2,6-bis(bromomethyl)-cis-1,3,5,7-tetraoxadecalin

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 2,6-bis(bromomethyl)-cis-1,3,5,7-tetraoxadecalin
• 英文别名: (2R,4aS,6R,8aS)-2,6-bis(bromomethyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxine
• 化学式: C₈H₁₂Br₂O₄
• 分子量: 331.989
• InChiKey: VHANEVHDWARCPI-RULNZFCNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2,6-bis(bromomethyl)-cis-1,3,5,7-tetraoxadecalin 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 100.0h， 生成 (4S,4'S)-2,2'-Bis-bromomethyl-[4,4']bi[[1,3]dioxolanyl]
  参考文献：
  名称：

  On Five- vs Six-membered Diacetal Formation from Threitol and the Intermediacy of Unusually Stable Protonated Species¹

  摘要：

  The long known, but hitherto poorly understood, thermodynamically controlled diacetalation of rac-threitol with alkylaldehydes provided bicyclic, cis-tetraoxadecalin (TOD) ("66") and bi(dioxolanyl) (BDO) ("55") products, shown to be formed in acid-concentration and temperature-dependent ratio. The configurational and conformational isomeric diacetals obtained in four such reactions of substituted aldehydes (RCHO, R = CH3, CH2Cl, CH2Br, CO2CH3) with rac-threitol were isolated and characterized. A variable acid-concentration analysis of the equilibrium mixture of products in one such case (R = CH2Br) was performed and provided equilibrium constants and, hence, free-energy differences among these products and their relatively stable protonated intermediates. The latter were rationalized by the unusually high proton-affinity calculated for the cis-TOD ("66") form.

  DOI：

  10.1021/jo9908952
• 作为产物：
  描述：

  (4S,4'S)-2,2'-Bis-bromomethyl-[4,4']bi[[1,3]dioxolanyl] 在 对甲苯磺酸 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 2,6-bis(bromomethyl)-cis-1,3,5,7-tetraoxadecalin
  参考文献：
  名称：

  On Five- vs Six-membered Diacetal Formation from Threitol and the Intermediacy of Unusually Stable Protonated Species¹

  摘要：

  The long known, but hitherto poorly understood, thermodynamically controlled diacetalation of rac-threitol with alkylaldehydes provided bicyclic, cis-tetraoxadecalin (TOD) ("66") and bi(dioxolanyl) (BDO) ("55") products, shown to be formed in acid-concentration and temperature-dependent ratio. The configurational and conformational isomeric diacetals obtained in four such reactions of substituted aldehydes (RCHO, R = CH3, CH2Cl, CH2Br, CO2CH3) with rac-threitol were isolated and characterized. A variable acid-concentration analysis of the equilibrium mixture of products in one such case (R = CH2Br) was performed and provided equilibrium constants and, hence, free-energy differences among these products and their relatively stable protonated intermediates. The latter were rationalized by the unusually high proton-affinity calculated for the cis-TOD ("66") form.

  DOI：

  10.1021/jo9908952

文献信息

• Polythiacrown Macro- and Gigantocycles with Chiral Diacetal Cores
  作者：Sarah Abramson、Dvora Berkovich-Berger、Shai Dagan、Israel Goldberg、Lara Golender、Mikhail Grabarnik、N. Gabriel Lemcoff、Sarah Weinman、Benzion Fuchs

  DOI：10.1002/ejoc.200601045

  日期：2007.4

  and gigantocyclic[9] systems, consisting of ethylene 1,2-dithioglycol (ETG) to poly(ethylene thioglycol) (ETGn) bridges over one to six diacetal units of the cis-1,3,5,7-tetraoxadecalin (TOD) type. The latter is a dissymmetric, chiral moiety, incorporating a cavity with built-in high electron lone pair concentration, serving as the “core” of chiral macrocyclic host systems with good inclusion ability

  我们提出了一类独特的聚噻冠大环和巨环 [9] 系统，由乙烯 1,2-二硫甘醇 (ETG) 到聚 (乙二醇) (ETGn) 桥接在顺式 1,3 的一到六个二缩醛单元上,5,7-四氧癸烷 (TOD) 型。后者是一个不对称的手性部分，包含一个内置高电子孤对浓度的空腔，作为手性大环主体系统的“核心”，具有良好的离子和极性分子包合能力。我们描述了两种方法：（i）2,6-双（溴甲基）-顺式-TOD podand（6）与ETG或更高ETGns（12n）的反应，在Cs2CO3促进过程中，导致先天但不受控制的形成多硫冠-TOD 大环具有 1:1 (7)、2:2 (8) 和进一步的 3:3–6:6 (111/m) 10 大环的 ETG/TOD 比，通过开放二硫醇中间体，(ii) 使用 K2CO3 明智地制备 ETGn:TOD 比率为 1:2、2:3 或 3:4 (14n/m) 的低聚二溴化物中间体，这导致（进一步
• Grabarnik, Mikhail; Goldberg, Israel; Fuchs, Benzion, Journal of the Chemical Society. Perkin transactions I, 1997, # 21, p. 3123 - 3125
  作者：Grabarnik, Mikhail、Goldberg, Israel、Fuchs, Benzion

  DOI：——

  日期：——
• On Five- vs Six-membered Diacetal Formation from Threitol and the Intermediacy of Unusually Stable Protonated Species¹
  作者：Mikhail Grabarnik、N. Gabriel Lemcoff、Ravit Madar、Sarah Abramson、Sarah Weinman、Benzion Fuchs

  DOI：10.1021/jo9908952

  日期：2000.3.1

  The long known, but hitherto poorly understood, thermodynamically controlled diacetalation of rac-threitol with alkylaldehydes provided bicyclic, cis-tetraoxadecalin (TOD) ("66") and bi(dioxolanyl) (BDO) ("55") products, shown to be formed in acid-concentration and temperature-dependent ratio. The configurational and conformational isomeric diacetals obtained in four such reactions of substituted aldehydes (RCHO, R = CH3, CH2Cl, CH2Br, CO2CH3) with rac-threitol were isolated and characterized. A variable acid-concentration analysis of the equilibrium mixture of products in one such case (R = CH2Br) was performed and provided equilibrium constants and, hence, free-energy differences among these products and their relatively stable protonated intermediates. The latter were rationalized by the unusually high proton-affinity calculated for the cis-TOD ("66") form.