2-methyl-2-(3-bromopropyl)-5,5-dimethyl-1,3-dioxane | 88128-58-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-2-(3-bromopropyl)-5,5-dimethyl-1,3-dioxane
• 英文别名: 2,5,5-trimethyl-2-(3-bromopropyl)-1,3-dioxane；2-(3-bromopropyl)-2,5,5-trimethyl-1,3-dioxane
• CAS: 88128-58-9
• 化学式: C₁₀H₁₉BrO₂
• 分子量: 251.164
• InChiKey: LMXZEIFLUKZZGD-UHFFFAOYSA-N

物化性质

• 沸点：
  90-105 °C(Press: 0.05 Torr)
• 密度：
  1.181±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-methyl-2-(3-bromopropyl)-5,5-dimethyl-1,3-dioxane 在 titanium(IV) isopropylate 、 盐酸 、 叔丁基过氧化氢 、 氢氧化钾 、 copper(l) iodide 、 lithium amide 、 (-)-diisopropyl tartrate 、 3 A molecular sieve 、 lithium 、 lithium bromide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 正戊烷 为溶剂， 反应 31.0h， 生成 (1S,5R,7R)-5-methyl-7-ethyl-6,8-dioxabicyclo[3.2.1]octane
  参考文献：
  名称：

  Synthesis of the enantiomers of endo-brevicomin

  摘要：

  DOI：

  10.1021/jo00381a044
• 作为产物：
  描述：

  α-乙酰基-γ-丁内酯 在 硫酸 、 氢溴酸 、 溶剂黄146 、 原甲酸三甲酯 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 4.5h， 生成 2-methyl-2-(3-bromopropyl)-5,5-dimethyl-1,3-dioxane
  参考文献：
  名称：

  缩醛官能化三烷基鏻盐的区域选择性叶立德形成：扩展羰基同系化的范围

  摘要：

  在缩醛和缩酮官能化的三烷基膦衍生的鏻盐上发现复合物诱导的邻近效应和区域选择性叶立德形成的范围被探索作为同系不饱和羰基衍生物的途径。

  DOI：

  10.1055/s-0036-1588551

文献信息

• Oxepanes from an unusual acetal cleavage of 6,8-dioxabicyclo[3.2.1]octanes
  作者：Scott D. Rychnovsky、Vilas H. Dahanukar

  DOI：10.1016/0040-4039(95)02167-1

  日期：1996.1

  On treatment with BF3·OEt2 and TMSCN, epoxy ketone 1 cyclized to the bicyclic acetal 2, which then cleaved to give primarily the oxepane 5 as a single stereoisomer. Reductive decyanation of 5 led to the oxepane 7, a structural unit present in the brevetoxin family of natural products. The scope and limitations of this reaction sequence were investigated.

  用BF 3 ·OEt 2和TMSCN处理后，环氧酮1环化成双环缩醛2，然后裂解产生环氧丙烷5，为单一立体异构体。5的还原性脱氰作用导致产生环氧丙烷7，环氧丙烷7是天然产品短毒素家族中的一个结构单元。研究了该反应顺序的范围和局限性。
• The composition and chemistry of the mixed higher-order cuprates (PhMe2Si)m(CH3)nCu(CN)Li(m+n)
  作者：Robert D. Singer、Allan C. Oehlschlager

  DOI：10.1021/jo00011a013

  日期：1991.5

  Low-temperature Si-29, C-13, and H-1 NMR spectroscopic techniques were used to probe the nature of THF solutions of cuprates derived from PhMe2SiLi, MeLi, and CuCN in the stoichiometric ratios 1:1:1, 2:1:1, and 1:2:1 (Si:Me:Cu). Unlike the corresponding mixed stannyl systems that yield R3Sn(R)2CuLi2 when the ratio of stannyl anion:alkyl anion:cuprous ion is 1:2:1, these mixed silyl systems only form R3Si(R)Cu(CN)Li2. Solutions wherein the ratio of silyl anion and alkyl anion to cuprous ion is greater than 2:1 contain alkyllithium uncoordinated with cuprous ion. The most striking result is the preferential displacement of RLi when R3SiLi is added to solutions of R3Si(R)Cu(CN)Li2 or R2Cu(CN)Li2. These mixed metallocuprate solutions preferentially transfer the PhMe2Si moiety in reactions with alpha,beta-unsaturated enones and other unsaturated organic substrates. However, the mixed alkylsilylcuprate (PhMe2Si)(CH3)Cu(CN)Li2 reacts with 1,2-epoxyoctane to afford up to 31% of the methylated alcohol. Frontier orbital analysis of both the predominant cuprates species and preferential ligand transfer provides a rationale for the observed behavior.
• Identification and synthesis of new bicyclic acetals from the mountain pine beetle, Dendroctonus ponderosae hopkins (Col.: Scol.)
  作者：W. Francke、F. Schröder、P. Philipp、H. Meyer、V. Sinnwell、G. Gries

  DOI：10.1016/0968-0896(96)00013-2

  日期：1996.3

  Head-space volatiles obtained from male mountain pine beetles, Dendroctonus ponderosae, were analyzed by coupled CC-MS and chiral gas chromatography. 5-Ethyl-7-methyl-6,8-dioxabicyclo[3.2.1] (6) was found as a new naturally occurring isomer of brevicomin (1). In addition, several stereoisomers of 7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1] (11) and 1-(5-methyl-6,8-dioxabicyclo[3.2.1]octyl)ethanol (12) could be identified. Relative and absolute configurations of the compounds were determined by unambiguous syntheses, which are described. Copyright (C) 1996 Elsevier Science Ltd
• Regioselective Ylide Formation on Acetal-Functionalized Trialkyl Phosphonium Salts: Extending the Scope of Carbonyl Homologation
  作者：Arkesh Narayanappa、David Hurem、James McNulty

  DOI：10.1055/s-0036-1588551

  日期：2017.12

  The discovery of a complex-induced proximity effect and scope of regioselective ylide formation on acetal- and ketal-functionalized trialkylphosphine-derived phosphonium salts is explored as a route to homologated unsaturated carbonyl derivatives.

  在缩醛和缩酮官能化的三烷基膦衍生的鏻盐上发现复合物诱导的邻近效应和区域选择性叶立德形成的范围被探索作为同系不饱和羰基衍生物的途径。
• Synthesis of the enantiomers of endo-brevicomin
  作者：Allan C. Oehlschlager、Blair D. Johnston

  DOI：10.1021/jo00381a044

  日期：1987.3