、杂环氨基、杂环(较低)烷基或芳基(较低)烷氧基，R⁵为酰氧基或杂环(较低)烷氧基，X为-O-或-CH₂-，或其药学上可接受的盐，以及其制备方法和包含它们作为活性成分的药物组合物。
• Salmi, Chemische Berichte, 1938, vol. 71, p. 1803,1807
  作者：Salmi

  DOI：——

  日期：——
• Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides
  作者：Akira Oku、Nobuhito Murai、Julia Baird

  DOI：10.1021/jo961844x

  日期：1997.4.1

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.

表征谱图